Science and Technology of Polymers and Advanced Materials Emerging Technologies and Business Opportunities - Yoshikazu - Ito - Professor - Paras - N. - Prasad

Science and Technology of
Polymers and Advanced Materials

Ernerging Technologies and
Business Opportunities
Science and Technology of
Polymers and Advanced Materials
Ernerging Technologiesand
Business Opportunities
Edited by
Paras N. Prasad
State University ofNew York at Buffalo
Buffalo, New York
James E. Mark
University of Cincinnati
Cincinnati, Ohio
Sherif H. Kandil
Alexandria University
Alexandria, Egypt
and
Zakya H. Kafafi
Naval Research Labaratory
Washington, D.C.
Springer Science+Business Media, LLC

Ubrary of Congress Cataloging-in-Publication Data
Science and technology of polymers and advanced materials: ernerging technologies and
business opportunities I edited by Paras N. Prasad ... [et al.].
p. cm.
"Proceedings of the Fourth International Conference on Frontiers of Polymers and Ad-
vanced Materials, held January 4-9, 1997, in Cairo, Egypt"-T.p. verso.
Includes bibliographical references and index.
1. Polymers-Congresses. I. Prasad, Paras N. II. International Conference on Frontiers of
Polymers and Advanced Materials (4th: 1997: Cairo, Egypt)
TA455.P58S38 1998
620.1'92-dc21 98-21006
CIP
Proceedings of the Fourth International Conference on Frontiers of Polymers and Advanced Materials,
held January 4-9, 1997, in Cairo, Egypt
ISBN 978-1-4899-0114-9 ISBN 978-1-4899-0112-5 (eBook)
DOI 10.1007/978-1-4899-0112-5
Cl Springer Science+Business Media New York 1998
Originally published by Plenum Press, New York in 1998
Softcover reprint of the bardeover 1st edition 1998
http://www.plenum.com
10 9 8 7 6 54 3 2 I
All rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any
means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written
permission from the Publisher
Honorary Chairperson
H. E. Professor Dr. Venice Kamel Gouda
MINISTER OF SCIENTIFIC RESEARCH
ARAB REPUBUC OF EGYPT
Honorary Council
MINISTER OF EDUCATION, H. E. Professor Dr. Hussein Kamel Baha EI Din
MINISTER OF PETROLEUM, H. E. Professor Dr. Hamdy EI Banby
MINISTER OF SCIENTIFIC RESEARCH, H. E. Professor Dr. Venice Kamel Gouda
MINISTER OF INDUSTRY, H. E. Eng. Soliman Reda Ali Soliman
MINISTER OF ECONOMY AND INTERNATIONAL COOPERATION, H. E. Professor
Dr. Nawal Abdel Moneim EI Tatawy
Conference Chairpersons
International Chairperson National Chairperson
Professor P. N. Prasad Professor H. A. Aziz Moursy

Director, Photonies Research Labaratory Vice President, Academy of
State University ofNew York Scientific Research and Tech.
Buffalo, N. Y., USA Cairo, EGYPT
Co-Chairpersons
Professor J. E. Mark Professor F. E. Karasz Professor Sherif Kandil

Distinguished Research Professor S.O. Conte Distinguished Prof. Institute ofGraduate Studies
Depar1ment of Chemistry Dept. of Polymer Scince and Engin. Alexandria University
University ofCincinnati University ofMassachusetts Alexandria, EGYPT
Cincinnati, Ohio, USA Amherst, MA, USA
International Coordinator
Dr. Zakya Kafafi
Naval Research Labaratory
Washington, DC USA
Internationational Advisory Committee
Dato' Dr. Ahmad Tajuddin Ali Prof V. Kouzminov

Director-General Chief, UNESCO Regional Office of Science
Standards and Industrial Research Institute and Technology Europe (ROSTE)
ofMalaysia (SIRIM) Venice, IT ALY
Shah Alam, Selangor, MALAYSIA
Dr. J. Lee
Professor I. S. Al-Naimi Director General
President, University of Qatar lndustrial Technology Research Institute
Doha, QATAR TAIWAN
i>r. M. I. Al-Qurtas Dr. F. Marruffo

Director General General Manager ofRefining
Research and Development and Petrochemieals
Saudi Basic lndustries Corp. (SABIC) Intevep, VENEZUELA
Riyadb, SAUDI ARABIA
Dr. R. A. Mashelkar
Dr. A. Baylis Director General, CSIR
Vice President Secretary, Dept. OfScientific & Research
Advanced Materials Group New Delhi, INDIA
Hoechst Celanese Corporation
Summit, New Jersey, USA Professor G. A. Olah
(1994 NobelLaureatein Chemistry)
Dr. G. Fearon University of Southem California
Vice President - Research Los Angeles, CA, USA
DOWCorning
Corning, MI, USA Dr. H. Rizk
Chairman, BMF Group of Companies
Dr. A. Guzdar Cairo, EGYPT
Vice President
Foster Miller Company, lnc. Dr. D. J. H. Smith
Waltham, MA, USA CEO & Director ofResearch
and Development
Dr. Y.lto Whatman plc, UNITED KINGDOM
Former Chairman ofthe Board
Senior Advisor and Dr. J. K. Yeo
SeniOt Counselor Director, Lucky Limited
Toray Industries, JAPAN Dae Jeon, KOREA
vi
International Program Committee
Professor Dr. M. A. El-Sayed (Chairman) Professor I. L. Kamel

Georgia Institute Of Technology Dean, College ofEngineering
Atlanta, GA, USA United Arab Emirates University
Al-Ain, United Arab Emirates
Dr. I. Ahmad
Army Research Office Professor I.C. Khoo
Research Triangle, NC, USA Pennyslvania State University
University Park, PA 16802 USA
Dr. D. D. Bhawalkar
Director, Center for Advanced Technology Professor S. C. Kim
Indore, INDIA Korea Advanced Institute of Science and
Technology
Dr. 0. H. Elbayoumi Seoul, KOREA
United States Air Force
International Corporative Programs Professor S. Lefrant
ESC/IAR Institut des Materiaux
HanscomAFB Nantes, FRANCE
Massachusetts, USA
Professor S. Mjyata
Professor A.S. Gomes Tokyo Univ. of Agriculture and
President, Brazilian Polymer Society and Technology
Director, Instiuto de Macromoleculas Tokyo, JAPAN
Professara Eloisa Mano
Rio de Janeiro, BRAZIL Professor N. Ogata
Sophia University
Dr. H. A. Hamroush Tokyo, JAPAN
American Embassy
Cairo, EGYPT Professor H. Schmidt
Institut fur Neue Materialien
Dr. F. Kajzar Universitat des Saarbrucken
CEAIIRDI GERMANY
Dein/Lpem FRANCE
Professor C. Taliani
Instituto di Spettroscopia Molecolare
Consiglio Nazionale delle Ricerche
Bologna, ITALY
vii
National Advisory Committee
Professor Nabil Y. Abou-Zeid (Chairman) Chemist Abdel Moez Okeil

Vice President, R & D, Academy Chairman, Misr chemical Company
ofScientific Research and Technology Alexandria, EGYPT
Cairo, EGYPT
Dr. lbrahim M. Hussein Mr. Al Motaz Bellah Abdel-Maksoud

Secretary General Chairman
Egypt-US President's Council Misr Co. for Spinning and Weaving
Cairo, EGYPT Mehalla El-Kubra
National Organizing Committee
Professor Badran M Badran (Chairman) Professor Abdel Rahman Moussa

National Research Center Faculty of Science, Ain Shams
Cairo, EGYPT University, Cairo, EGYPT
Professor Alaa Eldin A. Bahgat Dr. AshrafMansour

Al Azhar University Cairo University
Cairo, EGYPT Cairo, EGYPT
Dr. Mohamed Resharn EI-Sherif Professor Mohamed Abdella El Gamal

Supervisor, Cabinet Information and Head of Arab Society for Materials
Decision Support Center Science, Alexandria University
Cairo, EGYPT Alexandria, EGYPT
Professor Mahmoud Rashirn Abdel-Kader

National Institute ofLaser Enhanced Seiences
Cairo, EGYPT
viii
PREFACE
This book summarizes the state ofthe art research presented at the Fourth International
Conference on Frontiers of Polymersand Advanced Materialsheld in Cairo, Egypt in January 4-9,
1997. This conference follows the successful conferences held in Kuala Lumpur, Malaysia in 1995,
in Jakarta, Indonesia in 1993 andin New Delhi, India in 1991. These conferences focussed on the
most recent and important advances in a wide range of carefully chosen subject areas dealing with
advanced materials, their science and technology and new business opportunities resulting from
recent technological advances. As its predecessors, the conference held in Cairo was truly
international with strong participation of 488 deiegales representing 37 countries from the USA and
Egypt, as weil as Europe, South East Asia, Japan, South Africa and the Middle East.
The conference was organized by the Egyptian Academy of Scientific Research and
Technology, The Arab Society ofMaterials Science and the State University ofNew York at Butfalo.
The stated goals ofthe conference were:
To highlight advances and new.findings in the general area of polymers and advanced
materials. -
T o foster global collaboration between the USA, Egypt and other nations in the
general field of polymers and advanced materials.
To promote the development of scientific ilifrastructure in this field among the

different participating countries, especially in the Middle East.
To create a basisforfuture long-term scientific exchanges between the USA and

Egypt, and/or other countries.
T o induce Egypt and other countries in the Middle East to move to advanced
polymer/cerarnie production via international cooperation.
To prevent environmental contamination in the region through enhancing production

(~f environmentallycompatible polymers in existing polymer production.
At the inaugural session, distinguished guests were present and gave short speeches on the
importance of such conferences for the promotion of collaboration between scientists, industrialists
and business people worldwide. The Head of the Egyptian Academy of Seienlifte Research and
Technology who was also the National Chairperson ofthe conference, Dr. Hamdy Abdel Aziz
Moursy, opened the conference and introduced the keynote speaker The Minister of State for
Scientific Research, Dr. Venice Gouda. Dr. Gouda congratulated Professor Paras Prasad, The
International Chairperson, for bringing this conference to Egypt. She commented that this
conference was timely due to the recent science and technology agreement signed between the U.S.A.
and Egypt as part ofthe Gore-Mubarak initiative. Dr. Nawal El-Tatawy, Minister o.f Economy and
International Cooperation, gave a speech pointing to the importance of science and technology in
the development ofthe Egyptian economy through small businesses and entrepreneurial etfort Dr.
ix
Mohamed EI-Ghamaraawy, Minister ofState ofMilitary Produc.1ion welcomed the business forum
of the conference. This was foilowed by a speech from Mr. John Wisley, the Head of USAID
Mission to Egypt who represented the American Ambassador,. The Japanese ambassador, Kunio
Katakura made the final concluding remarks at the Inaugural session.
The proceedings reflect the subjects ofthe 288 oral and poster presentations discussed in
60 technical sessions which were held in eight parallel symposia on 1. Composites and Blends,
2. High Peiformance Materials, 3. Materials for Electronics and Photonics, 4. Biomaterials and
Biotechnology, 5. Degradation, Stabilization and Recycling of Materials, and Emimnmentally
Friendly Processing, 6. Sol-Gel Processed Materials, 7. Advanced Materials from Naturaland
Petroleum Products, and 8. Materials for Separation Technology. There was also a Business
Symposium focussing on new business opportunities and finances, technology transfer and
investment, internationallicensing and patents as weil as another session for Educational Needs and
Trends.
The Editors gratefuily acknowledge the help and cooperation of the members of the
International and National Advisory Committees, and the International and National, Program
Committees. Special thanks go to the Honorary Chairperson, Dr. Venice Kamel Gouda, Minister of
Scientific Research, Arab Republic of Egypt, and the members of the Honorary Council. The
conference sponsorships were provided by Ministry ofEconomics and International Cooperation,
Egypt; Cabinet's Information and Decision Support Center (IDSC) Cairo, Egypt; Dow Corning,
USA; European Office of Aerospace Research and Development, U. S. Air Force; European
Research Office, United States Army; Hoechst - Celanese, US~ International Development Research
Centre, IDRC. Canada; International Institute ofTheoretical Physics Trieste, Italy; Office ofNaval
Research, Europe; Office of Naval Research, USA; Saudi Basic Industries Corporation (SABIC);
Social Fund for Development, Egypt and TORA Y Industries, Japan.
lt is our hope that this book will serve as a useful reference for researchers in academic,
industrial and research institutes as weil as for those interested in new business opportunities in the
field of Polymers and Advanced Materials.
P. N. Prasad J. E. Mark SherifKandil Zakya Kafafi

State Univ. ofNew York Univ. OfCincinnati Alexandria University Naval Res. Lab.
Buffalo, New York Cincinnati, Ohio Alexandria Washington, DC
USA USA EGYPT USA
X
CONTENTS
GENERAL PLENARY SESSION
Light and the New Chemistry-Expectation for Photo Technologies ................... 1

Yoshikazu Ito
COMPOSITES AND BLENDS
Reactive Extrusion Compatibilization of Poly (Vinyl Alcohol)

Polyoietin Blends ....................................................................... 9
Uoyd M. Robeson, Amir Famili, and James F. Nangeroni
Miscibility and Properties of Liquid Crystalline P-Acetoxy Benzoic Acid

Copolyester/Polybutylene Terephthalate Blends .................................. 25
T. K. Kang, Y. Kim, W. J. Cho, and C. S. Ha
Analysis of Fracture Processes in Cross-Ply Laminates ............................... 35

J.-M. Berthelot
Thermoplastic Polymer Blends Containing Conductive Polyaniline .................. 51

Olli T. Ikkala, Pentti Passiniemi, and Jan-Erik sterholm
In-Situ Composite Processes from PEI/TLCP Blends .................................. 61

S. S. Hwang, S. M. Hong, Y. Seo, and K. U. Kim
Electrical and Mechanical Characterization of PEO-LiN(CF3 S~h

Electrolytes ............................................................................. 75
Hakima Halitim, Djafer Benachour, and Abderrezak Hammouche
ffiGH PERFORMANCE MATERIALS
Improved Elastomers through Control of Network Chain-Length Distributions ... 85

J. E. Mark
Surface Properties of Silicone High Voltage Insulators ................................ 99

Michael J. Owen
xi
Synthesis of Block and Graft Copolymers Containing Liquid Crystalline
Segments .............................................................................. 107
Allton S. Gomes, Mauricio R. Pinto, and Celton A. Barbosa
Recent Development of Chemical Resistant Styrenic Polymers for the

Refrigerator ........................................................................... 117
Kyung H. Ahn and SangS. Woo
Simulations on Thermoplastic Elastomers From Polypropylene ..................... 125

Tarek M. Madkour and James E. Mark
The Properties of Poly (Ethylene Naphthalate) (PEN) and lts Application ........ 141
Jiro Sadanobu and Hiroo Inata
Study of Energy Gap and Electronic Transitions in Model Polymer Systems:

Electronic Versus Optical Excitations ............................................. 153
J. J. Pireaux, G. Gensterblum, C. Gregoire, B. Y. Han, K. Hevesi,
C. A. Fustin, P. Rudolf, L. M. Yu, R. Caudano, D. A. Leigh, and F. Zerbetto
Template Polymerization of Dimethylaminoethyl Methacrylate in the Presence of

Poly(Acrylamide-Acrylic Acid) Induced by Gamma Radiation and lts Use
for Removal ofMetal Ions .......................................................... 165
T. Siyam and Z. H. Abd-Elatif
Acid Corrosion Inhibition of Nickel by Some Organic/Macrocyclic

Compounds ........................................................................... 175
F. M. Mahgoub, B. A. Abd-El-Nabey, M. Khalifa, and A. El-Hefnawy
MATERIALS FOR ELECTRONICS AND PHOTONICS
Advanced Spatial Light Modulator by Using Polymer Cell-Wall Type Liquid

Crystal Light Shutter ............................................................... 185
Tadahiro Asada
Efficient Fullcolour Light-Emitting Devices and Lasers with Polyphenyls ........ 193
G. Leising, F. Meghdadi, S. Tasch, C. Brandst.tter, W. Graupner, S. Hampel,
J. W. E. List, F. Stelzer, B. Winkler, C. Zenz, P. Schlichting, U. Rohr,
Y. Geerts, U. Scherf, and K. Mllen
Novel Organic Composites Based on N-Substituted Quinacridone Derivatives for

Molecular Organic Light-Emitting Diodes ....................................... 207
Hideyuki Murata, Chiules D. Merrit, and Zakya H. Kafafi
Photorefractivity and Optical Wave Mixing Effects in Nematic Liquid Crystals

Doped with Fullerene Derivatives and Dyes ..................................... 215
Brett D. Guenther, M. V. Wood, and I. C. Khoo
xii
A Model for Single-Moleeule Information Storage ................................... 231
Christopher B. Gonnan, Brandon Parkhurst, Kang-Yi Chen, Wendy Su, Michael
Hager and Igor Touzov
Cluster Size Effects as a Bridge to Molecular Electronics ............................ 241

Joshua Jortner
Electric Field Effect on Frenkel-Wannier-Mott Exciton States in Organic-

Inorganic Semieonductor Quantum Wells ........................................ 251
S. Jaziri
Chirality Effects in Second-Order Nonlinear Opties ................................... 259

Martti Kauranen, Thierry Verbiest, Sven Van Elshocht, and Andre Persoons
Highly Orientahle Liquid Crystalline Polymers for Quadratie Nonlinear Opties .. 275
C. Noel and F. Kajzar
Solution Properties of Conducting Polymers ........................................... 299

Jae Yoon Lee and Hoosung Lee
High-Speed Photonies Polymer-Transmission and Display ........................... 309

Takaaki Ishigure, Akihiro Horibe, Eisuke Nihei, and Yasuhiro Koike
High Density Disc Storage by Multiplexed Microholograms ........................ 329

Stefan Diez, Robert Elschner, Rainer Macdonald, Roland Schulz, Andreas
Wappelt, and Hans Joachim Eiehier
Polymersand Organie-Inorganic Hybrids for Second-Order Nonlinear

Opties ............................................................................... ... 333
Kwang-Sup Lee, Sung-Bae Lee, Kyung-Bok Lee, Hong-Ku Shim,
Ki-Jeong Moon, Han Young Woo, Choon Sup Yoon, and Yoo Hong Min
Recent Progress in Nonlinear Photonie Deviees and Phenomena Basedon Organic

Materials .......... : ................................................................... 349
George I. Stegeman, Akira Otomo, Mattbias Jaeger, Christian Bosshard,
Rien Flipse, and Michael Canva
Neutral and Doped States of Polymers with Aromatie Rings Studied by Resonance
Spectroscopies ........................................................................ 365
S. Lefrant, J. P. Buisson, M. Baitoul, I. Orlon, A. Simonneau and G. Froyer
Advanced Organie Materials for Optoelectronic Integrated Devices,

Interconnects, and Packaging ...................................................... 375
Sandalphon, E. Hendrickx, J. Herlocker, G. E. Jabbour, Y. Kawabe,
B. Kippelen, M. M. Morrell, S. E. Shaheen, D. D. Steele, J. F. Wang,
and N. Peyghambarian
xiii
Synthesis of a Covalent Square Grid ..................................................... 385
Thomas F. Magnera, Jaroslav Pecka, and JosefMichl
Nanoscale Synthesis and Processing of Multifunctional Polymers and

Composites for Photonies ........................................................... 393
N. Deepak Kumar, Manjarl Lal, and Paras N. Prasad
Interface Control of Polymer-Based Light-Emitting Devices ........................ 403

A. J. Epstein, Y. Z. Wang, and D. D. Gebier
Electrical Transport and Magnetoconductivity in Doped Polypyrrole .............. 411

M. D. Migahed, T. Fahmy, and S. Roth
Electrical Properties of Pure PVC ....................................................... 421

A. A. Bahgat, S. M. Sayyah, and H. S. Shalabi
Emission Characteristics of a New Class of Strongly Fluorescent Phenanthrene

and Phenanthrene-Like Derivatives ............................................... 429
Nahed M. Fathy, Essam. M. Hassan, and Khaled A. Abou-Zeid
BIOMATERIAL AND BIOTECHNOWGY
Gelatin-Poly (Vinyl Alcohol) Blends as Bioartificial Polymerie Materials ......... 449

Paolo Giusti, Niccoletta Barbani, Luigi Lazzeri, Giovanni Polacco, Caterina
Cristallini, and Maria G. Cascone
Production of Poly (3-Hydroxybutyrate) by Recombinant Bacteria ................. 463

Sang Yup Lee, Jong-il Choi, and Fulai Wang
Chemoenzymatic Synthesis of Water-Soluble Sugar-Branched

Poly (Vinyl Alcohol) ................................................................ 477
Yutaka Tokiwa and Masaru Kitagawa
Preparation and Potential for Application of Cationic Polysaccharides in

Cosmetic Formulations .............................................................. 493
William H. Daly, Melissa Manuszak Guerrini, Doris Culberson,
and Javier Macossay
Interaction of Oligopeptides with Heparin .............................................. 513

Ruifeng Zhao, Mamoru Haratake, and Raphael M. Ottenbrite
Dendrimeric Antenna Supermolecules with Multistep Directed Energy

Transfer ............................................................................... .521
Stephen F. Swallen, Michael R. Shortreed, Zhong-You Shi, Weihong
Tan, Zhifu Xu, Chelladuri Devadoss, Jeffrey S. Moore, and Raoul Kopelman
xiv
Cell Behavior on Polymer Surfaces with Different Functional Groups ............. 535
Jin Ho Lee, Jin Whan Lee, Gilson Khang, and Hai Bang Lee
Composite Hydrogels as Intervertebral Disc Prostheses .............................. 547

L. Ambrosio, R. De Santis, and L. Nicolais
Applications of Temperature-Responsive Polymers for Optical Resolution ........ 557

Naoya Ogata
Biodegradation and Medical Application of Chitosan Hard Capsule ................ 567

Tsutomu Suzuki, Takayuki Matsumoto, Yoshinori Hagino, Hideyuki Tozaki,
Akira Yamamoto, and Shouzou Muranishi
DEGRADATION, STABll..IZATION AND RECYCLING OF MATERIALS, AND

ENVIRONMENTALLV FRIENDLY PROCESSING
Degradation Studies of Activated Polyethylene in Polyethylene-Starch

Polyblends............................................................................. 573
N. M. Surdia, E. Noorlaila, E. Rohaeti, Kushardianti, and M. Zaenuddin
Wavelength Sensitivity in the Photo-Degradation of Polymethyl Methacrylate:

Accelerated Degradation and Gel Formation .................................... 581
Ayako Torikai
Photooxidation of Polyphasic Ethylene-Propylene Polymers......................... 587

Jean-Luc Gardette and Patrick Delprat
Nylon 66, Nylon 46 and PET Phase Transfer Catalyzed Alkaline

Depolymerization at Atmospheric Pressure ...................................... 597
Maleolm B. Polk, Leighton L. Laboeuf, Munish Shah, Chee-Youb Won,
Xiaodong Hu, and Wen Ding
Some Topics in Polymer Recycle in Japan .............................................. 603

Matsuo Hirami
Corporate Management in the Age of Global Environment Awareness - A

Case Study of PET Bottle Recycling Issues in Japan ........................... 613
Naoya Yoda
Recycling of Polyamide 66 and 6 ........................................................ 629

H. Peter Kasserra
SOL-GEL PROCESSEn MATERIALS
Sol-Gel Technology for French Inertial Confmement Fusion Program ............. 637
Philippe Belleville
XV
Smart Thin Films via the Sol-Gel Route ................................................ 649
Jacques Livage
Synthesis and Processing of Nano-Scale Materials through Chemistry ............. 663

Helmut K. Schmidt
ADVANCED MATERIALS FROM NATURALAND PETROLEUM PRODUCTS
Environmentally Friendly Adhesive Systems ........................................... 675

P.O. Oiesen and Peter Folting
Lignocellulosic Polymer Composites .................................................... 679

Ryszard Kozlowski and Malgorzata Helwig
'
Liquefaction of W ood and Its Applications ............................................. 699
Nobuo Shiraishi
Enzymatic Bonding Systems .............................................................. 709

Claus Felby and Per Oie Oiesen
Property Enhanced Natural Fiber Composite Materials Based on Chemical

Modification .......................................................................... 717
Roger M. Rowell
Chemical Modification of Lignocellulosics Using Microwave Technology ........ 733

Pia Larsson Brelid and Rune Simonson
New Resin System from ,Lignin ......................................................... 747

Bunichiro Tomita
Applications of Natural Fibers in Automotive Industry in Brazil -

Thermoforming Process ............................................................. 755
Alcides L. Leao, Roger Rowell, and Nilton Tavares
lmprovement in Sudace Properties of Lignocellulosics Using Cold-Plasma

Treatment ............................................................................. 763
F. Denes and R. A. Young
The Petrochemical Industry and Natural Gas: A Strategie Allience ................. 781
Jasern M. Al-Besharah
MATERIALS FOR SEPARATION TECHNOWGY
Preparation of Silica-Based Membrane for H 2 Separation by Multi-Step

Pore Modification .................................................................... 797
Jae-Hyun So, Seung-Man Yang, and Seung Bin Park
xvi
Application of Polymer Membranes to Alcohol Concentration in Fermentation
of Biomass ............................................................................ 805
Tadashi Uragami
Pervaporation of Alcohols by Using Tubular Type Cellulose Acetate and

Polysulphone Membrane with Ceramic Support ................................. 815
Kyu Min Song, Yeon Ki Hong, and Won Hi Hong
The Highest Gas Permeable Membranes of Poly [1-(Trimethylsilyl)-1-Propyne]-

Their Gas Fermeability and Modification ........................................ 821
Tsutomu Nakagawa
Sol-Gel-Derived Materials for Analytical Separations ................................ 835

Luis A. Colon
Transport of Multicomponent Gas Mixtures through Polymerie Membranes ...... 845

Mohammad Soltanieh and Mahta Momeni
EDUCATIONAL NEEDS AND TRENDS
Benefits of Capstone Design Courses in Materials Education ........................ 859

R. W. Heckel, W. W. Milligan, C. L. Nassaralla, J. Pilling,
and M. R. Plichta
BUSINESSOPPORTUNITrnS
Economic Opportunities in Natural Fiber-Thermoplastic Composites .............. 869

Roger M. Rowell
Silicone Surface Science Opportunities .................................................. 873

F. W. Gordon Fearon and Michael J. Owen
xvii
LIGHT AND THE NEW CHEMISTRY
- EXPECTATION FOR PHOTO TECHNOLOGIES
Yoshikazu Ito
Senior Advisor & Senior Counselor

Toray lndustries, Inc.
2-1, Nihonbashi- Muromachi 2- chome,
Chuo- ku, Tokyo 103, JAPAN
THE DAWN OF PHOTOCHEMISTRY
Sun light has been providing clean energy on the Earth since the mythical age. Almost all
livings on the Earth have been benefiting from the solar energy through photochemical and
biochemical processes in nature. So, photochemistry is fundamentally an eco- and
human- friendly technology. However, it took us a long time to utilize the photochemical
reaction practically. Table 1 shows the epoch- making discoveries at the dawn of
photochemistry.
Table 1. The Dawn of Photochemistry

h
Schultz ( 1727 ) Aao co. ........ Decomposilion Reslclue
hv
Daguerre ( 1840 ) Aal --+Ag+ 11212
Draper ( 1850) ""+ c~o ~2HCI

Einstein ( 1910) Law of Photochemlcal Equlvalency
I Elna1eln-Stark's Law)
Lynn ( 1919) C7H,o+ NOCI~ C'H=NOHHCI
Cl
Unden ( 1921) 0+3Cb hv Cl~:('

Taytor ( 1945) ....... Cl Cl
Cl
no ( 1961) +NOCI~ =NOH2HCI
In 1727, about 300 years ago, a German medical doctor Schulz found that silver
carbonate decomposes under sun light. Then, 100 years later from his discovery, Dr. Daguerre
in France invented the basic technology of photography based on silver salt reaction. This was
Science and Technology of Polymers and Advanced Materials

Edited by P. N. Prasad et al., Plenum Press, New York, 1998
the first application of photochemistry to practical use. In 1850, Dr. Draper observed that
hydrogen reacts with chlorine under ultraviolet light to form hydrogenchloride. This was the
first arti:ficial photosynthesis of chemicals. In 1921, Dr. Linden invented the photochlorination
of benzene which was industrialized by Dr. Taylor in 1945 for the mass- production of
benzenehexachloride, BHC. This compound was a very effective insecticide used widely after
World War II. The production is, however, prohibited today because of the pollution problem.
In 1919, Dr. Lynn reported the photonitrosation reaction of normal alkanes yields
alkanon-oxime. The author discovered that cyclohexane reacts with nitrocylchloride under
sun light to yield cyclohexanon- oxime in 1951. This new photochemical reaction called the
Photo Nitrosation of Cyclohexane, shortly PNC, was commercialized in large scale by Toray
Industries, Inc. for the production of t: - caprolactam which is used as a raw material of
Nylon 6.
PHOTO TECHNOLOGIESAND BUSINESSES IN TORAY
Table 2 shows some examples of basic research in Toray concerning photo technologies
and the new businesses derived from them. Toray industrialized PNC process for caprolactam
production in 1963, as described above. PNC technology and lamps developed were applied to
a system of waste water treatment later.
Basic research of holography resulted in the commercialization of Kanji (Chinese
Character) Printer in 1972, although the holographic memory was replaced by a silicone chip
few years later. Polymer chemistry is the core and strongest research field in Toray. The
Company developed various kinds of electronic and printing materials based on basic research
on photosensitive polymers. Basic research on light transmission functions has been bearing
fruit in the fields of optical goods or materials for information technologies. The newest
example is the optical disk, PHASEWRITE .
(1) PHOTO SYNTHESIS OF t: -CAPROLACTAM

In PNC process, cyclohexane reacts with nitrocylchloride under irradiation of light and
yield cyclohexanon- oxime in one step, which cau be easily rearranged into caprolactam by
Table 2. Photo Technologies & New Businesses in Toray
Basic Research New Business Commercialized
Photochmical &-Caprolactam in 1963

Reactions Waste Water Treatment ( LIGHTOX") 1974
Holography Kanji Printer ( Replaced by IC ) 1972
Nylon Printing Plate ( TORELIEF") 1977

Photosensitive
Waterless Printing Plate (ALP") 1979
Polymers
Polyimide Photoresist ( PHOTONEECE") 1981
Soft Contact Lens ( BREATHO) 1981

Dvr Optical Filter ( EFILTER ) 1983
Light Transmission
Plastic Optlcal Fiber ( RAYTELA) 1989
Functions
Color Filter for LCD ( TOPTICAL ) 1990
Optical Disk ( PHASEWAlTE ) 1995
2
Conventional Process
. . . . .-I
(0) (0) HzNOH
~~t,
(CHz)5 +Nylon&
PNC Process
/! ~NH
+ NOCI hv
Cij) &-Caprolactam
NOH
Figure 1. Synthetic Process of c - Caprolactam
famous Beckman rearrangement. The process scheme is shown in Figure 1 compared with the
conventional one. This photochemical reaction is a non- chain reaction, different from the
chlorination reaction of benzene. As one photon initiates only one reaction in this process, the
quantum yield of light is very low. In spite of inefficiency of the process, Toray succeeded in
commercializing this photochemical reaction for the mass- production of E - caprolactam.
The success of industrialization of PNC process much depended on the development of a
highly efficient mercury lamp with high capacity. Coworking with Toshiba Electric lnc. made
it possible to develop such an excellent lamp. The first lamp we developed in 1959 was a
10- kw Hg-lamp which was about 50 cm in length. It was the largest lamp in the world then.
The lamp has been continuously improved to the currently used one which is a 50 kw Na-lamp
of more than 300 cm in length.
A pilot plant was built in 1960 and the first production plant with a capacity of 30
tons/day was built in 1963 after 3-year developing work of the pilot plant. Toray made a
decision to replace all the conventional processes with PNC process after only one year
successful Operation at this plant. The replacement was completed in 1972. Today, Toray's
total production capacity is 180 X 10 3 tons/year, which corresponds to one-third of
caprolactam production in Japan.
PNC process has many advantages over conventional process. One is a high caprolactam
yield based on the raw materials. For example, cost unit of ammonia of PNC process in
production of E -caprolactam is 0.56 which is almost one halfofthat of conventional one. The
second is a sharp reduction of by- product, ammonium sulfate. The cost unit of ammonium
sulfatein PNC process is 1.4 which is almost one-third ofthat of conventional one.
PNC process consumes five times more electric power than conventional one dose because
of using light energy. The process, however, succeeded in remarkable reduction of steam
consumption. In total, PNC process consumes only 30% more energy than the conventional
one. From the view point of Life Cycle Analysis, that is, the analysis of the total consumption
of materials and energy, PNC process is more eco-friendly than conventional one.
(2) WASTE WATER TREATMENT SYSTEM

Toray applied PNC technology and the lamp to waste water treatment and succeeded in
the commercialization of the waste water treatment system named LIGHTOX in 1974.
LIGHTOX purifies waste water efficiently by the synergistic effect of UV-light and
oxidizing agent such as chlorine or sodium hypochlorite. The hypochloraus ion formed by the
dissociation of chlorine dissolved in water generates nascent oxygen under irradiation of light.
Nascent oxygen's oxidation power is 10 times stronger or more comparing with that of chlorine
itself in the dark. It also oxidizes the organic waste dissolved in water into carbon dioxide and
water efficiently. Unlike other processes such as a flocculation and an activated-sludge,
LIGHTOX forms no sludge. Therefore, this process is free from serious sludge problems at
the aftertreatment stage.
3
OC
ooc
.
.
XX1
&
CONH
..
coo
e
-o-
-
o -o-~
-
NH t. Pho~-
n
+Sensttizer
~ ~
CH3
I
R* : CH2=c-coo CH2 CH2-
R : CH3-
Figure 2. Photo-Sensitive Polyimide, PHOTONEECE
LIGHTOX can be applied to tbe purification of various kinds of waste water. It is

effective on (a)decoloration of dyes, (b)elimination of odor, (c)reduction of BOD & COD, and
(d)decomposition of surfactants. The only drawback of LIGHTOX is tbat it bas a relatively
high energy cost compared with other conventional processes.
(3) PHOTOSENSITIVE POLYMERS

Toray commercialized photosensitive polyimide named PHOTONEECE in 1981 based on
its in- house photochemical and polymer technologies. Figure 2 shows the chemical structure
of PHOTONEECE . The main cbain is a polyimide precursor obtained from pyromellitic
dianhydride and 4,4'-diaminodiphenylether. This precursor is unique as the photosensitive
groups are linked with main chain by ionic bonding.
PHOTONEECE has two main advantages over conventional photosensitive polymers.

One is better processability owing to the ionically bonded precursor which Ieads to sbarp
pattem formation and relatively low temperature curing. The other is excellencies of physical
properties such as high temperature and high insulation resistance and toughness based on
polyimide structure after curing.
Typical examples of PHOTONEECE applications are (a)protective and insulating coat
for IC devices, (b) a -ray shielding coat for IC devices, and (c)an orientation film for liquid
crystalline display devices as weil. PHOTONEECE is playing an important role in supporting
IC industries.
(4) PHASE-CHANGE TYPE OPTICAL DISK

Toray started the basic research of phase- cbange type optical disk in 1980, expecting tbe
information revolution in the future. The company succeeded in commercializing a rewritable
optical disk named PHASEWRITE whose memory capacity is 650 MB and diameter is
120mm. The disk consists of six layers in total as shown in Figure 3. The thickness from tbe
Figme 3. Structure of PHASEWRITE
4
reflective Iayer to overcoat resin is only 280 nm. The key technology of PHASEWRITE is a
composition of the recording material alloy consisting of four kinds of metals; antimony,
tellurium, germanium and palladium.
A rewritable optical disk should have a function to write and erase simultaneously in one
rotation of the disk which is called a directly overwriting function. The crystallization speed of
the recording material is a key factor for the function and it should be faster than a critical
Ievel in practical use. The basic recording material of PHASEWRITE is composed of
antimony-tellurium alloy, and a part of antimony is replaced with noble metals such as
palladium or gold. This partial replacement of antimony with noble metals accelerates the
crystallization speed of recording material to the suitable Ievel for practical use, which is about
three times faster than that of the unmodified alloy at around 400 "C
RECENTPROGRESSOFPHOTOTECHNOLOGrns
There are four types of energy conversion initiated by a photon in photochemical

processes for information technology as shown in Figure 4.
The first type is the chemical reaction triggered by a photon. Photochemical hole burning
and photochromism are the examples which are main1y applied to an optical memory.
Secondly, a photon generates heat. This is observed in Kerr effect and a phase-change
phenomenon applied in an optical disk. The third one is an electron-activation by a photon.
An example is photoconductor used widely in electrophotography. Photodiode applied to CCD
and photomultiplier is another example. Lastly, a new photon having different nature derives
from the original one. This is applied in optical fiber amplifier, the second and the third order
nonlinear optics.
As basic research on future technologies such as new photochemistry involves high risk
and is time and money consuming, the Japanese Government established in 1981 the new
research program. This was " Research and Development Project of Basic Technologies for
Future lndustries , we said shortly "JISEDAI Project in Japanese. The project aimed at
promoting collaborative basic research among private, academic and governmental sectors, on
the high-tech field, such as superconductivity, new materials, and biotechnologies.
Seventy- three projects already finished and 36 projects are now on going. In the field of photo
technologies, there were four typical projects whose titles and budgets are listed in Table 3.
The first project was the Photoreactive Materials under which there were two
sub- research themes, photochemical hole burning and photochromism. The second was
Bioelectric Devices focusing on photoelectric converting and photoswitching functions. The
I Enerw Connnlon J [ Example J ( Appllcatlon )
! PHB (Memory l
./..,.....
=....
Photochromtsm (Memory)
Kerr Effects ( Optlcal Dlsk)

Phase Change 1 Optlcol Disk)
Photoconductor
'
( Electrophotography )
Photodiode
( CCO, Photomultiplier)
2nd NLO 1SHG l

3rd NLO ( Switch, Tran~1stor,
Memory, Amplifler)
Figure 4. Photoactive Materials for Information Tecbnologies
5
Table 3. R & D Projects on Photo Tecbnologies in Japan(JISEDAI)
Project Subject TotalBudget

Term
[Bilion Yen)
( t ) Photoreactlve (a) PHB
Materials ( b ) Photochromism 1985-92 2.0
' ) Photoelectric
( 2 ) Bio-Eiectronic Converting Devices
Devices ( b ) Photo SWitching
1986-95 2.4
Devices
3rd NLO and its

(3) NLO
Fabricatlon for Devlces
1989-98 3.7*
( 4) Molecular Aaseinblies
for Functlonal Protein Photosynthesis Protein 1989-98 3.8*
sv--
* '89- '98
third one is Nonlinear Optics and their fabrication into devices. The last one is Molecular
Assernblies for Functional Protein Systems including research on photosynthesis proteins. The
last two arestill under progress now.
(1) PHOTOCHEMICAL HOLE BURNING(PHB)

There is no doubt that the 21st Century will become a higbly intelligent information
society. Such a society will require high speed information-processing systerns and high
density data rnernories. PHB is expected as one of the bighest density optical rnernories.
A Russian researcher found for the :tirst time in the world that phthalocyanine pigments
show the PHB phenornenon at 4.2 Kin liquid He in 1974. In 1978, IBM proposed a new type
of optical rnernory using PHB phenornenon, and dernonstrated 10 ' bitslern 2 of data rnernories,
which was 100 times higher than that of an optical disk. In 1985, mM dernonstrated the
photon-gated hole burning which is useful for nondestructive reading. In 1987 under JISEDAI
Project, Toray found that ionic porphyrin derivatives in PVA film can make hole formation at
bigher ternperature of 77 K in liquid nitrogen. The rnechanisrn of hole formation of this
cornpound was assumed to be photo tautomeric transition. Also under the same Project,
Mitsubishi Electric Co. achieved the hole density of 10 ' bits/cm 2 using anthraquinone dyes in
layered PHEMA :tilms, which was the highest value in the world at that time.
In 1991, a researcher of Univ. of Geneva reported PHB phenornenon at the room
ternperature using Srn-doped Sr cornpound.
(2) PHOTOSYNTHESIS PROTEIN

The purpose of this subject is to elucidate a natural, complex protein systern having a
speci:tic and selective function, and to reconstitute the novel systern for a practical application
leading to an arti:ticial photosynthetic systern. Almost alllivings have been obtaining clean and
inexhausti"ble energy through photosynthesis. lmprovernent and application of the
photosynthetic systern in the nature should resolve the energy problern and contribute to the
environmental problern on the earth.
Figure 5 shows how protein complexes convert solar energy into chemical one in a
photosynthetic systern. Sun light is collected and concentrated in Phycobilisome protein
systern and the energy is converted into the chemical energy by the water splitting reaction in
another protein complex or Photosystem ll.
Toray and Toray Research Center Inc. have been studying the photosynthetic systern of a
thermophilic cyanobacterium under JISEDAI Project. A challenging target was to isolate the
6
Photosynthetlc Energy Conversion System
Solar Energy
Solar Energy Absorbing Protein
( Phycoblllsome )
APC ,..............,,.nlne
PC:~ne
Photosystem U
Photosynthetic Protein Complex
Membrane IIIP : ........lllzlntl Potein
D1,DZ:C........,.
llllldlnl Protein
Figure 5. Molecular Assernblies for FunctiOD8l Protein Systems
proteins closely relating to the photosynthesis and to analyze the molecular structure. The
next challenge should be an improvement of their heat-stability and ef:ticiency by using gene
and protein engineering.
Phycocyanin is a major protein included in Phycobilisome protein system. A heat-stable
Phycocyanin was extracted from a thermophilic cyanobacterium. lts best growing temperature
is 60 "C which is 20 "C higher than that of usual cyanobacterium. Heat- stable Phycocianin
consists of two sub-units, Phycocyanin- a and- , both of which have molecular weight of
about 20,000. The structures of amino acids in special sites of a Phycocyanin- a and - are
different from those of normal Phycocyanin. Therefore, these special amino acid units
concerning the association of two subunits are assumed to play a role of improving the
heat- stability of a Phycocyanin.
Next target of this research should be the modification of proteins by protein engineering
to improve their stability and efficiency.
THE NEW CHEMISTRY
The researching frontier of photo technologies has shifted historically from photography,
synthesis of organic compounds and creation of photoactive materials toward on
electro-photonics and photo- bionies targeting artificial photosynthesis.
Table 4. New Chemistry
0.1f.1m 10nm ( 100)
IC 64M 1G 16G
Memory Magnetic Optlcal
Ultrafine Fiber
Polymer Polymer Alloy
ROMembrane
Biology Bacterla CeII Virus
: Domaln of Naw Chemistry
7
Table 4 shows the domain of the New Chemistry, or the Future Chemistry. The major
targets of the future technologies in chemistry are nonlinear optics, biochips, photonics, design
of nanostructure of materials, and proteins. The molecular design at the size of 10 nm or
100 A will become more important in these fields as shown in Table 4. lt will be achieved
mainly by photo technologies and protein engineering.
In conclusion, the New Chemistry is a type of science that comes from the fusion of
chemistry with hiotechnology and electro-photonics. The 21st Century will usher in the era of
New Chemistry in which the photo technologies will play a key rote and the Responsihle Care
for human and the Earth as well as strengthening of basic research are strongly desired to the
chemical industries.
8
REACTIVE EXTRUSION COMPATIBILIZATION
OF POLY(VINYL ALCOHOL) - POLYOLEFIN BLENDS
Lloyd M. Robeson 1, Amir Famili 1, James F. Nangeroni 2
1 Air Products and Chemicals, Inc.

7201 Rarnilton Boulevard
Allentown, PA 18195-1501
21. Nangeroni Associates, Inc.
SYNOPSIS
Reactive extrusion compatibilization of highly incompatible blend combinations

has been an active area of research for almost two decades. Polyamide-polyolefin
reactive extruded blends involving peroxide grafting of anhydride or acid groups onto
polyolefin followed by reaction with terminal polyamide amine groups has been well
demonstrated as a method for achieving mechanical compatibilization. Poly(vinyl
alcohol)-polyolefin blends comprise a combination of polar, hydrophilic polymers with
non-polar hydrophobic polymers and expectedly poor mechanical compatibility. A
similar procedure involving reactive extrusion grafting of maleic anhydride onto the
polyolefin followed by thermoplastic poly(vinyl alcohol) addition allows for anhydride-
alcohol reactions and thus compatibilization.
This procedure has been demonstrated to be effective for compatibilization of
blends of poly(vinyl alcohol) with polyethylene (linear low density), polypropylene,
ethylene-propylene rubber and ethylene-vinyl acetate copolymers. With more polar
ethylene copolymers (e.g. ethylene-acrylic acid, ethylene-methacrylic-acid ionomers), the
reactive extrusion procedure offers limited benefit (if any) as the polar copolymers
exhibit mechanical compatibility in unmodified blends. With the polyolefin-poly(vinyl
alcohol) reactive extruded blends, significant improvements in tensile strength, ultimate
elongation, area under the stress-strain curve (e.g. practical toughness) and notched
impact strength are obseived. This procedure Ieads to the formation of a polyolefin-
poly(vinyl alcohol) graft copolymer which provides a "surfactant" to stabilize the
interface between the phase separated constituents of the blend yielding mechanical
compatibilization.
INTRODUCTION
The vast majority of potential polymer blend combinations do not exhibit

miscibility thus mechanical compatibility is not assured and generally not achieved in
Edited by P. N. Prasad et al., Plenum Press, N ew York, 1998 9
simple blends. (1). There are exarnples where mechanical compatibility is achieved in
phase separated systems, however many of these systems achieve compatibility via
addition of temary components, grafting, and reactive extrusion procedures. Specific
examples ofhighly incompatible systems in~lude those where highly polar or hydrophilic
polymers are combined with non-polar or hydrophobic polymers. These exarnples
include the polyamide-polyolefin combinations of nylon 6-6-ethylene/propylene rubber
and polypropylene-nylon 6,6 or nylon 6. Simple mixtures have no useful properties,
however, reactive extrusion methods have been developed whereby commercially viable
blends of the noted polyamide-polyolefin systems have attained significant utility (e.g.
super-tough nylon). Reactive extrusion compatibilization of polyamide-polyolefin blends
generally involves peroxide initiated grafting of maleic anhydride followed by reaction
with a -NH2 terminal polyamide in a one-pass extrusion operation. The resultant
polyolefin-graft-polyamide copolymer yields a "surfactant" compatibilizer that
concentrates at the phase boundary and allows for transmission of stress across the
interface. The technology of reactive extrusion compatibilization of polyamide-
polyolefin blends has been discussed in numerous papers and patents including (2-8).
Additional exarnples of reactive extrusion include poly(phenylene ether) (PPE) -
polyamide blends compatibilized with polycarboxylic acid (9), poly(phenylene ether)-
polyamide blends with various additives including maleic anhydride (10), polyester-
polyolefin blends (11) employing epoxide functional polyethylene copolymers, and
poly(phenylene ether)-polyester blends involving a carbodiimide functionalized PPE
(12). Copolymers of styrene with isopropenyl oxazoline have been noted for reactive
compatibilization with acid functional polymers including polyolefins (13) mid
acrylonitrile-butadiene copolymers (14). Many more examples have been weil described
in a review on reactive extrusion by Brown (15).
Other methods of compatibilizing incompatible polymers blends include addition
of a third component which can concentrate at the interface and offer good adhesion to
both phases. Hobbs et al. (16) discussed the conditions whereby a temary component can
concentrate at the interface between two immiscible polymers and provide
compatibilization. The polyhydroxyether of Bisphenol A (phenoxy) has been noted as a
compatibilizer for polysulfone-ABS (17) and polysulfone-polyarnide (18) blends.
Compatibilization of polystyrene-polyethylene blends with an ABA styrene-
ethylene/butylene-styrene block copolymer is a dassie example of this approach (19).
Ester exchange of poly(ethylene terephthalate) in melt blends with polyarylate has been
shown to yield miscibility (20) thus assuring compatibility. Extrusion reaction of
polysulfone dissolved in E-caprolactam with Na-caprolactam as a catalyst yielded
polysulfone-nylon block copolymers. (21) The resultant block copolymers exhibited
excellentmechanical compatibility with either nylon 6 or polysulfone.
One of the most incompatible combination of polymer blends which one could
hypothesize would involve polyolefins with water soluble polymers such as poly(vinyl
alcohol)(PVOH). Poly(vinyl alcohol) is generallynot considered thermoplastic, however,
specific modifications allow for thermoplastic behavior such as the VinexlM products of
Air Products and Chemicals, Inc. Simpleblends ofthermoplastic PVOH and polyolefins
have been previously described (22). In fact, this blend is so incompatible that
orientation of a melt extrudate followed by water extraction yields fine fibers (0.2-2Jl
diarneter).
Ethylene-acrylic acid and ethylene-methacrylic acid copolymers and ionomers
offer improved mechanical compatibility over unmodified polyethylene, however,
improvements are desired as weil as the ability to utilize unmodified polyolefins. The
reactive extrusion concept should be applicable to polyolefin-PVOH blends, specifically,
the approach of maleic anhydride grafting onto the polyolefin. The chemistry involved
10
with polyolefin-graft-PVOH formation for interface stabilization is straight forward as
illustrated below:
HC=CH
........_ ~CH 2 CH2_ . /
o-:;:;:;.cf'o/b~o
+
...._", 'CH{ ...._",
PVOH
Polyoietin g PVOH
EXPERIMENTAL
The reactive extrusion experiments were conducted on a twin screw extruder

(Wemer-Pfleiderer:ZSK-40). The polymers chosen for this investigation are tabulated in
Table 1 including the thermoplastic PVOH's (Vinex) and polyolefins and olefin
copolymers. The extrusion procedure involved twelve extrusion sections as illustrated in
Figure 1. The polyolefin was fed to section I, the maleic anhydride was fed between
section 3 and 4, the peroxide was added to section 4, and the thermoplastic PVOH was
fed to an open throat to the extruder. A mixing zone was utilized to blend the maleic
anhydride grafted polyolefin with PVOH followed by a vacuum port to devolatilize
unreacted maleic anhydride. The product exited the extruder through six dies onto a
chilled belt followed by pelletizing.
The pelletized samples were injection molded into 118" thick 1/2" wide specimens
(tensile bar and izod bar). The mechanical properties were obtained as per procedures
generally described by ASTM-D-638 (tensile modulus, tensile strength, ultimate
elongation). The notched izod impact strength was determined according to ASTM-D-
256. The melt flow data was obtained at 200 "C using a procedure similar to that
described by ASTM-D-1238.
11
The peroxide employed for those studies was L-101 (Lupersol) {2,5-dimethyl-2,5-
bis (t-butylperoxy) hexane).
EXPERIMENTAL RESULTS
Thermoplastic PVOH Thermal Stability
As noted in patent reference (23), PVOH without modification offers limited to no

utility as a thermoplastic due to the high crystalline melting point and decomposition
occurring as low as 170 "C. With proper modification, these problems can be overcome.
Thermoplastic blends with polyolefins will generally be processed in the range of 180 "C
to as high as 230 "C. The melt flow stability ofthe thermoplastic PVOH employed in this
study was therefore evaluated. The activation energy of degradation of Vinex 2025 and
Vinex2034 thermoplastic PVOH was determined by measuring melt flow changes
Table 1 Sampie Designation

Polymer Type Designation!Source Characteristics
Thermoplastic PVOH Vinex 2025/APCI Density - 1.25 Melt Flow - 15-17 g/1 0 min.
(230C, 2.16 kg)
Vinex 2034/APCI Density = 1.25 MeltFlow= 6.8 g/10 min.
Polypropylene Profax 6723/Himont Homopolymer PP
Polyethylene LLDPE LL-1 002/Exxon Density = 0.918, Melt Index= 2.0 g/10 min.
Tuflin HS- Density = 0.934 Melt Index= 5.8 g/10 min.
7027/Union Carbide
Ethylene!Propylene EPR 3708/Exxon 65% ethylene; EPR terpolymer (contains diene monomer)
Rubber Vistaion 719/Exxon 75 wt. % ethylene, EPR Copolymer
Ethy1eneNiny1 LD-706/Exxon 15 wt.% vinyl acetate; Melt Index- 8.0 g/10 min.
Acetate Copolymer
Ethylene/Acrylic Primacor 1430/Dow 9 wt.% acrylic acid
Acid Copolymer
Ethylene/Methacrylic Surlyn 9950/duPont Density- 0.98; Zn++ ionomer, Melt Index- 5.6 g/10 min.
Acid Copolymer
Inomer
r Amr1~ j
PVOH
Maleie
\1 \ I r---
Vacuum
1 2 3 4 5 6 7 8 9 10 11 12
I>
Figure I. Extruder Block Diagram for PVOH/Polyolefin Reactive Extrusion Trial
12
versus temperature. The melt flow decreases with time (indicative of crosslinking).
Tinius Olsen melt index apparatus was employed to determine the exposure time to
reduce the melt flow by 50%. The time to reach 50% melt flow reduction can be plotted
(as log 1/t) versus 1/T (temperature in an Arrhenius type plot to obtain the activation
energy of crosslinking). This is illustrated in Figure 2 for Vinex 2034 yielding an
activation energy of 37.2 kcal/mole. Data on Vinex 2025 yielded an activation energy
of 43.9 kcallmole. Both Vinex 2025 and Vinex 2034 have excellent stability at 200
oc but above 230 oc severe crosslinking occurs. This data illustrate that stable blends can
be prepared with polyolefins for thermoplastic processing.
VINEX 2034
I. QL-----'----L-----'---....I------1---'
1.96 1.99 2.02 2.05 2.08 2.11 2.14
I I T (K- 1) x 103
Figure 2. Activation Energy for Thermoplastic PVOH (Vinex 2034) Mett Stability
Thermoplastic PVOH/Polypropylene (PP) Blends
The control blends and reactive extrusion variations for Vinex 2034 (PVOH)/
Profox 6723 (PP) blends are tabulated in Table 2 along with properties of the unblended
constituents. The data show a marked improvement in the tensile strength and ultimate
STRESS-STRAIN DATA 2"/min.

50/50 VINEX 2034/PROFAX 6723 POLYPROPYLENE (DRY~I.4
6000
5000
psi /.-.,, '

CONTROL
I..-2.2%MA
I 4000 ppm PEROXIDE
I
\ I
\ I
Figure 3. Stress-Strain Data for 50/SO Vinex 2034/polypropylene (Profax 6723) Blend and Reactive
Extruded Variants
13
elongation with maleic anhydride/peroxide addition. This is further illustrated by a
comparison of the stress-strain data on the control blend versus a reactive extrusion
variant (Figure 3).
The area under the stress-strain curve weil demonstrates the improvements derived from
the reactive extrusion procedure employed. The maleic anhydride/peroxide
concentrations were varied in additional experiments. The values shown in Table 2 are in
the optimum range.
Table 2. Property Results for Reactive Extmded PVOII/PP Blends

Vinex TM 2034 40 40 40 40 40 60 60 4 Control Control
PVOH Feed Rate PVOH Poly-
(lb.!hour) Vinex propylene
Polypropylene 40 40 40 40 40 40 404 2034 Profax
(Profax 6723) Feed 6723
Rate (lb. hour)
Maleie Anhydride* - 2.2 2.2 3.2 3.2 2.2 2.2 + -
Conc. (%)
L-101 Peroxide* - 3,000 4,000 4,000 3,000 3,000 3,000 - -
Conc. (ppm)
Melt Flow g/10 min. 10.2 62.6 110 86.8 59.3 36 2.7 16.0 83.2 (IOP)
200C (lP};t (lOP) (10P) (lOP) (lOP) (5P) (lP) (1P)
(230C)
Mechanical Properties (Dry)
Tensile Modulus 758 854 854 944 965 751 944 785 875
(MPa)
Tensile Strength 21.4 33.8 33.8 34.5 35.1 33.1 10.3 36.6 35.1
(MPa)
Elongation at Break 16 105 126 91 101 48 2.7 179 58
(%)
Notched Izod 59 42 41 44 42 76 25.6 154 117
Impact Strength
(J/m)
* based on polypropylene we1ght
'IP = 2.16 kg Ioad; 5P = 10.8 kg Ioad; IOP = 21.6 kg Ioad
"' PVOH and PP both fed to front of extruder
The beneficial effect of reactive extrusion on the uniformity of the extrudate was noticed
immediately after the maleic anhydride/peroxide was fed to the extruder. After a brief
transition region, the extrudate was visually more homogeneous. Orientation of
compression molded samples using a bubble forming method above the melting point
showed similar differentiation. The simple blends failed as the bubble was formed
whereas the reactive extruded blends could be successfully biaxially oriented
One variation noted in Table 2 involved changing the experimental procedure for
addition ofPVOH to the extruder. A pellet blend ofPVOH/PP was added to the front of
the extruder (where the polyolefin was typically added). The mechanical property results
clearly show this procedure is not desired presumably due to maleic anhydride
prematurely crosslinking the PVOH and peroxide degradation of the polypropylene with
minimal graft copolymer formed. As the II_laleic anhydride is fed to the extruder before
the peroxide, it has time to react with PVOH and thus may not be available for grafring to
polypropylene.
Blends of Vinex 2025 and Profax 6723 were prepared via extrusion.
Comparisons of the calorimetric data employing a Perkin-Eimer differential calorimeter
of control blends with reactive extrusion blends are noted in Figure 4. Compression
molded samples were subjected to a heating cycle of 10 C/min. followed by a cooling
14
PVOH=VINEl~025 PP= PROFAX 6723
50150 PVOH/PP 50/50 PVOH/PP 50/50 PVOH/PP
CONTROL 1.5% MA 3.0% MA
BLEND 4600 ppm L-101 4600 ppm L-101
HEAT
FLOW
HEATING
CYCLE
I0C/min.
HEAT
FLOW
COOLING
CYCLE
Figure 4. Calorimetric Data on Vinex 2025/Polypropylene (Profax 6723) Blend and Reactive
Extruded Variants
Table 3. Calorimetry Data

Heating Cycle Cooling Cycle
Tm (PVOH) Tm (PP) T,(PVOH) T, (PP)
(OC) (oC) (oC) (OC)
50/50 PVOH/PP 184.8 160.2 150.4 I 13.2

Control Blend
50150 PVOH/PP 181.2 159.6 * 116.8
1.5%MA
4600 ppm L-10 I
50!50 PVOH/PP -170 158.4 105.4 I 19.2
3.0%MA
4600 ppm L-10 I
*Could not be determmed, partmlly covered by PP crystalhzatwn exotherm.
cycle of 10 C/min. The melting point (Tm) ofPVOH and PP and the crystallization peak
temperature (TJ data are listed in Table 3.
The data show a decrease in Tm for PP and increase in Tc with conditions employed for
reactive extrusion blend. This is consistent with peroxide cleavage ofPP leading to lower
molecular weight. With PVOH, a decrease in Tm and a decrease in Tc is consistent with
grafting and crosslinking ofPVOH with maleic anhydride addition.
The dynamic mechanical data obtained on compression molded samples of
Vinex 2025 and Profax 6723 (control and reactive extruded) are shown in Figure 5. The
15
109 1.0
E'
TENSILE
MODULUS
dynes tan 15
108 0.10
cm2
- - - - - 50/50 PVOH/PP
CONTROL 0.01
- - - --50/50 PVOH/PP
1.5%MA
4600 ppm L-101
Figure 5. Dynamic Mechanical Results on Vinex 2025/Profax 6723 Control and Reactive Extruded
Blends
Tg ofpolypropylene (-0 C) appears as a shoulder and is slightly moreprominent for the

reactive extruded blend. The magnitude ofthe poly(vinyl alcohol) Tg (35 C) is larger for
the control blend. The reduction in the melting point of PVOH with reactive extrusion
processing is reflected in the lower modulus in the range of 160 C. The lower magnitude
of the PVOH glass transition is believed due to a lower Ievel of phase continuity in the
blend for the reactive extruded blend. Reactive extrusion will yield a increase in the
viscosity of PVOH and a decrease in viscosity for polypropylene. Phase continuity is
more favored for the Iower viscosity component.
Thermoplastic PVOH/Linear Low-Density Polyethylene (LLDPE) Reactive Extruded

Blends
Several PVOHILLDPE reactive extn.tsion blends were prepared as noted in Table

4. The optimum Ievels of maleic anhydride/peroxide employed were significantly lower
than with polypropylene. Employing the optimum Ievels for polypropylene (2-3%
MA/2000-4000 ppm peroxide) with LLDPE gave blends which were highly crosslinked
and not capable of being injection molded. Polyethylene Ieads to crosslinking with
peroxide addition unlike polypropylene where chain scission dominates thus lower Ievels
of peroxide are employed with polyethylene. The mechanical property data listed in
Table 4 illustrates significant improvements in ultimate elongation, tensile strength and
16
Table 4. Property Results for Reactive Extruded PVOH/LLDPE Blends
PVOH Type Vinex 2025 2025 2025 2034 2034 2034
LLDPE Type LL-1002 LL-1002 LL-1002 HS-7027 HS-7027 HS-7027
PVOH Feed Rate (lbs./hr.) 40 40 40 40 40 40
LLDPE Feed Rate (lbs./hr.) 40 40 40 40 40 40
Maleie Anhydride Conc. (%)* - 0.5 0.5 - 0.5 0.75
L-101 Peroxide Conc. (ppm)* - 400 600 - 600 600
Melt Flow g/10 min 200 11.5 (IP 2.3 (IOP) 0.9 (IOP) 9.2 (IOP) 10.6 (IOP) 2.3 (IOP
Tensile Modulus (MPa) 854 909 930 531 599 599
Tensile Strength (MPa) 22.0 31.7 29.6 18.6 24.1 26.2
Elongation at Break(%) 7 52 85 23 100 147
Notched Izod Impact Strength 69 101 181 80 75 139
J/m
Mechanical Properties (50% R.H./25 days)
Tensile Modulus (MPa) 517 427 358 331 324 276
Tensile Strength (MPa) 15.8 21.4 22.0 15.8 19.3 21.4
Elongation at Break(%) 30 120 171 41 135 235
Notched Izod Impact 112 629 No Break 107 352 No Break
Strength J/m
*based on LLDPE we1ght
* IP=2.16kgload; IOP=21.6kgload
notched impact strength under both dry and conditioned at 50% relative humidity
conditions. This is further illustrated in Figure 6 for PVOH/LLDPE (Vinex 2025/LL-
1002) blends where the stress-strain behavior of a simple blend is compared with reactive
extrusion variants of the same composition.
Another PVOHILLDPE blend (Vinex 2034/LLDPE(HS-7027):50/50) where the
reactive extrusion procedure was applied is illustrated in Figure 7. The comparison ofthe
stress-strain data for the control versus reactive extrusion variants clearly demonstrates
the improvements resulting from reactive extrusion processing.
STRESS -STRAIN DATA 2"/min.

VINEX 2025/LLDPE LL-1002 50/50 (DRY)
5000 r - - - - - - - - - - - - - - - - - ' - - - - - - , 3 4 . 5
--,
\
\ 0.5%MA
STRESS +-600ppm
psi 0.5%MA \
PEROXIDE
400ppm __.\
PEROXIDE \ MPa
2000 \
I \
'
+-CONTROL
1000 \ I
\
~--~--~~--~~---e----~--~~--~~o
o0
I
\
in/ in
Figure 6. Stress-Strain Data for SO/SO Vinex 202S/LLDPE (LL-1002) Blend and Reactive
Extruded Variants
17
One variation of the reactive extrusion procedure involved preparing a maleic
anhydridegrafred LLDPE followed by pelletizing and post-extrusion with thermoplastic
PVOH. This product was compared to the analogous PVOH/LLDPE reaction extrusion
product prepared by a single pass extrusion. The major difference observed was water
resistance. Tensile bars immersed in water for the singlepass reactive extrusion process
did not exhibit surface tackiness and retained their basic dimensions. The two pass
extrusion procedure yielded tensile bars with surface tackiness and significant
dimensional change with specimen disintegration. This may be due to maleic anhydride
excess not grafted on LLDPE leading to some crosslinking of the PVOH during the
singlepass operation (thus improved water resistance). Another factor isthat the residual
maleic anhydridewill increase the Mw ofPVOH (grafting) leading to a continuous phase
structure more prevalent in LLDPE. The resultant effect would be improved water
resistance.

VINEX 2034/LLDPE HS-7027 50/50 (DRY)
4000f- 0.75% MA -27.6

~ 600ppm PEROXIDE
---- --- - ....... .....
3000 r- '/"/ \ -20.7
I
STRESS \ MPa
psi ~/l \
2000
~ i 0.5%MA
600 ppm --+\
PEROXIDE
.,
-13.8
\
1000 - 1-cONTROL \ -6.9
\
I I I \ I
L---~--~------~------~--~--~--L--- ~0
00 0.20 0.40 0.60 0.80 1.0
STRAIN in/in
Figure 7. Stress-Strain Data for 50/50 Vinex 2034/LLDPE (HS-7027) Blend and Reactive
Extruded Variants
Thermoplastic PVOH/Ethylene-Propylene Rubber (EPR) Reactive Extruded Blends
Ethylene-propylene rubber (EPR) is commercially utilized in reactive extrusion

grafted blends with polyamides (e.g. nylon 6,6) to produce materials typically referred to
as "supertough" nylon. Simple blends of thermoplastic PVOH and EPR offer no useful
properties, and the impact strength of PVOH is not significantly improved (Table 5).
Peroxide addition alone yields no improvement. Peroxide and maleic anhydride addition
yield a marked improvement in practical toughness (area under the stress-strain curve:
Figure 8) and in notched toughness. The optimum peroxide and maleic anhydride Ievels
were found to be slightly higher than polyethylene (LLDPE) and significantly lower than
polypropylene.
18
Table 5. Property Results for PVOH/EPR Reactive Extruded Blends
PVOH type Vinex 2025 2025 2025 2025 2025 2025 2025 Control 1
1
Vinex 2025
EPR type 3708 3708 3708 719 719 719 719 --
PVOH feed rate (Jbs./hour) 54 54. 54 48 48 48 48 --
EPR feed rate (lbs./hour) 36 36 36 32 32 32 32 --
Maleie Anhydride Conc. (%)* -- 0.9 1.0 -- -- 0.9 1.25 --
L-101 Peroxide Conc. (ppm)* -- 900 1200 -- 1000 600 1000 --
Melt Flow g/10 min. 200C 2.1 (IP);e 2.4 (IOP) 2.5 (IOP) 61.1 (5P) 50.5 (5P) 1.27 (IOP) No Flow (IOP) 55.2 (5P)
Tensile Modulus (MPa) 951 772 944 806 854 1130 1054 1950
Tensile Strength (MPa) 22.7 26.2 30.3 24.1 22.0 37.2 35.8 72.8
Elongation at Break(%) 5 129 129 9 7 73 81 55
Notched Izod Impact 64 1071 1125 64 64 1082 1167 37
Strength (J/m)
*Based on EPR weight
;e!P = 2.16 kg Ioad; 5P = 10.8 kg Ioad; !OP = 21.6 kg Ioad
....
\0
Table 6. Property Results on Reactive extruded PVOH/Ethylene Copolymer Blends
PVOHType 2025 2025 2025 2025 2025 2025 2025 2025
Vinex
Ethylene EVA EVA EVA EVA EAA EAA Surlyn Surlyn
Copolymer (LD-706) (LD-706) (LD-706) (LD-706) Primacor Primacor 9950 9950
type 1430 1430
PVOHFeed 40 40 40 40 40 40 40 40
Rate lbs./hour
Etbylene 40 40 40 40 40 40 40 40
Copolymer
Feed Rate
lbs./hour
Maleie - 0.5 0.8 1.0 - 0.5 0.5
Anhydride
Conc. (%)*
L-101 - 500 800 1200 - 500 500
Peroxide
Conc. (ppm)*
MeltFlow 18.2 (IP);t 18.3 (5P) 5.2(10P) 3.9 (IOP) 5.4 (1P) 3.0 (5P) 4.8 (IP) 10.1 (5P)
g/IOmin.
200C"
Mechanical Properlies (Dry)
Tensile 661 462 606 854 971 751 1054 1082
Modulus
(MPa)
Tensile 15.8 18.6 21.4 25.5 32.4 27.6 37.2 37.9
Strength
(MPa)
Elongation @ 8 51 60 61 100 61 108 58
Break
Notched Izod 69 187 165 421 43 80 59 45
Impact
Strength (J/m)
*Based on Ethylene Copolymer we1ght. *- IP ~ 2.16 kg Ioad; 5P- 10.8 kg Ioad; lOP- 21.6 kg Ioad

VINEX 2025/ EPR-3708 54/36 (DRY)
5000...------------------------.34.5
I.O%MA
~ 1200 ppm PEROXIDE
STRESS ---------
psi \
I
MPa
0.9%MA I
900ppm-l
PEROXIDE I
I
I
I
0.20 0.40 0.60 0.80
STRAIN in/in
Figure 8. Stress-Strain Data for 54136 Vinex 2025/Etbylene-Propylene Rubber (EPR-3708) Blend
and Reactive Extruded Variants.
20
VINEX 2025/ EVA:LD-706 50/50 (DRY)
I.O%MA
;1200 ppm PEROXIDE
STRESS
psi 3000
0.10 0.20 0.30 0.40 0.50

STRAI N in/in
Figure 9. Stress-Strain Data for 50/50 Vinex 2025/Ethylene-Vinyl Acetate Copolymer (LD-706)
Blend and Reactive Variants
Thermoplastic PVOH/Ethylene Copolymer Reactive Extrusion Blends
Thermoplastic PVOH exhibits improved mechanical compatibility with ethylene

based copolymers containing polar groups. Fair mechanical compatibility is observed
with ethylene-acrylic acid copolymers and ethylene-(meth)acrylic copolymers partially
neutralized with Na+ or zn++ (ionomers). Reactive extrusion of these blends via the
peroxide/maleic anhydride procedure did not show any specific advantage. With an
ethylene-vinyl acetate copolymer, however, reactive extrusion gave marked
improvements as noted in Table 6 and illustrated in Figure 9 (stress-strain data).
CONCLUSIONS
The reactive extrusion procedure typically applied to compatibilize polyamide-

polyolefin blends, namely maleic anhydride grafting onto the polyolefin followed by
terminal amine reactions of the polyamide to yield a polyolefm-polyamide graft
copolymer is applicable to poly(vinyl al~ohol)-polyolefin blends. With poly(vinyl
alcohol), the grafted maleic anhydride reacts with the secondary hydroxyl inherent in the
PVOH repeat unit to form an ester bridge. Maleie anhydride (free or grafted) can also
crosslink PVOH. The balance between grafting and crosslinking must be maintained to
preserve thermoplastic behavior for the blends. The optimum Ievel of peroxide and
maleic anhydride addition is quite dependent upon the polyolefin. With polypropylene
higher Ievels are desired, however, with polyethylene lower Ievels are required as the
peroxidecrosslinks the polyethylene (chain scission occurs with polypropylene) and loss
of thermoplastic character is observed. Ethylene-propylene rubber optimum Ievels are
intermediate, although, closer to polyethylene values.
The reactive extruded PVOH-polyolefin blends exhibit significant improvements
in tensile strength, ultimate elongation and area under the stress-strain curve (e.g.
practical toughness). With polyethylene and ethylene-propylene rubber blends with
PVOH, large improvements in notched impact strength are observed. The notched
21
toughness of ethylene-propylene ruhher blends with PVOH are similar to that observed
with ethylene-propylene rubber/polyamide blends (e.g. "super tough" nylon).
The reactive extrusion procedure of mechanical compatibilization of PVOH-
polyolefms is also applicable to PVOH - ethylene/vinyl acetate copolymers. With
ethylene copolymers containing more polar monomers (e.g. ethylene-acrylic acid,
ethylene-methacrylic-acid ionomers), the reactive extrusion procedure offers limited
improvements (if any) due to the mechanical eompatibility of these blends without
modifieation.
The data clearly demonstrate the ability of the reaetive extrusion synthesis of a
poly(vinyl aleohol)-graft-polyolefin to stabilize the interface between the two highly
ineompatible constituents and then aehieve meehanieal compatibility.
Acknowledgments
The authors wish to acknowledge the suggestions and assistanee of F. R. Burbank

and S. Jaekson of Wemer Pfleiderer in the preparation of the reaetive extruded blends
diseussed in this paper. The calorimetry data were obtained by J. A. Kuphal, and the
mechanical properties were determined by J. N. Tallarieo.
References
1. 0. Olabisi, L. M. Robeson, and M. T. Shaw, "Polymer-Polymer Miscibility,"

Academic Press, New York, 1979.
2. F. Ide and A. Hasegawa, J. Appl. Polym. Sei., 18, 963 (1974).
3. S.Y. Hobbs, R. C. Bopp, and V. H. Watkins, Polym. Eng. Sei., 23, 380 (1983)
4. S. Cummins, F. Coppola, L. D'Orazio, R. Greeo, G. Maglio, M. Malineonieo, C.

Manearella, E. Martuscelli, and G. Ragosta, Polym., 27, 1874 (1986).
5. B. N. Epstein, U.S. Pat. 4, 174,358, assigned to E. I. duPont de Nemours and Co.,

Nov. 13, 1979.
6. S. Cimmino, L. D'Orazio, R. Greco, G. Maglio, M. Malinconico, C. Mancarella, E.

Martuscelli, R. Palumbo and G. Ragosta, Polym. Eng. Sei., 24,48 (1984).
7. S. S. Dagli, M. Xanthos and J. A. Biesenberger, Polym. Eng. Sei., 34, 1720 (1994).
8. R. J. M. Borggreve, R. J. Gaymans, J. Sehuijer, and J. F. Ingen Housz, Polym., 28,

1489 (1987).
9. R. R. Gallueci, R. van der Meer, and R. W. Avabian, U.S. Pat. 4,873,286, assigned
to General Electrie Co., Oct. 10, 1989.
I 0. K. Ueno and T. Mariyama, U.S. Pat. 4,315,086, assigned to Sumitonio Chemical

Company Ltd., Feh. 9, 1982.
11. S. S. Dagli and K. M. Kamdar, Polym. Eng. Sei., 34, 1709 (1994).
12. C. Y. Han and W. L. Gately, U.S. Pat. 4,689,372, assigned to General Electrie Co.
22
13. M. Saleem and W. E. Baker, J. Appl. Polym. Sei., 39, 655 (1990).
14. M. W. Fow1er and W. E. Baker, Polym. Eng. Sei., 28, 1427 (1988).
15. S. B. Brown, in "Reactive Extrusion: Principles and Practice," ed. by M. Xanthos,

pp. 75-199, Hauser Publishers, New York, 1992.
16. S. Y. Hobbs, M. E. J. Dekkers and V. H. Watkins, Polym., 29, 1598 (1988).
17. L. M. Robeson, U.S. Pat. No. 4,532,288, assigned to Union Carbide Corp., July 30,
1985.
18. D. Lausberg, G. Blinne, P. I. Hermann, G. Heinz, E. Seiler, and M. Knoll, U.S.

Patent 4, 798,855, assigned to BASF, Jan. 17, 1989.
19. M. C. Schwarz, J. W. Barlow and D. R. Paul, J. Appl. Polm. Sei., 35, 2053 (1988).
20. L. M. Robeson, J. Appl. Polym. Sei., 30, 4081 (1985).
21. J. E. McGrath, L. M. Robeson, M. Matzner, in "Recent Advances in Polymer

Blends, Grafts and Blocks," ed. by L. H. Sperling, p. 195, Plenum Press, New
York, 1974.
22. L. M. Robeson, R. J. Axelrod, M. S. Vratsanos, and M. R. Kittek, J. Appl. Polym.

Sei., 52, 1837 (1994).
23. F. L. Marten, A. Famili, and J. F. Nangeroni, U.S. Pat. 5,051 ,222, assigned to Air
Products and Chemicals, Inc., Sept. 24, 1991.
24.) N. G. Gaylord, in Reactive Extrusion: Principles and Practice," ed. by M. Xanthos,

pp. 55-71, Hauser Publishers, New York, 1992.
23
MISCIBILITY AND PROPERTIES OF LIQUID CRYSTALLINE
P-ACETOXY BENZOIC ACID COPOLYESTER I POLYBUTYLENE
TEREPHTHALATE BLENDS
1
T. K. Kang, 2
Y. Kiln, W. J. Cho, 3 and C. S. Ha1
1 Dept. of Chemistry, Pusan National University, Pusan 609-735, Korea

& Daelim lndustrial Co.,Ltd, Daeduk R&D Center, Daejon 305-345,
Korea
2 Dept. of Chemistry, Pusan National University, Pusan 609-735, Korea
3 Dept. of Polymer Science and Engineering, Pusan National University
Pusan 609-735, Korea
INTRODUCTION
Along with the development of new high-perfonnance resins, new trends are
being established in the processing of composites and polymer blends. However,
the addition of rigid fillers into a polymeric matrix continues to have an adverse
effect on the processability. 1.2 To improve the mechanical properlies of some
polymers, generally inorganic fillers are compounded with the polymers. But the
presence of solid fillers results in a dramatic increase in the melt viscosity.
Thennotropic liquid crystalline polymers(LCP) have been studied because of their
inherent high stiffness and strength, high use temperature, excellent chemical
resistance, low melt viscosity, and low coefficient of expansion. Because of these
excellent properties, the blending of LCP with conventional polymers could result
in materials that can be used as an alternative for short fiber reinforced
thennoplastic composites; the in-situ composites have many potential advantages as
compared with short fiber reinforced polymers3-9
Most of the blends, however, consist of a liquid crystalline copolyester
based on 60 mole % p-hydroxybenzoic acid(PHB) and 40 mole% poly(ethylene
terephthalate)(PET) ((PET/60PHB), first reported by JacltSon and Kuhfuss4
Among those blends, the blends of the PET/60PHB and its parent homopolymer
PET or its analogue poly(butylene terephthalate)(PBT) have been also intensively
studied.
Metha and Deop~ studied the blends of PBT and PET/60PHB in the form
of as spun and drawn fibers. By their results, DSC melting and crystallization
results show that PBT is compatible with the LCP and the crystallization of PBT
decreases by the addition of the LCP in the matrix. It was believed that this could
be associated with the dissolution of PBT phase in the PET rich phase of the
PET/60PHB blend6'7 Zaldau et al. 10 presented some results of the rheology of

Edited by P. N. Ptasad et al., Plenum Press, New York, 1998 25
blends of PBT and PET/60PHB, interpreted in the light of phase behavior and
compatibility analyzed by differential scanning calorimetry and dynamic
viscoelasticity.
The object of the present research is to investigate the properties of blends of
PBT and a copolyester(PETA-50) of PET with 50 mole % of p-acetoxybenzoic
acid(PABA). Although most of the previous works have reported on blends
containing PET/60PHB, no research on the blends containing a copolyester of 50
mole % of PET reacted with 50 mole % of PABA have been published.
EXPERIMENTAL
MateriaJs
PET of commercial grade were supplied by Sunkyung Industry Co. in Korea.

The number average molecular weight of PET was 26,000 and the molecular
weight distribution was 2.0. The inherent viscosity of PET was 0.82 d1/g, measured
using the Ubbelohde viscometer at 150t, in 0.5 g/dl of o-chlorophenyl solution.
The copolyester of 50 mole % of PET with 50 mole% of p-acetoxybenzoic
acid(PABA) was synthesized by the melt reaction without a catalyst as described
in the solid state polymerization by Jackson and Kuhffus4 The copolyester was
designated as PETA-50 in this work. Details of the syntheses of the PETA-50
will be reported elsewhere.
Preparation of Blends
PBT was powdered using a freezer mill and then the fine powdered PBT was
blended with powdery PETA-50. The dry blend was perfonned in a g1ass tube
agitating at 2000ppm with a vibrator for about 5 min. The blend ratio is 80/20,
50/50, and 20/80 (PBT/PETA-50). All of the blends contain antioxidants. These
mixtures were poured into Rheometrics Mechanical Spectrometer(RMS) test pot,
then melt mixing was perfonned at 240t in between the plates of RMS. After
RMS test the remained samples were collected from the plate and were used for
the measurement of the thennal analysis and mechanical properties.
Thermal Analysis
The thermal anlysis was perfonned under nitrogen with a heating rate of
lO"C/min using a Perkin Eimer Differential Scanning Calorimeter(DSC 7). Glass
transition tempertures(Tg) were detennined with a Thennal Stimulated Current(TSC)
Spectrometer(Solomat). Films of about 0.2mm thick were pressed by hand at
elevated tem;eratures using aluminium foil and the released films were cut to
about lOmm: area for TSC. The TSC spectra were obtained by polarizing the film
from polarizing temperature Tp(generally above Tg) and continuing to polarize
down to the quench temperature. The depolarization was then measured at a
heating rate of 7 t /min.
Dynamic Mechanical Measurement
Viscoelastic properties were measured on a RMS, using cone & plate and
parallel plates between 240t. A cone of radius 1.24cm and cone angle of 0.1
26
radian were used. The cone and plate measurements were commonly used for the
low melt viscosity, while the parallel plate geometry was used to measure
viscoelastic properties of high melt viscosity samples. Before measurements, the
PETA-50 powders were dried in a vacuum oven at 105't: for 24hr. The powder
samples were directly poured on the disc in the test chamber. During the
measurement, nitrogen flow was used to reduce sample oxidation. Strain was
fixed at 30% throughout the experiments.
X-ray Dift'raction
X-ray diffraction patterns were obtained with the Rigaku Denki X-ray
diffractometer using Nickel-filtered CuKa radiation(30KV,20mA). The PETA-50 was
ground to form a powder sample.
RESULTS AND DISCUSSION
Cbaracterization of PETA-SO
The X-ray pattem of PETA-50 was quite different from that of the PET base
polymer(Figure 1-a). For the PETA-50, it is seen that the broad single peak was
observed around 28=20 (Figure 1-b). This peak at around 28=20 is the
characteristic peak of poly(p-acetoxybenzoic acid)[PPABA], shown in Figure 1-c.
Liquid crystalline polyesters have typically colored streak textures that are
consistent with the anisotropic mesomotphic phases in the polarizing microscope.
The PETA-50 showed distinct liquid crystalline phase at 201 't: and typical crystal
texture was also weil developed even at very high temperature. Krigbaum and
Salarisll reported on the basis of the polarizing microscope and differential
scanning calorimeter experiments that the copolyester containing 30mole% PABA
exhibits the crystal -nematic transition temperature(Tm) at 207't: and the
nematic-isotropic transition temperature(Ti) at 244 't:. Once a virgin sample is
heated above Ti, then cooling and reheating produces a different thermogram,
showing Ti endotherm disappeared. They explained that the loss of the Ti
transition might be due to the molecular weight reduction, sequence randomization,
or erroneous identification of the transition. But, the reasons for disappearing Ti
endotherm are not solely due to the above phenomena. In fact, Lader et al.
suggested that the copolyester containing 30mole% PABA does not exhibit a
nematic phase, as in our experimental results12
On the other hand, Meesiri et al. reexamined the copolyester containing 32
mole% PABA13 They concluded that the highest endotherm was due to a more
perfect crystal, produced by the particular thermal history of this sample. They
found that none of the other samples showed comparable melting peak separation,
but all showed the mesophase melt. Birefringence of the 32 mole% of PABA
samples also did not disappear at 243 't: . The optical microscopy results indicated
that the transition to the isotropic phase is completed only above the
decomposition temperature, so that no thermal analysis for the nematic - isotropic
transition is possible13 In our studies, however, the phase transition of the
nematic - isotropic temperatures of the PETA-50 was not detected by DSC
method.
The melting temperature of PET before modified by PABA was about
250't:. The glass transition temperature of the PETA-50 was 48.3t, even though
27
2000
I-PET I
1600
i 1200
~
l.a 800
400
0
5 10 15 20 25 30 35 40
21HETA
(a)
2800
1-PETASOj
2400
2000
i
u 1600
~
;;
1200
~ 800
400
0
5 10 15 20 25 30 35 40
21F.ETA
(b)
2000
1-PAB~
1600
r;;-
~
u 1200
~
;;
c::
800
~
400
0
10 15 20 25 30 35 40 45 50
2TIIETA
(c)
Figure 1. X-my diffi:actograms of PET(a), PETA-SO{b), and PABA(c}.
28
Table 1. Thermal data of the PETA-50 in comparison with PET
Tg ("C) Tm("C) Tc("C) Mim (J/g)
Sampie
PET 83.0 250 209 50

PETA-50 48.3 191 168 3
that of PET is 83 t. Uke in the glass transition temperature, the melting

temperature and the overall crystallinity of PETA-50 were lower than those of
PBT. The results are indicative of an eutectic phase separation or isodimorphism.
That is, the PABA in the PET-based copolyester plays the role to decrease the
crystallinity of the modified-copolyester by their randomness in some sense. The
disruption in the sequencing of the monomer units along the backhone chain
reduces the crystallinity. The cold crystallization temperatures, Tc, was also
decreased, similarly as for the melting temperature. Table 1 summarizes the
thermal data of the PETA-50 as compared with the PET.
When polymers exist in the isotropic phase, the shear rate dependence of the
viscosity foilows a weil-known pattem: at sufficiently small shear rates, the
viscosity is constant(Newtonian plateau); at !arger shear rates, the polymeric liquid
exhibits shear thinning behavior. The fundamental reason for the shear thinning
behavior is also weil understood: as the shear rate increases, a progressive " lose
of isotropy" takes place, in the sense that the polymer molecules become
progressively more and more oriented in the shear direction. The behavior of LCPs
differs from that of ordinary polymers in at least one important aspect, i.e., there
is no indication that the viscosity trends to reach a Newtonian plateau when the
shear rate is decreased. Such phenomena as shear thinning viscosity at low shear
rates, low melt viscosities, negative first normal stress differences, long relaxation
times in the melt, as weil as little or no die-sweil are, in fact, peculiar features of
these materials that can influence the processing operations. In this regard, the
tendency of the molecules to be aligned along the flow direction is most
prominent feature of the LCP, and in processing thermotropic LCPs, the strong
coupling between flow and orientation is observed. The properties of thermotropic
LCPs are, therefore, influenced by the processing parameters to a greater extent
than traditional thermoplastic polymers are. The viscosity-shear rate data have
been reported for the PET/60PHB and other aromatic copolyesters and for the
ceilulose ethers14' 15 Recently, the most efforts on aromatic copolyesters have been
given to the PET/60PHB system16' 17
The melt viscosity behavior with different shear rates is represented in Figure
2. The viscosity behavior for the PETA-50 copolyester was measured at 240t.
The outstanding difference between isotropic and thermotropic polymers is the
oneset of the nonlinear viscoelastic behavior; for instance, the shear thinning occurs
at a much lower shear rate for thennotropic polymers than for isotropic polymers
of comparable viscosity. At low shear rates, the thermotropic polyesters could not
move smoothly because of the crystallinities, while at high shear rates the structure
was disrupted to allow stable flow. In tlrls study, the shear thinning behavior at
low shear rates were found in the PETA-SO which showed liquid crystalline
behavior.
29
1.00E+4
1.00E+3
o::-
~ 1.00E+2
-. ....
UJ
1.00E+1
1.00E+O
1.00E+-2 1.00E+-1 1.00E+O 1.00E+1 1.00E+2 1.00E+3
FREQUENCY(rad/s)
Figure 2. Complex viscosity(l{;ETA) as a function of frequency for PETA-50.
Blend Properties
Rheological properties
Th.ere are some differences when comparing the features of LCP with those
of conventional thermoplastic polymers. These thermoplastic polymer molecules
are long and, in the melt form, in a random coil configuration. When extruded,
injection molded and fiber spun, these long molecules tend to align, but the
continuity of the chain is low and the chains remain partially coiled; furthermore,
the molecules of these polymers tend to align and to uncoil in tensile and shear
field, but, on the removal of the stress, they partially lose the orientation and tend
to recoil. On the contrary, LCP's molecules, under appropriate processing
conditions, have the tendency to align and to remain in that orientation, thus
presenting the extended chain conformation. The willingness of the molecules of
LCP to remain in alignment accounts for their fibrous structure and their excellent
mechanical properdes which are similar to those of fiber reinforced thermoplastics,
so LCPs are often referred to as self reinforcing polymers. On the other hand, the
viscosity in the steady shear flow is the most investigated rheological property of
blends with thermotropic liquid crystalline polymers. Most of these data have
been obtained by capillary rheometry and only a few measurements have been
perfonned by cone and plate geometry. In this work, the rheological properdes of
those blends were measured by the cone and plate of the RMS.
Rgure 3 shows the effect of the PETA-SO contents on the complex viscosity.
It is seen that the viscosity is decreased with increasing PETA-SO contents.
Another interesting point is, in Figure 3, that the slope of the curve of viscosity
vs. shear rate is increased with the increasing PETA-SO contents. This means
that the liquid crystalline PETA-SO has two functions; one is lowering the
viscosity of the blend, the other is showing a non-Newtonian behavior by the
30
1.00E+05
.PBT

'. PBT /PETASO(B0/20)
'' :, APBTIPETA50(50/50) I
111 111!11 )(PBT /PETA50(20JBO) i
1.00E+04 )ICPETA50
Q.. I
II:.
' I I
"' 1.OOE+03 I .I lll!lil ' 111 :

~
w ' 'I,.
..
I I I ~ I ;
I 11
1 .OOE02 I d I~ 11111!
.. ',, . ,,
t'
111.
'II II, I I, I,. I
1.00E+01
i 1111111 I lllil!:: II I II I ll_ll_li
l.OE-02 1.0E-01 1.0E+OO 1.0E+01 1.0E+02 1.0E+03
FREOUENCY (rad/s)
F1gure 3. Complex viscosity(t{;ETA) as a function of frequency for PBT/PETA-50 blends.
1.0E+05
- ,,
II I'
II PBT/PETA50(20/80) Ll I
1\i! I 'f'
1.0E+04
PETA50
I
'
-
5 t::j PBT /PETA50( 50/50)
,,
A .,.
-
~ 1.0E+03 l=f PBTIPETA50(80/20) '\1
I
"C
' '
I
1.0E+02 ~ "'j"ll ~ f I
. '
I
PBT
'I
1.0E+01 I! II I :1[1 II
1.0E+02 1 .OE+03 1.0E+04 1.0E+05 1.0E+06
G" (dyn/crrt)
Flgure 4. G' vs. G" plot of PBT/PETA-50 blends.
incorporated PABA in PETA. Most of studies for the blend of thennoplasti.cs

with liquid crystalline polymer in rnany literatures reported also a drasti.c reducti.on
of the viscosity due to the presence of liquid crystalline polyesters, even at low
content of the liquid crystalline polyrner5"718
It bas been reported by several authors that the PBT as well as PET are
partially miscible with PET/60PHB, due to the similar molecular structure of the
copolyester and its parent polymer, PET. The miscibility is better as the PET or
PBT contents are highe?-7 In this work, previous analysis by a scanning electron
microscopy revealed that the PETA-SO is also partially miscible with PBT. It is
possible to deduce the miscibility of blends by the rheological f.roperties by
plotring the log G'(storage modulus) against log G"(loss modulus) 1 20 Figure 4
shows the result. In Figuie 4, the PETA-50 exhibited higher G' values than PBT
31
~0 r-------------~======~
+ Tru1(PBT)
--o- Tm2<PBTI
235
- ..t.- Tm3(PTI
215
210 ~-.. _ _ ____.__ _ _ _....__ _ _ __,~
100/0 80!.!0 50150 20/80

Blend ratlo or PBTJPETA-50
Figure 5. Melting tempemtmes of PBT in PBT/PETA-50 blends on the fust, second, and drlrd
DSC scans (Tm1, 'Iin2o and 'I'Db, respectively).
at the same G" values. The slope of the G' as a function of G" for the blends
approaches more closely to that of PBT as the PETA-SO contents decreases. In
other word, the slope deviates from that of PBT to more degree as PETA-SO
contents increases. The result implies that the miscibility of PBT and PETA-SO
becomes better as the PETA-SO contents decreases.
Thermal properties
Figure 5 shows the melting temperature of PBT in blends as a function of

blend compositions. In this figure, Tm., Tmz, and ~ denote the melting
temperatures taken from the fust, second, and third scans on DSC thennograms. It
was reported that PBT exhibits single melting temperature on the fust scan but
shows double-melting behavior on the second and third heating scans21.22. Thus,
the three melting temperatures were measured. No significant differences were,
however, observed in between the melting temperatures taken from each heating
scan. As expected, the melting temperature of PBT in blends was decreased with
increasing PETA-50 contents. The result means that the PETA-50 restricts the
crystallization of PBT.
CONCLUSIONS
In this work, A copolyester having 50 mole% of PBT and 50 mole % of

PABA was prepared by the melt reaction of PABA and PBT without catalyst
Blends were prepared by powder mixing .in a glass tube with agitating at 2000ppm
with a vibrator for about 5 min. The blend ratio of PBT and the PETA-SO is
80/20, 50/50, and 20/80. The powder mixtures were poured into the RMS testing
pot and then melt mixing was perfonned in between the plates. After RMS test,
the remained samples were collected from the plate and were used for the
measurem.ent of the thermal analysis and mechanical properties. The rheological
and thenna1 properties of the blends of PBT and the PETA-SO copolyester were
32
investigated using Rheometrics Mechanical Spectrometer and Differential Scanning
Calorimeter.
The blend system of PBT and PETA-SO e:xhibits a partial miscibility when
the PETA-SO contents is low. As the PETA-SO contents were increased, the melt
viscosity of the blends was decreased and the crystallization rate was decreased.
REFERNCES
1 S.Metba and B.L.Deopura, J. Appl. Polym. Sei., 47:857 (1993).
2. M.Amano and K.Nakagawa, Polymer, 28:263 (1987).
3. M.R.Nobile, E.Amendola, L.Nocolais, Aciemo.D., and C.Carfagna,
Polym. Eng. Sei., 29(4):244 (1989).
4. W.J.Jackson Jr. and H.F.Kuhfuss, J. Polym. Sei, Polym. Chem. Ed., 14:2043(1976); see also
H.F.Kufuss and WJJackson, US Patent 3,804,805 (1974).
5. M.Kimura, R.S.Porter, J. Polym. Sei. Polym. Phys. Ed., 22:1697 (1984).
6. J.H.Chang and RJ.Farris, Polym. J., 27:780 (1995).
7. J.H. Chang, B.W. Jo, and J.L Jin, Polym. Eng. Sei, 35(29):1605 (1995).
8. M.Paci, M.Liu, PLMagagnini, F.P.La Mantia and A.Valenza,
Thennochimica Acta, 137:105 (1988).
9. S.Metba and B.L.Deopura, J. Thennal Analysis, 40:597 (1993).
10. A. Zaldau, E. Munoz, JJ. Pena and A.Santamaria,
Polymer, 32(4):682 (1991).
11. W.R.Krighaum and F.Salaris, J. Polym. Sei. Polym. Phys. Ed., 16:883
(1978).
12. H.J.Lader and W.R.Krighaum, J. Polym. Sei Polym. Phys. Ed., 17:1661
(1979).
13. W.Meesiri, J. Polym. Sei. Polym. Phys. Ed., 20:719 (1982).
14. K.F.Wissbrun, J. Rheol. 25, 619 (1981); Br. Polym. J. 12:163 (1980).
15. R-E.Jennan and D.G.Baird, J. Rheol, 25:275 (1981).
16. Z.Ophir abd Y.Ide, Poly. Eng. & Sei., 23:792 (1983).
17. M.R.Mackley, F.Pinaud and G.Siekman, Polymer, 22:437 (1981).
18. A. Zaldau, E. Munoz, J. J.Pena and A.Santamaria,
Polymer, 32(4):682 (1991).
19. C.D.Han and J.K.Kim, Polymer, 34:2553(1984).
20. C.D.Han and J.K.Kim, Macromolecules, 22:4292(1989).
21. T.K.Kang,Y.Kim, W.J.Cho, and C.S.Ha, Polym.Eng.and Sei., 36(20):2525(1996).
22. J.K.Kim, M.E. Nichols, and R.E.Robertson, J.Polym. Sei., Part B: Polym. Phys., 32:887 (1994).
33
ANALYSIS OF FRACTURE PROCESSES
IN CROSS-PLY LAMINATES
J.-M. BERTHELOT
Institut d'Acoustique et de Mecanique

Graupe Composites et Structures Mecaniques
Universite du Maine, BP 535, 72017 LE MANS Cedex, France
INTRODUCTION
Cross-ply Iaminates are constituted of unidirectional fibre layers oriented

altematively at 0 and 90.
When cross-ply Iaminates are subjected to mechanicalloading, different failure
mechanisms are induced (figure 1) : transverse matrix cracking in 90 layers,
delamination between 0 and 90 layers, longitudinal matrix cracking which
develops along the fibre direction of 0 layers, fibre fracture in 0 layers.
When cross-ply Iaminates are subjected to uniaxialloading, the early stage of
darnage is dominated by transverse matrix cracking in 90 layers (figure 2). The
matrix cracks develop in the fibre direction and extend accross the Iaminates from
the free edges of the test specimen. Two different evolutions of the progression in
the test specimen width are observed according to quasi-static tests or fatigue tests.
These two type of evolutions will be considered in this paper.
TRANSVERSE CRACKING IN QUASI-STATIC TESTS
Stress and strain distributions
In the case of quasi-static tests, most cracks cross instantaneously all the test
specimen width from edge to edge (figure 3). The nurober of cracks increases with
the increase of the load, until a crack density saturation. So in static tests, the
analysis of stress and strain distributions is reduced to a two-dimensional approach,
inside an elementary cell (figure 3) between two consecutive craks. The elementary
cell is characterized by the distance between two consecutive cracks and by the
thicknesses of 0 and 90 layers.
The problern to be solved is to find the fields of displacements and stresses
inside the elementary cell, which must satisfy :
- the fundamental relations of a deformed continuum :
(1)

Edited by P. N. Prasad et al., Plenum Press, New York, 1998 35
- the strain-displacement relations :
Exx =-dU
dX
dw
Ezz= -
dZ
du
Yxx = dX
dw
+a.x (2)
- the compability equations (not reported here),

- the stress-strain relations, which relate the mechanical behaviour of
materials:
(3)
- the boundary conditions imposed to the elementary cell : here a tensile state.
In fact, the exact analytical solution of this problern cannot be derived. Only
approximate analytical models can be considered.
Considering the results obtained from finite element analysis [1] Ieads to
develop a generalized model [2]. The basic assumptions of this generalized model
are the following ones :
- firstly, assumption on the longitudinal displacements:
- the variation of the longitudinal displacement is supposed to be parabolic in
crossply
Iaminate
fibre rracture dclamination Irans' er..e cracking

Figure 1. Different fracture mechanisms induced in cross-ply Iaminates
o
90"
o
90
o
Figure 2. Transverse matrix cracking in cross-ply Iaminates
36
z
oo to
elcmcntary (;CII.
90
0
[ -
tgo
-
X
21
Figure 3. Transverse matrix cracking and the elementary cell
the thickness of 90 Iayer :

t2
u9o(x,z) = u9o(x) + (z 2 - ; 0 ) A9o(x) (4)
- the variation of the longitudinal displacement is to be determined in the

thickness of 0 layers :
uo(x,z) = uo(x) + /(z) Ao(x) (5)
- secondly, assumptions on the shear stresses, similar in 0 and 90 layers, which
can be obtained by assuming that the transverse displacement is independent of the
longitudinal coordinate :
i =0,90 (6)
These assumptions associated to the previous formulations which govern the

elasticity problern in the elementary cell, yield first the average longitudinal stress in
90 layer, the average longitudinal stress in 0 layers and the interface shear stress
between 90 and 0 layers:
cosh 1]aK)
~Z(x) = O"c E9o ( 1 - l (7)
E2 cosh 1]a
cosh 1]aK)
O:~x(x) = O"c Eo ( 1 + t9o E9o l (8)
E~ to Eo cosh 1]a
E cosh 1]aK
r(x) = O"c ___2Q_ 1] I (9)
E~ cosh 1]a
37
The formulation of this stresses introduces :
- the cracking aspect ratio :
a=_L (10)
tgo
- the Ioad transfer parameter between two consecutive cracks :
(11)
- the generalized shear modulus of the elementary cell :
G 90
G= xz (12)
1 _ 3 c2r f(tgo)
0 .
Gxz f (tgo)
Next are derived the longitudinal displacements in 0 and 90 layers, the

longitudinal stresses, the shear stresses and the transverse stresses. The relations
obtained [2] are somewhat complex, but they can be easily implemented in
numerical procedures.
At this step the variation function of the longitudinal displacement across the 0
layer thickness is to evaluate.
The figure 4 shows examples of the variations of the longitudinal displacement
across the Iaminate thickness. These results were obtained by finite element
analysis for different values of the cracking aspect ratio. Based on these results,
two different analytical functions of the variation function have been considered :
- a parabolic model [2] :
f(z) = z 2 - 2(to + tgo)z + i rJ + 2to tgo + tJo (13)
0.8 . - - - - - - - - - - - - - - - - - - - - - - .
--+-- a=10
0.7
- a=5
~ a =2.5
"0.6
~
N
iO 0.5
r--
2.
::::1 0.4
0.2 ....................~...~..................I...L.............L..L..&....&...L...&...L..................................L..I..J.....L..I...........I...I..J....J...I..J
-2 -1 .5 -1 -0.5 0 0.5 1.5 2
z!t 90
Figure 4. Variation of the longitudinal displacement across the thickness
38
~ finite element analysis
~ 3
u parabolic analysis
0
';.2.5 progressive shear
~
"' 2
"'2!
u; 1.5
(ij
c
'6
::J
',
c
..Q 0.5
0~~~~~~--~--~--~--~--__J
0 0.2 0.4 0.6 0.8 1.2 1.4
transverse coqrdinate ( zlt90 )
Figure 5. Cracking aspect ratio: a=l
1.4
.. .. .. ....... ....,
~ 1.2
p-
u
0
';.1 ~ finite elements
~
~
"'0.8
--- parabolic analysis
"'2! --- progressive shear

u; 0.6
(ij
c
'6
2 0.4
c;,
c
..Q 0.2
0
0 0.5 1.5 2 2.5 3
transverse coordinate ( z/t90 )
Figure 6. Cracking aspect ratio: a=5
Figures 5 and 6. Variation of the longitudinal stress through the thickness of Iaminate
- a progressive shear model [I] :
sin _!Q_ 77
f(z) = t90
_!Q_ 77
- cosh 11 (1 + _!Q__
f90
...L)
f90
(14)
t9o
characterized by the shear transfer parameter :

71r = Eo 1 (15)
oa
G xz
39
1.6
1.4
----
u
~ 1.2
><
~ 1
~
lh ~ finite elements
~ 0.8
Ui parabolic analysis
~ 0.6
' progressive shear
::l
'6,0.4
c:
.Q
0.2
0
0 0.5 1.5 2 2.5 3
transverse coordinate ( zft90 )
Figure 7. Cracking aspect ratio: a=2.5
2.--------------------------------------.
1.8 ---
.g1.6
........
~ 1.4
1:) /
/
~1.2
/
lh
/
e finite elements
lh
~
/
Ui /
iii 0.8 / prabolic analysis
c:
'g 0.6
S, progressive shear
. 0.4
0.2
0~~~~--~----~----~----~----~
0 0.5 1.5 2 2.5 3
transverse coordinate ( zft90 )
Figure 8. Cracking aspect ratio: a= 1

Figures 7 and 8. Variation of the longitudinal stress through the thickness of Iaminate
The figures 5 to 8 give some examples of the results obtained by the two
analytical models and by finite element analysis for the variation of the longitudinal
stress through the thickness of Iaminates. These results show that the two models
give similar results in the case of low thicknesses of 0 layers (figure 5) and in the
case of low crack density (figure 6). Moreover, the results show clearly that the
parabolic model is not adapted in the case of high thicknesses of 0 Iayers and Iow
crack density (figures 7 and 8), when the progressive shear model shows a very
good agreement with finite element analysis.
40
experimental resulls
--<>- finite elements

0.9
1 D analysis
0.8 90 shear
complete shear
o,.
~ 0.7
.
w
0.6
-- ....... __ ---
0.5
0.4 ~~~~~~~~~~~~~~~~~~~~~~~
0 100 200 300 400 500 600 700 800

crack density (m" 1)
Figure 9. Stiffness reduction for [0/903/0] glass fibre/epoxy laminates
0.975
0.95
o,.
~ 0.925
w
0.9
0.875
0 250 500 750 1000 1250 1500 1750 2000

crack density (m-1)
Figure 10. Stiffness reduction for [0/90JO] graphite fibre/epoxy laminates
41
I
}'-
Ec =0.40 11)-2
I"-
~-om ~ IIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIIII"
200.---------------------------------------------~
180
160
~ 140
::E
U) 120
!
1il 100
~
GI
~ 80
60
40
20
0 ~--~--~--~--~--~~--~--~--~--~--~--__J
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.1
Strain (%)
Figure 11. Examples of crack distributions and the stress-strain curve evaluated in the case of
grass fibre I epoxy laminares
Stiffness reduction
The stifness reduction can be evaluated by the longitudinal Young's modulus
of the damaged cross-ply Iaminates. The longitudinal modulus can be expressed [1]
as :
(16)
with
( 1) G Ex0
1]=3 1+- ____
a Eo E9o
42
2000
experimental results /
1750 ../
- 1500
--<>-- finite elements
1D analysis
>/.... .......... . . .
.......
'E 1250
90" shear I / "
-~ I : "
~ 1000 complete shear I ,I":,'"
Q)
"C
I!/'"
I.,

.:.:. 750
0
~
0
500
250
0
0 150 300 450 ' 600
average stress (MPa)
750 900 1050
1400
experimental results
1200
.:; 1000 1 D analysis

.s 800
90" shear
-~
fJ)
c complete shear
Q)
"C 600
.:.:.
0
llS
t; 400
200
0
0 100 200 300 400 500 600 700 800
1400
1200
experimental results
,, '
,, '
.:; 1000 1 D analysis ,'
.s>- 800
90"shear 1
11 ................ - -
.t:
fJ) 1
cQ) complete shear ,' / , . " . "..
"C 600 1/
.:.:.
0
llS
t; 400
200 [0/90i0J
0
0 100 200 300 400 500 600 700
Figure 12. Experimental and evaluation of the evolution of the crack density in the case of
carbon fibre I epoxy Iaminates
43
crack i
- edge of initiation (cdge 1 or 2)
position x;
lcngth a;
Figure 13. Matrix crack pattem in fatigue tests
Cycle Nj
- - -
-
'""'
n
L
V>
:,(.
<.> 20 - - .-,--r--,----
~
<.>
0
~ 10
E
::l
c
w
\
band i
position of the bands
n;(Nj)
( width Y;) unifom disuibution d;(NJ)=--
L
Figure 14. Evaluation of the crack distribution
44
Iaminate D [ 0,190 Js
Figure 15. D and S carbon fibre I epoxy Iaminates
5
(x10 3 )
4
Iaminates 0 o.aau
[] Iaminates 0 0.6au
i 3
~ 10 cycles
u;
c
V
""0 2

-"

u
"'t;
[] []
oo 15
w = 15 mm

[]
Iaminates D
Iaminates D
o.aau
0.60"u
4
'E Iaminates S o.aau
s 3
~ 104 cycles
.1

Qj
""0 2
-"
u [] []
~
u
[]
[] []
0

[] []
0 0 15
w = 15 mm
Figure 16. Examples of crack distributions for 10 and 1()4 cycles
45
The parabolic modeland the progressive shear model differ by the evaluation of the
shear parameter, introduced in (11) and (12).
The comparisons of the results obtained by different analytical models and by
finite element analysis with the experimental results are reported in the case of glass
fibre/epoxy Iaminates (figure 9) andin the case of carbon fibre/epoxy Iaminates
(figure 10). These results show a fairly good agreement of the stiffness reductions
derived by the progressive shear model with the experimental results.
Progression of the transverse cracking

Once the stress distribution has been evaluated as a function of the crack
spacing, the progression of the transverse cracking can be investigated by a stress
based approach. A new crack is assumed to be created, when the average
longitudinal stress in 0 layer reaches the ultimate stress of the 90 layer. The crack
progression is controlled by the fracture stress distribution in the 90 layer. A
statistical distribution of strengths along the length of specimen has been
considered. Then a numerial procedure, based on the progressive shear model, has
been implemented so as to investigate the multiplication of the transverse cracking.
Examples of cracks distributions in the 90 layer, obtained by the previous

procedure, are reported in figure 11. The cracks distributions were evaluated at
three Ievels of the longitudinal strain, applied to glass fibre/epoxy Iaminates. The
corresponding stress-strain curve obtained is also plotted in figure 11. The curve
shows the apparition of the first crack and the progressive stiffness reduction
during the progression of transverse cracking.
The experimental evolution of crack density as a function of the average
longitudinal stress applied to carbon fibre/epoxy Iaminates are reported in figures
12. Three stackings have been considered, differing by the number of 90 layers.
The experimental results are compared with the results deduced from different
analytical models and from finite element analysis. The different models Iead to
similar results at the beginning of transverse cracking. Next the experimental results
are fairly well described by the progressive shear model in the domain studied.
PROGRESSIVE CRACKING DURING F ATIGUE TESTS
Stress and strain distributions

During fatigue tests, matrix cracks in 90 layers initiate at the free edges of test
specimen, then grow slowly across the specimen width as a function of cycle
number. For a given cycle number, the matrix cracking pattern (figure 13) is
characterized by the edge of initiation, the position along the length of the Iaminate
and the length of each crack.
The analysis of the stress and strain distribution, the evaluation of the stiffness
reduction are very complex, and involve the resolution of a three dimensional
problem.
Finite element analysis has been implemented in the case of regularly spaced
cracks [3]. The influence of the crack length and the one of the aspect ratio have
been investigated. Schematically, the results obtained show that the displacement
field and the stress distribution can be evaluated reasonably by the previous
46
1.001
o,.
~
1.000
~
!i 0.999
Vl
::J
:;
"0 0.998
0
E
_Vl 0.997
Cl
c
::J
0
>- 0.996
0.995
1 10 10 2 103 104 10 5 10 6 107
Cycle number
fig. 17 .a. Laminates D 0.60'u
1.001 . . - - - - - - - - - - - - - - - - .
~
~t 1.000
!i 0.999
Vl
::J
:g
0
0.998
E
_Vl 0.997
Cl
c
0.996
0.995 .___,___.~....__...__....___...L..._....L__...J
1 10 102 1 0 3 104 105 106 107
Cycle number
fig. 17.b. Laminates D 0.80'u
1.0001 r - - - - - - - - - - - - - - - - .
"'
::J
:;
-g 0.9995
E
-"'Cl
0.9990
0
>-
0. 9985,L--..L___..J....__...L__....L__ _L__ _J__ _J
1 1o 1o2 1 o 3 1o4 105 1oG 1 o1
Cycle number
Hg. 17.c. Laminates S 0.60'u

Figure 17. Stiffness reduction as a function of cycle number
47
1.0001......------- ---------,
,......,
0~
~
~ 1.0000
"'
:::l
:0 0.9995
E
"'
-Cl

.
0.9990
0
>-
0. 9985L-_..L..__ _ L _ _ . . . J _ _ . . . . L __
_L__ _L__ _J
1 10 10 2 10 3 10 4 10 5 10 6 10 7
Cycle number
fig. 17.d. Laminates S 0.80'u

Figure 17 (continuation). Stiffness reduction as a function of cycle number
1.001
_.......
~)(
1.000
Laminates D

0
O.BO"u
0.60"u
....__
!:! 0.999
'S
"'
:::l
0.998
"0
0
E
"'
-Cl
0.997
c:
:::l
0
>- 0.996
0.995
0 2 3 4 5 6 7 (x1 o-3)
Crack area Sc (m 2/m)
1.0001
_.......
o,.
J.u
Laminates S 0.80"u
0 0.60"u
....__
'S
"'
:::l
"0
0
0.9995
E
"'c:
-Cl
:::l
0
>-
0.9985
0 2 3 4 5 6 7 (x1 o-3)
Crack area Sc (m 2 /m)
Figure 18. Stiffness reduction as a function of the crack area
48
generalized model in the cracked band and by the classicallaminate theory in the
uncracked band (in fact, except near the crack tip ).
Modelling of the stiffness reduction
Based on the previous results, a procedure has been developed to simulate the
initiation and the propagation of transverse matrix cracks.
A typical distribution of matrix cracks in 90 layer is reported in the figure 14.
The crack distribution in the test specimen can be characterized by dividing the test
specimen into bands along the width, and evaluating the distribution of cracks
crossing each band (figure 14). Fora given cycle number Nj. the modulus can be
evaluated, as a function of the crack density in the band :
Exi =Ex [di(Nj)] (17)
Next, the longitudinal Young's modulus of the darnage Iaminated can be derived as
a contribution of the whole bands :
E
__!_(Nj) = _1_. Ln Ex[di(Nj)] (18)
E~ wE~ i= 1
In this way, the stiffness reduction has been evaluated : i) considering either the
actual random distribution in every band or a uniform crack density along the length
of the test specimen ; ii) using the progressive shear model of finite element
analysis to estimate the stress distribution between two consecutive transverse
cracks. The results obtained by the different processes do not show significant
differences.
The previous analysis has been applied to carbon fibre/epoxy Iaminates,
studied in fatigue tests [4]. Two stacking sequences have been studied (figure 15),
differing by the number and the thickness of the 90 layers : two layers of a single
ply (thickness equal to 0.125 mm) for the first sequence (denoted S), and one layer
of a double thickness (two plies) for the second sequence (denoted D). The figure
16 shows examples of crack distributions in the two Iaminates studied, evaluated in
the case where the specimen width is divided into eight bands. The distributions are
reported for two cycle numbers (10 and 104) and for a maximum fatigue tensile
stress of 0.6 and 0.8 the static failure stress of Iaminate (<Tu = 1440 MPa). The
figures 17 show the results obtained by the previous procedure, for the Young's
modulus reduction as a function of the cycle number. The reduction of the modulus
is very Iow, due to the Iow thickness of 90 Iayers. Next, the longitudinal Young's
modulus as a function of the crack area can be deduced from the previous curves,
by multiplying, for a given cycle number, the crack density in each band by the
thickness of the 90 Iayers and the width of the bands. The results obtained (figure
18) are independent of the maximum fatigue stress and show a linear relationship
between the stiffness reduction and the crack area (Sc) :
Ex = 1 _ a s a = 0.357 m- 1 for S Iaminates ( 19)
E~ c a = 0.667 m-1 for D Iaminates
WORKS IN DEVELOPMENT
Further to the results considered in the previous sections, different works are
in development. Some elements were presented at the conference. These works
49
concern firstly the modelling of the crack propagation during fatigue tests and
secondly the analysis of the progression of transverse cracking and delaminations.
These works will not be reported here.
CONCLUSIONS
It has been observed that, in the case of static tests, the transverse matrix
cracks initiate at the free edges of the specimen and cross instantaneously all the
specimen width. Thus, the analysis of stress and strain distributions is reduced to a
two-dimensional analysis. A generalized model, with parabolic shear in 90 layer
and progressive shear in 0 layers, has been developped. Based on this analysis, a
numerical procedure, associated with a statistical distribution of fracture stress, has
been implemented to investigate the transverse cracking progression.
During fatigue tests, matrix cracks grow progressively across the specimen
width. In this case, the stress and strain analysis needs a three dimensional
investigation. Three-dimensional finite element analysis has been implemented. The
results show that the displacement field and the stress distribution can be evaluated
by the generalized model in the cracked band. Thus, the stiffness reduction can be
evaluated by dividing the specimen width in bands.
At last, the modelling of the crack initiation and propagation during fatigue
tests and the analysis of transverse cracking and delamination are part of works in
development.
ACKNOWLEGMENTS
The analysis of fracture processes in cross-ply Iaminates is part of the works

developped by the Composites and Mechanical Structures Group of the Acoustic
and Mechanical Institute, at the University of Le Mans, France.
REFERENCES
1. Bertheiot, J.-M., Leblond, P., EI Mahi, A., and Le Corre, J.-F., 1996, Transverse cracking of
cross-piy Iaminates : Part I. Analysis. Composites, 27 A. 989:1001
2. Berthelot, J.-M., Analysis of the transverse cracking of cross-ply Iaminates : a generalized

approach. Journal of Composite Materials (tobe published)
3. Berthelot J.-M., EI Mahi, A., and Leblond P., 1996, Transverse cracking of cross-ply
Iaminates: Part 2. Progressive widthwise cracking. Composiles, 27 A, 1003:1010
4. Henaff-Gardin C., Lafarie-Frenot M.-C., Brillaud J., and EI Mahi A., 1992, Influence of the
stacking sequence on fatigue transverse ply cracking in cross-ply Iaminates. In ASTM STP 1128
(Ed. J.E. Masters), American Society for Testing and Materials, Philadelphia, PA, 236:255
50
THERMOPLASTIC POLYMER BLENDS CONTAINING CONDUCTIVE
POLYANILINE
Olli T. Ikkala/ Pentti Passiniemi,2 and Jan-Erik sterho1m2
2 Neste Oy
Technology Center
FIN-06101 Porvoo, Finland
1 Helsinki University of Technology
Department of Engineering Physics and Mathematics

P.O. Box 2200
FIN-02015 HUT, Espoo, Finland
INTRODUCTION
In polymer science there hardly exists another field that has been so
interdisciplinary as the development of conducting polymers from a scientific curiosity to
technological applications (for a general background, see1-3). In addition to polymer
chemistry, conducting polymers have greatly benefitted from solid state physics to
understand conduction mechanisms, colloidal chemistry to understand solubilization,
science of polymer blending and processing to achieve co-continuous structures in
multicomponent polymer systems, and even biochemical sciences to suggest tailored
polymer-solvent or polymer-plasticizer complexes to achieve processibi1ity. All of these
aspects will be discussed here in some detail. Because this presentation is included in the
Session on Polymer Blends, instead of showing the most recent subtleties of polyaniline,
we selected to emphasize general aspects how to achieve polyaniline phase co-continuous
when blended with polyolefins. Background on conducting polymers is discussed to
illustrate the state-of-art. The selected priorization is subjective and thus we apologize
possibly incomplete referencing.
The topic to construct co-continuous phases in multicomponent polymer systems is
relevant in many respects. Scientifically, it has aroused much interest to achieve synergistic
blend properties, i.e., to achieve favourable combination of the attractive properties of the
individual blend components. The present methods can be applied to other fields of
polymer science, as well. Technologically, there are applications where electrical
conductivity of a commodity polymer is required. The economics and the required
properties in a given application would best be met by blends where the smallest amount of
Science and Technowgy of Polymers and Advanced Materials

electrically conducting polymer renders the cominodity polymer sufficient electrical
conductivity. For example, mixtures with polypropylene (PP) are required where less than
10 %-wt fusible polyaniline composition renders PP fibers electrically conductive for
antistatic clothing purposes. Other applications are antistatic floorings, tubings, bags, and
in the most demanding applications, electromagnetic shielding in electronics.
ON CONDUCTING POLYMERS
Although some related observations had been published already early,4,5 a high
volume research activity was launched by an observation that polyacetylene (a conjugated
carbon chain consisting of altemating single and double bonds, see Figure 1) could be
doped to obtain high conductivity. 6 Also other types of conjugated polymers were
searched, such as polythiophene, polypyrrole, and polyphenylene where one of the
motivations was to overcome the instability of polyacetylene. Models were constructed to
explain the band gap structures, conduction mechanisms along the individual chains using
concepts of solitons, polarons and bipolarons, and the nature of interchain hopping
conductivities. 7
Figure 1. The undoped forms of polyacetylene, poly(3-alkyl thiophene), polypyrrole, and emeraldine base
form of polyaniline.
The overoptimism to rapidly commercialize products slowly faded for several

reasons: the early conjugated polymers were "intractable", i.e., they did not melt before
their decomposition (thus not allowing conventional melt processing), and it was difficult
to find feasible solvents (for solution processing). The quite rigid polymer chains had a
strong tendency to crystallize in addition to the small available conformational entropy.
An interest revived when it was observed that the undoped polythiophenes could be
plasticized by incorporating alkyl side chains to the thiophene rings. They allowed
conventional melt processing.S-10 However, a complication still remained: in the doped
form, it was not fusible and had to be doped afterwards.
POLYANILINE AND ITS PROCESSING
Polyanilineil is probably the most feasible candidate for technological

applications. lts emeraldine base form (EB) is a polymeric base with aminie and iminic
52
nitrogens. MacDiarmid et ai12 observed that EB could be doped by proton transfer, see
Figure 2. A polymeric salt can be formed upon complexation with strong acids (A-H+),
such as sulphuric acid (H 2 S04), hydrochloric acid (HCl), and sulphonic acids (R-S03H). At
present, it seems that the iminic nitrogens are predominantly doped, in which case ca. 2
moles of strong acid is required for 4 moles of PhN repeat units of PANI. For example, the
fully metharre sulphonic acid (MSA) doped PANI can be denoted by PANI(MSA)x, where
X"'0.5.
Undoped PANI:
Polymerie base H
(uNn UNffN" )n
N I
I
H
+
An example of a dopant:
Acid CH3-S03H
lI
Doped PANI:
Polymerie salt
H H
(UNffNUNffN'- )n
I I
I + I +
H H
Figure 2. Doping of the emeraldine base form of PANI using a strong acid. Methane sulphonic acid is used
as an example without a loss of generality.
MSA is an illustrative example of an "unfunctionalized" dopant: R=CH3 does not

provide surface activity or hydrogen bonding, and it is also too small to effectively
plasticize PANI. Therefore, it was not regarded easy to find technologically feasible
solvents that would allow high solubility of PANI(MSA) 0 .5 . In order to have dissolution in
the electrically conducting form, basic solvents cannot be used due to dedoping effects. m-
Cresol is an example of a weakly acidic hydrogen bonding solvent. Although, the solubility
of PANI(MSA)o in it is rather small, it still allows preparation of solution cast thin films
with a conductivity of ca. 120 S/cm.l3
MacDiarmid et al also discussed that PANI is not totally rodlike but has a tendency
to form coils due to the stereochemistry of aminesl3. Accordingly, and as is also
classically known in polymer science, the solvent quality controls the coil size.14
lt was an important and originally astonishing observation by Cao et al15 that there
exists a unique sulphonic acid, i.e. camphor sulphonic acid (CSA), which allows a
particularly high solubility in m-cresol (up to ca. 10 %) and high conductivity (300 S/cm)
of solution cast thin films after its evaporation.l6 Ikkala et ai17 suggested explanation
based on molecular recognition where a strong specific interaction is formed between a
phenolic solvent and CSA doped PANI due to a steric match of the three molecular
53
structures and the three "elementary interactions": a) the proton transfer between PANI and
CSA, b) the hydrogen bonding between the carbonyl group ofCSA and the hydroxyl group
of the phenol, and c) the phenyl stacking between the phenol ring and one of the PANI
rings. Thus, PANI(CSA)0.5 allows an additional specific interaction to bond phenols and
one could, therefore, expect that phenols are better solvents for PANI(CSA)o 5 than for
PANI(MSA) 0.5, for example.
BLENDS OF POLYANILINE
The high solubility of CSA doped PANI in m-cresol can be used to prepare solution
cast polymer blends if also the second polymer component is soluble in m-cresol. Thus
Yang et al showed that co-continuous polymer structures with low percolation Iimit of
PANI(CSA)o 5 can be prepared in polymethylmethacrylate (PMMA) after evaporation of m-
cresot18 Although not specifically discussed there, it could be expected that these network
structures arenot reversible: We argue that heating above the softening point of PMMA
would cause drastic and irreversible change of the morphology to macroscopic
nonpercolating dispersions. Thus, we expect that the structures are not fusible.
To allow conventional melt processing, methods had to be developed to allow
formation of reversible network structure in repeated meltings and coolings. Plasticizers 19
correspond to solvents which, instead of being evaporated at the end of the processing,
remain as an integral part of the composition. They can form complexes with the polymers.
The above discussions suggested to search for plasticizers (solvents) that have a strong
specific interaction with the polymer a) to dissolve doped PANI as much as possible, and
b) to "open" the doped PANI coils. The first requirement is due to minimization of the
amount ofplasticizer. The second requirement is to promote high conductivity.
It initially turned out difficult to find feasible plasticizers for generic sulphonic acid
doped PANI. The ciassically used plasticizers (such as the ester plasticizersl9) tend to
macroscopically phase separate. Careful consideration to achieve strong specific interaction
between doped PANI and potential plasticizers suggests, however, a variety of feasible
alternatives. Firstly, another type of molecular recognition could be identified for PANI
doped by a generic sulphonic acid, such as MSA (for the concepts, see20,21 ). Phenols Ph-
OH do not effectively plasticize PANI(MSA) 0.5. However, it turned out that incorporating
another hydroxyl group to the phenols drastically improved the dissolution, i.e. dihydroxy
benzenes plasticize P ANI(MSA)o.s effectively at ca. 200 oc.22 The oversimplified
explanation can be given by noting that in sulphonic acid doped PANI there are hydrogen
bond acceptors at intervals of ca. 6 A (i.e. sulphonate groups due to protonating acids and
amines due to PANI) and also aromatic rings exactly at the same periodicity, see Figure 2.
This suggests that compounds having the same periodicity of aromatic rings and hydrogen
bonding donors could be plasticizers, such as hydroquinone, resorcinol, bisphenol A, or
2,4-dihydroxy benzophenone. Ca. 10-20 %-wt PANI doped by a generic sulphonic acid can
be dissolved at ca. 200 C.21 Such concepts resemble the steric match due to molecular
recognition in biochemical systems.23 Another method to achieve a strong specific
interactions is offered by coordination complexation of meta! cations, as was suggested by
complex formation of Zn(II) with amine containing polymer polyvinyl pyridine.24,25
Finally, there is the possibility (however, the technologically unfeasible alternative) of
using strong acids also as plasticizers (solvents) in addition to dopants, such as dodecyl
benzene sulphonic acid (DBSA)26 in which case the bonding is probably due strong
54
hydrogen bonding between the acidic group of DBSA and basic amines of PANI. Typical
interacting groups have been summarized in the right hand side of Figure 3.
Nonpolar moiety: Polar moiety:
Surface active Strong specific interaction

to low polar medium to doped PANI
Figure 3. Some candidates for functionalities of amphiphilic plasticizers of sulphonic acid doped PANI.
In this way fusible (plasticized) electrically conducting PANI compositions are

obtained. For example, PANI doped by MSA or another sulphonic acid becomes melt
processible when plasticized using resorcinol. 21
POLYANILINE MOLECULAR BOTTLE BRUSHES AND THEIR BLENDS
In order to construct co-continuous network structures in multicomponent systems,

it is not enough to achieve fusibility but proper surface activity has to be incorporated, as
weiL Such reasoning is suggested from colloidal surfactant/water/oil systems where co-
continuity of the phases can be achieved due to self-assembly into cylindrical or lamellar
phases (for review, see27). This suggests to use dopants and plasticizers that are
amphiphilic, i.e. have a nonpolar tail to be surface active to the nonpolar medium, such as
nonpolar solvents or polyolefins, see Figure 4. PANI complexed with amphiphilic dopants
and amphiphilic plasticizers is an example of a structure called molecular bottle brush, see
Figure 4. They have aroused much interest in the recent Iiterature as their own right (i.e.
even without a connection with conductive polymers).28-32 It has been claimed that an
isolated flexible polymer which has densely been loaded with side chains would become as
55
much extended to form liquid crystalline structures in good solvents of the side chains.29
Another school claims that the persistence length and the diameter grow in similar fashion
(and thus no liquid crystallinity would not be achieved).28 At present the situation is still
unclear whether individual bottle brushes really could form liquid crystalline structure. 30-
32 However, it is known that as soon as the molecular bottle brushes start overlapping, they
may self-assemble into lamellar, cylindrical or more complicated phases, taken that there is
repulsion with the main chain and the side chains.33-39 Therefore, polymeric bottlebrushes
based even on flexible polymers have extended conformation and may form block-
copolymer like micro phase separation and phase behavior, as indicated in X-ray
scattering37 and dynamic rheology39. In the case of PANI with its stiffer backbone, the
organization into layered structures is expected to be even more pronounced. In fact, Levon
et al observed that PANI doped and plasticized using DBSA forms lamellar structures.26
Amphiphilic dopant
---> Amphiphilic plasticizer
- \__/ N
H
Figure 4. PANI complexed with amphiphilic dopands and plasticizers to form a molecular bottle brush
structure.
The molecular bottle brushes allow co-continuous phases in multicomponent

systems. It has recently been observed that the PANI(DBSA) molecular bottle brushes form
thermoreversible gels in additional DBSA.40 Below the transition temperature (Tgel), the
material behaves elastically in compression experiments, its moduli as a function of
frequency does not have a strong temperature dependence and the materials are
electronically conductive. Heating above Igel causes the materal to melt with fluid-Jike
flow and the conductivity drastically drops.40 Theseobservations agree with formation of
network structures of PANI(DBSA) bottle brushes within DBSA medium that melts above
Tgel
There is only a small conceptual step to polymer blends consisting of polyolefins
(such as polyethylene and polypropylene) and PANI bottle brushes complexed with
amphiphilic dopants (such as DBSA) and amphiphilic plasticizers, see Figure 5. In the
following examples, the actual selection of the amphiphilic plastizicer and its amount
remain confidential to Neste Oy (Finland) due to considerable technological interests. In
spite oftbis inconvenience, however, the general concept becomes obvious.
56
Cr--.JI Amphiphilic plasticizer
i___ J Plasticized and doped PANI

I I Polyoietin
Figure 5. A possible scheme of PANI complexed with an amphiphilic dopant and plasticizer blended with
polyolefin.
iii"
ta 105
~ Amount of amphlphlllc plastlclzer
~
Cii
0
104
103
. - - - - --.........
Low
u
!/)
>
1-
102
z
"i"'
w 101
z
0
Q.
100 ".!1:: iii
~ 190 200 210 220 230 ID Cll
0 1::
u EXTRUSION TEMPERATURE ("C) llt ;:
1:: u
e
';: :II
u
:II "u~
u
~
101 Level of amphlphlllc plastlclzer
"u
1::
0 1::
..
0
10-3 z
>-
1-
> 10-5
~ ~
I
High
i=
u 107
::>
c
z 10"' I
0
u 10-11 / lntermedlate I
!I
low
1013
190 200 210 220 230
EXTRUSION TEMPERATURE ("C)
Figure 6. The upper figure shows the component viscosities at the shear stress value 0.1 MPa for PP and
PANI doped with DBSA and plasticized using three confidential different Ievels of plasticizers (Low,
lntermediate, amd High). The lower figure shows the corresponding conductivities of the blends consisting of
15 %-wt ofPANI-DBSA-plasticizer in 85 %-wt PP.
57
PANI doped by DBSA has been plasticized using a confidential amphiphilic
plasticizer (see Figure 3). Three Ievels of it has been used, here denoted as "High",
"Intermediate", and "Low". In this way fusible and surface active PANI bottle brushes are
formed that allow conventional melt processing. Their viscosity vs. shear stress curves
have been measured using conventional capillary rheometer Gttfert 2002 at different
temperatures (190C, 2l0C, and 230C).41 In Figure 6, the viscosity values at a particular
shear stress value 0.1 MPa have been plotted as a function of the temperature. The
viscosity of pure PP at the same shear stress 0.1 MPa is also plotted. One observes, as
could be expected, that higher amount of plasticizer and higher temperatures render lower
viscosities, due to better plasticization. Therefore, given the PP matrix and the processing
temperature, the viscosity ofthe PANI-complexes can be tailored tobe less than that ofPP
in the processing conditions.
In blends of PANI-DBSA-plasticizer bottle brushes with PP, substantial electrical
conductivity suggests co-continuity of the PANI-phase. As an example, take the samples
consisting of 85 %-wt of PP and 15 %-wt of PANI-DBSA-plasticizer. The blends have
been extruded using a capillary rheometer and the strands corresponding to each individual
shear stress value have been collected separately. After cooldown to the room temperature,
the conductivities were measured. In this way, information on the electrical conductivity (at
room temperature) vs shear stress could be obtained, in addition to the conventional
viscosity vs shear stress data. The lower part of Figure 6 shows the conductivity data of the
blends. One observes a gratifying correlation with the viscosities of the blend components
and the conductivity ofthe blend. Figure 6 suggests that ifthe PANI-DBSA-plasticizer has
a small viscosity at the processing conditions as compared with the PP matrix, the blends
will be conducting.
lt is noteworthy that such a behaviour is long known in other fields of polymer
blending, see for example.42-44 In two-component systems, the simplest equation to
predict the phase inversion condition is given by
71PA-complex fPPA-complex
where T/PA-complex and T/PP represent the viscosities of the two components at the processing
conditions and (/JPA-complex and tppp represent their volume fractions. This equation would
suggest PANI-complex to become continuous when its viscosity vs the matrix viscocity
becomes less than ca. 17%. We are fully aware that the present model might be too simple
to describe the behavior quantitatively. Nevertheless, qualitatively the results of Figure 6
are remarkable in the sense that the processibility of a polymer that was previouly regarded
intractable has been developed and, importantly, conventional devices and concepts are
applicable.
The morphologies. of melt spun PANI-DBSA-plasticizer blends with PP were
investigated using transmission electron microscopy to gain more convincing
understanding on the phase continuity of the PANI-phase.45 The pictures indeed show
fibrous structures ofPANI-phase in the PP matrix, in complete agreement with the above
reasoning.
The above concepts are not limited to polypropylene. Conducting blends can
similarly be prepared using high density polyethylene, low density polyethylene,
poly(ethylene-co-propylene), poly(styrene-b/ock-butadiene) and poly(styrene-b/ock-
(butylene-ethylene)-b/ock-styrene). For the latter ones, blends are demonstrated that are
electrically conducting even at high elongation of200-300 %.46
58
CONCLUDING REMARKS
In this talk, combining our and others' results, we have presented a scheme how to
render polyaniline soluble and fusible, and how to control the networking (and thus
conductivity) of polymer blends by viscosity ratio between the plasticized PAN{ complex
and a nonpolar matrix, taken that the PANI-complex is rendered sufficiently surface active
to the matrix polymer. Wehave demonstrated that the processing ofPANI has become near
to conventional polymers.
Therefore, methods exist for solution and melt processing of PANI, as weil its
blending using both methods. At present several products are at precommercial stage
becoming near to commercialization.
ACKNOWLEDGEMENTS
J. Laakso, E. Virtanen, H. Ruohonen, P. Kirmanen, H. sterholm, K. Levon, J.

Tanner, L.-0. Pietil, L. Ahjopalo, and T. Vikki are acknowledged for their contributions
to develop processible PANI and its blends. G. ten Brinke, J. Ruokolainen, I. Szleifer and
M. Saariaho are acknowledged for their contibutions to understand conformational
behavior and self-assembly of molecular bottlebrushes.
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Samuelson, eds.; Hilger: Bristol (1990).
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16. Y. Cao, J. Qiu, and P. Smith Synth. Met., 69: 187 (1995).
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(1995).
18. C.Y. Yang, Y. Cao, P. Smith, and A.J. Heeger Synth. Met., 53:293 (1993).
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34. M. Antonietti, J. Conrad, and A. Thnemann Maeromoleeu/es, 27: 6007 (1994).
35. M. Antonietti, A. Wenzel, and A. Thuenemann Langmuir, 12:2111 (1996).
36. J. Ruokolainen, J. Tanner, G. ten Brinke, 0. Ikkala, M. Torkkeli, and R. Serimaa Maeromoleeules,
28: 7779 (1995).
37. J. Ruokolainen, M. Torkkeli, R. Serimaa, E. Komanschek, 0. Ikkala, and G. ten Brinke Phys. Rev.
E, 54: 6646 (1996).
38. J. Ruokolainen, M. Torkkeli, R. Serimaa, S. Vahvaselk, M. Saariaho, G. ten Brinke, and 0. Ikka1a
Maeromolecules, 29: 6621 (1996).
39. J. Ruokolainen, M. Torkkeli, R. Serimaa, B.E. Komanschek, G. ten Brinke, and 0. lkkala
Maeromoleeules, 30: 2002 (1997).
40. T. Vikki, J. Ruokolainen, O.T. Ikkala, P. Passiniemi, H. Isotalo, M. Torkkeli, and R. Serimaa
Macromolecules, in press (1997).
41. J. Tanner, O.T. Ikkala, J. Laakso, and P. Passiniemi In Electrieal, Optieal and Magnetie properlies
ofOrganic Solid Materials 111; Materials Research Society: Boston (1996).
42. S. Wu Polym. Eng. Sei., 27: 335 (1987).
43. G.M. Jordhamo, J.M. Manson, and L.H. Sperling Polym. Eng. Sei., 26: 517 (1986).
44. J. Lyngaae-Joergensen and L.A. Utracki Makromol. Chem., Macromol. Symp., 48/49: 189 (1991).
45. P. Passiniemi, J. Laakso, H. sterholm, and M. Pohl Synth. Met., 84: 775 (1997).
46. O.T. Ikkala, J. Laakso, K. Vkiparta, E. Virtanen, H. Ruohonen, H. Jrvinen, T. Taka, P. Passiniemi,
J.-E. sterholm, Y. Cao, A. Andreatta, P. Smith, and A.J. Heeger Synth. Met., 69: 97 (1995).
60
IN-S/TU COMPOSITE PROCESSES FROM PEI/TLCP BLENDS
S. S. Hwang, S. M. Hong, Y. Seo, and K. U. Kim
Division of Polymer Research

Korea Institute of Science and Technology
Cheongryang, Seoul, Korea 130-650
INTRODUCTION
Blends of isotropic polymers and liquid crystalline polymers have been studied for
their potentials to generate in-situ composites yielding high strength/modulus
characteristics 12 . In this composite, the thermotropic liquid crystalline polymer (TLCP)
reinforcing agent comes out as a low viscous melt during the compounding process, and
crystallizes upon cooling to form needle-like reinforced structures in the final fabrication
step. This in-situ composite process is advantageaus since melt processability and
mechanical properties can be simultaneously improved. Also in in-situ composite, the
geometry of reinforeerneut can be easily controlled, through which mechanical properties
are abruptly increased. These are great advantages over conventional composite in which
geometry of reinforeerneut is fixed prior to processing and the aspect ratio of reinforeerneut
is reduced during conventional processing such as extrusion. Whereas in the in-situ
composite process, reinforeerneut is deformable so that the aspect ratio of reinforeerneut
can be increased by the extensional flow field3.4: the aspect ratio of reinforcement as weil as
reinforeerneut volume is crucial factor for improving mechanical properties of composites5 .
Also this process can be applicable to blow molding 6 and film processing 7, which never be
achieved in conventional composite processes.
One of the drawbacks of in-situ composites is that they tend to be highly anisotropic.
That is, the mechanical properties in flow direction can be enhanced by the formation of
fine TLCP fibrils with a large aspect ratio, however, those of transverse direction are much
lower89 . Also the skin-core morphology 410 formed during in-situ composite process
requires more TLCP because of low fiber reinforcing efficiency. Low interfacial adhesion
between two phases due to poor compatibility results in brittle behavior of the in-situ
composites 11 . The anisotropy in properties and skin-core morphology can be improved by
process optimizations48710 . Recently, several researchers 12- 16 have reported that
compatibilized TLCP blends exhibit much enhanced mechanical properties, and they have
attributed it to the improved interface adhesion between TLCP and matrix phases. For
improving interfacial adhesion and compatibility, some ideas in the ordinary blend systems
have been introduced such as reactive processing 1213 , addition of third component as a
compatibilizer 1415 and incorporation of the TLCP miscible with matrix polymer16.
In this study, in-situ composite processes based on PEI/Vectra B950 blends were
investigated systematically. In binary blend, the role of TLCP as processing aids and
reinforcements was studied. For ternary blends, an isotropic polymer was incorporated to
the binary blends as a compatibilizer to solve the problems caused by interface instabilities.
Also the effect of compatibilizer (a kind of surfactant) on the properlies and morphologies
of the in-situ composites was discussed. In the view point of processing, the film blowing
process using binary blends was studied to solve the problems of anisotropy and skin-core
morphology of in-situ composite.
EXPERIMENTAL
Materials
As a matrix polymer, polyetherimide (PEI) Ultem 1000 of General Electric was used.
The reinforcing component was thermotropic liquid crystalline polymer (TLCP) Vectra
B950 of Hoechst-Celanese, which is a polyesterimide based on 6-hydroxy-2-naphthoic acid
(58%), terephthalic acid (21%) and p-aminophenol (21%). As a compatibilizer, newly
designed imide polymers, polyesterimide(PEsi) was used. Synthetic method of PEsi was
described in previous work17 The chemical structures of PEI, Vectra B950 and PEsi are
presented in Figure 1.
Preparation of Blends and Specimens
The pellets of all materials used were dried in a vacuum oven at 12oc for at least
24hrs before use. For binary blends, TLCP contents were 0, 5, 25, 50, 75 and lOOwt%.
Polyetherimide(PEI) (Uitem 1000)
to~olf 1fo ol
~~rrz-0-orr~-o-~r
TLCP (Vectra 8950)
Polyesterimide(PEsl) (Synthesized)
Figure 1. Chernical structures of PEI, TLCP and PEsl used.
62
Temary blends were formulated on fixed TLCP content at 25wt% with various amounts of
PEsi compatibilizer. For film blowing, TLCP content was Swt%. The blends were prepared
by melt extruding the formulated components through a Brabender twin-screw compounder,
quenching in a cooling water bath, followed by drawing and pelletizing. The blending
temperature ranged from 300 and 34oc according to the blending ratio.
The fibers w:ere spun using a capillary rheometer (Instron 3211) with a capillary UD
ratio of 40 and diameter of 1.27mm. Draw ratio, defined as the ratio of die and the fiber
diameter, was controlled by the speed of the take-up roll. The spinning temperature ranged
from 300 to 340"C. The films were prepared by film blowing using Brabender film blowing
machine with annular die: slit thickness of lmm and inner diameter of 25.4mm. Draw ratio
(DR) in machine direction (MD), defined as the ratio of slit thickness of annular die and
film thickness at the film diameter of 25.4mm, was controlled by the speed of the take-up
roll. Blow-up ratio (BUR), defined as the ratio of die and the film diameter, was controlled
by the pressure in the film bubble. In this study, draw ratio in machine direction was
controlled same as BUR for equal biaxial stretching of the film. In case of film blowing, the
extrusion temperature was 34oc.
Measurement of Physical Properties
The dynamic rheological properties were measured by RDS-7700 with the parallel
plates under nitrogen atrnosphere. The thermal properties were measured with a Du Pont
Thermal Analysis 2000 equipped with a 910 DSC. The fracture surface was observed by
Hitachi scanning electron microscope S-510. The tensile properties were measured by
Instron Universal Testing Machine (model 4204). Optical microscope was used for
measuring diameters of reinforcing TLCP fibrils in the composite films. Anisotropy of the
composite film was measured with tansmittance differences of the polarized light between
machine and transverse direction using He-Ne Iaser (Uniphase) as a light source and Si
photo diode (Newport 818S) as a detector.
Fiber Spinning Using PEIJTLCP Binary Blend System
PEI is an amorphous polymer of high melt viscosity, whereas TLCP that forms
nematic liquid crystalline phase has much lower viscosity than that of PEI. As frequently
observed in other TLCP blends, TLCP lowers the viscosity of PEI in the processing
temperature range, suggesting that TLCP acts as lubricant 12 . Figure 2 shows the complex
viscosity of PEI as a function of frequency at different temperatures. The overall behavior
of PEI viscosity follows that of typical thermoplastics, i.e. Newtonian behavior at low shear
rate and shear thinning at high shear rate. Figure 3 shows the flow curves of Vectra B950. It
is well-known facts that the viscoelastic behavior of TLCP in not so simple because of
strong dependency on the thermal and mechanical histories 19 Thus all rheological
measurements were performed afterremoval of prehistory by heating to 350"C for lOmins.
TLCP shows yield behavior rather than Newtonian behavior even at low shear rate, which
is a characteristic rheology of heterogeneous system including liquid crystalline polymer 19
Also abrupt decrease of viscosity was observed between 290 and 300"C, which may be due
to the transition from crystalline to liquid crystalline phase, i.e. pure nematic phase is
formed above 300"C. One of the principal factors that determines whether the dispersed
phases form elongated fibrils or are stabilized as droplets is the viscosity ratio of dispersed
to matrix phases, which should be smaller than unity20 . The viscosity of TLCP is much
lower than that of PEI in the processing range (between 320 and 340 "C), which infers that
63
TLCP can play the role of a processing aid and fibrous reinforcement for the highly viscous
PEI resin, in these binary blends.
0 : 290C
: 300C
: 310C
: 320C
: 330C
: 340C
Frequency(rad/sec)
Figure 2. Dynamic viscosity versus frequency for PEI at various temperatures. Source: Reference 21. With
perrnission.
0 : 290C

6
: 300C
: 310C

0
: 320C
: 330C
: 340C
Frequency(rad/sec)
Figure 3. Dynamic viscosity versus frequency for TLCP at various temperatures.
The tensile modulus and tensile strength of as-spun PEI!fLCP fibers are plotted
against the TLCP content in Figure 4 and 5. Tensile modulus and tensile strength are
increased with increasing TLCP content, as expected. Up to 50wt% TLCP content, tensile
64
properties show around the value of additive rule of mixing. If the TLCP content exceeds
50wt%, however, tensile properties exhibit some deviation from the additivity rule. These
deviations are attributable to lower aspect ratio of TLCP fibrils formed resulting from phase
inversion, interfacial debonding, unstable extension and non-uniform dispersion2 1 From
the tensile modulus results, the aspect ratio of the fibrils can be calculated using a modified
1200=-~--~--~--~--~~~~--~--~---
Draw ratio = 8
1000 : spun at 320C
: spun at 340C
Draw ratio =4
~
-=i'll
800 <> : spun at 320C
6 : spun at 340C
-:=
~
C l}
600
~
= 400
200
0
0 20 40 60 80 100
LCP content (wt%)
Figure 4. Tensile strength versus 1LCP content for PEI/TLCP blend fibers. Source: Reference 21. With
perrnission.
Draw ratio =8
: spun at 320C
80 : spun at 340C
Draw ratio = 4
<> : spun at 320C
60 6 : spun at 340C
40
20
20 40 60 80 100
LCP content (wt%)
Figure 5. Tensile rnodulus versus 1LCP content for PEI!fLCP blend fibers. Source: Reference 21. With
perrnission.
65
Tsai-Halpin equations. The maximum aspect ratio (>100) occurs at about 23vol%, which is
equal to 25wt%. If the TLCP content exceeds 25wt%, however, the aspect ratio was
decreased with increasing TLCP content21 On the other band, the tensile property at 320"C
is greater than at 34oc. This is because of the partial heterogeneity in liquid crystalline
phases formed. Sarlin et al. 22 reported that TLCP blends showed higher tensile strength
when the processing temperature was close to the crystal-nematic transition temperature, at
which homogeneous nematic phases were formed.
Improvement of tensile properties of blend fibers containing TLCP is due to the
formation of TLCP fibrillar struct~re, whose morphology depends on the composition of
blend and draw ratio in the spinning process. This can be verified by SEM photographs21
For blend fibers spun at draw ratio of 1, TLCP particles have been pulled out from the
matrix during cryogenic fracture, indicating poor adhesion between the two phases. For the
75/25 PEI/TLCP blend, a well-dispersed TLCP phase is shown. However, many irregular
fibrils with non-uniform domain size are shown in the 50/50 blend. For the 25175 blend, a
typical skin-core morphology appears: the central portion looks the same as that of 50!50
blend with non-uniform domain size, but the outer portion clearly shows fibrils of the
TLCP phase. For pure TLCP, the surface looks Iike the cross-section of a tree with many
coaxiallayers. With increasing draw ratio, the diameters of the TLCP phases are decreased.
Also the shapes of dispersed phases become more needle-like, which means increasing
aspect ratio with increasing draw ratio. This fibril formation is due to the fact that the
viscosity of matrix polymer (PEI) is high enough to elongate the dispersed TLCP phase.
Fiber Spinning Using PEI!I'LCP/PEsl Ternary Blend System
As a compatibilizer, PEsl is designed in consideration of imide-imide interaction with

PEI and ester exchange reaction during melt processing with Vectra B950(polyesteramide).
It is well recognized in the binary polymer blends that the two components are partially
miscible if the glass transition temperatures (Tg) of the two components approach each
other. The 50/50 PEI/PEsl blend shows single Tg at 230"C, in which Tg of PEI decreased
from 235"C and Tg of PEsl increased from 225"C17 In the 70/30 TLCP/PEsl blend, Tg of
TLCP increased from 124 (Tg of pure TLCP) to 152c and Tg of PEsi is decreased from
225 (Tg of pure PEsl) to 190"C. These results verify that PEsi has at least partial rniscibility
with both PEI and TLCP, which means the synthesized PEsl can be a useful compatibilizer
in PEI/TLCP blends. For the ternary blend including compatibilizer, 75/25 PEI/TLCP blend
was selected because this composition shows maximum aspect ratio, as mentioned above.
The effect of introducing PEsl on the tensile strength of 75/25 PEI/TLCP blend fibers
is shown in Figure 6. As shown in the figure, an introduction of PEsi improves the tensile
properties of the binary blend within limited level. The most notable improvement is
obtained at the loading level of PEsl of 1.5phr. A tensile strength of 520 MPa was obtained,
which is 50% higher than that of the PEI/TLCP blend without the compatibilizer. Tensile
modulus (not shown), also shows similar trend to that of tensile strength 18. The interfacial
tension as well as viscosity ratio between dispersed and matrix phase, influences the
geometry of dispersed phase in shear field34 Within limited Ievel, added compatibilizer
reduces the interfacial tension so that reduces the diameter of the dispersed phase particle in
the die (shear flow). And smaller particle in the die results in finer fibril of TLCP in the
following drawing process. Such a formation of finer fibrils may account for the improved
tensile properties, which are confirmed by morphology results in Figure 8. From these
results it may be recognized that the concept of compatibilizer in the ordinary blends can be
applied to the in-situ composite systems.
Figure 7 presents the effect of introducing PEsi on the impact strength of 75/25
PEI/TLCP blend fibers. The impact strength was measured by impacting the non-notched
fibrous extrudate to the vertical direction of the fiber. In the impact measurements, fibers of
66
700
600
IV
D.
-..
~ 500
.s:::.
-
C)
~ 400
tn
.!!!
'iii 300
c
Q)
1-
200
100
0 2 4 6 8
PEsl (phr)
Figure 6. Effect of PEsl on tensile strength of 75/25 PEI{I'LCP in-situ composites at a draw ratio of 4.
Source: Reference 18. With permission.
2.0 ~-~-~-~-~--,.--,....---,..----,
-
.s:::.
1.8
--
C)
c
I!!
tn
u 1.6
111
c.
E
"C
Q) 1.4
.~
.
iii
z
E
0
1.2
4 6 8
PEsl (phr)
Figure 7. Effect of PEsl on impact strength of 75/25 PEI{I'LCP blend fibers at a draw ratio of 1. Source:
Reference 18. With permission.
draw ratio 1 are used. The measured impact value has been normalized to the impact
strength of the absolutely incompatible blend. The normalization factor is 8Kpa. An
incorporation of 1.5phr of PEsl gives the greatest impact strength.
Figure 8 show SEM photographs of the fractured surfaces of 75/25 PEI/TLCP blend
fibers at several PEsl contents. The photomicrographs provide a morphological evidence
for the improvement in the tensile properties by incorporating PEsl. In the binary blends
67
(a) PEsl: 0 phr (b) PEst: 0.75 phr
(c) PEsl: 1.5 phr (d) PEst: 2.25 phr
Figure 8. SEM photographs of fractured surfaces of PEI(ILCP blend fibers at a draw ratio of 1. Source:
Reference 18. With permission.
without PEsl, the domain size of the dispersed TLCP phase is large and lots of holes are
observed, from which TLCP fibrils have been pulled out. This is probably because interface
adhesion between PEI and TLCP is poor. However, the TLCP domain size is greatly
reduced and the dispersion of TLCP domains is more uniform at the loading Ievels of PEsl
of 0.75 and l.Sphr. In addition, the fibrous TLCP domains seem tobe coupled with matrix
phase in the ternary blends, which is comparable with the binary blend morphology in
which the TLCP domains are simply embedded in the PEI matrix. This indicates that
adding PEsl makes the interface adhesion better, and in this in-situ composite, PEsl can be
a role of coupling agent same as in the conventional fiber composite. The enhanced
adhesion between PEI and TLCP phases is attributable to intermolecular interaction and
transesterification reaction through PEsl, as expected 17 .
On the other hand, if the loading Ievel of PEsl exceeds a critical value, the size of
TLCP domains is increased again and a poor fibrillation and dispersions of the TLCP
domains result as observed at the loading Ievel of PEsl 2.25phr in Figure 8(d). Thus
mechanical properties of the in-situ composites are deteriorated at the excessive loading
Ievel of PEsl. This is ascribable to the fact that the TLCP domains are coagulated before
they are deformed if the PEsl Ievel is too high, just like in the emulsion systems stabilized
with a surface active agent23 . Consequently, the optimum rage of loading Ievels of PEsl for
the 75/25 PEIJTLCP blend has turned out tobe 1.5phr.
68
Film Blowing Using PEI/TLCP Binary Blend System
It is generally recognized that extensional flow is required for TLCP blends to develop
characteristic fibrous structure 24 . However uniaxial stretching process such as fiber
spinning may produce products with anisotropic properties. Tensile properties in machine
direction may be outstanding, but the transverse properlies are grossly inferior 11
Anisotropy in the physical properties can be reduced in biaxial stretching processes such as
blow molding and film blowing. Also several authors reported the presence of a skin-core
morphology in in-situ composite process, with TLCP fibrils occurring in the skin region
and spherical or low aspect ratio particles of TLCP in the core (central region) 4 10 21 . Those
are crucial factors for cost-effective applications of in-situ composites, which could be
solved using film blowing process. Because the film blowing is essentially biaxial
stretching process and the gap of annular die is narrow enough to exclude a skin-core
morphology, which is resulted from the differences of deformation histories and heat
removal rates during cooing process between skin and core region.
Tensile properlies of in-situ composite films are increased with increasing stretching
ratio (BUR or DR), as shown in Figure 9 and 10. With increasing of draw ratio from 1 to 3,
MD tensile strength of blend film is increased up to two times (from 170 to 340 MPa),
whereas a negligible improvement is observed up to lOwt% TLCP level in case of as-spun
blend fiber 21 . Also in comparison to the blend fiber, the tensile strength of PEI(fLCP 95!5
blend film at draw ratio 3 is higher than that of PEI(fLCP 75/25 blend fiber at draw ratio 4.
Consequently, in the in-situ reinforcing of PEI/TLCP blends, the biaxial stretching (in film
blowing) is more effective than the uniaxial stretching (in fiber spinning). Another possible
reason for this result is that since the thickness of the film is thin enough, the skin-core
effect evident in thicker cross sections was absent and the reinforcing efficiency of TLCP
was correspondingly increased7 . Increment of tensile properlies is higher in the blend film
than in the PEI film, which may be due to the formation of TLCP fibril as discussed in fiber
spinning.
350
:: PEIITLCP 9515, TD
300

4
PEI/TLCP 95/5, MD
: PEI, TD
"' :PEI, MD
~
~
250
e
~
-=.....
~
c ..
........
200
rrJ
~
150
..
;;
c
E-< 100
50
o~~-L~~~~-L~~~~-L~~~~
0 2 3 4
BUR (for TD) or DR (for MD)

Figure 9. Tensile strength versus Stretching ratio for PEI/TLCP blend films.
69
20
:PEI,
18 : PEI!fLCP 95/5, 1D
: PEI!fLCP 95/5, MD
,-.. 16 1D
"
~
~ 14
... :PE!, MD
:1
=
-=
0
::g
12
~
10
=
"'
~
E-4 8
2
0 2 3 4
BUR (for TD) or DR (for MD)
Figure 10. Tensile modulus versus stretching ratio for PEI/TLCP blend films.
220
PEI film : BUR=3, DR=3
-
fl
200
! Turn over point
e ~
"'
~
TD
~ MD
;
..! 180
~
160L-------~------~-------L------~
0 5 10 15 20
Scanning width (mm)
Figure 11. Relative transmittance of polarized light with stretching direction for PEI film at BUR=3 and
DR=3.
70
110~------.--------.-------,-------.
PEI!fLCP 95/5 composite film : BUR=3, DR=3
Turn over point
1D
MD
50L-------~------_L _______ L_ _ _ _ _ _~
0 5 10 15 20
Scanning width (mm)
Figure 12. Relative transmittance of polarized light with stretching direction for PEI/TLCP 95/5 composite
film at BUR=3 and DR=3.
120~------------------------------~
Turn over point
~
MD
TD
PEI!l'LCP 95/5 composite film : BUR=l, DR=3
SOL-------~-------L _______ L_ _ _ _ _ __
0 5 10 15 20
Scanning width (mm)
Figure 13. Relative transmittance of polarized light with stretching direction for PEI/TLCP 95/5 composite
film at BUR=l and DR=3.
TD tensile strength as a function of BUR follows the same trends as with MD.
However, the tensile strength in TD is slightly lower than that in MD, which may be
corresponding to the fact that MD was more oriented by shear effect in the die and self
gravity of molten parison. On the other hand, tensile modulus of the films shows same
tendency as tensile strength. Tensile moduli of blend films show 19 (for MD) and 16 GPa
71
(for TD) at the stretching ratio of 3, which are even higher than those of pure TLCP films 7 .
This is also due to the formation of finer (that is, Ionger aspect ratio) fibril and exclusion of
skin-core morphology in in-situ composite process using film blowing. The reason why the
tensile properties of blend films are higher than those of pure TLCP films is not clear in this
time, but it is thought that two phase morphology or irregular fibril forrned 7 deteriorates the
expected tensile property of the pure TLCP film.
An anisotropy of the film was measured by the transmitance of polarized light. Figure
11 and 12,13 show variation of trasmittance in both MD and TD with film width at several
processing conditions. As predicted in tensile property's data, the anisotropy in both PEI
and PEI(TLCP 95/5 blend film is not so high in equal biaxial Stretching condition. A little
higher tranmittance is due to a little more orientation in MD by shear effect in the die and
self gravity of molten parison in addition to mechanical stretching. To investigate the effect
of stretching condition to the anisotropy, the results of equal and unequal biaxial stretching
films are compared in Figure 12 and 13. In case of unequal stretching, there is a great
difference in the transmittance between MD and TD. From these results, it is concluded tht
the anisotropy of in-situ composite can be improved by biaxial Stretching such as film
blowing. Structure analysis of binary blend films and film blowing process using ternary
blends will be 1eported in near future.
CONCLUSION
The in-situ composite processes based on PEINectra B950 blends are investigated.
The viscosity of Vectra B950 as TLCP was at least hundred times lower than that of PEI in
the processing temperature range. Thus in binary blends, TLCP lowered the viscosity of
PEI suggesting that TLCP acts as processing aid. Also the tensile properties of the binary
blend are increased with increasing TLCP content due to forming TLCP fibrils in the blend,
which means that TLCP fibril acts as reinforcing agent same as fiber in the conventional
fiber composite. An introduction of PEsi as a compatibilizer into the binary blends has
proved to be effective in improving the impact strength as weil as tensile properties of
TLCP blends. It enhances the interfacial adhesion between reinforcing TLCP fibrils and
matrix isotropic polymer phase similar to coupling agent between fibers and matrix in the
conventional composite. There is an optimum Ievel of compatibilizer used, above which the
mechanical properties were decreased by forming thicker TLCP fibrils. The film blowing
process using binary blends suggests the possibility to solve the problems of anisotropy and
skin-core morphology of in-situ composite. The improvement of tensile properties is much
higher in film blowing than in fiber spinning process, which is due to exclusion of skin-core
morphology. By equal biaxial blowing, the blend films having almost isotropic properties
can be obtained. Consequently, the combinatory study of biaxial Stretching with ternary
TLCP blend may be effectively utilized in manufacturing cost-effective in-situ composite
with high performance.
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Advanees, Al. lsayev, T. Kyu, and S.Z.D. Cheng, ed., ACS Symposium Series 632,
Washington, DC (1996).
16. C. Ryu, Y. Seo, S.S. Hwang, S.M. Hong, T.S. Park, and K.U. Kim, Miscibility and
mechanical properties of poly(ether imide)!liquid crystalline poly(ester imide) blends,
Intern. Polym. Proe. 9: 266 (1994).
17. Y. Seo, S.M. Hong, S.S. Hwang, T.S. Park, and K.U. Kim, Compatibilizing effect of a
poly(ester imide) on the properties of the blends of poly(ether imide) and a
thermotropic liquid crystalline polymer 2, Polymer 36: 525 (1995).
19. K.F. Wissbrun, Rheology of rod-like polymers in the liquid crystalline state, J. Rheol.
25: 619 (1981).
20. AM. Sukhadia, D. Done, and D.G. Baird, Characterization and processing of blends of
polyethylene terephthalate with severalliquid crystalline polymers, Polym. Eng. Sei.
30: 51 9 (1990).
21. S. Lee, S.M. Hong, Y. Seo, T.S. Park, S.S. Hwang, K.U. Kim, and J.W. Lee,
Characterization and processing of blends of poly(ether imide) with thermotropic
liquid crystalline polymer, Polym. Eng. Sei. 35: 519 (1994).
22. J. Sarlin and D.J. Tormala, Fiberformation and characterization of a thermotropic LCP,
J. Appl. Polym. Sei. 40: 453 (1990).
23.1. Piirma, Polymerie Surfaetant, Mercel Dekker, New York (1992).
24. D. Berry, S. Kenig, and A Siegman, Structure development during flow of polyblends
containing liquid crystalline polymers, Polym. Eng. Sei. 31: 451 (1991).
73
ELECTRICAL AND MECHANICAL CHARACTERIZATION
OF PEO-LiN(CF3S02)2 ELECTROLYTES
Hakima Halitim, Djafer Benachour, and Abderrezak Harnmauehe
Laboratoire d'Energetique et d'Electrochimie des Solides, ICI, Universite

F.Abbas de Setif, 19000- Setif, Algeria
INTRODUCTION
Solid electrolytes based on complexes of poly(ethylene oxide) with Iithium salts seem
to be very promising materials for use in high energy density Iithium batteries. 1-3 Such
e1ectro1ytes may also have the important attribute of mechanical flexibility which greatly
facilitates the design of an all-solid state battery and, on the other hand, allows the
electrolyte to accommodate for the volume change of the cathode during the charge-
discharge cycles of the battery. Since it was revealed that ionic conduction takes place
principally in the amorphaus phase,4 several sturlies have focused on the synthesis of
amorphaus solid e\ectrolytes; in most cases the solution has been sought with regard to the
solvent by means of cross-linking5.6 or by addition of small-molecule plasticizers, 7 but few
sturlies have been directed towards the salts.
In this scope, Armand et al.8 have recently proposed the Iithium bis(trifluoromethane
sulfone) imide, (CF3SChhN,Li +, as a new salt which is capable of yielding a poly(ethylene
oxide)-based amorphaus electrolyte having better conductivities at any temperature than
the previously-used Iithium salts. In addition to its low lattice energy owing to the presence
of two strong electron-withdrawing groups CF3S02- on the nitrogen atom, the flexibility
of the nitrogen covalent bonds allows the lowering of both melting and glass transition
temperatures. Arecent comparative study, performed by Vallee et al.,9 on poly(ethylene
oxide) (Mn = 4.103) electrolytes made with LiN(CF3S02)2, LiCF3S3 and LiCI04, has
confirmed the amorphous character of LiN(CF3S02h based complexes with 1011 and 811
(EO units I salt) molar ratios. SyllalO confirmed also the amorphous character and the high
conductivites of PEO(S.l06)-LiN(CF3S02h complexes.
In the present work and for the purpose of evaluating the performances of the
LiN(CF3SChh based electrolytes in the long term, films of P(EO)u(9.105)LiN(CF3S02h
and undoped PEO were prepared and characterized several months after synthesis. The
tensile properties of these films were also investigated by drawing tests.
EXPERIMENTAL
Materials
Films 100-120 J.tffi in thickness were prepared by dissolving PEO (Aldrich, 9.105) and
LiN(CF3S02h (IREQ Hydro-Quebec) in acetonitrile, following the common synthesis
procedure described elsewhere.lt,l2 P(EO)uLiN(CF3S02h compositions were prepared
over the range [EO units]/[salt] = n = 4, 8, 12, 16, 20 and undoped PEO. For the sake of
comparing electrical conductivities, other salts such as LiCl04 (Merck), LiCF3S] (Fluka)
and LiAsF6 (Aifadivision) were used. The films were then stored in a glass endosure
Science and Techno/ogy of Polymers and Advanced Materials

maintained under dynamic vacuum (l-3 torr) for a long period. From the first few days,
the aspect of the films was different depending on the salt content. The more dilute
specimens (n ;;;?: 16) were opaque pointing to the crystalline character whereas the more
concentrated ones (n::;; 12) rernained transparent for several weeks. However, after storage
for about five months, the aspect of the Iatter tumed to translucent indicating a very low
crystallization rate. Exceptionally, the n =4 film became visibly heterogeneous and brittle.
Methods
The P(E0)0 LiN(CF3S02h complexes were cut into discs (13 mm in diameter) for
electrical measurements. The disc sample was sandwiched between stainless-steel
cylindrical electrodes. ac conductivity measurements were carried out under dynamic
vacuum. A Tacussel impedancemeter under computer control was used over a frequency
range of O.IMHz-lHz, from room temperature up to 90C.
Differential thermal analysis (DTA) was carried out on a Netzsch STA 409 DSC
apparatus, under helium flow, at a heating rate of 10 K/mn. Glass transition (T g) and
melting ( or dissolution) (Tm) temperatures were defined as the points of intersection
42 30 18
20
Figure 1. X-ray pattcrns for P(EO)nLiN(CF3S02)2 films.
76
between the extrapolated base lines and the extrapolated steepest part of the DTA curve
corresponding to the heat capacity change and, respectively, the endothermic peak of the
melting (or dissolution) process.
For X-ray analysis, the films were p1aced in a diffraction chamber that was flushed
with nitrogen and exposed to Ni-filtered Cu-Ku radiation in a Philips X-ray diffractometer.
Drawing tests were performed on films with 0.5x0.5 cm2 central area stamped
according to the VSM 10921-AFNOR Norm, using a piloted MMT Mecatest, under argon
flow and at 25C. The rate of Stretching was 1 mm/min.
X-Ray Characterization
X-ray diffraction diagrams of the PEO-LiN(CF3SOzh system, performed at room

temperature, are presented in Figure 1. The pattem corresponding to pure PEO, exhibiting
the main peaks at 28 = 19.12 and 23.45, was identical tothat published in the literature.l3
A hump-shaped pattem, characteristic of amorphous phases, appeared also in this range of
angles. The intensity of these peaks decreased as the salt concentration increased and the
second one eventually disappeared altogether for the n = 8 and 4 compounds.
Simultaneously, a distinct peakwas observed at 22.~ for compositions with n s 12. This
may correspond to the existence of an intermediate compound of stoichiometry
P(EO)<jLiN(CF3SOzh as already mentioned by Armand et al.S The pattern of the
P(E0)4LiN(CF3SOz)z electrolyte consisted of several new peaks which were different
from those main characteristic of the pure salt, suggesting the existence of a definite
compound with stoichiometry less than 4.
The degree of crystallinity Xe(%) of these specimens was estimated from the surface
area located under the whole of the peaks and the hump. As expected, the degree of
crystallinity of pure PEO was evaluated at about 70%. The curve of the Xe variations as a
function of salt concentration, represented in Figure 2, shows that crystallinity is greatly
reduced by the presence of LiN(CF3SOz)z and that the minimum of Xe is observed for the
n =8 composition.
DT A Measurements
The thermograms of different compositions, plotted five months after synthesis

(Figure 3), were characteristic of semi-crystalline compounds and the values ofTg and Tm
I- 1
r 1
ll<lu 60 f_ / 1
i
l
r
I i1
40 ~ l
,-
: 1
2o
!
rI
i
l
! j
i I
0 !- , , I , , , I , , , I , , , I , , , I , , , I , b, I , , , I , , 1
4 8 12 16 20 "
{EO]/{Li]
PEO
z.
Figure Evolution of eristallinity ratio as a funetion of sah eontent for P(EO)nLiN(CF3S02)2. dcduced from
X-ray patterns.
77
are assembled in Table I. They show that the introduction of LiN(CF3SOz)z increased the
T g values against the free salt compound but these latter were lower and exhibited 1ittle
variation with concentration than those obtained for other Iithium salts,s confirming the
plasticizing effect of the LiN(CF3SOzh salt. Two endothermic peaks appeared for the
complexes with 8 s; n s; 16 in the 30- 60C temperature range but somewhat higher for the
n =4 composition. According to the genera1 feature of phase diagrams established for the
Table 1. Influence of salt concentration on the characteristic

temperatures of P(EO)nLiN(CF3SOz)z.
n= [EO]IIlil
4 48;88
8 -48 36;44
12 -45 35 ;43
16 -44 29;44
20 -40 - ;45
PEO -60 60
~- n=4
12
16
20
PEO
ende ~
Figure 3. DTA curves for P(EO) nLiN(CF3S02)2 complexes. (Note that the curve for PEO is /2.)
PEO-LiX systems, the first peak observed at a mean value of 31 C, may be attributed to the
eutectic existing between the pure PEO and the less concentrated crystalline compound
P(EO)f}LiN(CF3SOz)z. As the intensity of this peak increases gradually up to the
composition with n = 12 and decreases for the n =8 composition, it could be inferred that a
eutectic mixture can take place near to n = 12. In the same way, the second peak observed
on the thermograms may correspond to the liquidus curve. lt can be noticed that these
temperatures move towards lower values compared with the other Iithium salts. Such a
result could be foreseen with regard to the melting temperature of LiN(CF3SOz)z (234C)
which is relatively lower than that of LiCI04 (236C) and that ofthermal decomposition of
78
.......
~ l
I
~
...... 1
u r 1
H 60 r- l
i
t .! I
40
i
l
r 1
l
t
j
20 J
L J
L J
0 I I I I I I II I I I I I I I I I I I I I I I I I I
lf
II. I I I I I I I I I
4 8 12 16 20 PEO
[EO] /[Li]
Figure 4. Evolution of cristallinity ratio against salt content for P(EO) nLiN(CF3S02)2, deduced from DTA
curves.
10- 2 .-------------------------
~r
0
~
~
~ 1
~ :
r n =
r
1
I I I ' I
o
I I II
n = 20
PEO
i I ' I I t II " I I I I ( i I " I I ! I !! I I I I ' I I I I
1
I
'
2.7 2.9 3.1 3.3
..'
~
10- 2
_u
E ~ (b)
10- 3
b:
~~~~ 1
'::
1o-
~ '- +"' 1
10- 5
10- 6
~~ :~:r ~~~ +,
t j
I'''' I'''' I'''' I'''' I'''' I'''' I'''' I'''' I''' ,I
2.7 2.9 3.1 3.3
10 3 /T (K- 1 )
Figure 5. Dependence of ionic conductivity on reciprocal temperature for P(EO)nLiN(CF 3S02)2 films.
79
LiAsF6 (280C) and LiCF3S0:3 (430C). For the n =4 compound, the peaks were observed
at higher temperatures appearing to indicate that it belongs to a domain delineated by the
6/1 and 3/l crystalline compounds, as already reported for PE0(4.103)-LiN(CF3S02 )z
complexes 9 andin agreement with the aforementioned X-ray diffraction resu1ts.
The value of 70%, evaluated from X-ray analysis for the crystallinity of the pure PEO,
was used to estimate the evolution of the degree of crystallinity of the doped samples from
the peaks area of the DTA curves. lt can be observed that the Xe variations versus salt
concentration, presented in Figure 4, match satisfactorily those deduced from X-ray
characterization (Figure 2) and confirm the great decrease of crystallinity for the highly
doped compounds.
Electrical Measurements
The curves of conductivity plotted in Arrhenius coordinates (Figure 5-a) displayed for
the more dilute specimens (n = 16 and 20) two regions on both sides of a transition
temperature T 0 which was close tothat of the second endothermic peak observed on the
DTA plots. Thus, forT< T 0 , the linear dependence of log(o) versus 1/T, which could be
described by Arrhenius law, may be ascribed to a conduction process in amorphaus regions
which can be considered as confined in a given volume by the crystallites. I Such a behavior
has also been related with the change of the nurober of charge carriers due to the
dissolution of the definite compound which obeys an Arrhenius activation mechanism. For
higher temperatures, the curvature corresponded to a free-volume behavior characteristic of
amorphaus phases. For the n = 8 and 12 compositions, the conductivity curves (Figure 5-b)
exhibited a free-vo1ume behavior in the whole temperature range as it bad been expected
owing to their low crystallinity. The conductivity curve of P(E0)4Li(CF3SOzh is thought
tobe constituted of two straight lines and the failure to observe a curvature specific to the
free-volume behavior in the explored temperature range allows us to infer that the
formation of a completely amorphaus conducting phase could take place at higher
temperatures according to the DTA results.
-
....I
Ei
....I u 10- 3
c......
0
80C
60C
" 40C
20C
4 8 12 16 20
[EO]/[Li]
Figure 6. Conductivity isothenns as a function of n = [EO units)l[salt] ratio for P(EO)nLiN(CF3S02)2 films.
80
-
....I
E!
10- 2
....I u
c
-0
10- 4
10- 6
i
::t
10- 8
~
2.7 2.9 3.1 3.3
1 0 3 /T (K-1)
Figure 7. Log(o) =f(l!T) plots for: () P(E0)12LiN(CF3S02)2, (n) P(E0)20LiAsF6, (') P(EO)t2LiC104,
( t) P(EO) t6LiCF3S03.
Qualitatively, these results match those obtained by Sylla on P(EO)n(Mw=5.106)-

LiN(CF3S2)2.lO Nevertheless, the present conductivity values show less Variations with
composition and the maximum that he observed for n = 8 shifts to n = 12. Even after
storage for several months, these complexes displayed high ionic conductivity reaching
2.1-5 Q-1cm-1 at 25C and I0-3 Q-1cm-1 at 75C (Figure 6).
In order to highlight the positive effect of the (CF3S02hN- anion on electrical
transport, complexes with other anions, namely C104 (n = 12), CF3S03 (n = 16) and AsF6
(n = 20), were prepared and examined in the same conditions. In fact, the chosen Iithium
salt concentrations correspond to their maximum electrical conductivity.B.t4 Figure 7
compares the log(o) = f(lff) curves tothat corresponding to P(EOhz-LiN(CF3SOz)z. The
shape of the curves and the order of magnitude of their conductivity agree with those
published by Fauteux.B lt can be observed that the conductivity obtained with
LiN(CF3SOzh is significantly higher especially at low temperatures. This feature
apparently confirms that the large flexible anion of this salt acts as a plasticizer.8
Mechankal Properlies
An electrolyte material with viscoelastic properties presents the great advantage that,
during cell discharge, it is able to accommodate for the volume change of the intercalation
positive electrode. With TiS2 and VOx intercalation compounds, such a sandwiched
electrolyte may undergo a transversal compression strain generated by about 10% in
volume expansion for the intercalation of Iithium cations.t.5,16_
The mechanical strength of P(EO)nLiN(CF3SOz)z films, subjected to uniaxial traction
is illustrated by the stress-strain diagrams. The results from the drawing experiment were
normalized with respect to the initial cross-sectional area and gauged length of the samples
to exhibit variations of nominal stress versus nominal strain. The set of curves
corresponding to the more dilute compounds shows very similar generat features (Figure
8). They present both elastic and plastic domains at low and high deformations,
respectively, and stretches greater than 700% were obtained without rupture. For the more
concentrated compositions (n = 12 and 8), the rupture took place for about 250 and 120o/o,
81
-a"'
111
6
~
!II
!II
G* 16
~
"'
111
.-t 4
I#
a
oi
8
= 2
0
200 400 600
1.6
0.8
0
100 200
Nominal strain (%)
Figure 8. Stress-strain CUITes for P(EO)nLiN(CF3S02)2 films. (Note that thc stress cuiTe for n = 8 is xS and
that for PEO is /5.)
respectively. The elastic Hooke domain was observed with stretches of approximately 10%
for all the samples but the value of the yield stress (sy) was greatly affected by the salt
content. The compound with n = 4 could not be exarnined due to its brittleness.
Figure 9 presents some mechanical characteristics deduced from stress-strain curves.
The shape of variations of both Y oung's modulus, yield stress and resilience versus salt
content is common. All these quantities decrease as the salt concentration increases
82
s (10 - 1MPa) u (mJ)
J
E (MPa)
0.5
40
0.3
20
I

0.1
0
8 12 16 20 PEO
[EO]/[Li]
Figure 9. Evolution of Young's modulus (E). yield stress (sy) and resilience (U) as a function of salt contcnt
in P(EO)nLiN(CF3S02)2.
showing that LiN(CF3S02h improves the viscoelastic properties ofthe tilms. However, an
exception is noticed for n = 20 composition. The shape of these curves has already been
observed for the evolution of the degree of crystallinity presented above. Therefore, it
seems likely that the investigated mechanical properties can relate to polymer crystallinity
as reported in the Iiterature on semi-crystalline polymers.l7.18 Indeed, in semi-crystalline
polymers, the great ductility of the amorphaus regions is responsible on the material
elasticity. The rigid crystallites, linked by van der Waals, polar or hydrogen interactions,
act exactly as the reinforcing Ioads introduced in composites. Thus, a decrease in degree of
crystallinity Ieads to a reduction in tensile modulus and yield stress values.
It may be possible to deduce certain compression characteristics from those of traction
using the equation inter-relating bulk modulus (8) and Young's modulus (E) by means of
the Poisson ratio ( v), which is evaluated at 0.37 for poly(ethylene oxide): 19
B =E/3(1-2v)
Fora film of a thickness e, the relative contraction (11e/e) in the transversal direction
could also be estimated by measuring its relative stretch (/11/l) under a drawing test assumed
tobe occurring at a constant volume. These two parameters are linked by:
/1e/e =(111/1)/( 1+11Ul)
According to this relationship, the elastic stretches, not exceeding 10%, observed in the
case of our samples, involve relative contractions of the same order of magnitude. Such a
result fulfils the requirements of accommodation to the fraction, involved in the transversal
direction, of electrode expansion. Thus, the secondary electrochemical cell may operate in a
reversible fashion during the charge-discharge cycles.
CONCLUSIONS
Films of PEO-LiN(CF3S02h have exhibited low crystallinity even several months
after synthesis. They have shown higher ionic conductivities than those obtained with
conventionallithium salts owing to the plasticizing effect of the (CF3S02hN new anion.
Moreover, good mechanical properties, related to the degree of crystallinity, have been
obtained for such films ensuring their ability to accommodate the volume change of
intercalation electrodes in secondary Iithium batteries.
83
Acknowledgments
The authors would like to acknowledge J.Y. Sanchez (LEPMI, Grenoble) for helpful
discussions.
REFERENCES
1. M. Annand, Polymer solidelectrolytes- an overview, Solid State Ionics, 9-10; 745 (1983).
2. C.A. Vincent, Polymer electrolytes, Prog. Solid St. Chem., 17; 145 ( 1987).
3. Y. Chcn, and J.W. Evans, Thrce-dimcnsional thermal modcling of lithium-polymer batteries undcr
galvanostatic discharge and dynamic power profile, J. Electrochem. Soc., 141; 2947 (1994).
4. C. Berthier, W. Gorecki, M. Minier, M. Armand, J.M. Chabagno, and P.Rigaud, Microscopic investigation
of ionic conductivity in alkali metal salts-poly(ethylene oxide) adducts, Solid State Ionics, II; 91
(1983).
5. M. Watanabe, S. Nagano, K. Sanui, and N. Ogata, Ionic conductivity of network polymers from poly-
(ethylene oxide) containing Iithium pcrchlorate, Polymer J., 18; 809 (1986).
6. A. Killis, J.F. Le Nest, A. Gandini, and H. Cheradame, Dynamic mechanical properlies of crosslinked
polyurethanes containing sodium tetraphenylborate, J. Polymer Scicnce: Polymer Physics, ed., 19;
1073 (1981).
7. Y. lto, K. Miyauchi, and T. Kudo, lonic conductivity of electrolytes fonned from PEO-LiCF3S03 complex
with low molecular weight poly(ethylene glycol), J. Mat. Sei., 22; 1845 ( 1987).
8. M. Annand, W. Gorecki, and R. Andreani, Perfluorosulphonimide salts as solute for polymer electrolytes,
in: Proceedings of the Second International Symposium on Polymer Electrolytes, B.Scrosati, ed.,
Elsevier Applied Science Pub., London (1990).
9. A. Vallee, S. Besner, and J. Prud'Homme, Comparative study of poly(ethylene oxide) electrolytes made
with LiN(CF3S02)2, LiCF3S03 and LiCl04: thermal properlies and conductivity behaviour,
Electrochim. Acta, 9; 1579 (1992).
10. S. Sylla, J.Y. Sanchez, and M. Armand, Electrochemical study of linear and crosslinked PEO-based
polymer electrolytes, E!ectrochim. Acta, 9; 1699 ( 1992).
11. A. V. Chadwick, J.H. Strange, and M.R. Worboys, lonic Iransport in polyether electrolytes, Solid State
lonics, 9-10; 1155 (1983).
12. S. Bhattachruja, S. W. Smoot, and D.H. Whitmore, Cation and anion diffusion in the amorphous pha'le of
the polymer clectrolyte (PEO)gLiCF3S03, Solid State Ionics, 18-19; 306 (1986).
13. C.D. Robitaillc, and D. Fauteux, Phasediagrams and conductivity characteri7.ation of some PEO-LiX
electrolytes, J. Electrochem. Soc. 133; 315 (1986).
14. D. Fauteux, Diagramme de phase, proprietes dc Iransport et stabilite electrochimique d'electrolytes
polymeres, These de Doctorat, Universire du Quebec ( 1986).
15. B. Zachau-Christiansen, K. West, and T. Jacobsen, Lithiuminsertion into V2, Mat. Res. Bull., 20; 485
(1985).
16. S. Sinha, and D.W. Murphy, Lithium intercalation in cubic TiS2, Solid State lonics, 20; 81 (1986).
17. G. Champetier, and L Monnerie, Introduction a Ia Chimie Macromoleculaire, Masson, ed., Paris ( 1969).
18. A.J. Wills, G. Capaccio, and I.M Ward, Plastic defonnation of polypropylene: effect of molecular weight
on drawing behavior and structuml chamcteristics of ultra-high-modulus products, J. Polymer Sei.:
Polymer Physics, ed., 18; 493 ( 1980).
19. D.W. Van Krevelen, Properlies of Polymers, Elsevier Science Publishing Company, New York (1976).
84
IMPROVED ELASTOMERS THROUGH CONTROL OF
NETWORK CHAIN-LENGTH DISTRIBUTIONS
J. E. Mark
Department of Chemistry
University of Cincinnati
Cincinnati, OH 45221-0172
INTRODUCTION
The effect of network chain-length distribution, 1 2 is one aspect of rubberlike elasticity
that has not been studied very much until recently, because of two primary reasons. On the
experimental side, the cross-linking techniques traditionally used to prepare the network
structures required for rubberlike elasticity have been random, uncontrolled processes. 1 3
Examples are vulcanization (addition of sulfur), peroxide thermolysis (free-radical
couplings), and high-energy radiation (free-radical and ionic reactions). All of these
techniques are random in the sense that the number of cross links thus introduced is not
known directly, and two units close tagether in space are joined irrespective of their locations
along the chain trajectories. The resulting network chain-length distribution is unimodal and
probably very broad. On the theoretical side, it has tumed out to be convenient, and even
necessary, to assume a distribution of chain lengths that is not only unimodal, but
monodisperse! 2 3
There are a number of reasons for developing techniques for determining or, even
better, controlling network chain-length distributions. One is to check the "weakest-link"
theory 4 for elastomer rupture, which states that a typical elastomeric network consists of
chains with a broad distribution of lengths, and that the shortest of these chains are the
"culprits" in causing rupture. This is attributed to the very limited extensibility associated
with their shortness, which is thought to cause them to break at relatively small deformations
and then act as rupture nuclei.
A variety of model networks can be prepared using the new synthetic techniques that
closely control the placements of cross links in a network structure. 3 5- 23 Thus, end linking
functionally-terminated chains, instead of haphazardly joining chain segments at random
controls the structure of the resulting network. As already mentioned, the functionality <1> of a
cross link is the same as the number of functional groups on the end-linking agent. More
important in the present context, the molecular weight Mc between cross links and its
distribution are the same as those of the starting chains prior to their being end linked.
An example of such an end-linking reaction is shown in Figure 1. 3 24 One of the most
important networks ofthistype are those having unusual chain-length distributions.I9, 25-28
One of the uses of those having abimodal distribution is to clarify the dependence of ultimate
properties on non-Gaussian effects arising from limited-chain extensibility. Another is to
maximize the ultimate properties of an elastomer. The following parts of this review provide
more detail on these applications, and on others as weiL
Science tJJUl Techrwlogy of Polymers arul Advanced Materials

Edited by P. N. Prasad et al., Plenum Press, New York, !998 85
Figure 1. Sketch showing an end-linking reaction for producing a network of known structure.
BIMODAL NETWORKS
Bimodal networks prepared by these end-linking techniques have very good ultimate
properties, and there is currently much interest in preparing and characterizing such
networks, 3, 14, 16, 23, 24 29-37 and developing theoretical interpretations for their
properties. 38-42
Materials and Synthetic Techniques

Most bimodal networks synthesized to date have been prepared from
poly(dimethylsiloxane) (PDMS). One reason for this choice is the fact that the polymer is
readily available with either hydroxyl or vinylend groups, and the reactions these groups
participate in are relatively free of complicating side reactions. 43 Also, the polymer is non-
crystallizable under most conditions because of its very low melting point (- -40 C).44 45
These bimodal networks are in fact generally studied at sufficiently high temperatures (-25
0 C) to easily avoid contributions from strain-induced crystallization, when desired. The end-
linking reactions have generally involved hydroxyl-terminated chains, which are readily
obtained from the usual ring-operring polymerizations ofthe cyclic trimer or tetramer. 46 The
ends of the chains are reacted with the alkoxy groups in a multifunctional organosilicate, as
described in Figure 1.43 In the application of interest here, a mixture of two polymers is
being cross linked, one component consisting of very short chains and the other, of much
Ionger chains. 24 29 An alternative approach involves the addition reaction between vinyl
groups at the ends of a polymer chain and the active hydrogen atoms on silicon atoms in the
[Si(CH3)HO-] repeat units in an oligomeric poly(methyl hydrogen siloxane). As a final
example, a network may be cross linked using a trifunctional reactant carrying side chains
terminated in some reactive group such as NH2. 47 Complexing two of these NH2 groups
with a metal ion provides a set of additional rather short chains that could be elastically
effective. This approach is illustrated in Figure 2. These ideas can obviously be extended to
higher modalities (trimodal, etc., eventually approaching an extremely broad, effectively-
unimodal distribution).48-5I
Figure 2. End Iinking of side chains by a complexation reaction. 22 Since the number of bonds formed
between the chains being joined is more than twice the number in each side chain, the cross-linking chains
could be elastically effective and act as the short chains in a bimodal network. 22 23
86
The distribution of network chain lengths in a bimodal elastomer can be extremely
unusual, and much different from the usual unimodal distribution obtained in less-controlled
methods of cross linking. Figure 3 shows a schematic distribution, for the important exam-
:::E
z
M
Figure 3. Network chain-length distributions, in which NM is the number of chains in an infinitesimal
interval araund the specified value of the molecular weight M.23 A broad unimodal distribution is shown by
the thinner line, for reference purposes.
ple in which there is simultaneously a large number percent of short chains and a !arge
weight percent of long chains. The major difference is the /arge amounts of both very short
chains and very long chains in the bimodal network, which contrasts sharply with the small
amounts of such chains in a typical unimodal distribution. The case shown here, where the
short chains predominate numerically, is of particular interest with regard to improvements in
mechanical properties. 24 Obviously, such peculiar distributions can be obtained only by
carefully-controlled techniques such as the end-linking reactions being described. One of
their uses is to test the molecular description of elastomer rupture, as described in the
following Section.
Testing of the Weakest-Link Theory
The weakest-link theory 4 was tested by preparing end-linked networks containing

increasing amounts of short chains, the order of 10- 20 mol %. 3 29 Remarkably, there were
no significant decreases in ultimate properties with these increases in the numbers of short
chains, in striking disagreement with the suggested mode of elastomer failure. Networks are
apparently much more resourceful than given credit for in this theory. Apparently, the strain
is continually being reapportioned during the deformation, in such a way that the much more
easily deformed long chains bear most of the burden of the deformation. Thus, the short
chains do not contribute significantly until just prior to rupture. This is consistent with
Nature preferring the low-energy route, unless overruled by entropy increases. The flaw in
the weakest-link theory is thus the implicit assumption that all parts of the network deform in
exactly the same way, i. e., "affinely", whereas the deformation is markedly non-affine. 3
These two limiting behaviors are illustrated schematically in Figure 4.
The above conclusion is supported by the common observation that stress-strain
isotherms are generally reversible right up to the rupture points. 3 24 This contradicts the
weakest-link theory assumption that short-chain breakage occurs first, weil before the
rupture point. Also, in an affine deformation, a decrease in the number of short chains in a
bimodal network should decrease the magnitude of the upturn in modulus but not the
elongation at which it begins. Experiments, however, indicate that the fewer the short chains
in the bimodal network, the higher the elongation required to bring about the upturn in the
modulus. 52 Thus, a decreased number of short chains apparently facilitates the
reapportioning of the strain.
87
The weak:est-link issue having been resolved, it became of interest to see what would
happen in the case of bimodal networks having such overwhelming numbers of short chains
that they can not be ignored in the network's response. In fact, there turns out to be an
exciting bonus if one does put a very large number of short chains into the bimodal network.
Specifically, there is a synergistic effect leading to mechanical properties that are better than
those obtainable from the usual unimodal distribution! These results are the focus of most of
the remaining parts of this review.
Elongation Results
Characterization of Upturns in the Modulus. Stress-strain isotherms in
elongation for bimodal PDMS networks were generally obtained in the vicinity of 25 C, a
temperature sufficiently high to suppress strain-induced crystallization. The results thus
determined were of considerable interest since they indicated that the bimodal nature of the
distribution greatly improved the ultimate properties of the elastomer. 3 8 18 19 This is
Non-affine
Figure 4. Sketch showing the vertica1 deformation of a network segment consisting of a long chain
bracketted by two short chains. 22 In the Iimit of an affine deformation, all chains deform by the same
fractional amount, whereas in the non-affine deformation, the more easily deformed long chains deform more
than the average and the short chains deform less than the average.
illustrated schematically in Figure 5, in which the data are plotted in such a way that the area
under a stress-strain isotherm corresponds to the energy required to rupture the network. If
the network consists entirely of the short-chain component, then it is brittle (which means
that the maximum extensibility is very small). If the network consists of only the Iong-ehain
component, the ultimate strength is very low. Neither type of unimodal material a tough
elastomer. As can readily be seen from the figure, the bimodal networks are much improved
elastomers in that they can have a high ultimate strength without the usual dirninished
maximum extensibility. This corresponds to high values of the energy required for rupture,
which mak:es them unusually tough elastomers, even in the unfilled state. 27 Related
improvements in mechanical properties have also been reported for polyurethane
elastomers. 53
Since this internally-generated improvement in properties is of considerable practical and
fundamental interest, a number of studies on PDMS elastomers were carried out to deterrnine
its dependence on the molecular weights of the short chains, 54 the proportians of short and
long chains,54, 55 and cross-link functionality. 26 55, 56 These results can be used to optimize
the improvements in properties obtained.
88
Bimodal
Unimodal, short chains
Unimodal, long chains
Figure 5. Sketch showing the typical dependence of nominal stress against elongation for two unimodal
networks having either all short chains or alllong chains, and a bimodal network having some of both.
The syntheses and properties of several additional types of bimodal networks were also
investigated. The first of these involves pre-reacting the short chains prior to incorporating
the long ones in the bimodal structure. 25 57 This makes the resulting network spatially as
weil as compositionally heterogeneous, in that many of the short chains will be segregated
into densely cross-linked domains which are only lightly cross linked to other such
domains. 25 These networks could serve as models for inhomogeneously cross-linked
elastomers, for example those cured by thermolysis of a partially-immiscible peroxide.
Another type is based on the fact that the condensation and addition types of end-linking
reactions can be carried out simultaneously and independently. This can give rise to the
interpenetrating network structure. 10 58 The distribution of network chains can obviously be
made bimodal, even though the short chains and long chains communicate only through their
entanglements. Finally, it is also possible to reinforce any type of bimodal network with
filler particles, thereby further improving its mechanical properties.59-62
Measurements of the mechanical and optical properlies of these networks as a function
of temperature and degree of swelling were used to test further the conclusion cited above
that crystallization or other intermolecular organization was not the origin of the improved
properties.3, 18 19, 27, 60 63 64 For example, stress-strain measurements on such bimodal
PDMS networks exhibited upturns in modulus which were much less pronounced than those
in crystallizable polymer networks such as natural rubber or cis-1 ,4-polybutadiene. In
another experiment, temperature was found to have little effect on the Mooney-Rivlin
isotherms for bimodal PDMS networks, as would be expected in the case of lirnited chain
extensibility. 27 Also, stress-temperature ("thermoelastic") and birefringence-temperature
measurements showed no discontinuities or discernible changes of slope. 27 Sirnilarly,
swelling can even make the upturns in modulus more pronounced. 52 65 Apparently, the
enhanced upturns are due to the chains being stretched out in the solvent dilation process,
prior to their being stretched further in the elongation experiments. In contrast, the uptums in
crystallizable polymer networks disappear upon sufficient swelling. 66, 67 A final experiment
of relevance concerns the spatially-heterogeneous PDMS networks mentioned above. 25 65
Any ordering that rnight have been present would presumably have been effected by this
change in spatial heterogeneity, but there was no discernible effect on the measured
elastomeric properties.
The above findings argue against the presence of any crystallization or other type of
intermolecular ordering,52 65 and the uptums thus seem to be intramolecular in origin. In
addition, infrared and Raman spectroscopy indicate that bond-angle distortion is of relatively
rninor importance, at least in PDMS networks. 30 The observed increases in modulus and
ultimate strength therefore have to be due to the limited extensibility of the very short
network chains. In qualitative terms, the chains soon exhaust their spatial configurations,
their entropies plummet, and the elastic force rises correspondingly. 1t is possible to
89
characterize this non-Gaussian limited extensibility more quantitatively in a number of ways,
some of which are described below.
The first involves the interpretation of limited chain extensibility in terms of the
configurational characteristics of the PDMS chains making up the network structure.68 The
first important characteristic of limited chain extensibility is the elongation au at which the
increase in modulus first becomes discemible. Although the deformation is non-affine in the
vicinity of the uptum, it is possible to provide at least a semi-quantitative interpretation of
such results in terms ofthe network chain dimensions. 52 At the beginning ofthe upturn, the
average extension r of a network chain having its end-to-end vector along the direction of
stretching is simply the product ofthe unperturbed dimension68 <r2>ol/2 and a.u. Similarly,
the maximum extensibility rrn is the product of the number n of skeletal bonds and the factor
(1.34 A) which gives the axial component of a skeletal bond in the most extended helical
form of PDMS, as obtained from the geometric analysis of the PDMS chain. 52 65 The ratio
r/rrn at a.u thus represents the fraction of the maximum extensibility occurring at this point in
the deformation. The values obtained indicate that the upturn in modulus generally begins at
approximately 60- 70% of maximum chain extensibility. 19 52 This is approximately twice
the value which had been estimated previously 2 from stress-strain isotherms of elastomers
which may have been undergoing strain-induced crystallization not accounted for in reaching
this conclusion.
lt is also of interest to compare the values of r/rrn at the beginning of the upturn with
some theoretical results by Flory and Chang28 69 on distribution functions for PDMS chains
of finite length. Of relevance here are the calculated values of r/rrn at which the Gaussian
distribution function starts to over-estimate the probability of extended configurations, as
judged by comparisons with the results of Monte Carlo simulations. The theoretical
results65 69 soggest, for example, that the network of PDMS chains having n =53 skeletal
bonds which was experimentally studied should show an upturn at a value of r/rrn a little less
than 0.80. The observed value was 0.77,52 which is thus in excellent agreement with theory.
More quantitative characterization of this limited chain extensibility requires, of course,
a non-Gaussian distribution function 2 for the end-to-end separation r of the short network
chains. Ideal for this case is the distribution obtained by Fixman and Alben70 and
recommended particularly for very short chains. lt was found to give a much better
approximation to the highly reliable Monte Carlo simulated results than does the Gaussian
Iimit, particularly in the most important region of very high extension. 38 The parameters in
the Fixman-Alben distribution function can be adjusted to give very good approximations to
the Monte Carlo distributions for the short PDMS chains. These Fixman-Alben distributions
can then be combined with the constrained-junction theory and reasonable values of the
constraint parameter 1e38 to calculate stress-strain isotherms in elongation for bimodal PDMS
networks. The observed uptums in the reduced stress [f*J at high values of the elongation a.
were found to be weil reproduced by the calculated results. 38 Other non-Gaussian
distribution functions have also been successfully used for this purpose. 71 72 The
experimental isotherms can also be interpreted using the van der W aals theory of rubberlike
elasticity .73 74
Another approach, Monte Carlo simulations, utilizes the wealth of information that
rotational isomeric state theory provides on the spatial configurations of chain molecules. In
brief, Monte Carlo calculations based on the rotational isomeric state approximation are used
to simulate spatial configurations and thus distribution functions for the end-to-end
separations of the chains. 3 75 These distribution functions are then used in place of the
Gaussian function in the standard three-chain model 2 in the affine Iimit to give the desired
non-Gaussian theory of rubberlike elasticity. Stress-strain isotherms calculated in this way
are strikingly similar to the experimental isotherms obtained for the bimodal networks. 3 75
The overall theoretical interpretations are thus quite satisfactory and would encourage other
applications of these distributions, for example to segmental orientation in networks
containing very short chains. Such segmental orientation is of critical importance, for
example, with regard to strain-induced crystallization.
90
Characterization of the Rupture Process. A second important characteristic of an
elastomeric network is the value O.r of the elongation at which rupture occurs. The
corresponding values of r/rm show that rupture generally occurred at approximately 80- 90
% ofmaximum chain extensibility.52 These quantitative results on chain dimensions are very
important but may not apply directly to other networks, in which the chains could have very
different configurational characteristics and in which the chain length distribution would
presumably be quite different from the very unusual bimodal distribution intentionally
produced in the present networks.
Strain-Induced Crystallization. PDMS networks were found tobe unsuitable for

characterizing the effects of bimodality on strain-induced crystallization, because of their
very low crystallization temperatures. The polymer chosen instead for these end-linked
bimodal networks was poly(ethylene oxide), which has a relatively high melting point (- 65
0 C)44, 45 and thus readily undergoes strain-induced crystallization. 76 The aspect of relevance
here is the use of these networks to elucidate the dependence of strain-induced crystallization
on network chain length distribution. Decrease in temperature was found to increase the
extent to which the values of the ultirnate strength of the bimodal networks exceed those of
the unimodal ones. 76 This suggests that bimodality facilitates strain-induced crystallization,
possibly through increased orientation of the more easily crystallizable chains, into
crystallization nuclei. Sirnilar conclusions have been reached in studies of elongated bimodal
networks of poly(tetrahydrofuran).77
Thermosets. In practical terms, the above results demonstrate that short chains of
lirnited extensibility may be bonded into a Iong-ehain network to improve its toughness. It is
also possible to achieve the converse effect. Thus, bonding a small nurober of relatively long
elastomeric chains into a short-chain PDMS thermoset greatly improves both its energy of
rupture and impact resistance. 61 Approximately 95 mol% short chains gives the maximum
effect for the molecular weights involved. Lower concentrations give smaller improvements
than can otherwise be achieved, and higher concentrations will gradually convert the
composite from a relatively hard material to one that is more rubberlike.
Results in Other Mechanical Deformations

Biaxial Extension. There are numerous other deformations of interest, including
compression, biaxial extension, shear, and torsion. All of the associated equations of state
may be derived from the generat equations for the free energy of deformation by proper
specification ofthe deformation ratios. 1-3 In the case of compression (a. < 1), the equation of
state is the same as that for elongation (a. > 1). Some of these deformations are considerably
more difficult to study than simple elongation and, unfortunately, have therefore not been as
extensively investigated.
Some of the earliest studies of biaxial extension have involved the direct stretching of a
sample sheet in two perpendicular directions within its plane, by two independently-variable
amounts. Equi-biaxial extension, however, is equivalent to compression, and can be more
conveniently be imposed by inflation of sheets of the elastomer. 2 A good account of
experimental biaxial extension results on typical unimodal networks78 has been given by the
simple molecular theory, with improvements at lower extensions upon use of the
constrained-junction theory. 3
Equi-biaxial extension results have been obtained by inflating sheets of unimodal and
bimodal networks of PDMS.7 9 80 Upturns in the modulus are seen to occur at high biaxial
extensions, as expected. Also of interest, however, are the pronounced maxima preceding
the upturns. This represent a chanenging feature to be explained by molecular theories
addressed to bimodal elastomeric networks in general.
Shear. Elastomeric networks can be stu'died in pure shear by Stretching a sheet of the
material which has a large ratio of width to length, in the direction perpendicular to the
width. Experimental results on natural ruhher networks in shear8 1 are not well accounted for
91
by the simple molecular theory of rubberlike elasticity. The constrained-junction theory,
however, was found to give excellent agreement with experiment. 24
In shear measurements on some unimodal and bimodal networks of PDMS, 82 the
bimodal PDMS networks showed large upturns in the pure-shear modulus at high strains
which were similar to those reported for elongation and biaxial extension. End linking in
solution gave smaller upturns in modulus, presumably because of diminished chain-junction
entangling.
Torsion. Very little work has been done on elastomers in torsion (twisting a cylindrical
sample around its long axis). There are, however, some results on stress-strain behavior and
network thermoelasticity. 2 83 84 More results are presumably forthcoming, particularly on
bimodal networks and on networks containing some of the unusual fillers introduced in-situ
by hydrolyses of organometallic compounds such as silicates or titanates. 3 24 85-87
The same types of bimodal PDMS networks showed rather different behavior in
torsion. 88 Specifically, no unambigous upturns in modulus were observed at large
deformations. lt has not yet been established whether this is due to the inability, to date, of
reaching sufficiently large torsions, or whether this is some inherent difference in this type of
deformation.
Tear. Tear tests have been carried out on bimodal PDMS elastomers, 14 16 using the
standard "trouser-leg" method. Tear energies were found to be considerably increased by the
use of a bimodal distribution, with documentation of the effects of compositional changes
and changes in the ratio of molecular weights of the short and long chains. The increase in
tear energy did not seem to depend on tear rate, 14 an important observation that seems to
suggest that viscoelastic effects are not of paramount importance in explaining the observed
improvements.
A subsequent series of shear tests 16 established the dependence of the tearing properties
on the composition of the bimodal networks and the lengths of the chains used to prepare
them. Of particular interest was the dependence of the tearing energy on the amount of the
short-chain component, since the maxima in such curves locates the composition giving the
greatest increases in tear energy. Also of importance are experiments showing how the
tensile strength depends on the ratio of molecular weights of the two components. The
observed increases in strength with decease in the molecular weight of the short chains must
eventually become decreases when the chains become too short. lt would obviously be
important to carry out additional studies to establish the molecular weight at which this
occurs.
Cyclic Deformations. Some Rheovibron viscoelasticity results have been reported

for bimodal PDMS networks. 89 To provide guidance for the desired interpretations,
measurements were frrst carried out on unimodal networks consisting of the types of chains
used in combination in the bimodal networks. One of the important Observations was the
dependence of crystallinity on the network chain-length distribution.
Some measurements have been made on permanent set for PDMS networks in
compressive cyclic deformations. 90 There appeared tobe less permanent set or creep in the
case of the bimodal elastomers. This is consistent with some early results for polyurethane
elastomers. 24 91 Specifically, cyclic elongation measurements on unimodal and bimodal
networks indicated that the bimodal ones survived as much as an order of magnitude more
cycles before the occurrence of fatigue failure.
Results on Non-Mechanical Properties

Birefringence. Birefringence measurements have been shown to be very sensitive to
bimodality, and have therefore also been used to characterize non-Gaussian effects resulting
from it in PDMS bimodal elastomers.92-95 Relevanthereis the effect of strain on the stress-
optical coefficient (defined as the ratio of the birefringence to the stress ). 92 There was found
to be a large decrease in this coefficient over a relatively small range in elongation,
presumably from the limited extensibility of the short chains in the bimodal structure. lt is
therefore a sensitive way of characterizing non-Gaussian effects in network deformation.
92
Freezing Points of Absorbed Solvents. This type of experiment is based on the
fact that solvent molecules constrained to small volumes form only relatively small
crystallites upon crystallization, and therefore exhibit lower crystallization temperatures. 96-
100 Some differential scanning calorimetry measurements on solvent molecules constrained
in the pores of PDMS elastomers gave evidence for several crystallization temperatures,
which could be indicative of an unusual distribution of pore sizes. The effect seemed to be
most pronounced for trimodal networks, which are discussed later in this review.
Related Investigations. Calorimetric measurements on bimodal poly(ethylene
oxide) networks indicated that the short chains seemed to decrease the amount of crystallinity
in unstretched state. 101 This is an intriguing result since, as mentioned above, they increase
the extent of crystallization in the stretched state. A similar study on a different polymer,
poly(tetrahydrofuran), did not show any decrease, however. 32
When cyclic molecules are present during the end-linking reaction, the larger ones tend
to get trapped by being threaded with chains subsequently bonded into the network structure.
Such experiments have also been carried out using a bimodal distribution of end-linkable
PDMS chains.102
Dynamic light scattering experiments,33 neutron scattering calculations,40 and computer
simulations 41 have also been used to obtain insight into the dynamics and structure of
bimodal elastomers.
TRIMODAL NETWORKS
As mentioned above, there have been differential scanning calorimetry measurements on
solvent molecules constrained in the pores of a variety of PDMS elastomers. Some results on
networks having a trimodal distribution have been reported. 48 The several crystallization
temperatures which were observed for the benzene in such networks could possibly be used
to obtain additional information on the pore sizes present.
Although there have been attempts to evaluate the mechanical properties of trimodal
elastomers, this has not been donein any organized manner. The basicproblern isthelarge
number of variables involved, specifically three molecular weights and two independent
composition variables (mol fractions); this makes it practically impossible to do an
exhaustive series of relevant experiments. For this reason, the only mechanical property
experiments that have been carried out have involved arbitrarily chosen molecular weights
and compositions. 49 50 103 Not surprisingly, only modest improvements have been
obtained over the bimodal materials.
Some recent computational studies, 41 however, indicate that it is possible to do
Simulations to identify those molecular weights and compositions which should maximize
further improvements in mechanical properties. Such simulations are being extended in a
search for optimum properties of trimodal, trifunctional networks, 104 specifically (i) the
elastic modulus, (ii) maximum extensibility, (iii) tensile strength, and (iv) segmental
orientability.
NETWORKS OF VERY HIGH MODALITY

The interpretation of the attractive mechanical properties of bimodal networks has been
in terms of a "delegation of responsibilities", with the short chains serving in one role and
the long chains in another. If this is picture is true, then it would be interesting to prepare and
study networks having extraordinarily broad molecular weight distributions, in that there
would be network chains of all conceivable lengths, available for any conceivable
mechanism that would improve properties. 24 51 A polymer prepared from a single
polymerization would not have a broad enough distribution, but the combination of a series
of samples of gradually differing average molecular weight could provide the desired
broadness. It should be possible to achieve a polydispersity index of 100 or higher. This is
93
illustrated in Figure 6. An elastomer of this type has apparently never been synthesized, and
might weil have unusually attractive mechanical properties.
,.
z
Figure 6. Network chain-length distributions, in which NM is the number of chains in an infinitesimal

interval around the specified value of the molecular weight M 23 A typical unimodal distribution is shown by
the area filled with diagonal slashes, a bimodal distribution by the heavily dotted areas, and an extremely
broad, pseudo-unimodal distribution (obtained by combining separately-prepared polymers) by the lightly
doned area.
ELASTOMERS THA T MA Y HA VE BEEN INADVERTENTL Y

BIMODAL
Elastomers cured with sulfur frequently have improved mechanical properties when the
curing conditions are chosen to give cross links that consist of chains of sulfur atoms.105 It
has been suggested that if such polysulfidic cross links can themselves act as elastomeric
network chains, then abimodal network is produced, albeit inadvertently. 106 This is shown
schematically in Figure 7. Calculations conducted to take into account this possible
bimodality gave results in good agreement with experiment. 106
Figure 7. Sketch showing the difference between a monosulfidic cross link (left protion), and a
polysulfidic one (right portion). In the lauer case, the chains of sulfur atoms can possibly act as additional
elastically-effective chains in what is essentially abimodal network.
A similar situation may occur in the case of networks end linked using the addition
reaction involving vinyl chain ends and hydrogen atoms in an oligomeric poly(methyl
hydrogen siloxane). 107 - 110 In the case of incomplete reactions, the segments between the
reacted silicon atoms on the oligomer may be long enough to act as elastically-effective
chains in a bimodal structure. A sketch of this possible situation is shown in Figure 8.
Finally, a bimodal chain-length distribution has also been proposed to explain some unusual
properties of polysiloxane networks that have been post cured. 111
94
Figure 8. Sketch illustrating how incompleteness of reaction in the case of a vinyl hydrosilation end
linking can Iead to additional network chains. The oligomeric poly(methyl hydrogen siloxane) chains are
shown vertically, and the segments between reacted SiH sites on them possibly contribute elastically-effective
short chains in what would be an inadvertently bimodal distribution of chain lengths.
OTHER MATERIALS IN WHICH BIMODALITY MIGHT BE

ADVANTAGEOUS
There appear to be other cases where a bimodal distribution of chain length or some
other physical property can be advantageous, possibly again through this idea of a delegation
of responsibilities.
For example, in the area of thermosets, there seems to be an improvement in mechanical
properties when the polymer being cured has abimodal distribution of molecular weights. 112
In this case, the improvements may be due to different morphologies resulting from the fact
that the long chains in abimodal distribution could have considerably lower solubilities than
the short chains. Also, it is weil known that the flow characteristics of a polymer during
processing 113 can frequently be adjusted by the addition of a small amount of polymer of
either very low or very high molecular weight. Another example is in the area of rubber-
toughened thermoplastics in which an elastomer is dispersed as domains within the
thermoplastic matrix to improve its mechanical properties. 114 115 It has been found that a
bimodal distribution of particle sizes gives the largest improvements. ll6, 117 Perhaps the
small particles are most efficient at stopping one type of failure mechanism, and the large
particles another type. In a related application, there is the possibility that a mixture of two
chemically different particles, such as silica [Si02] and titania [Ti02], 118 - 120 could have
significant advantages in elastomer reinforcement.
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98
SURFACE PROPERTIES OF SILICONE HIGH VOLTAGE INSULATORS
Michael J. Owen
Dow Coming Corporation,

Midland, Michigan 48686-0994, USA
INTRODUCTION
The chief advantages of polymeric insulators over conventional porcelain and

glass insulators in outdoor high voltage (HV) insulation applications are given by Gorur
and Orbeck 1 as light weight, superior vandal resistance and better contamination
performance. However, polymers are more easily degraded than inert inorganic materials
under exposure to discharges and arcing. Corona discharges and dry band arcing occur
when the surface of an energized insulator is covered by an electrolytic film formed by
the presence of moisture and contamination. The intense localized energy of the dry band
arcs can cause material degradation in the form of tracking and erosion. Other
environmental factors such as ultraviolet (UV) radiation from sunlight, temperature and
flammability must also be considered.
Polydimethylsiloxane (PDMS) has a variety of characteristics that make it
particularly suitable for this HV application. The various product types testify to this
suitability. They range from time-proven grease-like coatings and elastomer dispersions,
that can be applied to existing insulators to improve water-filming resistance and prevent
arcing and flashover, to lightweight, composite insulators made from silicone rubber for
new or upgraded electrical systems. The following list of qualitative attributes
summarizes the desirable properties contributed to these silicone insulator options by the
PDMS polymer.
QUALITATIVE ATTRIBUTES OF PDMS POLYMER
Low surface energy

Hydrophobic/oleophilic
Non-adhering surface (but prone to oily soiling)
Water insoluble
Low MW polymer component
Science and Techrwlogy of Polymers and Advanced Materials

High surface mobility
Low glass transition temperature
Good dielectric properties
High thermal and oxidative stability
Excellent resistance to weathering
Low reactivity, toxicity and combustibility
Low environmental hazard
Small temperature variation of physical properties
Flexible to low temperatures
Transparency to UV in normal atmosphere
LOW INTERMOLECULAR FRCES

HIGH BACKBONE FLEXIBILITY
HIGH SILOXANE BOND ENERGY
PARTIALLY POLAR BACKBONE (ca 40% ionic)
In this Iist, the terms high and low refer to comparison with organic hydrocarbon
polymers. The capitalized subset are the more fundamental characteristics that are the
reason for the other attributes. The ramifications of this set of characteristics are further
discussed in what follows with emphasis on the surface properties of PDMS elastomers,
the role of filler, the effect of corona discharge and other environmental aspects.
SURFACE PROPERTIES OF PDMS ELASTOMERS
Polymer surfaces are best characterized by a variety of techniques. Generally

information of a morphological or structural nature coupled with some eiemental or
chemical group identification plus wettability changes is needed. The combination we
use of scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS)
[also known as electron spectroscopy for chemical analysis (ESCA)] and contact angle
(0) has proved tobe very useful for silicone surfaces 2 . Wehave examined a variety of
commercially available and experimental high consistency HV silicone elastomers
(HCRl Typically, these are silica-filled PDMS gums with alumina trihydrate (ATH) in
an approximate ratio of 2:3. Minor amounts of filler treatments, pigments, and eure
agents are also present.
A filled elastomer usually shows a high contact angle hysteresis (difference
between advancing and receding equilibrium contact angles). We found contact angle
hysteresis to be a function of surface roughness measured by SEM, the roughest surfaces
having a hysteresis of almost SO deg. The advancing angle of water, the index of
hydrophobicity, averaged 108 deg, typical of other PDMS elastomer surface
characterizations. Higher values can be obtained by incorporation of significant amounts
of free PDMS fluid. Combined with other contact angle data, such as those of methylene
iodide, surface energies (cr.) of circa 25 mN/m are obtained, somewhat high er than the
familiar 20-22 mN/m of smoother unfilled coatings.
PDMS is more hydrophobic and lower surface energy than most organic
polymers. A comparative table is given in Table 1. The glass transition temperature (Tg)
data in this table are taken from the Polymer Handbook 4 . Higher water contact angles
generally correlate with lower surface energy. The polypropylene (PP) water contact
angie of 116 deg is unexpectedly high considering the optimum close-packed methyl
group case of paraffin wax gives only 112 deg. Only polymers containing aliphatic
IOO
fluorocarbon, such as polytetrafluoroethylene (PTFE) have lower surface energies. This
is because the intermolecular forces between CF2 and CF3 groups are lower than those
between CH2 and CH3 groups. However, the bulkier fluorine atom causes the glass
transition temperature of fluoropolymers to be much higher. Consequently when a
surface such as PTFE is damaged by corona its hydrophobic recovery is much slower.
Fluorosilicones such as polymethylnonafluorohexylsiloxane (PMNFHS, also shown in
Table I) offer an excellent, albeit expensive, compromise in this regard.
Table I: Quantitative Polymer Property Comparison
Polymer T8,K E>, deg a,,mN/m Ref.
PDMS I46 108 25 This work

PE 148 94 33 5
PMNFHS 198 115 IO 6
EPR(50/50) 213 3I 7
PP 260 116 29 8
PTFE 390 108 19 5
The atomic composttton of these PDMS silicone HV insulator surfaces

determined by XPS sturlies closely reflects that ofthe PDMS polymer gum: 50% carbon,
25% oxygen, 25% silicon. Fillers, particularly ATH, are almost never seen in the XPS
sampling region (approximately 5 nm thick for the usual measurement configuration)
despite high loading. Nor does there seem to be any concentration of catalysts, pigments,
contaminants, etc. in the surface region.
ROLE OF FILLER
The common absence of filler in the surface indicated by XPS analysis, referred
to in the preceding section, does not imply a macroscopic depletion. This could hardly be
the case when filler Ievels typically exceed polymer gum Ievels. XPS analyses a depth of
the order of 5 nm and the filler particles could easily be coated by a polymer film of this
thickness. Even uncoated and close-packed in the surface they would still only constitute
less than I% of the volume of the top 5 nm thick layer of a flat topography where the
filler was spherical micron-sized particles with polymer filling the interstices. Up to a
few atomic % of aluminum is sometimes seen by XPS after extensive weathering and
surface damage.
Two varieties of filler are usually used in silicone HV elastomers, reinforcing
fillers to provide elastomeric nature and thermally conductive fillers to dissipate heat
from energetic events such as corona discharge and dry band arcing. Sufficient energy
can be generated in bot spots to dissociate chemical bonds9 . The usual reinforcing filler
used is silica, the heat dissipating filler is alumina trihydrate (ATH). The polymer/filler
combination is important in both cases. Elastic properties such as elastic modulus,
hardness, etc., depend on the number and type of polymer crosslinks and the molecular
weight between crosslinks as weil as filler type, size, shape and surface treatment.
Likewise, thermal darnage is a function of the intrinsic thermal stability of the polymer,
101
the conductive properties of the heat dissipating filler, and extraneous factors such as
residual catalysts and catalytically active contaminants which can markedly affect
thermal depolymerization of silicones.
Despite its absence from the outermost molecular layers, the presence of filler has
a profound influence on surface behavior. Filled silicone elastomers exhibit marked
contact angle hysteresis compared to monolayer films, also the softer the elastomer
surface then the higher the contact angle hysteresis. Release behavior is a complex
function of elastomer structure. At slow release speeds soft (but not tacky) elastomers
seem to release better than harder resinous materials so the former type of silicone should
have the better chance of being cleaned of contamination in a rain storm. On the other
hand, at much higher release speeds, there is a well-established correlation of decreasing
release force with increasing crosslink density in the distantly-related field of pressure-
sensitive adhesive release Iiners.
EFFECT OF CORONA DISCHARGE
Exposure to severe corona treatment is both physically and chemically damaging

to elastomers. Cracking of the surface and an increase in wettability by water are the
usual consequences which can be shown by modern surface analytical techniques, such
as XPS, to be associated with an increase in the oxygen content of the surface. Clearly, a
polymer such as PDMS with a higher threshold of thermal and oxidative darnage than
hydrocarbon polymers has a considerable advantage in practical use as a high voltage
insulator material. Cracking in use does occur but can be difficult to see optically or by
SEM because ofthe rough surface caused by high loadings of ATH filler. It can be more
readily seen with lower filler Ievels. lt is also evident that cessation of the corona
treatment causes a progressive reversion to the non-wetted state in most cases, the so-
called "hydrophobic recovery" effect, first described for silicone HV insulators by Lee
and Homan 10 .
Table 2 illustrates this hydrophobic recovery effect for a variety of silicone
elastomers, primarily PDMS with different crosslinking systems and fillers. Sampies A,
Band C are from Lee and Homan 10 and samples D and E from Smith et al. 3 with data
interpolated from their graphs. D is a conventional heat-cured (peroxide) silicone HV
material, E is a liquid silicone rubber cured by platinum-catalyzed hydrosilylation (both
materials containing silica and ATH). The data for sample F is taken from Fritz and
Owen11 and included to show the similar effect of RF plasma treatment to corona
discharge.
On exposure to corona, the oxygen content of the surface increases depending on
treatment conditions up to 50 atomic %, with carbon reducing to 25% and silicon
remaining virtually unchanged. This fits well with a methyl to silanol (SiOH) oxidation,
less weH with a carbinol (SiCH20H) type structure proposed in the original study of
corona-modified PDMS by Hollahan and Carlson12 . The carbinol structure is less stable
than the original methyl and should be prone to further reaction under corona conditions,
e.g. with water to eliminate methanol and form a silanol or thermally rearranging to
SiOCH3 . The XPS Si 2p peak of corona exposed silicone HV insulator surfaces can be
resolved into two peaks, one at 103.5 consistent with a silica or silicate-like material
resulting from condensation of the silanols, and one at 101.5 eV consistent with the
unmodified control. That this mixture of different surface components is heterogeneaus
with respect to depth is revealed by angle-resolved XPS studies shown in Table 3.
102
Table 2: Hydrophobie Recovery of Silicones
Sampie Type of exposure Advancing water contact angle (deg)
Before After After 24 hr RT

exposure e:xposure recovery
A 20 kV corona, 5 min 98 10 83
B 20 kV corona, 5 min 101 10 79
c 20 kV corona, 5 min 103 13 71
D 14 kV corona, 10 min ll6 0 84
E 14 kV corona, 10 min 106 0 46
F 0 2 plasma, 10 min 107 30 90
F N 2 plasma, 10 min 107 0 52
F Ar plasma, 10 min 107 13 72
F He plasma, I 0 min 107 0 40
The grazing angle data, which represent the outermost surface region (0-2 nm)
suggest a composition corresponding to only mildly oxidized PDMS whereas the normal
angle (90 deg) XPS data, which aresensitive to deeper material (up to 10 nm), indicate
highly oxidized PDMS. Corona treatment must oxidize from the outermost layers down
and the only way to rationalize this apparent contradiction is to suppose a layer of
unmodified PDMS diffusing to the surface in the time between cessation of the corona
and measurement in the XPS instrument. Exactly the same situation pertains with radio
frequency (RF) plasma treatment ofPDMS.
Table 3: XPS Atomic Composition %
0 c Si
Control 26.8 49.2 24.0

(PDMS Theory 25 50 25)
Treated, grazing angle 39.5 35.9 24.6
Treated, normal angle 54.6 17.6 27.6
Treated, no angular resolution 42.0 32.3 25.2
Sampies were treated at 14 kV for 10 minutes.
The diffusion mechanism is only one of at least seven possible mechanisms of

hydrophobic recovery of insulating polymers listed below:
Possible Mechanisms of Hydrophobie Recovery
* Reorientation of surface hydrophilic groups away from the surface (i. e. the
"overtum" ofpolar groups in the polymer surface).
* Migration of treated chains from the surface to the bulk.
* Migration of untreated polymer chains from the bulk.
103
*Loss of volatile oxygen-rich or other polar species to the atmosphere.
*
Further reaction of polar or other active species (e. g. transient radicals)
producing linkages that hinder chain reorientation (for PDMS, surface silanol
condensation is a possibility).
* Change in surface roughness.
* Extemal contamination of the polymer surface.
The two main mechanisms that most likely operate are surface reorientation and
diffusion of low MW species. Surface reorientation of polymeric solids and this
dependence on different environments is a familiar phenomenon. The extreme flexibility
of the siloxane chain and the low intermolecular forces between methyl groups, which
result in the low glass transition temperature and high free volume of PDMS, allow
PDMS to reorient its surface readily. It has the most mobile surface of all common
polymers.
Likewise, the low MW component that is usually present in most commercial
PDMS materials provides an ample reservoir of diffusable material even if such
unreacted components have not been deliberately added. Moreover, the same factors that
permit facile reorientation will allow ready diffusion of such species. More than any
other polymer, PDMS exhibits the most marked hydrophobic recovery.
OTHER ENVIRONMENTAL ASPECTS
The long service life of silicone elastomers and coatings in a variety of

environments is widely recognized. This outstanding durability is a general consequence
of the hybrid nature of silicones occupying the regime between silicate materials and
organic polymers and exhibiting attributes of each.
Residual carbon-carbon double bonds in polymers are the major Iocus of attack
for oxygen and ozone. A saturated polymer such as polyethylene oxidizes much more
slowly than unsaturated materials such as natural rubber. PDMS has no unsaturation and
its methyl groups on silicon are even more resistant to oxygen because of the partially
ionic nature of the siloxane backbone. The positively polarized silicon atom acts as an
electron drain polarizing the methyl group and rendering it less susceptible to attack
provided the manufacturer has ensured no catalytically active residues are present. In
order for light energy to initiate chemical change it must be absorbed by the molecules in
question. PDMS does not absorb near-UV radiation in the 300-400 nm region which is
the wavelength range that causes problems with polymers at or near ground Ievel. This is
consistent with the fact that over twenty years of outdoor weathering in sunny climates
produces no significant changes in silicone elastomer properties.
A chink in silicone's armory of defenses against environmental attack is water.
The considerable ionic nature of the siloxane bond renders it susceptible to hydrolysis at
extremes of acidity or alkalinity, i.e. the very conditions under which the bonds were
formed in the first place. In practice we know that silicone HV insulators continue to
function weil in high humidity environments, for example, foggy coastal installations, so
we can presume that adequate hydrolytic stability and hydrophobicity are preserved in
environments usually encountered. No fundamental studies on this aspect have been
carried out on actual silicone HV products but recent studies of medical-grade silicone
elastomers confirm this stability 1 . Exposure to pure water and saline solutions for
various times and temperatures show little change in the advancing contact angle of
water and considerable change in the receding contact angle. Such behavior is common
to many polymers and is not indicative of chemical change such as hydrolysis in the
104
aqueous environment. Elastomeric properties such as tensile at break, elongation at
break, and elastic modulus also did not change significantly under the test conditions (up
to 100C for 45 hours). Even if exceptionally acid rain were to cause surface hydrolysis,
the silanols produced would participate in the formation of a silica-like layer in the same
manner as that produced by corona discharge, and hydrophobic recovery by chain
reorientation or migration would ensue when the rainstorm abated.
It is also interesting to question how a hydrophilic silicone surface resulting from
corona discharge will change in an aqueous environment. There are no specific studies
on corona-treated silicones but such studies have been carried out on plasma-treated
silicones. Assuming that the parallel behavior of the two treatments in air persists in
water, then these plasma treatment studies are a useful indication of probable behavior.
Interestingly, the plasma treated surfaces show partial hydrophobic recovery in water
contrary to what might be expected from simple low surface tension arguments. Soaked
plasma-treated PDMS surface seem to recover in general to an advancing water contact
angle of circa 70 deg. Presumably, diffusion of free siloxane chains occurs through the
silica-like layer as before. On reaching the interface with water such chains are prevented
from diffusing away by adopting a configuration exposing as much of the siloxane
backhone as possible. This will minimize the interfacial tension locally but the resulting
multiple hydrogen bonds with the water phase will anchor the chains at the interface and
prevent migration away. Thus the advancing water contact angle of 70 deg reflects a
configuration where as many methyl groups as possible are oriented away from the
surface, I 05 deg represents the situation where methyl groups are oriented towards the
surface. Of course, hydrophobic recovery continues to this latter state if the sample is not
retumed to aqueous immersion after contact angle measurement.
SUMMARY
This brief overview of the surface properties of silicone elastomers has illustrated
how the fundamental, inherent characteristics of polydimethylsiloxane make it a
particularly suitable choice for high voltage insulation applications. The combination of
low intermolecular forces between methyl groups, high backhone flexibility, high
siloxane bond energy and partially polar backhone produce one of the lowest surface
energy, most hydrophobic polymers available with unique ability to recover from
exposure to electrical discharges and arcing. Its highly mobile surface, reflected in the
very low glass transition temperature, ensures facile hydrophobic recovery by the two
main mechanisms, diffusion of low molecular weight species and surface reorientation.
Clearly the performance of a silicone high voltage product will depend on its
specific formulation, degree of purity and filler type and loading. Our general conclusion
that corona discharge forms a wettable silica-like layer on the surface which recovers
primarily by diffusion of low molecular weight polydimethylsiloxane components
applies only to the high consistency rubbers we have mostly investigated. Not all silicone
materials will necessarily behave similarly. In particular, some liquid silicone rubbers
cured by platinum catalyzed hydrosilylation rather than conventional peroxides behave
rather differently. This different behavior is not fully understood but involves oxidized
carbon species in the surface rather than oxidized silicon. Reorientation or overturn of
surface polar groups is a plausible primary mechanism for the hydrophobic recovery of
corona-treated liquid silicone rubbers. Contact angle studies show clear differences in
their hydrophobic recovery rates suggesting probable mechanistic differences.
105
Attention should also be drawn to the parallel between the effects of corona
discharge and radio-frequency plasma treatment in air, oxygen, nitrogen and inert gases.
Again generalities should not be taken too far as some plasmas, particularly microwave
plasmas, affect silicone surfaces very differently.
ACKNOWLEDGMENTS
Thanks to Peter Holm, Pat Smith and Jenny Stasser for their invaluable con-
tributions.
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8. B. B. Sauerand N. V. Dipaolo, Surface Tension and Dynamic Wetting ofPolymers
Using the Wilhelmy Method: Applications to High Molecular Weights and
Elevated Temperatures, J. Co//oidlnterjaee Sei., 144:527 (1991).
9. S-H. Kim, E. A. Cherney and R. Hackam, Thermal Characteristics ofRTV Silicone
Rubber Coatings as a Function ofFiller Level, IEEE Trans. Eleetr. Insul.,
27(6):1065 (1992).
10. C. L. Lee and G. R. Homan, Silicone Protective Coatings for High Voltage
Insulators, Annua/ Report (81 CHI668-3) IEEE CEIDP Conf., 1981, p. 435.
11. J. L. Fritz and M. J. Owen, Hydrophobie Recovery of Plasma-Treated
Polydimethylsiloxane, J. Adhesion, 54:33 (1995).
12. J. R. Hollahan and G. L. Carlson, Hydroxylation ofPolymethylsiloxane Surfaces by
Oxidizing Plasmas, J. Appl. Polym. Sei., 14:2499 (1970).
13. J. J. Kennan, Y. A. Peters, D. E. Swarthout, M. J. Owen, A. Namkanisom and M. K.
Chaudhury, accepted by J. Biomed Mater. Res.
106
SYNTHESIS OF BLOCK AND GRAFT COPOLYMERS
CONTAINING LIQUID CRYSTALLINE SEGMENTS
Allton S. Gomes, Mauricio R. Pinto, and Celton A. Barbosa
Instituto de Macromoleculas Professara Eloisa Mano - UFRJ

PO.Box 68525, 21945-970 Rio de Janeiro- RJ- Brasil
INTRODUCTION
Block and graft copolymers are interesting state of matter in respect to their
morphologies, while the liquid crystalline state contribute with unique thermal scientific and
and flow properties. The combination of these different states of matter has been allowed
many technological attributes to the obtained materials. If a system is composed by
segregated amorphous and side chain liquid crystalline segments, some desirable and eligible
non-LC characteristics can be originate from the non-LC moieties without critical
disturbance ofthe mesomorphic properties ofthe LC counterparts. For example: mechanical
strength and stiffness, film forming and compatibilizing aid. In this way, the liquid crystalline
state can be physically supported by a stiff and resilient film. Several relevant and recent
methodologies of synthesis have been worked up: (i) polymer-analogaus reaction of AB
type prepolymers (Adams et al., 1994; Arnold et al., 1994); () ionic living block
copolymerization between conventional and LC monomers and organametallic catalyzed
living insertion polymerization (Bohnert and Finkelmann, 1994; Yamada et al., 1995) and
(i) the use ofmacromonomer and macroinitiator systems (Pugh and Percec, 1986; Chiellini
and Galli, 1994). Our synthetic goal to the synthesis ofblock and graft copolymers are based
on:
(1) radical polymerization of a liquid crystalline acrylate monomer (LC monomer) in the
presence poly(ethylene-co-vinyl acetate) functionalized with thiol groups as macrotransfer
agent;
(2) chemical modification ofpoly(styrene-b-acrylic acid), ionomers and t-butyl ester derived
therefrom by reactive low molecular weight liquid crystals and,
(3) radical block copolymerization between styrene and a LC monomer by INIFERTER
techniques.
The chemical routes used in these proposed methodologies are outlined in Scheme 1-3.
The synthetic approach used for grafting the LC monomer, 4-phenylazophenyl 4-(4-
propenoyloxy-butoxy)benzoate (LCM), onto EVA copolymer samples was based on the use

of a macrotransfer agent (EVA-SH) obtained by the condensation of 2-mercaptoacetic acid
with totally hydrolyzed EVA copolymer, Scheme I. Grafring was performed at LC
monomer/EVA-SH mass ratio of IO, 5, 2 and I in the feed and using AIBN as radical
initiator. The grafring degree, i.e., the fraction of LC polymer in the grafr copolymer, was
deterrnined by eiemental analysis and ranged from ca. 5-300/o (Tab. I). These low values
were due to easy radical transfer reaction to monomer, which is competitive with radical
transfer reaction to EVA-SH matrix, since azo compounds react with free radicals. In these
reaction low quantity of LC homopolymer fractions were obtained and they were efficiently
removed from the copolymer sample by successive solubilization in bot toluene and
precipitation on cooling. The LC homopolymer has good solubility in cold toluene.
Scbeme 1
Table 1. Reaction feed composition and yelds ofthe grafr copolymerization

ofthe LC monomer onto EVAL-SH (8.8 x 10'3 wt.-%).
RunI I03[SH]/ Recovered Recovered Copolymer

[LCM]2 LCM LChomop. fraction
(Wt.-%) (Wt.-%) (Wt.-%)
I 39,1 49,0 5,6 45,4
2 19,5 57,9 3,8 38,3
3 7,8 65,3 4,9 29,8
4 3,9 56,1 15,0 28,9
homop. 40,2 56,8
1Polymerizations were carried out at 80C, i. vac., for 48 h using 2 m1 oftoluene per
gram of monomer and 1,5 mol-% of AIBN with respect to the LC monomer quantity.
2Molar ratio. Initial [SH] was obtained from iodometric analysis.
The DSC analysis of a pure LC homopolymer sample properly synthesized showed two
enantiotropic transitions, which were assigned as K ~ N B I transitions and were
confirmed by cross polarized light microscopy observations (Fig. 1). The DSC curves of the
grafr copolymers samples showed only the polyethylene melt and crystallization transitions
108
t
tw
80 100 120 140 160 180

Tempersture in oc
Figure 1. DSC curves of the poly(4-phenylazophenyl 4-(4-propenoyloxy-butoxy)benzoate): (a) 3rd heating
and (b) 3rd cooling scans.
./'.\
-----
. _ ..... ~ '- (a)
...... ---- -
(b)
t (c)
Iw ""-----
"''. (d)
.._. -----
50 100 150 200
Temperaturein C
Figure 2. DSC curves ofthe copolymer samples: (a) EVAL-SH, (b) copolymer 1, (c) 2, (d) 3 and (e) 4. For
each sarnple the upper curve is related to the 3rd heating scan and the Jower one to the 3'd cooling scan.
due to the low runount of LC segments statistically distributed in the EVA chain (Fig. 2).
The enthalpy ofthe crystallization process had a straight-line relationship with composition.
In a different route, block copolymers containing amorphous polystyrene and mesogenic
acrylic segments (based on biphenyl mesogenic unit as a model for liquid crystalline units)
were produced by chemical modification of block copolymer precursors and using low
molecular weight liquid crystals with reactive end groups - LMWLCs, Scheme 2.
Poly(styrene-b-t-butyl acrylate) (I) was synthesized by living anionic block copolymerization
technique, poly(styrene-b-acrylic acid) (II) and ionomers (III) were obtained therefrom.
Poly(styrene-b-t-butyl acrylate) (I) was submitted to transesterification with 4-(4-
hydroxy-butoxy)biphenyl and 4-(4-acetoxy-butoxy)biphenyl catalyzed by organotitanium
under drastic reaction conditions, otherwise it was catalyzed by p-toluenesulfonic acid under
109
Table 2. Degree of substitution obtained from UV quantitative analysis of
chemically modified poly(styrene-b-t-butil acrylate) by 4-(4-hid.roxy-butoxy)-
biphenyl and 4-(4-acetoxy-butoxy)-biphenyl.
Reactive groups: Method Degree of substitution 1

(%)
polymer/LMWLC
-CO:zt.Bu l-OH Ti(n-BuO)J200C 28,6
-CO:zt.Bu 1-0Ac Ti(n-BuO)J200C crosslinked
-CO:zt.Bu l-OH TsOH/100C 7,8
1Mass ratio beween initial acrylic acid mer content and final acrylic ester content
Schemel
1) Buli
2) t-Butyl acrylate
WIA
..
(II)
Z,-(C~),o-OQ
(I)
()
Ar20/2000CITi(OBu) 4
Z,.-(C~),o-00
6
-E CH2CH)xfCH2TH ~CH2TH X
C02H C02
I
(CH 2) 40
condensation catalyst ~,
~
Z,.-(C~),o-OQ
(I)
HMPA/900C
dioxane reflux. The former reaction gave better incorporation degree, as indicated in Tab. 2,
although some high molecular weight material was achieved, due to crosslinking reactions.
Poly(styrene-b-acrylic acid) (II) was submitted to esterification with 4-(4-hyd.roxy-
butoxy)biphenyl promoted by DCC!Pyridine, Ar3P/Et02C-N=N-C02Et) (Mitsunobu
condensation agent) and catalyzed by organotitanium under drastic reaction conditions. The
results are summarized in Table 3. The Mitsunobu system are something less effective as the
traditional DCC/Py one. The former system is highly reactive, the reaction took place in just
a few minutes (as depicted by observation of gas and heat evolution). In this way, the
contact between reactants was not effective, hence the reaction was controlled by diffusional
110
factors. Both reactions showed an increase in molecular weight in relation to the expected
value due to inter and intramolecular carboxylic anhydride linkage formation. The reaction
conducted at drastic conditions in presence of organotitanium catalyst underwent to cross
linking reactions.

chernically modified poly(styrene-b-acrylic acid) by 4-(4-hidroxy-butoxy)-
biphenyl.
Method Degree ofsubstitution (%)

DCC/Py 25,2
Ar3P/ (Et02CN=)2 16,0
Ti(n-BuO)J200C crosslinked
1Mass ratio between initial acrylic acid mer content and final acrylic esther content in
the block copolymer sample.
Poly(styrene-b-acrylic salts) (III) and poly(lithium acrylate) (previously synthesized for

comparison of reactivity) were alkylated by LMWLCs with easy leaving end groups in
HPMA. Except for the Bll4N' ionomer all runs were initially heterogeneous, however they
became homogeneous as the alkylation proceeded. Although the homopolymer has a higher
molecular weight in relation to the block copolymer ionomers, it showed to be slightly more
reactive. This can be explain by the fact that it is an atatic matrix and it showed more
solubility in HMPA than the others. If the block copolymer ionomers undergo to rnicellar
structures formation in solution (or in suspension), probably would result in low reactants
difusibility, and hence lower reactivity. The Lt cation showed better results than the others.
As it is a small cation with high charge density, consequently it is weil solvated, which
enhance the nucleophilicity of the carboxylate anion. On the other hand, larger cations are
more close to the carboxylate ions as they are less solvatable, in this way, the nucleophile is
less reactive. Another problern which comes from the use oflarge cations is the possibility of
formation of aggregates, which frustrates the contact of the reactants. The n-Bll4N' cation
showed medium conversions due to its intermediate polarizability, as it is a bulk organic
cation, it can be weil solvated by organic solvents but still remains somewhat interacted with
the carboxylate anions. The tosyl as leaving group in the LMWLCs showed slightly better
results than the bromine one.
DSC curves of the modified polymers showed only two glass transitions. One near
105C corresponds to the polystyrene segments, while the other, which oscillates with the
degree of substitution between 40 and 60C correspond to the acrylic segments as depicted
inFig. 3.
Block copolymerization between styrene and 4-biphenyl 4-(4-propenoyloxy-
butoxy)benzoate was achieved by INIFERTER techniques, Scheme 3. Thiuram terminated
polystyrene was synthesized by thermal polymerization of styrene in the presence of N,N'-
thetramethylthiuram-disulfide (TMTD).
The functionality ofthe telechelic polystyrene was measured from integration ofthe 1H-
NMR signals at 3.1-3.6ppm (unique to the C:fu-N protons present in the terminal groups)
and at 6.2-6.8ppm in conjunction with the molecular weight values obtained from SEC
analysis, which gave approximately 1.8. The block copolymer was obtained from UV
radiation of the LC monomer in the presence of the telechelic polystyrene in THF. SEC
analysis showed an increase in molecular weight of the block copolymer in relation to the
polystyrene precursor, Fig. 4. The peak of the copolymer sample was bimodal. SEC
fractionating gave a LC homopolymer fraction, which had higher molecular weight, and a
block copolymer fraction, which had lower one. The relative amount of these fractions was
111
chemically modified poly(styrene-b-acrylic sahs) by 4-(4-bromo-butoxy)-
biphenyl and 4-(4-tosyl-butoxy)-biphenyl.
Counter-ion Displaced group Degree of substitution (%)

poly(Lt acrylate) Br 33,7
u Br- 24,4
Lt Tso- 30,2
Na+ Br- 15,6
K+ Tso- 2,8
es Br- 5,6
es Tso- 4,6
n-Bu..W Br- 17,9
Scbeme3
c?;
V
_("---Me__IIK:_~_:_*.:..-.
6QOCf20h
uv
112
(a)
(b)
(c)
200 600
Temperaturein C
Figure 5. DTGA curves (20C/rnin) of (a) thiurarn terminated polystyrene (b) LC homopolymer and (c)
block copolymer sarnples
i
0
.."-- ...........
V ,_,.
--- --"\,----
~
c:
UJ
40 80 120 100 200
Temperature in C
Figure 6. DSC curves (20C/min.) of(a) LC homopolymer and (b) block copolymer. Fulllines are related to
the 3n1 heating scan and the dotted lines to the 3n1 cooling scan.
113
t
0
"'0
c:
w
40 80 120
Temperaturein C
Figure 3. 3nl DSC heating curve of the poly(styrene-b-lithium acrylate) modified by 4-(4-bromo-butoxy)-
biphenyl, heating ratio of20C/min.
(b)
.
I .
. I \
\
(a)
I
\
- I ............ ~.
20
Retention time in min.

Figure 4. SEC curves of (a) thiuram terminated polystyrene and (b) block copolymer sample obtained
therefrom.
respectively 1:5. The block copolymer fraction 13 C-NMR spectrum showed the presence of a
peak at 42ppm, which was assigned to the C.H3-N present in the thiuram end groups. The
composition was determined by 1H-NMR spectrum, which showed a molar ratio between
114
polystyrene and LC segments of 1:9. This value was expected since the mass ratio between
polystyrene and LC monomer in the reaction feed was 1:10, and some unreacted polystyrene
precursor was recovered. Thermal properties ofthe polystyrene precursor, LC homopolymer
and block copolymer samples were determined by DTGA and DSC analysis. The
comparison of the DTGA curves of these samples indicated actual block copolymerization,
Fig. 5. The DSC curves ofthe LC homopolymer and block copolymer sample were similar.
Three enantiotropic transitions were assigned in conjunction with cross polarized light
microscopy observations, as g ~ S ~ N ~ I transitions, Fig. 6. The slight difference
between the homo and copolymer curves was attributed to differences in molecular weight
of the LC segments. The Tg of the polystyrene segments was overlapped by the K ~ S
liquid crystalline transition. Preliminary study showed the block copolymerization between
thiuram terminated polystyrene and the same LC monomer can be attained by thermal
treatment ofthe reaction media.
ACKNOWLEDGMENTS
Financial support from CNPq, CAPES and FINEP is gratefully acknowledged.
REFERENCES
Adams , J., Snger, J., Tefehne, C., and Gronski, W., 1994, Liquid-crystalline/amorphous dib1ock and
trib1ock copo1ymers- influence of morpho1ogy and microstructure on phase behaviour, Macromol.
Rapid Commun., 15: 879-886.
Arno1d, M., Poser, S., Fischer, H., and Utschick, W., 1994, Liquid-crystalline side chain b1ock copo1ymers-
synthesis, morpho1ogy and LC behaviour, Macromol. Rapid Commun., 15: 487-496.
Bohnert, R, and Finkehnann H., 1994, Liquid-crystal1ine side-chain AB b1ock copo1ymers by direct anionic
po1ymerization ofa mesogenic methacry1ate, Macromol. Chem. Phys., 195: 689-700.
Yamada, M., lguchi, T., Hirao, A., Nakahama, S., and Watanabe, J.,1995, Synthesis of side-chain liquid-
crystalline homopo1ymers and block copolymers with well-defined structures by living anionic
polymerization and their thermotropic phase behaviour, Macromolecules, 28: 50-58.
Pugh, C., and Percec., V., 1986, Graft copolymers containing thermotropic side-chain liquid crystalline
backbones, ACS Polym. Prepr., 27(1): 366-368.
Chiellini, E., and Galli, G., 1994, Hibrid thermotropic liquid-crystalline block copolymers, Macromol.
Symp., 77: 349-358.
115
RECENT DEVELOPMENT OF CHEMICAL RESISTANT
STYRENIC POLYMERS FOR THE REFRIGERATOR
Kyung H. Ahn 1 and Sang S. Woo 2
1R&D Center, Chemieals Division

Cheil Industries Ine.
332-2 Goehun-Dong, Euiwang-Shi
Kyoungki-Do, 437-010 Korea
2R&D Center
Samsung General Chemieals Co.,Ltd.
103-6 Moonji-Dong, Yusong-Gu
Taejeon, 305-380 Korea
INTRODUCTION
Environmental issue on ozone layer destruetion is regulating the use of CFC 11, whieh
is known as a Freon gas, depending on the eeonomie Ievel of eaeh country. All the
materials and the proeesses using CFC 11 have been destined for ehange. Refrigerator is an
example. As a blowing agent, CFC 11 has long been used. Reeently HCFC-141 b and
eyclopentane are being used as alternatives. However, the former deteriorates the
meehanieal properties of eurrent plasties and Iiners in the refrigerator, while the latter does
not harm the material but very explosive. Novel material is under development, but still not
eommereial. Feasible way is to inerease the ehemieal resistanee of the plastie parts, whieh
is mostly made of aerylonitrile-butadiene-styrene (ABS) resin, enough toresist the ehemieal
attaek of HCFC-141 b. In this paper, the ehange of blowing agents and new teehnologies
to enhanee the ehemieal resistanee of styrenie polymers will be presented. First, historieal
perspectives on the environmental issues will be summarized. The requirements of styrenie
polymers for the new blowing agents will also be mentioned. And then, the key
teehnologies to enhanee the ehemieal resistanee of ABS resin, and the aeeompaning
problems as weil as the way to evaluate the ehemieal resistanee of a plastie will be diseribed.
Finally, future prospeets for the styrenie polymers in relation to the refrigerator industry will
be mentioned.
Science and Technology of Polymersand Advanced Materials

HISTORICAL PERSPECTIVES
Environmental Issues 1' 2
The issue of the ozone layer destruction did not attract significant attention until 1974
when F.S.Rowland and M.Molina, who later recieved the 199S Nobel Prize in Chernistry
due to thls contribution, proposed that CFCs would photodissociate when exposed to UV
radiation to yield atornic chlorine, whlch would eventually destroy ozone layers. Toward
the end of 198S members of the British Antarctic Survey team reported that the quantity of
ozone in the stratosphere over the Antarctic was dropping by as much as SO% just after the
winter season. This, and the earlier work done by Rowland and Molina, led the United
Nations Environmental Program (UNEP) in 198S to organize the Vienna Convention on the
Protection of the Ozone Layer. And in 198 7, thls resulted in the signing of the Montreal
Protocol on Substauces that Deplete the Ozone Layer, which comrnitted every signatory
state to reduce its use of certain CFCs by SO% of their Ievel of use in 1986 by 1999. Three
years later, at a meeting in London, the Montreal Protocol was strengthened in a number of
ways. The use of many CFCs and halons was to be eliminated by the turn of the century,
and new controls were to be introduced on a variety of other ozone-depleting substances.
During 1992, researchers discovered ozone Iosses ofup to 20% in the Northern Hernisphere
and a maximum depletion over Russia ofbetween 40 and 4S% below normal for a few days.
Moreover, the danger of ozone layer depletion became clear: The incidence of skin cancer,
cataracts, and infectious diseases among humans would increase; agricultural yields of
certain crops would fall; many manufacturing materials would weaken prematurely; and
ecosystems would destabilize.
In 1992, in the Copenhagen meeting, most parties agreed that the CFCs should be
eliminated by 1 January 1996. However, this agreement does not mean that CFCs be extict
withln a couple of years because some production continues for two reasons. Some
essential applications for CFCs for which no practical substitutes exist are the exceptions.
Their use as propellants in anti-asthma inhalers is one example. Another reason is that
parties in the developed world can continue to produce CFCs after 1996, as long as the
production is used to meet the basic domestic needs of developing countries during their
grace period, that is until2006.
The most frequently identified alternatives for CFCs are the hydrochlorofluorocarbon
(HCFC) farnily of chemicals. These substances are now being produced and can replace
CFCs in many applications. Nevertheless, HCFCs also contain some chlorine and therefore
destroy some stratospheric ozone. The ozone depletion potential (ODP) for HCHC-141b
is 0.1, while ODP for CFC11 is 1.0 and the one for halon is as high as 10. And HCFC-
141b has a global warming potential (GWP) 1800 timesthat ofC02. Forthis reason, it is
generally accepted that HCFCs are not the final and definitive solution to the CFC problems.
And the parties agreed to reduce their use ofHCFCs by 3S% by 2004, 6S% by 2010, 90%
by 201S, and 100% by 2030. In the United States, HCFC-141b is scheduled tobe phased
out by the year 2004, under the Clean Air Act. Although there are problems associated
with the use of HCFCs and they will be faded out withln tens of years depending on the
situation of each country, they are, at present, most attractive alternatives and widely used.
Trends in Blowing Agents 3
While CFC 11 has dominantly been used as a blowing agent in refrigerator industry,
situation becomes changed according to the reasons explained above. There seems to be
two main streams for the alternatives of CFC 11; HCFC-141 b and cyclopentane. The
former is regarded as quite a good alternative but still depletes the ozone layer, while the
118
latter is clean but dangerous to use due to its flammability. The nature of chemical attack
on ABS resins is quite different. HCFC-141b severely deteriorates the common ABS,
while cyclopentane does little. In addition, new technology which will replace the
traditional or transitional substances uses the hydrocarbons. As hydrocarbons as weil as
cyclopentane deteriorate ABS resins little, chemical resistance of styrenic polymers is
focused on the chemical attack of HCFC-141 b. In the next section, the characteristics of
ABS resins resistant to HCFC-141 b will be described.
ABS FOR HCFC-141b
As ABS consists of dispersed rubber phase and continous SAN phase, chemical
resistance of ABS resin can be enhanced by controlling either phase, that is, by modifying
the rubber phase or by increasing AN content in the matrix SAN phase. Rubber phase can
be modified through the change of morphology, grafr ratio, rubber size, and so on, however,
acryl rubber is introduced in most cases. More precesely, SAN grafred acryl rubber is
compounded with free SAN, either solely or combined with SAN grafred butadiene rubber.
Another method is to increase AN content of the matrix SAN. This signi:ficantly enhances
the chemical resistance to HCFC-14lb, however, there are some difficulties. As the
polymerization of high AN SAN is non-azeotropic and highly exothermic, reaction control is
very important to get the high quality products. In addition, rubber particle agglomeration
occurs afrer processing due to the mismatch of AN content between the grafred SAN and
the matrix SAN, which might cause some quality problems. From the practical point of
view, most commercial grades use either or both of the methods, however, the latter causes
more interesting phenomena and attracts more attention. Technical difficulties followed by
the enhancement ofchemical resistance of ABS by increasing AN content ofthe matrix SAN
will be explained in more detail.
Non-Azeotropic Reaction
Since monomers have different reactivity ratios, they tend to enter the polymer chain
during the propagation reaction at different rates, and the polymer being formed at any one
instant does not necessarily have to be of the same composition as the unreacted monomer
mixture. By definition, the azeotropic composition is the composition at the point where
the composition of polymer being formed is the same as that of the unreacted monomer
mixture. If the relation between monomer composition of the feed and that of the
copolymer is expressed as in Figure 1, the azeotropic point is the one where the composition
curve crosses the diagonalline. At the azeotropic point, the composition of the copolymer
and the monomer feed are identical. For monomer compositions to the left of the eross-
over point, acrylonitrile will enter the copolymer faster than styrene and for the monomer
compositions to the right of the eross-over point, styrene will enter the copolymer faster
than acrylonitrile. The azeotropic composition of SAN is about 62 mol% styrene and 3 8
mol% acrylonitrile, or 76 wt% styrene and 24 wt% acrylonitrile.
In the production of ABS resin, it is important that the composition of the copolymer
be uniform. If not, physical properties of ABS resins such as tensile and impact strength
will be adversely affected. At any feed composition other than the azeotropic point, as in
high AN SAN copolymer, the composition of the copolymer formed depends on the initial
monomer composition and the degree of conversion. And one can obtain the SAN
copolymer having uniform composition (a) by keeping the feed composition at the
azeotropic point; (b) by keeping the composition of the monomer rnixture in the reactor
almost the same as that in the monomer feed; or (c) by lirniting the conversion of the
119
reaction. In order to get the homogeneous composition ofhigh AN SAN, it is necessary to
fully understand the non-azeotropic nature of the polymerization of high AN SAN, and
carefully control the reaction.
1.0
~
<r
w
::!l
g 0.8
()
~
~
0.6 -;
~

0.4
~
~ /
/"'-------- ------
~
.... 0.2
<r
d
::!l
I
0.0
0.0 0.2 0.4 0.6 0.8 1.0
MOL FRACTION OF ACRYLONITRILE IN MONCMER FEED MIXT\J<E
Figure l. SAN copolymer composition depending on the mol fraction of acrylonitrile in monomer feed
rnixture. The azeotropic composition is 38 mol% or 24 wt% acrylonitrile. To reach high AN content, feed
composition needs tobe higher, and careful reaction control is necessary.
Rubber Partiefe Agglomeration 4 5 6 7 8
Rubber particle agglomeration in rubber dispersed thermoplastics such as ABS has

often been reported by many research groups. It is observed when the sample experiences
sufficient thermal history, and is known to be caused by various molecular structures: !arge
compositional acrylonitrile mismatch between grafted and matrix SAN, insufficient or too
high graft ratio, high rubber Ievel, high matrix SAN molecular weight, small rubber size, and
so on. This phenomenon is easily detected by transmission electron microscopy (TEM) as
shown in Figure 2, and is related to the minimum of the viscoelastic function such as storage
modulus in the second plateau region. This plateau arises from the interaction between the
particles and is strongly correlated with the state of particle dispersions. For example,
when the graft ratio is low, the rubber particles are not sufficiently covered by grafted SAN,
and there may be some space on the surface of the rubber particles which is devoid of
grafted SAN, leading to agglomeration and poor dispersion. As the graft ratio becomes
high, the entropic repulsion between neighboring particles becomes stronger, resulting in the
uniform dispersion of rubber particles in the SAN matrix. When the graft ratio increases
further, as the grafted chains are stretched more and more, the matrix chains are
progressively expelled from the grafted layers, leading to agglomeration and poor dispersion
again. When the difference between AN% of grafted and matrix SAN is small, storage
modulus in the second plateau region has the smallest value, which is obtained for the case
that the rubber particles disperse uniformly. Storage modulus becomes higher with
increasing the difference of AN% resulting from the agglomeration of rubber particles. As
it is more probable that the AN mismatch becomes !arge for the high AN ABS even though
the AN content of grafted SAN can also be raised according to the increase of AN content
120
of matrix SAN, the problern of rubber particle agglomeration can often be observed in the
ABS samples in which chemical resistance is enhanced by increasing the AN content. From
the theoretical point ofview, this phenomenon is explained from the thermodynamic theory 7
as resulting from the thermodynamic incompatibility between the components, and can also
explained from the mean field theory 8 as resulting from the balance between the attractive
and repulsive potentials.
Figure 2. Digitalized TEM pictures of ABS resins. Sampies are taken after processing. Magnification factor
is 5000. AN mismatch issmall (left) and !arge (right) respectively.
EVALUATION OF CHEMICAL RESISTAN CE 9 10 11 12 13
There are some test methods for resistance ofplastics to chemical reagents. However,
the limitations of the results obtained from these test methods should be recognized. The
choice of types and concentrations of reagents, duration of immersion, temperature of the
test, and the properties to be reported are necessarily arbitrary. The specification of these
conditions provides a basis for standardization and serves as a guide to investigators wishing
to compare the relative resistance of various plastics to typical chemical reagents.
Correlation of test results with the actual performance is necessarily dependent upon the
similarity between the testing and end-use condition. In this sense, the chemical resistance
of plastics for refrigerator is very hard to evaluate a priori in the laboratory. As the plastic
parts in the refrigerator contacting blowing agents are highly strained during the thermo-
forming process, the chemical resistance should be evaluated under the stress. Therefore,
the Environmental Stress Crack Resistance (ESCR) should be measured. For polyethylene
pipe, standard test method is issued under the designation ASTM F1248. In this test, a
121
ring specimen of the polyethylene pipe, having a controlled imperfection at one location, is
exposed at an elvated temperature to the action of a surface active agent while compressed
to deformation between parallel plates, and the elapsed time to observation of a stress crack
failure in the specimen is recorded. Likewise, similar test methods to evaluate the ESCR of
polyethylene and styrenic polymers are applied depending on each situation.
Testpiece
thickness (2mm)
a (250mm)
Figure 3. Schematic diagram ofthe ESCR test. The samples ofthe size 2mmx35mmxl20mm areloaded on
the apparatus and put in the gas chamber for 24 hours at room temperature under the saturated vapor of the
corresponding chemical such as HCFC-14lb. Critical strain is calculated from the distance of the crack
generation point.
There is no standard method to evaluate the ESCR of ABS resins to HCFC-14Ib. It

is presumed that the sample experience high stress and severe chemical attack. If the
samples of the size 2mmx35mmx 120mm are loaded on the apparatus of one quarter of the
ellipsoidal shape as in Figure 3 and put in the gas chamber for 24 hours under the saturated
vapor of HCFC-14lb, critical strain can be calculated from the distance of the crack
generation point. If there is no crack, critical strain is 2.0, if not, it is between 0 and 2.0;
the higher the more resistant to chemical attack. As a rule, if the critical strain is !arger
than 0.8, it is usable, if !arger than 0.5, it is conditionally usable, if !arger than 0.3, it is not
recommended, and below 0.3, it cannot be used. Though this is not a standard method, it
discriminates the chemical resistance of ABS resins for refrigerator. Ifthe common grades
of ABS are testedunder the HCFC-14lb environment, they deteriorate quite fast, and the
critical strain decreases fast and then keeps the constant low value, 0.3 for example.
However, ifthe chemical resistant ABS which is made either by raising the AN content or by
applying the acryl rubber, it rarely deteriorates, and the critical strain keeps 2.0 for a long
time.
CONCLUDING REMARKS
Recent development of chemical resistant styrenic polymers has been reviewed. Due
to the environemental issues, the blowing agents as weil as refrigerants are changing. As
the HCFCs which seem to be the most attractive alternatives at present are transitional
substances, the requirements of the plastics for the refrigerator are destined to change.
Styrenic polymers will follow the same way. High AN ABS shows many interesting
phenomena as weil as good chemical resistance to HCFC-141b. Difficulties in controlling
122
the polymerization reaction and the rubber particle agglomeration phenomena are the
examples. Recently the latter has attracted much attention in both experiments and theories.
More thorough understanding is anticipated according to the advances in polymer physics.
Evaluation method of the chemical resistance under stress environment has also been
explained.
REFERENCES
I. http://www.unep.org/unep/secretar/ozone/
2. http://sedac.ciesin.org/ozone/
3. http://www.greenpeace. orgl-ozone/
4. Y.Aoki and K.Nakayama, Dynamic viscoelastic properties of ABS polymers in the molten
state III. Effects ofthe composition ofgrafted AS copolymer, J.Soc.Rheol.Jpn. 9: 39
(1981).
5. M.Bertin, G.Marin, and J.Montfort, Viscoelastic properties ofacrylonitrile-butadiene-
styrene (ABS) polymers in the molten state, Polym.Eng.Sci. 35(17): 1394 (1995).
6. Y.Aoki, Dynamic viscoelastic properties of ABS polymers in the molten state. 5. Effect of
grafring degree, Macromolecules 20: 2208 (1987).
7. M.C.O.Chang and R.L.Nemeth, Rubber particle agglomeration phenomena in
acrylonitrile-butadiene-styrene (ABS) polymers. II. Rubber particle agglomeration
elucidated by a thermodynamic theory, J.Polym.Sci. B: Polym.Phys. 35: 553 (1997).
8. R.Hasegawa, Y.Aoki, and M.Doi, Optimum graft density for dispersing particles in
polymer melts, Macromolecules 29: 6656 (1996).
9. ASTM D 543: Standardtest method for resistance of plastics to chemical reagents.
10. ASTM Fl248: Standardtest method for determination ofenvironmental stress crack
resistance (ESCR) ofpolyethylene pipe.
11. T.J.Stolki, Environmental stress and strain testing, SPE Journal, Oct. 48 (1967).
12. R.R.Dixon, Environmental stress testing of ABS materials, SPE-ANTEC 12: :XXIX-2
(1966).
13. C.J.Singleton, E.Roche, and P.H.Geil, Environmental stress cracking ofpolyethylene,
J.Appl.Polym.Sci. 21: 2319 (1977).
123
SIMULATIONS ON TBERMOPLASTIC ELASTO:MERS
FROM POLYPROPYLENE
Tarek M. Madkour* and James E. Mark**
DepartrnentofCherrristry,and
the Polymer Research Center
The University of Cincinnati
Cincinnati, OH 45221-0172
ABSTRACT
Computer simulations have been carried out to investigate sequence lengths, and
sequence-length distributions in Stereoregular polymers. Simulations were also used to
investigate the development of reinforcing crystallites in thermoplastic elastomers. New
types of stereoblock polypropylene which have been prepared from some metallocene
catalytsts and which function as thermoplastic elastomers through controlled crystallization
are of particular interest in this regard. While it is widely believed that the sequence
distributions in these polymers is of primary importance in their crystallization, no adequate
theory is currently available. In the present investigation, the Windle approach with Monte
Carlo methods was used to simulate one hundred copolymeric chains in order to search for
crystallizable sequence matches in these polymers. Based on the amounts of crystallinity
reported for these polymers at various feed compositions, estimates were made of melting
points, interfacial free energies, standard free energies of fusion, and Young's moduli at
small extensions. The approach is also useful for predicting the sizes of the crystallites and
the minimum sequence lengths required for crystallization.
* Fulbright Senior Scholar on a leave of absence from the Department of Chemistry, Faculty of
Science, Helwan University, Ain-Helwan, Egypt 11795
** jem@ucbeh.san.uc.edu, http://jemcom.crs.uc.edu/
Science and Technology oj Polymers and Advanced Materials

INTRODUCTION
Isotactic polypropylene, consisting of regular arrangements of stereocenters, is a

crystalline thermoplastic material with a melting point of nearly 187.7 C, whereas atactic
(stereorandom) polypropylene is an amorphaus gum elastomer. 12 Natta, 3 however,
reported the polymerization of a rubbery polypropylene which exhibits elastomeric properties
attributed to a stereoblock rnicrostructure. Blocks of crystallizable isotactic stereosequences
and amorphaus atactic sequences are the basis for this thermoplastic elastomeric material.
These elastomers, unlike vulcanized rubbers, soften and flow upon heating.
A number of research groups 14 -7 reported a new strategy for the dynamic stereocontrol
of the polymerization of a-olefins. They described a polymerization catalyst, a type of
metallocene, which was designed to isomerize between an achiral (meso-like) and chiral (rac-
like) coordination geometries in order to produce atactic-isotactic Stereoblock polypropylene,
with the interesting properties of a thermoplastic elastomer. The behavior of the catalyst has
been interpreted in terms of its isomerization through rotations of the unbridged 1t ligands.
Depending on the reaction conditions, a wide distribution of the isotactic and atactic
sequences is obtained, and this Ieads to polymers with a wide variety of elastomeric
properties.
The rnicrostructure of the produced polypropylene is considered tobe built up of blocks
of atactic and isotactic sequences, with the latter being of sufficient length to cocrystallize
with similar sequences on the other polymeric chains. The rate of rotation of the catalyst
ligands was shown using dynarnic NMR to be quite rapid at room temperature and in fact,
this process could not be frozen out even at -100 C.1 A phenyl substituent on the indene
Iigand could in fact 1 inhibit the rate of Iigand rotation such that it would be slower than that
of monomer insertion yet faster than the time required to construct a single polymer chain.
This mechanism produces the long atactic and isotactic stereosequences. The high melting
points (Tm- 137 C) of stereoblock polypropylene with low percentages of isotactic meso
pentads ( 18 % ::::; [ mmmm] ::::; 73 %) does support a blocky structure for these materials. 8 9
Whole polymers produced using the metallocene catalysts consist of several fractions
that can be separated using a series of boiling solvents. The properties of the various
fractions vary from a serni-crystalline plastic (with a yield point) for the highest isotactic
content, otherwise referred to as the heptane-insoluble, to a weak gum elastomer with almost
no isotactic content for the ether-soluble fraction. The hexane-soluble or heptane-soluble
fraction is elastomeric in nature, which indicates the presence of stereoblock isotactic
sequences among the atactic sequences. The isotactic pentad content [mmmm] increases with
each successive fraction to reach ca. 70 % for the hexane-insoluble fractions.
The distribution of block sizes also affects the mechanical properties of the Stereoblock
polypropylene. Natta3 reported that whereas mixtures of amorphaus and isotactic polymers
having an overall crystallinity value up to 25 % (with very low initial elastic modulus),
stereoblock polypropylene with the same % crystallinity shows good elastomeric properties
and reaches reversible elongations of up to 200 %. Stress-strain isotherms 10 of Stereoblock
polypropylene indicate that such polymers have low initial elastic moduli, reversible
elongations, and relatively high tensile strengths. The observation that creep is small in these
polymers could be attributed to the isotactic crystallites acting as crosslinks, which oppose
the irrevesible flow of the network chains. 310
126
The productivity of the catalyst and the molecular weight of the polymers produced were
found to be sensitive to the reaction conditions. 1' 11 lncrease in the propylene pressure and
decrease in the polymerization temperature usually lead to an increase in molecular weight,
probably because of increase in monomer concentration and slowing of the ligand rotations.
High molecular weights could also be obtained using some metallocenes, 7 a possible
consequence of the high regioselectivity. 12 However, molecular weight of the polypropylene
produced had lower values than those produced using industrial catalysts. 13 This is probably
due to an increased rate of chain termination andlor a decreased rate of olefin insertion. 14
While polyolefines obtained with heterogeneaus catalysts have large polydispersities X
of Mw!Mn = 5-10, 15 homogeneaus catalysts produce polymers with polydispersities of
1.5-2.8_1 6 This was predicted using Schultz-Flory statistics 17 for polymers arising from
identical catalyst centers with fixed rates of chain propagation and chain terrnination.
Equilibrium melting points were shown 13 to increase with increasing molecular weight and
narrowing of the molecular weight distributions.
SIMULATION METHODOLOGY
Sequences and Their Distribution
Long Stereoblock polypropylene chains were simulated using Monte Carlo methods so
as to resemble polypropylene chains consisting of blocks of Stereoregular and stereoirregular
chernical structures. The Stereoregular sequences were all of an isotactic nature whereas the
stereoirregular ones were atactic. The multichain arrangements in this case will resemble
stereoblock polypropylene generated using some of the metallocene catalysts. Every
simulated chain was divided into equally long sections and every section consisted of one
isotactic sequence and one atactic sequence. The study of their crystallization was carried out
by fixing the length of the isotactic sequences at fifteen units, thus resembling low-
isotacticity Stereoblock polypropylene. 4 The length of the atactic sequences, however, was
allowed to change from zero units for the first sample to a hundred units for the final sample
with an increment of five units, as illustrated in Figure 1. The stereo-configuration of the
first unit of any given isotactic block, (d) or (!) as defined in the older terminology, was
chosen randomly by comparing a computer-generated random nurober with 0.5. This unit
was then followed by fourteen other polypropylene units of the same configuration.
A value of the replication probability Pr of 0.5 was also used to produce the atactic
sequences that followed the isotactic ones. This value was chosen so as to produce
completely random atactic sequences. Units of the atactic sequences were generated in such a
way that the fraction of the isotactic placements (replication) within the atactic sequences
would equal2 the value chosen for Pr The simulations of the stereochernical structures were
carried out for chains having degrees of polymerization DP of 2,000 units. One hundred
simulated chains were then placed in parallel two-dimensional arrangements to allow for the
search for crystallinity. The present approach parallels that taken earlier for stereoregular
siloxane polymers. 18 Each unit in the chains was given the opportunity tobe involved in
the crystallzation process so long as they occurred in a sequence of a minimum length
suitable for crystallization and were adjacent to other isotactic sequences on neighboring
127
115 ___......... ~""'- h'1...,...... r.E: ....".,.-:;e.-
118 _ _ _ l.if.11: ..._, ot: ::" .. -:- ......
II _. ..:wy... ::.ot.-:-
185
188 ---r.
___ .....
95 . . : 11
~
ot
... :r
~ ..
-1.:.11:: .........::.-..
.:II: .~-"./',.;;I .....,.l ..-:.1'1- :le.":""..e'!.......o'l" ...
..:..,...a.r-:. .......-.:
rvc.~~W~~Jo .r:
1""'P: ...::
98 -=:~~ .JIItN ...... 11"1!.-.or.e. -:w:~~ ... :. ....:...-" ... -
85 - L"" .:. "-1: ,.......~..:..a"rY".e 1"- .:.-."-1.. K
88 ====-:-. _. :ri ....: ...-
-r~
_ __.. ..... '".11:"'1 !'alifVIII
a:-~ :a.:
75 "WH~...... ~ ~
18 =-I ......
I J1lwl-t ._-..~il!olallll ..........:..:
65 .. 1111!.- 1. c..-.-.. :-r.:-:.: ___ .,..,!-".-=..: r. !"
68 - - -..--. ':- -:.. ". .. oll.: ( ..... :+ rfi"r."...:- :.:
55 .:. :-1..--".: J L1 ._ I ... -..~:"""""....
58
45
48
:==~--~..-.~r---:.:.-~.-
....... Jo ......:t 1
r- r.:: (Pul
:1.-...: -:.a, 11-.T1'1. . . ..ot
..,.... .,_-, 1-U:PI---..:
.
35 . . . . . .... lll':la" ":1'-1. I-:-#':.

38 ---.IJ ( .:iLL .:.ri:'I':--- ....Jr."-
-,} {'"...
25
28 :-::=-::::-..,..~=ot::=;;.~"-~.J-=.::~u;:
. =;=~==~~~~-~-r-~=:::1 ~
1
15
Figure 1. Graphical representation of simulated chains of Stereoblock

polypropylene having various section repeat lengths. Black and white squares
represent the Qand 1 Stereoisomers of the units, respectively.
chains. The minimum number of repeat units in a sequence required for crystallization was
taken tobe fourteen. 2 This number corresponds to the thickness of the smallest crystallite
(3.0 nm) detected for the ether-soluble, elastomeric polypropylene of low-range isotacticity.
Isotactic sequences in proper arrangements 19 with neighboring sequences and having
sufficient sequence length would be expected to crystallize. 18 Crystallites formed during
slow crystallization would grow longitudinally until meeting a unit of the other type, and
laterally so long as sequences of the crystallizable component of a minimum sequence length
were available from the amorphous regions.
Modefing of the Block Size
Different stereoblock polypropylene fractions of increasing isotactic block lengths were

also simulated using Monte Carlo methods to model the effect of increasing the isotactic
block length. Every simulated chain was divided into equally long sections and every section
consisted of one isotactic sequence as weil as one atactic sequence. For all the computations
carried out in this case, the increase in the length of the isotactic sequences was done at the
expense of the length of the atactic ones so as to keep the section length constant. 4 An
illustration of this arrangement is shown in Figure 2.
The increase in the isotactic block length will naturally reflect on the values of the
isotactic pentad content [mmmm].
128
115
118
185
.
188
95
98
------------------------------=~
~=====~z....
85
88 -.-.:.:,....
75 ~".....-;.,.
~-- .... ~..

78
65 :~~~~~~~~~~~~~~~~
68 - - - - - - - - - - - - .. r- .....:.-c"'' +:ol,ol""
55 - - - - - - - - - - ..... ~ .:'T'rll :.I .:.I._.
:=======::": .....,. ":-.: . . . ..r.. . ~.

=-
58 - - - - - - - -.. :K.I- ..-.-:.:.. ... 'W'L.. ..
45
48
r.n.
r' ,#': ~ --: :r'r,riV ......... I
======
Ii,)
35 "J...o.:ol.:.. ":-.1 T.l ""TC ...............
38
25
28 v:.rn
":.. ::-.: ......-: .....: :- -: Jwlr fltl ": ......
15 Li-: ......... "111:1....:0.:. .....:-.r""'"~ 1.-1-.:i ..
Figure 2. Degree of crystallinity of the polymers as a function of the isotactic

pentad content [mmmm].
Modeling of Block Size Distribution
In this case, the lengths of the isotactic and atactic blocks were allowed to increase
proportionally, so as to keep the isotactic content at approximately 30 %. Some of the results
are shown in Figure 3. The numbers on the left of the figure refer to the lengths of the
128
68
48
38
25
28
Figure 3. Young's modulus at infinitesimal extension as a function of the
isotactic pentad content.
isoactic blocks in that particular run. Moving upward in the rows corresponds to increasing
the lengths of both the isotactic and the atactic blocks.
129
Modeling of Polydispersity
The effects of polydispersity were also modeled at a constant value of approximately 30

% isotactic content. The average length of 30 isotactic units described above could be
variously achieved, for example by altemating isotactic sequences of 20 and 40 units, for
sequences of 10 and 50 units, or for sequences of 0 and 60 units. This keeps the isotactic
content constant at 30 %, and allows for more realistic comparisons with experimental
results. Naturally, in the case of 0 and 60 units, this would rbe equivalent to an isotactic
block of 60 units for every 200 section repeat units.
Modefing of Molecular Weight'-and Molecular Weight Distribution
In this case, the simulations of the stereochemical structures were carried out for chains
having different degrees of polymerization DP ranging from 100 repeat units in length to
2,000 units so as to permit study of the effects of molecular weight.
The effects of molecular weight distribution was also modeled by assuming
polydispersity values rauging from 1.5 to 2.8. 16 Values of the molecular weight distribution
were chosen for a particular molecular weight of 84,000 g mof 1, which corresponds to the
2,000-unit degree of polymerization. The lengths of the chains for each molecular weight
distribution were simulated using a Gaussian distribution.
Melting Points
The extent to which the melting point of the crystallizable units in a polymer is
depressed by the presence of the other units is given by 17 18
- 1 - - 1- =- __B_ [ln (L) ] (1)

Tm Tom AHu
where T0rn and Trn are the melting points of the pure crystallizable polymer and the polymer
under study, respectively. The melting point of isotactic polypropylenewas determined tobe
187.7 C using extrapolation methods, 4 and AHu is the enthalpy of fusion per mole of
crystallizable units, 8.79 KJ/mol. R is the gas constant, and L is the degree of crystallinity
deterrnined with respect to the number of units with potential for crystallization.
Chain Matehing
Sliding the chains past one another longitudinally to search for the largest possible
nurober of matcheswas done to model annealed samples (searched "S", as opposed to
quenched "Q"). 18 The longitudinal movement of the chains relative to one another, out of
register, approximately models the lateral sorting out of sequences in polymeric chains
during slow crystallization. In sliding the chains by one another in these searches, protruding
sections were relocated from one end of the array to the other so as to keep the nurober of
comparison pairs constant.
130
MODELING RESULTS
Degrees of Crystallinity
Values of the degree of crystallinity of the various simulated samples were determined
by counting the units involved in the melting sequences relative to the total number of units.
The results are shown in Figure 4 as a function of [mmmm]. As expected, the degree of
100
80
--
60
?fl.
..J
40
20
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
[mmmm]
Figure 4. Degree of crystallinity of the polymers as a function of the isotactic
pentad content.
crystallinity increases with [mmmm] as a consequence of the increase in the crystallizable

isotactic content. As expected, the chain-matching process has resulted in a decrease of the
percent crystallinity, because of the artificially high degree of order in the unrealistic
reference state chosen for the start of the simulations. Crystallinity values predicted for the
quenched and searched (annealed) cases are obviously less than those predicted using the
melting point depression relationship and are closer to values determined experimentally .11 1t
should be noted here that for the whole range of [mmmm], some crystallinity is predicted.
This is in marked cantrast to the case of atactic polypropylene which does not show any
signs of crystallinity at all. This crystallinity is the result of the presence of the isotactic
blocks in the stereoblock polypropylene which are capable of segregation and separation
from the amorphaus part of the polymer to form crystallites. These crystallites can act as
crosslinks thus reinforcing the polymer networks and causing the attractive properties of
stereoblock polypropylene first described by Natta. 3
131
Melting Points
Table I presents the melting points of various polymers simulated using different values
of [mmmm]. Column two of the table gives the melting points predicted by eq (1), the
melting point depression relationship, 17 using the total number of units with potential for
crystallization in place of the degrees of crystallinity. The predicted melting points using this
relationship are, in fact, much higher than those determined experimentally. This is readily
explained by the fact that only part of the crystallizable component can actually undergo
crystallization. Using our simulated values of the percent crystallinity determined with
respect to units with potential for crystallization in eq (1) should therefore provide more
reliable predicted melting points. These values are given in columns three and four of the
table for the quenched and annealed (searched) samples, respectively.
Table 1. Melting points of stereoblock polypropylene structures having different isotactic

pentad contents [mmmm], as predicted from melting point depression theory and from the
Simulations for the quenched and annealed cases.
Tm (oC)
Simulation
[mmmm] eqn Ia quenchedb annealedc
0.871 181.1 141.7 103.5
0.644 157.8 125.1 93.2
0.535 143.5 106.6 71.5
0.461 134.1 91.5 27.4
0.400 126.9 77.5 21.9
0.350 121.5 67.8 28.1
0.324 117.9 59.4 -6.7
0.300 113.9 49.3 8.8
0.281 111.6 44.6 -20.1
0.261 109.4 37.5 -29.4
0.244 107.1 31.5 -35.2
0.231 105.8 27.3 -39.4
0.213 104.1 22.2 -48.5
0.207 102.4 16.8 -30.3
0.206 101.7 13.4 -56.9
0.194 100.9 11.3 -56.9
0.180 99.3 5.7 -58.3
0.185 98.5 3.6 -48.6
0.179 98.0 -1.1 -63.1
0.174 98.1 -2.5 -76.1
0.165 97.0 -3.5 -81.2
a Melting point depression equation. 17

b Calculated for simulated chains.
c Calculated after chain-matching process is performed on simulated chains.
132
lt should be recalled that in the annealed case, chains were perrnitted to slide past one
another for a specified length to locate the best matehing density nearest to the starting
points.
Moduli of the Elastomeric Networks
The theory of rubberlike elasticity 17 18 relates the modulus of elasticity to the number of
crystalline sequences acting as crosslinks, with the sequences in the amorphous state
contributing the elastomeric chains. If the number of crystalline sequences per unit volume is
represented by uco then Young's modulus at infinitesimal deformations is given by
(2)
where N 1 is the number of the units actually participated in the formation of the crystallites.
Values of Young's modulus predicted from the simulated values of Uc are presented in
Figure 5.
-
m
-
c.. 3
::!:
0
> 2
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
[mmmm]
As indicated in the figure, a wide variety of polypropylene samples with different

mechanical properties could be produced, depending on the isotactic content of the samples.
Materials could range from plastic polymers with high initial elastic modulus, high tensile
strength, and low reversible elongation, to an elastomeric polypropylene with essentially the
opposite properties.
133
100
80
--
60
'#
...I
40
20
0
0.15 0.32 0.49 0.66 0.83
[mmmm)
Figure 6. Degree of crystallinity of the polymers as a function of the isotactic pentad content.
1.2
-GI
0.8
-
g,
:E
0 0.6
>
0.4
0.2
0.15 0.32 0.49 0.66 0.83
[mmmm)
134
Effect of Block Size
Values of the degree of crystallinity of various polypropylene samples with different

isotactic block sizes are shown as a function of [mmmm] in Figure 6. As expected, the
degree of crystallinity increases with [mmmm] as a consequence of the increase in the
crystallizable isotactic content. The chain-matching process has also resulted in the decrease
of the percent crystallinity. Values of Young's modulus predicted from the simulated values
of Uc in this case are shown in Figure 7. lt is obvious from the figure that the increase in the
degree of crystallinity increases with [mmmm] as a consequence of the increase in the
crystallizable isotactic content. The chain-matching process has also resulted in the decrease
of the percent crystallinity. Values of Young's modulus predicted from the simulated values
of Uc in this case are also shown in Figure 7. It is obvious from the figure that the increase in
the isotactic block length might had a marked effect on the thermodynarnic properties related
to the crystallization, but almost no effect on Young's moduli for nearly the entire range of
isotactic content. This is because the elasticity of the samples was assumed to depend only
on the number of crystallites acting as cross links in the polymeric networks. At high
isotactic contents, the number of effective cross links decreases as a result of the fusing of
several crystallites into a single one, causing a decrease in the elastic modulus.
Effects of Block Size Distribution and Polydispersity
The effects of increased lengths of both blocks and increased polydispersity are shown
in Figures 8 and 9, respectively. In Figure 8, increasing the lengths of both the isotactic and
25 I I
L (%)
20
15
10
F n. r
rr n. [
AF,
h E h B
v.l
t::l p
r
-
0
20 24 30 40 60 120
lsotactic Sequence Length

Figure 8. The various thennodynamic and mechanical properties of
polypropylene as a function of the isotactic block size distribution.
135
25
20 1- l(%)
15 -
10
5
r~
J2. ' n
aF,
f-, _IT
r
;-
~L ~
Yo
;-
---,
0
0 10 20 30
lsotactic Sequence Length
Figure 9. The various thennodynamic and mechanical properties of

polypropylene as a function of polydispersity of the isotactic blocks.
the atactic blocks corresponds to moving from left to right along the abscissa. In both
figures, there is a grouping of five vertical bars for each value of the isotactic sequence
length. As marked in the figures, their heights correspond, from left to right, to the fraction
crystallinity L (% ), the adjacent-unit probability (Pe~), the standard free energy of fusion
(LlF~), the interfacial free energy (cre), and the Young's modulus (Y 0 ), all calculated as
described previously. 18
As can be seen, most properties do not show much dependence on the lengths of the
two blocks. This is presumably because these lengths are all sufficient for the isotactic
blocks to crystallize. The simulated values of the modulus show an interesting decrease as
the isotactic length goes up, however, apparently because of the already mentioned fusing of
crystallites, with corresponding increases in size but decreases in number.
The effects of polydispersity shown in Figure 9 indicate that most properties do not
show much dependence on polydispersity, with the modulus again representing an
interesting exception. The abscissa, in this case, represents the length of the shorter of the
two isotactic blocks in the pair averaging to a length of 30 repeat units. The largest values of
Y 0 occur when all isotactic blocks have the same value, specifically 30 units in the case
illustrated. Having pairs of disparate values such as 10 units and 50 units is detrimental in
this regard, since now only one of the two sequences is of sufficient length to participate in
the crystallization process. The decrease in the effective nurober of crosslinks decreases the
modulus correspondingly. In these two figures, the scale is suchthat the bars for pe~ were
barely discernible; in any case this probability was small and quite independent of these
changes in sequence length.
136
15 1.0
0.80
10
-....
:.-e
~
0.60
-s::
<
0
5
0.40 -
"C
I
0.20
0 0.0
0 200 400 600 800 1000
Mn X 102
Figure 10. Degree of crystallinity and Young's modulus at infinitesimal
extension of the polymers as a function of the molecular weight.
18.0 1.0
17.0
0.80
16.0
+
15.0
0.60
-....
~
14.0
-
;<
s::
13.0
0.40
-
"C
I
12.0
0.20
11.0
10.0 0.0
1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8
X
Figure 11. Degree of crystallinity and Young's modulus as a function of the
molecular weight distribution.
137
Effect of Molecular Weight and Molecular Weight Distribution
V alues of the degree of crystallinity of the simulated polypropylene are shown in Figure
10 as a function of the molecular weight. As found experimentally, 4 the degree of
crystallinity increases with molecular weight as a consequence of the increased probability
for isotactic sequence matching. This is unusual since the increase in the molecular weight
usually increases the chain entanglement and reduces the molecular mobility. However, in
this case the increase in molecular weight will increase the chances for long matehing
isotactic blocks, thus facilitating the crystallinity.
The effect of the molecular weight distribution is shown in Figure 11. Obviously, the
more dispersed the polymer is, the fewer chances there are for the crystallizable isotactic
sequences to match with each other to finally form the polypropylene crystallites.
Figures 10 and 11 also show the dependence of Young's moduli on the number of
crystalline sequences within the elastomeric networks. In general, the higher the degree of
crystallinity, the more crystallites and amorphous network chains there are, and the higher
the values of the elastic moduli.
ACKNOWLEDGMENTS
lt is a pleasure to acknowledge the financial support provided by the National Science

Foundation through Grant DMR-9422223 (Polymers Program, Division of Materials
Research), and by Amoco Chemicals. We also wish to thank R. M. Waymouth and M. D.
Bruce of Stanford University and C. L. Myers of Amoco Chemieals for very helpful
discussions, and the Fulbright Programfora Senior Scholar Award (#413/96) to TMM.
REFERENCES
(1) Coates, G. W.; Waymouth, R. M. Science 1995,267, 217.

(2) Madkour, T. M.; Mark, J. E. J. Polym. Sei., Polym. Phys., subrnitted.
(3) Natta, G. J. Polym. Sei. 1959,34, 531.
(4) Collette, J. W.; Tullock, C. W.; MacDonald, R. N.; Buck, W. H.; Su, A. C. L.;
Harren, J. R.; Mlhaupt, R.; Anderson, B. C. Macromolecules 1989,22, 3851.
(5) Mallin, D. T.; Rausch, M. D.; Lin, Y. G.; Doug, S.; Chien, J. C. W. J. Am. Chem.
Soc. 1990, 112, 2030.
(6) Cavallo, L.; Corradini, P.; Guerra, G. Polym. Mat. Eng. Sei. 1996, 74, 421.
(7) Coates, G. W.; Bruce, M. D.; Waymouth, R. M. Polym. Prepr. 1996, 37, 337.
(8) Newman, S. J. Polym. Sei. 1960, 47, 111.
(9) Cheng, S. Z.; Jonimak, J. J.; Zhang, A.; Hsieh, E. T. Polymer 1991, 32, 648.
(10) Natta, G.; Mazzanti, G.; Grespi, G.; Moraglio, G. Chim. e ind. 1957, 39, 275.
(11) Gauthier, W. J.; Corrigan, J. F.; Taylor, N. J.; Collins, S.Macromolecules 1995,
28, 3771.
(12) Grassi, A.; Zambelli, A.; Resconi, L.; Albizzati, E.; Mazzocchi, R. Macromolecules
1988,21,617.
(13) Resconi, L.; Jones, R.; Rheingold, A.; Yap., G. Organometallics 1996, 15, 998.
138
(14) Brintzinger, H.; Fischer, D.; Mlhaupt, R.; Rieger, B.; Waymouth R. Angew.
Chem. lnt. Ed. Eng!. 1995, 34, 1143.
(15) Kashiwa, N. Polymer 1980, 12, 603.
(16) Kaminsky, W.; Miri, M.; Sinn, H; Woldt, R. Makromol. Chem. Rapid Commun.
1983,4, 417.
(17) Flory, P. J. Principles of Polymer Chemistry ,Comell University Press, Ithaca,
New York, 1953, Chap. 5.
(18) Madkour, T. M.; Mark, J. E. Macromolecules 1995,28, 6865.
(19) Stocker, W.; Magonov, S. N.; Cantow, H.-J.; Wittmann, J. C.; Lotz, B.
Macromolecules 1993, 26, 5915.
139
THE PROPERTIES OF POLY(ETHYLENE NAPmHALATE) (PEN)
AND ITS APPLICATION
Jiro Sadanobu and Hiroo Inata
Polymers and Materials Research Laboratory

TEIJIN Limited
2-1 Hinode-cho, lwakuni, Yamaguchi, 740 Japan
INTRODUCTION
TEIJIN Ltd. entered on the investigation of 2,6-naphthalene dicarboxilic acid (NDA)
containingpolymers in early 1960s. Wehave devoted a great deal of effort to the research
and development toward its industrial application since then. Our research area has ranged
from monomer synthesis to polymerization, fabrication processes and application
technology. Finally we commercialized Poly(ethylene naphthalene) (PEN) in 1990 first in
the world.
PEN shows excellent chemical and physical properties compared to conventional
polyesters as Poly(ethylene terephthalate) (PET) as follows: (l)higher glass transition
temperature, (2)higher young's modulus, (3) enhanced gas barrier property and (4)improved
hydrolytic stability. Now PEN proves tobe highly prospective materials for many kinds of
industrial applications as resins, fibers and films.
We will describe PEN properties from the view point of the effect of naphthalene
introduction into polymer chain in this paper. We will show experimental results in
connection with practical application and also illustrate the results of advanced computer
simulation to clarify atomistic origin of the improved properties.
PROPERTIES AND APPLICATIONS

Figure 1 shows the chemical structures of PET and PEN. Both are very similar to each
other except for aromatic part. The only structure change from phenylene of PET to 2,6
naphthalene of PEN results in much improvement in chemical and physical properties. In
this chapter we describe PEN properties from the view point of practical applications.
yCC/~"' yY~"'
0 PEN PET
Flgure I. Chemical Structure of PEN and PET
Science anti Technology of Polymers anti Advanced Materials

Thermal Properties
TableI summarizes thermal properties ofPEN in comparison with PEr. PEN has about
lO degree higher melting temperature (Tm) and about 40 degree higher glass transition
temperature (Tg) than PET. Figure 2 illustrates relationship between Tm and Tg for
homologue series of PEN and PET. We see that PEN series has systematically higher Tg
than PET series at the same Ievel of Tm. The result indicates introduction of 2,6-naphthalene
unit has the effect of enhancing Tg with suppressing increase in Tm.
150.------.------.-------.------,
100
.0
so
Tg ( 'C)
Figure 2. Relationship between melting temperature, Tm, and glass transition temperature, Tg, for
homologue series of PEN and PET. PBT: Poly(butylene terephthalate), PBN: Poly(butylene naphthalate),
C6T: Poly(hexamethylene terephthalate), C6N: Poly(hexamethylene naphthalate).
Figure 3 compares mechanical relaxation behaviors of PEN and PET. PET has two
typical relaxation processes: a-process corresponding to glass transition and low tempemture
-process. PEN has a- and -processes, and another relatively strong 11*-process at
tempemture higher than room tempemture. The ~process is assigned to the local motion of
ester linkage. The *-process is typical for homologue poly(alkylenenaphthalate)sl and
related to local motion of naphthalene ring. Weakness of low tempemture relaxation in PEN
indicates suppressed local segmental motion at the tempemtures below 11*-process.
From the enhanced thermal stability PEN is applicable to films and containers for high
temperature use. High dimensional stability resulting from high Tg has recently been open
for new prospective application as basefilm for Advanced Photo System (APS).
Table 1. Thermal chamcteristic properties of PEN and PET
PEN PET
Melting Tempemture ("C) 265 252
Glass Transition Temperature ("C) 113 69

Half Crystallization Time at 180"C (min) 7
Density (glcm3) : Crystal 1.41 1.46
Amorphous 1.32 1.33
142
1011 40
35
-
1010 ~~~
30
"'8
u 10
9 25 g
=
"C
>. 108
'-'
-PEN
--PET
20
15~
0>
'-'
fJ;J 10
107
~ ...
.....---
-
i 5
/
106 0
-150 -100 -so 0 50 100 150
Temp ( "C)
Flgure 3. Temperature dependence of storage modulus, E', and mechanicalloss, tan , for PEN and PET
Meebanical Properlies
PEN has relatively slow crystallization rate(Table 1), that endows quenched polymer
from melt with high ductility . Stretching at high draw ratio results in the formation of highly
oriented fibers and films with high young's modulus and high tensile strength. Figure 4
illustrates laboratory data on the relationship between fiber modulus and draw ratio for PEN
and PEf. We see the attainability to higher draw ratio of PEN results in higher young's
modulus compared to PEr case. For biaxially oriented balance film, PEN also has improved
mecbanical properties compared to PEr as shown in Table 2.
The Y oung's modulus of PEN is highest among commercial melt-processable polymers
as biaxially oriented balance film. This feature has been utilized in the application of thin base
films for high density magnetic recording media, for example, backup tapes for computer,
long-run video tapes and so on.
Gas Barrier Properlies

PEN has excellent gas barrier properties. Table 3 compares gas permeation coefficients
of as castfilm and biaxially oriented films for PEN and PEr. We see that PEN has a few
times smaller gas permeation coefficients than PEr for carbon dioxide, oxygen and moisture.
Theorientation effects on enbancement of the gas barrier properties. We consider restricted
local motion in amorphous PEN constrain diffusive motions of small molecules through free
volume.
These properties are utilized for many applications to packaging and containers.
- 250
/
~
~ 200
"':::s
"3 PET
"0 150
/
0
~
"'
-Cll) 100
=
:::s
0
Laboratory Data
>< 503 4 5 6
Draw Ratio
Figure 4. Dependence of fiber Young's Modulus upon draw ratio for PEN and PEr.
143
Table 2. Mechanical properties biaxially stretched films of PEN and PEf with 25r.tm
of Thickness.
PEN PET
Y oung's Modulus (Kglmm2) 620 540
Tensile Strength (Kglmm2) 28 23

Elongation at Break (%) 90 120
Hydrolytic Resistance
One of the weak points of polyester is hydrolytic instability. PEN shows much
improved hydrolytic resistance compared to conventional polyesters. Figure 5 shows
comparison of the rate constant of hydrolysis for PET and PEN evaluated from the retention
of molecular weight during hot water treatment. Generally, the rate of hydrolysis for
polyester is highly affected by the content of carboxylic end groups. PEN shows high
durability to hydrolysis exceeding PET, beyond the effect of end group. We consider this
feature would be basedonnot chemical but physical mechanism: the low diffusivity of water
molecules in solid PEN.
The improved hydrolytic resistance enables PEN tobe durable to hot alkaline treatment.
This feature provides us with the application of PEN to refillable and retumable bottle
containers for beverages. We can expect another application using the hydrolytic stability for
paper machine clothing as dryer canvas.
ATOMISTIC COMPUTER SIMULATION

Introduction of 2,6-naphthalene unit into polymer chain results in dramatically
improvement of chemical and physical properties of polyester. It is, however, very difficult
to understand microscopic mechanism of the effect only from experimental data. We
introduce the advanced computer simulation techniques to analyze the structure-property
relationship in PEN atomistically. In this chapter we will discuss configurational statistics,
molecular motion and dynamic structure in amorphous state, and energy calculation of
ordered state by using static Monte Carlo Method, Molecular dynamic method and Molecular
mechanics, respectively.
Table 3. Gas Permeation Coefficient for PEN and PETfilms
AsCast Film Biaxially Griented Film
C02 2 C02 2 H20
PEN 9.0 2.8 3.7 0.8 3.4
PET 33 7.6 13 2.1 8.4
X w-12 cccrnJcm2 sec mmHg
144
Fipre 5. Comparison of rate constant of hydrolysis for PEN and PET.
Monte Carlo Simulation

We consider introduction of rigid naphthalene unit mak.es a chain stiffer. The chain
stiffness is considered as an origin of the long relaxation time of chain contour motions.
Another feature of naphthalene unit is the geometrical asymmetry. lntrodnction of
asymmetric units into a chain causes an additional confignrational entropy. To quantify the
chain stiffness and the additional configurational entropy, we implemented static Monte Carlo
method for chain statistics.
Procedure. We use static Monte Carlo method that is the continuous extension of
Flory's rotational isomeric state model2. In this method the partition fnnction is calcnlated by
equation 1.
z .. N- 1!( ~exp[ -fJ{Et(t/Ji)+ E,.( t/Ji,t/Ji+tm) (1)
N: total sample nurober of Monte Carlo calculation

tjlj: ith torsionangle
Et: torsion energy
Ez: correlatio energy for snccesive torsions
Any static thermodynamic and dimensional properties are evaluated by statistical average
in conventional manner.
Configurational entropy.Sca. is calculated by Equation(3), wbere Ais Helmboltz free

energy.
Scont=(<E>-A)IT
(3)
A -kTlnZ
Chain Stiffness. Chain stiffness was evaluated by the persistence length, that is the
model parameter of Kratzky-Porod worm like chain model3. From the theory the
unpertnrbed mean square end-to-end distance, <R2>0, is described by the persistence length,
145
102
600K
PEN
i=
._.. 101
(q=0.53nm)
\
A
t.=V 10
(q=0.38nm)
10-1
10 10 105
MW
Fi1ure 6. Simulated molecular weight dependence of mean square end-H:nd distance, <R~o at 600K
for PEN and PET. q is persistence length. '
q and the chain contour length Las Equation 4. Simulated <R2>0 was fitted to Equation 4 to
obtain persistence length.
< If > 0 2qL-2l[t-exp(-L/q)] (4)
Figure 6 shows simulated molecular weight dependence of <R2>0 and evaluated

persistence length, q, at 600K for PEN and PEr. The persistence length of PENis about
1.5 times larger than that of PEr. This increase of chain stiffness explains slower chain
contour relaxation qualitatively, tbat is related to high glass transition tempemture of PEN.
Geometrieal Asymmetry. Figure 7 shows tempemture dependence of simulated

configurational entropy, S<n, per unit weight for PEN and PET. Rotation around
C(carbonyl)-C(aromatic) bond of PEN causes an additional entropy because of geometrical
asymmetry of naphthalene ring. If we neglect this effect, the entropy of PEN is smaller than
that ofPEf over all tempemtures because of contour chain stiffness of PEN. The additional
entropy from the ring asymmetry has about 15% of contribution to overall entropy at 600K
for PEN. We can understand that the ring asymmetry has a major source of entropy in case
of PEN. Since it is independent of tempemture, the entropy from asymmetry becomes more
important at low tempemture.
The configurational entropy is a measure of the melting entropy, if the configumtional
entropy in crystal state is negligible. The simulation results explain the relatively lower Tm
ofPEN homologue series compared tothat ofPEf Counterparts with the same Ievel ofTg.
so~-------------------,
45 PET
~~
u 30
PEN
'-'... 25
c
r;n8 20
15 EN
without asymmetry contribution
102~oo=---:3~o::-::o:---:4:':::o=-o-.:...~so::-:o:-'--:s~o::o--~700
Temperature (K)
Flpre 7. Temperaturedependenceof configumtional entropy, Soor, per unit weight for PEN and PET.
146
1.0
t=100ps
0.9 0.9
0.8 0.8
.::; 0.7 .::; 0.7

~
~
.c:; 0.6 0.6
=.
PEN, n
~
N
0.5 .\ .. PEN, n
~
N
0.5
0.4 0.4
\
PET, n
0.3 0.3 (b)
(a)
0.2 ........................................................................................................
0 2zoo 300 400 500 600 700 800 200 300 400 500 600 700 800
Temperature (K) Temperature (K)
Flgure 8. Theorientation auto correlation function at 100 ps for vectors fixed at ethy1ene glycol part(a)
and aromatic ring part(b) for PEN and PET.
Moleeular Dynamies Simulation(MD)
The static Monte Carlo simulation reveals the configurational characteristics of PEN in
comparison with PEf. However, we can easily imagine there exist more complicatedchange
in chain dynamics by introducing naphthalene unit. To simulate chain dynamics
atomistically, we introduce Molecular Dynamics method (MD). Our attitude to this
simulation is to clarify how rigid bulky planar form of naphthalene unit effects on the chain
dynamics and chain packing.
Proeednre. The generic force field Dreiding 114 with Lenard-Johns type non-bonding
interactionwas used with no electrostatic interaction. Initial guess structures were
constructed by using RIS I MC method. MD simulations were proceeded in NPT ensemble
with using Nose-Parrinello method. Simulated temperature ranged from 300 to 600K. Time
step was set to lfs. We consider PEN with 40 monomers (MW::9,680) and PEr with 50
monomers (MW::9,700). All the simulated properlies attained equilibrium in at least 50 ps
for every run of MD simulation. The data for initial lOOps were discarded and the remained
partwas used for statistical analysis.
Orientational Relaxation. The time evolution of segmental molecular motion for

PEN and PEr was analyzed by using the orientational relaxation function. We define two
types vectors, chain direction vectors (t) and chain normal vector (n), fixed on local
segments along a chain. We consider these vectors for the aromatic ring part and the ethylene
glycol residue part as depicted in Figure 8. Orientational relaxation is usnally analyzed by
using the time decay of orientation autocorrelation function. The orientation autocorrelation
functions, M2,t(t) andM2,n(t), are definedas follows:
M2, 1(t) (3 < t(t) t(O) > -1) /2

(5)
M2.n(t) (3 < l(t) n(O) > -1) /2
Generally, time dependency of the orientation autocorrelation function could not be

described by single relaxation time. For convenience we use the values of M2,t(t) and
M2,n(t) at a specific time interval of lOOpsec for analysis ofthe orientational relaxation.
Figure S(a) shows the temperature dependence of the orientation autocorrelation
functions for the vectors, n and t, fixed on ethylene glycol part of PEN and PEI'. We see
therelaxationofn isfasterthan that oft ateach temperature. Bothof M2,t(t) and M2,n(t) at
100 ps for PEN and PEf almost coincides with each other, except for the highest temperature
147
1.6 1.6
1.4 (a) PEN 1.4 (b) PET
1.2 1.2
1.0 1.0
'1:' 0.8 '1:'
'-"
CO
';0 0.8
0.6 0.6 --300K
-----400K
0.4 0.4 -------SOOK
0.2 0.2 600K
0.00 8 10 O.q) 2 10
2 4 r(A) 6 8
Flgure 9. Theradialdistribution function of naphthalene ring center for PEN(a) and phenylene ring center
for PET(b) at various temperatures.
simulated. Tbis result indicates that PEN and PEr have the similar mode of local segmental
motion around ethylene glycol unit . This feature appears to explain the similarity of jl-
relaxation in PEN and PEr.
In contrast to the ethylene glycol part, there are many differences in the orientation
relaxationof aromaticringpartfor PEN and PEr, as shown in Figure 8(b): the motion of
naphthylene ring part of PEN is much slower than that of phenylene ring part of PEr both
for n and t. We assume tbat these relaxation behaviors would be directly related to the
difference in the position of a-relaxation. The results imply that introduction of bulky
naphthaJene structure may affect only on the local motion in vicinity of aromatic part itself in
glassy state.
Amorphons Strueture. We expect introduction of bulky planar naphthalene affects

on the amorphous chain packing. To analyze amorphous structure we consider the positional
and orientational correlation for naphthalene ring pairs. We define the radial distribution
function for aromatic ring center, g(r), and orientational coefficients for ring normal vector
(n) and chain direction vector (t) setting on the aromatic ring center as the function of ring
center separation, Pz,n(r) and Pz,t(r), respectively, as described in Equation 6.
1
g(r) c? < N(r) > (6)
C: number density of aromatic ring

<N(r)>: distribution function of ring center
P2 ,11(r)- (3 < n(r)n(O) > -1)/2

(7)
P2 ,1(r) (3 < t(r)t(O) > -1) /2
1.0 1.0
(a) (b)
0.8 0.8 -400K
----- 300K
'1:'
'-"
=.
ll..N
0.6
0.4
,..............
-....
0.6
'-";:1 0.4
-------SOOK
-600K
0.2 .......... ll..

0.2
0.0 0.0
-0.2 -0.20
0 2 4 6 8 10 2
r(A)
Flpre 10. The orienlational coefficient of ring normal vector(a) and cbain direction vector(b) for PEN at
various temperatures.
148
Figure 9 shows the mdial distribution functions of ring centers for PEN and PEr. The
mdial distribution function for PEN clearly shows a peak at around 4A . This result indicates
naphthalene ring pairs have a strong positional correlation in condensed state of PEN. The
peak in the mdial distribution function appears at every tempemture simulated and the height
of peak gmdually decreases with increasing tempemture. On the other band PEr shows no
special correlation between phenylene rings.
Figure 10 illustmtes the orientation coefficient, P2,n(r) and P2,t(r) for PEN. At the peak
position of g(r), P2,n(r) has high value of 0.95, corresponding to high orientation. on the
other band P2 t(r) hassmall value. These results for the orientational coefficients indicate that
nearest neighbr pairs of naphthaJene rings have an alignment almost pamllel to each other
ring, with no chain contour orientation.
In our force field, non-bonding energy minimum for C-C occurs at 3.9A of distance,
that is very near to the nearest neighbor distance of naphthalene ring pair corresponding to the
peak position of the radial distribution function. This result implies that there exists the
formation of compact parallel stack of naphthalene ring pair in amorphaus PEN. We did not
use any special intemction between aromatic rings.Therefore, the local alignment occurs only
by the effect of Van der Waals intemction between bulky planar structure units of
naphthalene.
The local alignment between naphthaJene ring is just tmnsienL It appears and disappears
with elapsing time. W e assume that this transient process would be related to some
relaxation processes of PEN, especially ~*-process.
Molecular Mechanics Calculation

PEN has a relatively slow mte of crystallization from melt and can be easily quenched to
amorphaus solid. However, the chain orientation enhances crystallization power
dmmatically. To analyze crystal packing and related properties, we introduce the molecular
mechanics energy minimization techniques for ordered states of PEN and PEr.
PEN has two crystalline forms of a and ~ The a form has trans zigzag conformation
and usually appears in conventionally prepared materiafsS. The ~ form is induced by high
tempemture crystallization from melt. However, the structure detail is still unknown. In this
analysis we only consider a type structure.
Procedure. We consider polymer chains in the three-dimensional periodic boundary

condition and minimize total potential energy, starting from the initial guess structures of
PEN and PEr with all tmns configumtion. We define crystalline packing energy as a total
non-bonding intermolecular potential energy permonomer unit.
Theoretical modulus, M, is calculated from stress(o)-stmin(l..) relationship and
energy(E)-stmin relationship by minimizing total energy with applying external force along
fiber direction. We impose the translational symmetry for monomer unit throughout the
elongational deformation. Theoretical modulus is finally evaluated by using Equation 8.
(8)
Table 4. Molecular Mechanics Simulation Results
PEN PEr
Crystal Packing Energy (KcaVmol) -27.4 -21.0

Theoretical Y oung's Modulus (GPa) 230 175
149
Crystal Paeking. PEr and PEN have large souree of the eonfigurational entropy
originated from the rotational isomerism around C-C bond of ethylene glyeol unit. As
experimentally well-known the population of gauehe eonformation is larger than that of trans
eonformation. The theoretieal ealeulation for energy gap between gauehe and trans is about
1 keallmol6 . On the other band both PEN and PEf1 have planar trans zig-zag conformation
in erystal strueture. This large discrepaney of preferred eonformation between amorphous
and erystal state results in the slow rate of erystallization (see Table 1).
One of driving foree of orientational erystallization is erystal paeking energy. Table 4
Iist simulated erystal paeking energy. For PEN and PEr the erystal paeking energy is over 20
keal/mol per monomer and high enough to overeome gauehe-trans energy gap and stabilize
planar trans zigzag eonformation.
6.0 2.0
(a) .-. (b)
4.0 ] 1.5
~ g_
C!:l
.
2.0
I
'-"
1.0
"'
~"'
Cll
0.0
0.5
-2.0 ~
!-<
-0.02 -0.01 0 0.01 0.02 0.03 0.03

Strain
Flgure 11. Simulated stress-strain(a) and energy strain(b) relationship for PEN and PEr.
Theoretieal Young's Modulus. We expeet the planar trans zig-zag eonformation

originate high erystallize modulus for PEN and PEr. Figure 11 shows simulated stress-
strain relationship and energy-strain relationship for fully oriented PEN and PET. Both
relationships give eompletely the same value of the theoretieal Young's modulus (Table 4).
W e see that PEN has about 1.5 times higher modules eompared to PEr. This is the atomistic
manifestation of intrinsie high modulus ofPEN.
Figure 12. The distribution of change in bondangle on applyuing force of 4 OPa for PEN and PET.
150
To understand the origin of improved modules for PEN over PEr, we analyze
distribution of the local deformation at applied force. Most of contribution to total strain
stems from bend deformation. Figure 12 shows the distribution of charge in bond angles on
applying force of 4 GPa. PEN and PET have just similar distribution of local deformation.
The largest change in bond angle occurs at 0-C-C angle of ethylene glycol unit and 0-C-C
angle of carbonyl for both cases. The reason of improved modulus for PEN is just increase
in the proportion of rigid ring part.
CONCLUSION
We show the effect of naphthalene introduction into the polyester chain with the
experimental data and give a theoretical basis on structure-properties relationships by using
the advanced computer simulation analysis. We can understand how the geometrical features
of bulky rigid planar structure affect on the chain configuration, molecular motion and
molecular packing.
We expect the excellency of PEN properties will give dramatic impact on modern
industry with new concept of polymer materials.
REFERENCES
1. J.Sadanobu and M.Tsukioka, Proceedings of ANTEC'97 (1997)
2. J. P.Fiory, "Statistical Mechanics ofChain Molecules", John Wiley & Sons, Inc., ,1969
3. H.Yamakawa, "Modem Theory ofPolymer Solution", Harper & Row, New York, 1971
4. S.L.Mayo, R.D.Olafson and W.A.Goddard III, J. Phys. Chem., 94:8877(1990)
5. Z. Mencik, Chemicky Prumysl., 17:78 (1967)
6. P. Lautenschlager, J.Brickmaann, J. van Ruiten and R.J.Meier, Macromolecules,
24:1284(1991) .
7. R.P.de Daubeny, C.W.Bunn and C.J.Brown, Proc. Roy. Soc., A226:531 (1954)
151
STUDY OF ENERGY GAP AND ELECTRONIC TRANSITIONS IN MODEL
POLYMER SYSTEMS: ELECTRONIC VERSUS OPTICAL EXCITATIONS
J. J. Pireaux, 1 G. Gensterblum, 1 C. Gregoire, 1 B. Y. Han, 1 K. Hevesi, 1

C. A. Fustin, 1 P. Rudolf, 1 L. M. Yu, 1 R. Caudano, 1 D. A. Leigh/ and
E Zerbetto3
1Laboratoire USE
Facultes Universitaires Notre-Dame de la Paix
rue de Bruxelles 61
B-5000 Namur, Belgium
2Department of Chemistry
UMIST
Sackville Street
Manchester M60 IQD, U. K.
3Dipartimento di Chimica G. Ciamician "
Universita di Bologna
Via F. Selmi 2
1-40126 Bologna, Italy
ABSTRACT
This short review attempts to rediscover an old surface sensitive electron

spectroscopic technique, namely ELS (or EELS, for Electron Energy Lass Spectroscopy);
when applied to study polymers and related advanced materials, it allows to characterize the
material energy gap and its electronic transitions. Four sample cases are presented: the
measurement of electron induced radiation darnage in polyethylene, the study of the energy
gap of C60 , the evidence of copper meta! diffusion in poly(phenylquinoxaline) during
annealing, and a preliminary study of the electronic excitations in a catenane, a macrocycles-
containing molecule.
INTRODUCTION
Polymers are not new materials, but it is only recently that many of their chemical
and physical properties can be tailored almost at will. Increasingly evident is the need to
develop new analytical tools to better ascertain, if not understand, the new attributes of those
advanced materials; nowadays, only a multidisciplinary and multitechnique approach is
capable to unravel the richness and the peculiarities of new organic polymers. Materials
surfaces are best studied with charged particles. Photoemision spectroscopies (XPS/ESCA,

UPS, synchrotron photoemission), Auger Electron Spectroscopy (AES), electron diffraction
techniques (LEED and RHEED), ion-based spectroscopies like Time-of-Flight Secondary
Ion Mass Spectroscopy (ToF-SIMS), and Rutherford Back-Scartering (RBS) ... are probably
the best known... and the most useful ones. Although some publications appeared in the
literature 12, this is not the case for Electron Energy Loss Spectroscopy (EELS or ELS) in its
low energy resolution mode, by opposition to HREELS (High Resolution Electron Energy
Loss Spectroscopy).
The purpose of this contribution is to re-discover the attributes of E(E)LS, by
presenting first a rapid description of the experimental parameters, summarizing the basic
concepts ofthe data interpretation, and showing a few sample cases. lt is hoped that this will
help to emphasize the very large potentialities of the ELS spectroscopy, that is not enough
known and used, to our opinion.
Formost applications of advanced polymer materials, the knowledge ofthe occupied
valence bands, of the frrst empty conduction Ievels, and all of the electronic details
pertaining to the width ofthe energy gap and the absence ofimpurity/surface states andlor
the presence of doping states .. .is a must. lt suffices indeed to recall for example the basic
principles of the operation of a polymer light emitting diode (LED) - Figure 1. In the
simplest design of the LED, a single layer of a conjugated polymer is sandwiched between
two conducting films, usually one indium-tin oxide substrate and an aluminium overlayer;
polarized under electrical bias, the LED sees electrons and holes injected from the metal
electrodes into the polymer band gap, where they eventually recombine to produce light.
Clearly, the carriers injection and mobility, the conversion into light ... depend on the details
ofthe electronic structure around the energy-gap ofthe metal-polymer-substrate sandwich
system. Surface and interface states, dopant, (bi)polaron bands are known to modulate the
electronic performances ofthe device; they do deserve, for further better tailoring ofthe
system, better characterization.
VACUUM LEVEL
<J:lMl
POLYMER
V -+
Figure l.Schematic design of a polymer based light emitting diode. Composed of a metal!conjugated
polymer/substrate ensemble under electrical bias, the LED emits light from the radiative recombination in the
polymer layer of electrons and holes injected from the electrodes. This is an example of real device for which a
detailed knowledge ofthe material energy gap, e.g. with the ELS spectroscopy, is a must
154
EXPERIMENTAL DETAILS
(HR)EELS is an ultra-high vacuum technique that uses a monoenergetic (L'lE: 2 to 50

meV) low energy ( 0 to 100 eV) e1ectron beam to probe asolidmaterial surface in the back-
scartering geometry. The experiment has been described in detai1s elsewhere3 . Let us here
stress upon a few properties of the technique, like
- its very high surface sensitivity42 ,
- the absence ofbeam induced darnage in standard Operating conditions,
- its very broad dynamic range, as the tuning ofthe probe beam energy from E0=0 to 100 eV
allows to study molecular and electronic excitations from the far IR to the UV range.
This last point has been convincingly evidenced in a recent work on fullerenes 56
Indeed, in the high resolution mode, the technique -then named HREELS- allows to study
molecular vibrations, and phonons, and to compare them with IR and Raman spectra;
applications are almost countless in the Iiterature for the study of molecular adsorbates,
polymers, and dielectrics 12 . As for the low resolution mode, it is used to study electronic
excitations ( valence to conduction band transitions,), and plasmon excitations. Although
less widespread in research laboratories, this E(E)LS technique should deserve more
attention, particularly to study polymer systems, as we will try to demonstrate in the
following sections.
BAND GAP OF POLYETHYLENE
For polymers, information available with electron energy loss spectroscopy is indeed
very substantial: the study of a thick polyethylenefilm will demonstrate this 7
Figure 2 presents a so-called complete spectrum recorded with an electron impact
energy Eo = 15 eV; different electron energy loss windows are clearly distinguished, with
different physical content:
- at maximum energy loss, a peaked structure terminates with the cut-off; this is the true
secondary electron emission (SEE) from the material;
- at intermediate loss energy (here between 8 and 12 eV), the electronic interband transitions
(IB) and the plasmon excitations are observed;
- close to the elastic peak, at small energy loss (<1 eV), the vibrational spectrum contains
fingerprints ofthe polymer molecular vibrations.
1B lransilions SEE struclures

1-- -t
Vibralional EpISeV
Slruclures
I
0 5 10 15 20
Loss Energy (eV)
Figure 2. Complete electron loss spectrum of a thick polyethylene film. Vibrational bands, electronic interband
transitions and secondary electron emission can be studied
155
Energy (meVl
0 200 400
POLYETHYLENE
-
0 2000 4000
Wave Number (cm"1)
Figure 3. HREELS spectrum of polyethylene. The observed vibrational bands are assigned with the aid of
IRgroup theory information
Although it is not the purpose of this contribution to detail the full potentialities of
this electron induced vibrational spectrum, figure 3 will simply suggest them, for example
to scientists familiar with optical (IR and Raman) spectroscopies. The polyethylene
vibrational spectrum extending in the 0- 400 meV ( 0- 3200 cm- 1) range shows about ten
(ij'
:t:
1:
..
:::J
.ri
.!!.
....c
Cl)
~:
:::J
0
0
0.0 4.0 8.0 12.0 16.0

Energy loss (eV)
Figure 4. ELS spectrum of hexatriacontane, after ovemight electron-beam irradiation. The inset reports the
loss spectrum measured by Ritsko 16 with a high energy electron beam, in the transmission mode. The bands
measured in the gap are attributed to radiation induced darnage (radical formation) in the polymer
156
bands to be resolved , seen as peaks, shoulders or bumps; this raw HREELS experimental
energy resolution is indeed presently limited to a few ten wavenumbers (resolution can be
artificially enhanced through computer algorithms 8). IR and Raman handbook Iiterature has
been used to assign those structures - the theoretical numbering of the group theory shown
on the figure can indeed be translated into CHn stretch, scissor, wag, twist and rock modes,
and in C-C stretch vibration. Specialists will recognise that the HREELS data are closer to a
Raman spectrum7 .
The electronic transition spectrum of polyethylene (figure 2), say from 1 to 10 eV,
will be studied in more detail, as it will serve as illustration for further spectroscopic use of
electron loss spectroscopy. Usually, clear electronic transitions are readily observed when
the polymer contains 1t electrons: this is due to the fact that 1t electrons are localized in
narrow electron energy bands, below (occupied states) and above (empty states) the insulator
energy gap 9 11 When the polymer does not contain 1t bands but only cr electrons, the
orbitals are broader, and the related electronic transitions appear less sharp - this is
absolutely comparable to what is observed in (vacuum) ultraviolet spectroscopy. On figure
2, we distinguish the onset for -very broad indeed- electronic transitions at about 8 eV loss
energy. lt is known that the polyethylene energy gap is about 8.8 eV 12 , whereas its detailed
electronic structure below and above it have been measured by Seki 13 and Ueno 14 ; thus
electronic interband transitions, most exclusively between 's-like' electronic bands, are
allowed above 8 eV - they are not resolved in our ELS spectrum. But, a few structures
appear where they shouldn't in the energy gap. This is moreevident on figure 4, showing a
similar spectrum recorded from a thin hexatriacontane film (n-C3 6H 74 ). Between 4 and 8
eV, at least two sharper transitions ( at 4.5 and 6.0 eV) are evident, when the film has been
-;;;
....w
;t'"'''' '!'"' .l,fl'r
1, f:l/1) 1,1/, ul/,/;,';f,',f! 52
w
Condudion band Vl
____ .+{ 0.4eV
l
Egap: </): Evacuum -6.5
8.8eV 4.0eV -5.2
- -----EF .
4.4eV erm1
iluilli/111/IMln/l}llld
Yalence band
~II!IIIIII!l!llll/11/1111/1
-10.8
16
-12.2
Qj
52 -14.
w
Vl -1s.
Figure 5. Summary of our knowledge gained from photoemission and ELS spectroscopies on the electronic
structure of polyethylene
157
irradiated ovemight. These structures are not recorded for fresh polyethylene or
hexatriacontane; they appear only after prolonged electron irradiation (e.g. from the electron
flood-gun used to neutralize surface charging 15). It has been suggested these peaks testify to
electron induced radiation darnage. A proposed mechanism 16 assurned electron induced C-H
bond scission, and radical forrnation; if two radicals appear on adjacent carbon atoms, they
might combine to form unsaturated bonds. One isolated unsaturated bond within the
polyethylenebackhone shows up as a peak at 6.5 eV in UV absorption spectroscopy; when
combined in pairs, triads,etc, thesemultiple defects are spectroscopically seen at 5.3, 4.3 eV,
etc. These are the markers identified with the index n = 1 to 5 on spectrum 4, and its inset
reproduced from the work by Ritsko 16
As a conclusion to this study of the electronic structure of polyethylene, figure 5
schematizes our present knowledge of the electronic structure of polyethylene: indeed, by
combining spectroscopic information of valence band XPS, and low and high energy ELS, a
quite thorough picture of the occupied and empty electronic states of this material has be
obtained.
ELECTRONIC/OPTICAL GAP IN C60
The quite recently discovered fullerene molecule farnily has been the subject of all
the kinds of spectroscopic investigations. For C60 , an ideal textbook molecule, the richness
of inforrnation gained by the electron energy loss spectroscopy technique is quite
remarkable: indeed, EELS ability to cover the very broad energy range extending from the
Energy loss (eV}

0 2 3 4
3.7
C60/Si(1 00)
-=
I
EP = 10 eV
1/l X 100
r::
:l
0.04
.ci
--
....
ca
cn
r::
:l
0
(.)
CNDO/S-CI
singlets
QCFF/PI '
triplets :
0 2 3 4
Energy (eV}
Figure 6. ELS spectrum of purified C60 , Iogether with results of theoretical calculations with two methods
(CNDO/S-CI and QCFF/PI), allowing the assignment of singlet and triplet excited states in the molecule
158
far infrared to the vacuum ultraviolet on a single sarnple in a single experiment is very
attractive. Moreover, it has - in some sense- the enormous advantage that it can provide
information not only on the dipole active transitions but also on the dipole or spin forbidden
states of the molecule. The spectra presented and discussed hereunder were recorded from a
thin fullerene layer sublimedunder ultra high vacuum on a clean Si(l 00) surface 171819
Figure 6 shows a C60 loss spectrum recorded in the specular direction with a primary
electron bearn of 10 eV and an overall instrumental resolution of 40 meV. Not to be
discussed here are the IR vibrational bands on the right hand side of the elastic peak
extending down to a small C-H contamination peak at around 0.36 eV, which is also
detected trough its multiple excitations (n x 0.36 eV). Further up in energy to 1.4 eV, one
notes only a very flat and low intensity spectrum : this is a direct picture ofthe energy gap of
the fullerite. This is followed by a sharp onset (1.45 eV) and a very distinct peak at 1.55 eV.
This first electronic excitation across the gap has to be of excitonic origin. The intensity of
this peak is decreasing with increasing primary energy (right hand side of figure 7): this
suggests that an exchange resonant-like process is the dominant excitation mechanism and
pointsout to the triplet character ofthe Frenkel-like exciton corresponding to the first hu-t 1u
intrarnolecular excitation across the gap. This attribution is corroborated by optical,
fluorescence, phosphorescence, photoluminescence spectra, and by quantum chemical
calculations 19 On figure 6, semiempirical results from both CNDO/S-CI and QCFF/PI
codes20 are shown, with the calculated excited states being shifted so that the first triplet
(singlet) corresponds to the peak at 1.55 (1.87) eV. The broad shoulder observed at 1.9 eV is
thus composed of the singlet Counterparts of the C60 excitons. Other observed features up to
3 eV (including the well defined 2.2 eV peak) are assigned to other excited singlet/ triplet
states ofthe molecule 519 Further in energy, the spectrum becomes dominated by the dipole
(a) (b)
C60/Si(1 00) EP =
..j 10 eV
--
111 --
111 15 eV
"E
:::1
.c....
'E
:::1
.c ::..: ....'.
--
:. :
..,
--
C'CI
....
C'CI
-:.;..-: ,
:
111
c
111
c
....I
-... 20eV
:::1
0
(.)
:::1
0
(.) ...--.. ~~
~
........"
,i:........./' i
o(
.~
~ 30 eV
10 eV
x3
_...,..,!~
0 2 4 6 8 1.5 2.0
Energy loss (eV} Energy loss (eV)
Figure 7. ELS spectra of C60 recorded in the VIS-UV region for increasing primary energies. Assignment of
the peaks is detailed in the text
159
allowed transitions: from the first 1Ag ground state to the first 1Tu excited state, one gets
probably the weak peak at 3.0 eV, and then the very strong 3.7 eV band, which corresponds
to the first strong optical absorption feature (2 1T 1u- 3 1T 1u states).
Recorded at higher impact energies ( and with a slightly worse instrumental
resolution), spectra presented on figure 7 show fingerprints of more energetic energy
transitions. At 4.8 eV appears one ofthe largest ELS peaks, which definitely correlates with
the weil known strong optical absorption band observed at 4.7 eV ( 264 nm) - for solid
films, and at 4.84 eV ( 256 nm)- for C6o hexane solution. This band corresponds to the first
dipole allowed HOMO- LUMO transition ( 1 1Ag- 6 1T 1u). The next group of intense peaks
at around 6 eV ( 5.5; 5.8 and 6.3 eV) whose intensity grows continuously with the increase
of the electron impact energy, is assigned in a similar way ( further dipole allowed one-
electron transition, like HOMO-I to LUMO, HOMO to LUMO +1 etc) except for the 6.3 eV
peak : this strong band corresponds to the so-called 1t plasmon , the quantum of collective
motion ofthe whole 1t electronic system in the molecule. Together with the 4.8 eV peak, the
6 eV band forms the familiar camel back structure so characteristic of the originally
observed absorption spectrum of C6o- Not shown in this short surnmary are spectra recorded
with primary energies from 30 to 100 eV 19 . They do evidence other features: we will cite
only for sake of completeness, a peak at 7.6 eV corresponding to the threshold ionization
energy of the molecule, and a very broad band centered at 28 eV; this last structure, also
recorded for graphite, is understood as resulting from the excitation of multipolar cr-
plasmons, the quanta of collective motions of all the 240 (cr + 1t) valence electrons of the
fullerene molecule.
More details on the extremely rich information contained in the ELS spectra of C60
and the related C7o molecule can be found in the literature5' 6' 171819 . We would like to stress
the fact that these HREELS measurements are the only ones which have revealed the
presence of the triplet exciton at 1.55 eV. This further evidences the potentialities of this
spectroscopy to render the best details of the energy gap and electronic transitions of new
organic/polymer advanced materials.
COPPER DIFFUSION IN PPQ
One simple analytical application of the use of Electron Energy Loss Spectroscopy will be
illustrated hereunder. lt is related to the study of the interfacial properties of a metallpolymer
ensemble, like the ones that are used in the microelectronics industry. Polyphenyl
quinoxaline (or PPQ) is indeed a material (containing only carbon, nitrogen and hydrogen
atoms) with a high dielectric constant, and which is stable up to elevated temperature, like
most polyimides. .
Figure 8 reports the ELS fingerprints of both pure copper and polymer materials: for
the metal, its conducting character is clearly seen from the absence of an energy gap, and
from the high intensity of the scattered electrons over the whole electron energy loss range;
the sharp electron intensity onset just above 2 eV loss energy corresponds to the weil known
first electronic transition in this material, as justified by the superimposed theoretical loss
function for pure copper. As for PPQ itself, one sees on the ELS spectrum a very smallloss
intensity between 1 and 3 eV: this corresponds to the energy gap ofthis insulating polymer;
the first electronic transitions appear at about 3.5 and 4.5 eV. On figure 9 are collected five
spectra recorded from Cu/PPQ interfaces, after various treatments: trace a (top figure)
corresponds to a 40 A Cu layer on PPQ, after half an hour 200 C heating - it clearly shows
the loss band at 2 eV, characteristic of the metal, and the first electronic transitions of PPQ
at higher energy (we will concentrate on the polymer fingerprint at about 3.3 eV). On
spectrum b, recorded after heating the layers to 400 C, the metal characteristic transition
160
. '::.... ,~ : -.. : .,
...
~ .
. -:- -
... :. ~ .
. xsoo
1 0 2 3 4 5 6
Energy loss (eV)
Figure 8. Fingerprinting ELS spectra ofa thick Cu metallic layer (top), and ofa clean PPQ surface after anneal
(botttom). The calculated theoreticalloss function of copper is also shown (fullline)
x100 ,.::': v. '''' .,_ a)

/..' . . . . :. ..:r ....... . -.. ... . .~.:.-..".:
/.~ ,;..:.x50 \-"':.- -.~~~
!
x50
........
d)
-.
.-.'
x200
,::o
~-
...... ,,. . _...........,.~
-1 0 2 3 4 5 6
Energy lass (eV)
Figure 9. Evolution of the ELS spectra of a Cu-PPQ interface, after different anneals. Copper is seen to diffuse
into the polymer
161
t\t..
/.\.
100eV
,.l
, f
\
/
15eV
2 3 4 5 6 7 8
Energy Loss (eV)
Figure 10. ELS spectra of the new octabenzoamide 2-catenane, recorded with different electron irnpact
energies
has disappeared, and a clear energy gap has developped between 1 and 3 eV. After
subsequent deposition of another amount of copper (total thickness of about 250 A), the Cu
electronic transition appears again ( trace c), and remains, even after heating at 200 C
(spectrum d). But when the ensemble is further heated at 400 C, the signal of copper
disappears again, leaving on the surface only 'clean' PPQ. Evaporation of copper from the
polymer surface when heated at 400 C is very unlikely; more probable is the diffusion of
the metal (islands?) into the material, as this has been confirmed later on with Rutherford
. expenment,
bac kscattenng . and TEM piCtures
. 21 '22 .
ELECTRONIC EXCITATIONS IN CATENANES
Catenanes form a class of topologically complex molecules in which a few

macrocycles are interlocked to initiate the commencement of a chain: rings are not
connected via a covalent bond and, under given conditions, they can circurnrotate one
another. This macrocycles circumvolution represents a conformation change, that may find a
role in the growing arsenal of 'smart' materials, operating at the nanoscale. Study of the
vibrational and electronic properties of these catenanes is now required.
Some prelirninary results are here summarized for the electronic states of an
octabenzoamide 2- catenane 23 , that has been sublimed in UHV on a clean Au(111) crystal.
As seen on figure 10, the lowest-lying electronically excited states, that are detected for
different energies ofthe prohing electrons, are located at 3.8 and 4.6 eV. As they are present
only for the low impact energies, these excitations must correspond to dipole-forbidden
transitions which are excited through an exchange process during a resonant-like electron-
molecule interaction: these peaks are fingerprinting singlet states of the molecule which are
delocalized over the whole molecule, as confirmed by CNDO/S calculations. As for the
162
bump appearing at 5.4 eV, calculations suggest it could be attributed to a large set of charge
transfer states, whereas, the peak with almost constant intensity at 6.5 eV is identified to
electronic 1t to n* transitions localized within the aromatic moieties of the catenane
molecule. A more detailed analysis of these data is in progress.
CONCLUSION
This brief overview of older and more reeent studies of polymer/organic materials
with the use of Electron Loss Spectroscopy should have demonstrated that with this
technique it is easily possible to measure
the material eleetronie gap
its excitonie states
the different HOMO to LUMO transitions
the eolleetive exeitations ( plasmons).
It should be clear that this kind of analysis could extend and eneompass the reeording of
possible
surfaee states
polaronie bands
doping levels
... ete
within the energy gap of a polymer material. This information is eomplementary to the one
obtained with more eonventional optical speetroseopies, but obeys different (and thus
complementary) seleetion rules. Therefore, we think that ELS spectroseopy could be more
frequently used to eharacterize polymer systems.
REFERENCES
l.H. Ibaeh and D.L. Mills, Electron Energy Loss Spectroscopy and Surface Vibrations,
Aeademie Press, New-York, 1982
2. J.J. Pireaux, Eleetron Induced vibrational Speetroseopy (HREELS), in Surfaee

eharaeterization of advanced polymers , L. Sabbatini and P.G. Zambonin (Eds), VCH -
Manheim (1993) 47
3. P.A. Thiry, J.J. Pireaux, and R.Caudano,Physiealia Magazine, 4 (1981) 35
4. J.J. Pireaux, C. Gregoire, M. Vermeerseh, P.A. Thiry, and R. Caudano, Surf. Sei. 189/190
(1987) 903
5. G.Gensterblum, J.J. Pireaux, P.A. Thiry, R. Caudano, Ph. Lambin, and A.A. Lueas,
Physiealia Magazine 14 (1993) 239; K. Hevesi, C.-A. Fustin, P. Rudolf, L.-M. Yu, B.-Y.
Han, G. Gensterblum, P.A. Thiry, J.J. Pireaux, and R. Caudano, J. Eleetr. Speetrose. 76
(1995) 115
6. B.-Y. Han, K. Hevesi, L.-M. Yu, G. Gensterblum, P. Rudolf, J.J. Pireaux, P.A. Thiry, and
R. Caudano, J. Vae. Sei. Tehnol. Al3 (1995) 1606
7. J.J. Pireaux, P.A. Thiry, R. Caudano, and P. Pflger, J. Chem. Phys. 84 (1986) 6452
8. C. Gregoire, J.J. Pireaux, A. Cros, and R. Caudano, Appl. Surf. Sei. 84 (1995) 163
163
9.W.D. Jennings, G.S. Chottinger, C. Natarjan, A.V. Melo, R.W. Hoffman, W.E. O'Grady,
J. Lundstrom, and W.R. Salaneck, Appl. Surf. Sci.21 (1985) 80
10. A.M. Bothelo do Rego, M. Rei Vilar, J. Lopes da Silva, M. Heymann, and M. Schott,
Surf. Sei. 178 (1986) 367
11. J.J. Pireaux, C. Gregoire, P. A. Thiry, R. Caudano, and T.C. Clarke, J. Vac. Sei.
Technol. A5 (1987) 598; J.J. Pireaux, M. Vermeersch, C. Gregoire, P.A. Thiry, R. Caudano,
and T.C. Clarke, J. Chem. Phys. 88 (1988) 3353
12. J.J. Pireaux, J. Riga, R. Caudano, J.J. Verbist, J. Delhalle, S. Delhalle, J.M. Andre, and
Y. Gobillon, Phys. Scripta 16 (1977) 329
13. K. Seki, U.O. Karlsson, R. Engelhardt, E.E. Koch, and W. Schmidt, Chem. Phys. 91
(1984) 459
14. N. Ueno, K. Suigta, K. Seki, and H. Inokuchi, Phys. Rev. B34 (1986) 6387
15. M. Liehr, P.A. Thiry, J.J. Pireaux, and R. Caudano, Phys. Rev. B33 (1986) 5682; P.A.
Thiry, M. Liehr, J.J. Pireaux, and R. Caudano, J. Electr. Spectrosc. 39 (1986) 69
17. G. Gensterblum, J.J. Pireaux, P.A. Thiry, R. Caudano, J.P. Vigneron, Ph. Lambin, and
A.A. Lucas, Phys. Rev.Lett. 67, (1991) 2171
18. A.A. Lucas, G. Gensterblum, J.J. Pireaux, P.A. Thiry, R. Caudano, J.P. Vigneron, Ph.
Lambin, and W. Kratschmer, Phys. Rev. B45, 13694 (1992)
19. G. Gensterb1um, J. Electr. Spectrosc. 81 (1996) 89
20. F. Negri, G. Orlandi, and F. Zerbetto, Chem. Phys. Lett. 144 (1988) 31; J. Chem. Phys.
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21. M. Fontaine, J.M. Layet, C. Gregoire, J.J. Pireaux, and A. Cros, Appl. Phys. Lett 62
(1993) 2938
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Nechstchein, J. Appl. Phys. 76 (1994) 1244
23. A.M. Brouwer et al. (unpublished); for the structural properties of the benzoamide 2-
catenane, see A.G. Johnston, D.A. Leigh, R.J. Pritchard, M.D. Deegan, Angew.Chem. Int.
Ed. Engl., 34 (1995) 1209
164
TEMPLATE POLYMERIZATION OF DIMETHYLAMINOETHYL
METHACRYLATE IN mE PRESENCE OF POLY(ACRYLAMIDE-ACRYLIC
ACID) INDUCED BY GAMMA RADlA TION AND ITS USE FOR REMOVAL OF
METALIONS
T. Siyam and Z. H. Abd-Elatif 1
Nucl. Chem. Dept. Hot Laboratories Centre

Atomic Energy Authority, P. Code 13759
Abstract
The polymeric material of poly (acrylamide-acrylic acid-dimethylaminoethyl

methacrylate) "PAM-AA-DMAEM" was prepared by gamma radiation-induced
polymeriza-tion of dimethylaminoethyl methacrylate (DMAEM) in the presence of
prepared poly(acrylamide-acrylic acid) "PAM-AA" as a template polymer using a
template polymerization technique.
The effect of gamma radiation on the polymerization process showed that the
conversion increases with increasing the radiation dose. The obtained polymer is
water-soluble polymer at low doses <10 KGy. On increasing the radiation dose the
polymer was convetted into a gel with the s\velling degree vary from 15-36. It was
found that the capacities of the obtained polymeric gels toward Cu2+ increase with
increasing the absorbed dose, monomer concentration and the template polymer/
monomer molar ratio.
Spectroscopic studies showed that the mechanism ofthe floc formation is due to
the interaction between the polymer and copper sulphate is a bond formation between
the active groups of polymer chains and ions of copper sulphate. The amide and
tertiary amino groups form complex with Cu2+ while carboxylic group interacts with
ion through ion-exchange mechanism.
1National Resarch Centre, Dokki, Giza, Egypt

Edited by P. N. Prasad etal., Plenum Press, New York, 1998 165
Introduction
For preparation ofmacromolecular compounds Abd-Ellatif(l,2) was studied the

photopolymerization of dimethylaminoethyl methacrylate (DMAEM) in the presence
of the polyacrylic acid PAA using azobisisobutyronitrile (AJBN) as the radicals
initiator the rate of polymerization was found to be a maximum value at a ratio of
template/ monomer [T]/[M] up to a value of ab out 1. 5 . TI1e author was also studied
the photopolymerization of DMAEM in the presence ofPAA as a template in the
absence of AIBN. The initial rate of polymerization increases initially with increase of
[T]/[M] up to a value of 1. 5 before sta1ting to decline. In the case of aqueous tem-
plate polymerization using AIBN, the polymerization was faster and a gelwas precip
itated. For this template system, ionic bonds (hydrogen bonding) are formed between
the monomer and the template polymer farnring a complex. This association helps
the monomer to adsorbed on strougly ionized PAA. The adsorbed monomer is excited
by induced polymerization aggregates to generate an initiation radical species. llris
complex is similar to plurimolecular aggregates which is formed in the case of
polymerization of AA in the polar solventC3-5) The complex between PAA and
DMAEM may restut in delocalization of the electron in the double band of the
complex monomer.
In the present work we shall study the effect of absorbed dose, the ratio of added
polymer/monomer and the monomer concentration an the polymerization ofDMAEM
in the presence of poly(acrylamide-acrylic acid) "PAM-AA". The capacity of the
obtained polymeric materials toward Cu 2+ was determined.
Material and Experimental Technique
Poly(acrylarnide-acrylic acid) PAM-AA was prepared by the copolymerization of

ac1ylamide with ac1ylic acid at the optimum conditions for the copolymerization
process< 6 ).
Dimethylaminoethyl methac1ylate (DMAEM) was a product of Koch-light
labmatmies ltd. Inhibited by hydroquinomnonoethylether which was used after distilla-
tion m1der vacuum. The template polymerization technique for the polymeiization
process was canied using gamma radiation fiom Co-60 of dose-rate -3KGy/hr as
desc1ibed previously{7)_ The percent conversion was determined gravimetrically. The
percent of DMAEM in the obtained gel was deterrnined using the following equation:
The percent ofMDMAEM = Weight ofDMAEM/Total weight ofpolymer
The swelling degree(s) is calculated using the following equation:
S=(Ws-W)/W
166
where Ws and Ware the weight ofthe polymer after and before the polymer swelling,
respectively.
The capacity ofthe obtained polymeric gel toward Cu2+ was also determined as
described previously (8).
Result and Discussion
1- Influence of the radiation dose on the polymerization process:

The influence ofthe radiation dose on the polymerization of DAMAEM in the
presence of PAM-AA (0.86:0.14) was studied at equal molar ratio ofmonomer and
polymer [M] = [T] = 0.64 MIL. The result are shown in Fig.(I) which shows that the
conversion percent increases with increasing the radiation dose. At higher doses, the
conversion percent increases slowly. The increase in the conversion can be attributed
to the gel-effect of such system and the complex formation between the monomer and
the polymer as shown in structure l.
""""""-CH2 - CH-CH2 - CH ___..

I
coNH2 coo-
l
---.I
CH3 +
~NH
CH3
CH2= C-COO-CH2-CH2-CH 2
t
CH3
"Structure I" monomer-polymer complex
This complex formation helps the monomertobe adsorbed on strongly ionized

PAA. The adsorbed monomer is excited by induced polymerization aggregates to
generate an initiation radical speciesOl. However, the formation ofthe complexed
polymer radical retards the termination and enhances both the polymerization rate and
the average molecular weight (8-11).
In this gel-state as the conversion percent increases the viscosity ofthe medium is
highly increased due to the formed polymer complex in the presence ofthe template
polymer. The growing chains are traped in the viscous medium Accordingly, the
conversion percent is suddenly increased. However, the propagation reaction is
reduced as a result of slowing migration of monomer molecules to react with the active
growing chains. It has suggested that the propagation reactions are changed into
diffusion-controlled reactions02,13). The termination reaction is bindered to much
extent as it required by migration of macromolecular. In addition, the penetration or
diffusion of the monomer may complex with the added polymer in the process
decreasing the mobility and the chemical reactivity of the monomer-polymer
167
100r--------------- -----------------,
cC1J
u
\...
C1J
0..
c
.Q
Vl
L
C1J
>
c
0
u
5 10 50 100
Dose, K Gy
Figure 1. Influence of absorbed dose on the polymerization of DMAEM.
Table 1. lnfluence of the absorbed dose on the composition, the swelling degree and
the capacity of the obtained p (AM-AA-DMAEM).
CO!TIQOSition Qercent swelling capacity,

Dose, KGy degree m mollg
AM AA DMAEM
5 49.6 9.6 40.73 sol. sol.
10 46.2 9.2 44.59 sol. sol.
30 44.0 5.9 50.1 15 3.68
50 42.0 6.4 51.6 21.2 3.67
70 24.5 6.5 69.01 34.48 3.51
100 21.4 4.18 74.42 36.08 4.57
168
complex04). So, the conversion increases slowly at high doses. This is similar to the
previous findings< 715 16l in the polymeriza-tion of acrylic acid on poly( diallyethylamine-
hydrochloroide) "PDAEA-HCL-" "poly( acrylamide-diallylamine-hydrochloride)
"PAM-DAA-HCI" and poly(acrylamide diallylethylamine-hydrochloride) "PAM-
DAEA-HCl".
The composition ofthe formed polymer ofis shown in Table(l) which shows that
the percent ofthe polymerized DMAEM increases with increasing the radiation dose.
This is due to increasing the conversion percent. The amine percent in the copolymer
reaches its maximum value at complete conversion. At dose >30 KGy the complex
copolymer is collve1ted into a gel with swelling degree ranging from 15 to 36. The
structure ofthe obtained polymeric gel is shown in possible structures 2&3.
The influellce of the radiationdoseOll the capacity ofthe obtained polymer are
shown in Table( I) which shows that both the capacity of the resin toward Cu2+
increase with increasing the radiation dose. The increase in the capacity may be
attributed to the increase in the degree of crosslinking between polymer chains. This is
similar to the previous finding (8) in effect ofradiation doseOll the capacity of PAM-
AA resin.
2- Influence of template polymer/monomer ratio:

The influence of the added template polymer on the capacity ofthe obtained
polymer toward Cu2+ was studied at monomer collcentratioll 0.64 MIL and absorbed
dose 30 KGy. The results are shown in Fig.2 which shows that the capacity increases
with increasing the polymer/monomer molar ratio to reach its maximum value at molar
ratio of 1.5. At very low polymer collcentratioll syneresis occurs, yielding strongly
inhomogelleous gel; even if syneresis is avoided large proportioll of dangling chains
and loop is produced. Higher concentration of precursor polymer increase the
probability for permanent trapped entanglements to occure. Moreover, a very high
viscosity ofthe medium may be favorable for the formatiom ofinhomogenetities within
the gel at which iterpenetration of chains beginsCl 7). Consequently, the capacity ofthe
gel increases. In addition, on increasing the amount of added polymer, the complex
formation(I8,19) between the monomer and polymer increases which Ieads to higher
extent of crosslinking between polymeric chains. Consequently, the capacity ofthe gel
increases.
3- Influence of monomer concentration

The influence of the monomer concentration Oll the capacity ofthe obtained gel
toward Cu2+ was studied at polymer/monomer equal molar ratio and at absorbed dose
30 KGy. The result are shown in Fig.3 which shows the capacity increases with
increasing the monomer concentration. On increasing the monomer concentration the
probability of complex formation increases. This increases the degree of crosslinking
between the polymeric chains. In addition, the number of amino groups increases
169
6
-

O'l
E 4
E
>-
.-:=
u
C1
a.
C1 2
u
0~----~----~----~----~
0 0.5 1.5 2
T IM
Figure 2. Influence of TIM molar ratio on the capacity of the obtained polymer gel.
8 ------------------------------------~
6
!:!'

E
E
"'
>-
u
C1
a.
0
u
2
0.2 0.4 o.s o.a

[M] .J MIL
Figure 3. Influence of monomer concentration on the capacity of the obtained gel.
170
which Ieads to increase the interaction with the cation. These increase the capacity of
the gel. This is similar to the previous finding(I5) in polymerization of AA on PMA. It
was found that the capacity ofthe resin increases with increasing the concentration of
the polymerized monomer along the template polymer (15).
fH3
--cH2-CH--; CH2--CH , CH2 ----f-
CONH21 COOH! N--CH2-CH2-0-C=O
: :c~ 'cH3
I
Structure 2: PAM-AA-DMAEM
-CH2-rH-;C~2-r i;:
t--
CH3
CONH2 coo- 4;--nCH2--H2CO-C=O

CH3 CH3
Structure 3: PAM-AA-DMAEM (Complex form)
4- Interaction between the gel and ions:

The formed gel was treated with CuS0 4 .5H20 as discribed previously (7). The
infrared spectrum of the formed floc produced fiom interaction of p (AM-AA-
DMAEM) with CuS0 4.5H20 is summa1ized in Table (2). The spectrum shows
absorption bands at: 560 and 1412 cm-1 charactedstic for coo- indicate that the
carboxylic group of the polymer chain forms bonds with Cu2+. In addition, the
presence of covalent sulphate group at 1412 cm-1 indicate that covalent bond is
formed between the polymer chain and the sulphate group.
The absorption bands show that:
a. Amide group like tertiary amino group interact with Cu2+ through the complex
formation. This is in agreement with the finding of other investigators in interac-
tion ofCu2+ with acrylamide polymers (15, 16, 20-23) and with the finding ofother
autherC24-27) in interaction of poly(4-vinylpYJ.idine)(PVP), poly(ethyleneimine)
"PEI" ,poly(vinylamine), poly( amidoamines ), poly(N,N,N' ,N' ,tetramethylethane-1,2-
diamine), ( 4-(3,4-dihydroxylphenyl-L-alanine) and polydioximes with cations such
as: Cu, Ni, Cd, Fe, Cr and Hg.
b. Carboxylic group interacts with Cu2+ through chemical reaction or cation-exchange
mechanism.
c. Carboxylic group interacts with Si- through anion exchange mechanism.
d. Hydroxyl groups from coordinated bonds with polymeric chains or ions of
CuS04 .5H20.
This is also in agreement with the previous findings (15,16,20-22).
171
Table (2): LR spectral data of p(AM-AA-DMAEM)
Absorption bands of original groups, cm-1 Experimental absorption bands, cm-1
Amide:
Free NH stret., 3500, 3500 (Amide ll) 3453
Bonded NH stret., 3350, 3180 1560
NHbond, 1620-1590 1638
C=O stret., 1650
(Amide I)
Carboxylate: 1610-1550 1560

-coo- 1410-1300 1412
Hydroxyl:
Free -OH stret., 3650-3590 3685,3666
Bonded -OH stret., 3400-3200
C-0 stret.
and -OH bend, 1200 & 920
Amine:
C-N stret., 1410 1412
Sulphate:
Ionic 140-1070,
480-400
Cova1ent 1450-1350 1412
1230-1150
& 650-550
REFERENCES
1- Z.H.Abd-Ellat: The Ist Arab Intern. Conf on Polymers Applications p. 67,

Fac. ofSci. Univ. of Mansoura, Egypt Sept. (1991).
2- Z.H.Abd-Ellat: Polym. Intern., 28, 301 (1992).
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5- A.Chapiro and RGouloubandi, Eur. Polym. J., 10, 1159 (1974).
6- T. Siyam, Studies on Gamma Radiation-induced copolymerization of Acrylamide-
Sodium Acrylate as Flocculant, M. Sc., Fac. of Sei., Cairo Univ. (1982).
172
7- T. Siyam, J. Moeromol. Sei. Pure. Appl. Chem A31 (314), 383 (1994).
8- T. Siyam, M.M.Abde1-Hamed & I.M.E1-Naggar, J. Maeromol. Sei. Pure. Appl.
Chem A32 (516), 871 (1995).
9- K.Fujimori, G.T.Trainor, Polym Bull., 9, 204 (1983).
10- K. Fujimori, G.T.Trainor and M.J.Costigan, J. Polym Sei. A-1, 22,2479 (1984).
11- C.H.Bamford and Z.Shiki, Polym, 595 (1968).
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IV, 121 (1962).
13- G.Odian, Principles ofPolymerization, MeGraw-hill Co. N.Y. Chap 3, 255
(1970).
14- A.F.Nikolayev, V.M.Ga~ Perinm Vysoknmol Soedinm Ser, A, 9, 2469 (1967).
15- T. Siyam and R.Ayoub, 3rd Arab Inter. Conf On Polymer Sei. and Teehnology,
4-7 Sept. Fae. ofSei. Mansouria Univ., Mansoria, Egypt (1995).
16- T. Siyam, I.M.El-Naggar and H.F.Aly, Nuclear and Hazardous Waste Managem-
ent Inter. Topieal Speetrum, 96, 66, 18-23 Aug. Seattle, Washington (1996).
17- Candau, J. Bastide and M.Delsanti, Strueturea~ Elastie and Dynamie Properties of
Swolen Polymer Networks, In: Advanees in Polymer Seienee (Polymer Netwarks)
Springer-Verlag Berlin Heidelberg N.Y. ( 1982 ).
18- K.Fujimore, Polym Bull., 8, 207 (1982).
19- K.Fujimore, G.T.Trainor & M.J.Costigan, J. Polym Sei., A-1, 22,2479 (1984).
20- T. Siyam and E.Hanna, J. Maeromol. Sei. Pure Appl. Chem A31 (314) 349
(1994).
21- T. Siyam, J. Maeromol. Sei. Pure Appl. Chem. A32(516) 801 (1995).
22- T. Siyam, "Gamma-Radiation-Indueed Preparation ofPolyeleetrolytes and Its use
for Treatement ofWaste Water" In: Chermis noff(ed), Handbook ofEngineering
Polymerie Materials, p. 119-135, Marel Dekker Ine. Under Puplieation.
23- M.A.Moharram, S.M.Rabie and A.Y.Daghistuni, J. Appl. Polym Sei., 50(3),
459 {1993).
24- E. J. Goethals, Polymerie Amines and Ammonium Salts, (International Symposium
on Polymerie Aminesand Ammonium Salts), Ghent, Belgium, 24-26 Sept. 1979,
pp. 229,255, 263271, 282, Pregamon Press (1979).
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(1993).
26- S. Savost'yanov, V.V.Pbyugin, D.A.Kvitska:'s and A.N.Pohmarev, Bvestiya-13
Vestiya Akadernii-Nauk-Seria-Khimieh, 6, 1070 (1993).
27- A.A. Mmau, S.V.Probysh, Yu. P. Bajdarovtesv, V.S.Savost, Yanov and AN.
Pohomarev, ibid, 5, 865 (1994).
173
ACID CORROSION INHIBITION OF NICKEL BY SOME
ORGANIC/MACROCYCLIC COMPOUNDS
F. M. Mahgoub, 1 B. A. Abd-El-Nabey, 2 M. Khalifa, 2 and A. El-Hefnawy 1
1 Department of Material Science

Institute of Graduate Studies and Research
Alexandria University, 163 Horreya Av., Alexandria, Egypt
2 Department of Chemistry
Faculty of Science
Alexandria University, Egypt
ABSTRACT
The corrosion inhibition of nickel in 0.5 M sulfuric acid solution by 2-(triphenyl

phosphoranylidene) succinic anhydride (2TPSA),1,4,8,11 tetraazocyclotetradecane (cy-
clam), and N,N'-bis(2-aminoethyl)-1,3-propane diamine (2,3,2 tet.) have been investigated
using DC polarization technique.
The anodic polarization curves ofnickel in 0.5 M H 2 S04 at different concentrations
ofthe three inhibitors were recorded at room temperature. The critical current density values
were used to calculate the percentage inhibition for each inhibitor concentration. The results
were compared with fits obtained from the application of Langmuir, Frumkin, Flory-
Huggins isotherm, and also from the application of kinetic-thermodynamic model. The re-
sults obtained were correlated to the chemical structure and the macrocyclic effect ofthe in-
hibitors.
INTRODUCTION
The importance of nickelas a basicmaterial for corrosion resistant alloys and its cata-
lytic properties with respect to many organic reactions is weil recognized. Nickel is also
well-known as corrosion resistant metal in many aggressive media, although it corrodes at a
significant rate in the presence ofmineral acidssuch as sulfuric acid. Due to its excellent cor-
rosion resistance when used in the commercially pure form, and its use as an alloying ele-
ment. Few papers have appeared in Iiterature dealing with inhibitors and corrosion inhibition
of nicke! in aqueous acid solutions I-s. Since work on the corrosion inhibition ofNi is not ex-
tensive, abrief description ofthe mechanism ofthe inhibition process and inhibitors reported
in the Iiterature is useful.

Edited by P. N. Ptasad etal., Plenum Press, New York, 1998 175
The adsorption behaviour6 of polar organic compounds on anodically polarized Ni
electrode in 3.0M HC10 4 was confirmed by impedance and polarization measurements. The
compounds used as corrosion inhibitors were those ofwhich polar atoms were elements of
VA and VIA groups ofthe periodic table. Double layer capacitance ofthe electrode-solutions
interface in the active region ofthe polarization curves showed that the compounds classified
as a softbasewas more readily chemisorbed on the surface actingassoft acid than that a hard
base. Hence, inhibition efficiency of a soft inhibitor for Ni dissolutionwas higher than that if
hard base inhibitor. In a passive region, compounds classified as a hard bases lowered the pas-
sive current density of the electrode, while some soft bases stimulated it.
Mono-,di,triethanolanol amines and some amine-type compounds have been studied
as inhibitors for nicke! dissolution in H2S04 7 . These inhibitors do not alter the rate-
determining step (RDS) of either the anodic or cathodic reaction. The mechanism ofthe ad-
sorption process has been thus discussed in terms ofLangmuir isotherm. The relationship be-
tween the adsorption process and inhibition mechanism of a number of S-containing
molecules toward the corrosion ofNi in HO4 has been reported 89 Compounds investigated
include dithio and seleno carbonates and their esters. These compounds generally improve
attachment into the metal surface compared to thioether groups 3
In previous work 10-- 12 the macrocyclic compounds (cyclam and 2,3,2-tet) have been
testedas corrosion inhibitors for the acid corrosion of steel, in this work we investigated these
compounds as corrosion inhibitors for nickel in 0.5 M H2S04
Recently 13 , 2-(triphenosphoranylidene) succinic anhydride (2 TPSA) has been used
as corrosion inhibitor ofthe acid corrosion ofnickel. In this work the kinetic-thermodynamic
model of inhibition has been applied to fit the results of the inhibitor for the acid corrosion of
nickel by this compound and also by the macrocyclic compounds. Results and parameters ob-
tained were compared to those obtained from fitting the data to the Langmuir, Frurnkin and
Flory-Huggins isotherms. 14--15
EXPERIMENTAL
Electrode Preparation
The experiments were performed with nickel wires (99.99%) 0.25 mm in diameter
from (BDH). The sample was cleaned and degreased in ethanol before mounting in a glass
tube using epoxy-patch. Before each run, the electrode was mechanically polished with a se-
ries of emery papers, starting with a coarse one and proceeding in steps to finer grades. The
sample was then ultrasonically degreased in methanol and finally rinsed in doubly distilled
water.
Electrochemical Measurements
The potentiodynamic polarization measurements were recorded using an Winking

potentiostat (Model MP 87); the scanning rate used was 1 mvs-t. All the electrode potentials
were measured with reference to a saturated calomel electrode (SCE).
Before each measurement, the solutions was purged with N 2 gas for 1.5 hours. All
measurements were conduced at 27 0.1 C in the presence ofN2 gas to avoid oxygen entrance
into the electrolyte.
The Chemieals
The inhibitors employed in this work have the chemical formulas presented below as
shown in Figure (1). The N,N'-bis (2-aminoethyl)-1,3-propane diamine (2,3,2-tet), was pur-
176
n n
( )
N N
( )
LJ
N ,N' -bis(2-aminoethyl)
1,4,8, 11-tetraazocyclodecane 1, 3-propandiamine
(Cyclam) (2,3,2 tet.)
H
I
(Ph) 3 - P = C - C - H
I I
o=c c=o
'--....o/
2-( triphenosphoranylidene )succinic anhydride

(2TPSA)
Figure 1. The investigated compounds.
chased from (BDH), the 1,4,8,11-tetra-ozocyclo-tetradecane, (cyclam) from (Aldrich) and

2-(triphenyl phosphoranylidene) Succinic anhydride (2TPSA) was prepared 13 .
RESUL TS AND DISCUSSION
Figure (2) shows the anodic polarization curves ofnickel specimen in 0.5 M sulphuric
acid solution without and with different concentrations of2 TPSA ((2-triphenyl phosphora-
nylidene) succinic anhydride ). The anodic curves obtained exhibited all ranges of dissolution
and passivation of nicke!. Inspection of Figure (2) shows that the addition of different con-
centrations of (2TPSA) have a significant effect on the anodic behaviour. A systematic de-
crease ofi.e. (critical current) with the increase ofthe concentration of2TPSA is obtained;
while no significant effect on the EP (passivation potential) at all concentrations used is re-
ported. Table (1) shows that (i0 ) critical current decreases as the concentration of 2TPSA is
increased.
Figure (3) shows the anodic polarization behavior of nicke! in O.SM H2 SO 4 solution in
the presence of 1x 1o-3 M 2TPSA, cyclam or 2,3,2-tet at room temperature. Inspection ofFig-
ure (3) shows that the addition of 1 X 10-3 WL of2TPSA, cyclam or 2,3,2-tet does not have
any significant effect on the passivation potential (E ), while critical current (i ) decreases
with increasing the concentration of the inhibitor. P c
Figure (4) shows the variation of the critical current (i 0 ) with the concentration of
2TPSA, cyclam and 2,3,2-tet individual. It appears that the value ofi 0 decreases with the in-
177
1.4 -- ----
-<>-O.OM
-t 1X0.0001M
-- 2 XO.OOOl M
6 X 0.0001 M
0.001 M
- .2 ~
0 20 40 60 80 100 120 140 160

lpA
Figure 2. Anodic polarization behaviours ofnickel in 0.5 M aqueous solution ofH 2 S04 containing different
concentrations of2TPSA.
crease of the concentration of the compounds. The curves show that the order of decreasing
of ie is 2TPSA > Cyclam > 2,3 ,2-tet.
Figure (5) shows the variation ofthe protection efficiency as a function ofthe loga-
rithm ofthe molar concentration ofthe three inhibitors. The protection efficiency P ofthe in-
hibitor was calculated by applying the relationship (I)
(l)
where ico and ie are the critical current in the absence and in the presence of a certain concen-
tration of inhibitor respectively.
Inspection ofFigure (5) indicates that the protection efficiency ofthe three inhibitors
used in this study is ordered in the sequence:2TPSA > Cyclam > 2,3,2-tet. These results was
interpreted as due to structure effect. Where the higher efficiency of the first inhibitor
(2TPSA) was interpreted as due to the easier polarizability and the presence ofthree phenyl
Table I . Electrochemical parameters obtained from D.C. polarization

measurements ofnickel in a 0.5 H 2S04 as a function ofthe three
inhibitors concentrations
2-TPSA Cyclam 2,3,2-tet

Concentration %Inh %Inh % Inh
O.OM 155 0.0 155 0.0 155 0.0
I X 104 M 108 30 125 20 140 10
2 X 104 M 100 36 106 32 133 14
4 X 104 M 92 41 99 36 128 18
6 X 104 M 70 55 87 44 107 31
103 M 38 76 78 50 95 39
178
1.5 - -
-<>- o oM
000 1 M te l
0.00 1 M Cyclam
0 00 1 M 12TPSAI
w
u
(/)
(/)
>
w
= 'c,
-- _:;:;
20 40 60 80 100 120 140 160

lf.JA
Figure 3. Anodic polarization behaviours ofnickel in 0.5 M aqueous solution ofH 2 S04 containing I x 10-3 M
M of(2TPSA), cyclam and 2,3,2-tet.
0< 2 .3 . 2-uu
+ cvclam
+
... 2TPSA
* . +*. 0
0.0002 0.0004 0.0006 0.0008 0.001

[I)
Figure 4. Critical current (ic) as function of concentration of the three inhibitors.
179
80 ~--------------------------------~
2,3,2 ltetl
+ Cyclam
l!E 12 TPSA)
60 -
+
c:
0
:~
:e
..c: 40
_)Ii
c:
liE ' -+
+'
20 -
-.
0 I I I I I I I I
-4.4 -4.2 -4 -3 .8 -3.6 -3.4 -3.2 -3 -2.8
Log 111
Figure 5. Relation between inhibition efficiency and Log [I] for the three inhibitors.
groups attached to the phosphorus atom leading to the electron density increase and then in-
crease the adsorption on the surface ofthe meta!.
On the other hand, the cyclam is more efficient than 2,3,2-tet due to macrocyclic ef-
fect, where the cyclam is cyclic while 2,3,2-tet is open molecule.
Kinetic-Thermodynamic Model and Adsorption Isotherms Analysis
Generally the understanding of the nature of adsorption process of various types of

Iigands or any organic adsorbate on the surface of a meta) is regarded as a simple substitu-
tional adsorption process between the inhibitor in the aqueous phase (inh.)aq and, x, ofwater
molecules adsorbed on the electrode surface (H 20)sur
(2)
180
where x is the size ratio that is the nurober ofwatermolecules replaced by one molecule ofin-
hibitor adsorbate. The above process reaches equilibriuro at which point the chemical poten-
tial (Jl) on the left side is equal tothat ofright side. Now, depending on the expression ofJl as
related to the physical model adopted to describe adsorption, one may obtain different expres-
sions of the adsorption isotherm. For example the most used are the Langmuir isotherm is
given by: 14
(9/[1 - e]) =K [I] (3)
where 9 is a degree of coverage and K is the equilibrium constant of the adsorption reaction
and [I] is the inhibitor concentration in the bulk ofthe solution. A plot ofthe left side of equa-
tion (3) should give a straight line, ifLangmuir isotherm is applicable.
The Frumkin isotherm is given by: 15
[9/(l- 9)] EXP (-2a) =K[I] (4)
where "a" is a molecular interaction parameter depending on the molecular interactions in the
adsorption layer and degree ofheterogeneity ofthe surface. In the limit when x = 1 and a = 0
the isotherm reduce to the Langmuir isotherm, Equation (3).
The Flory-Huggins 16 isotherm is
[9 /x( 1 - e)'] =K[I] (5)
where x is a nurober of water molecules replaced by one molecule of inhibitor adsorbate.

The kinetic-thermodynamic model 10 published that kinetically the inhibition process
is taking place via adsorption or occupation of a given inhibitor molecule a nurober 1/y of sur-
face active sites according to
s + yl = SIY
Where y is the nurober of inhibitor molecules occupying one active site. This leads to the rela-
tionship
[9/(1 - 9)] = K'[I]Y (6)
or log [9/(l - 9)] = logK' + y log [I] (7)
The binding constant, K, corresponding to that obtained from Langmuir, Frumkin or Flory-
Huggins curve fitting is given by K =(K') 11Y
Curve fitting of2TPSA, cyclam and 2,3,2-tet data to the Langmuir isotherm Equation
(3) is given in Figure (6) which shows that the Langmuir isotherm is not applicable to fit the
data ofthe adsorption of2TPSA and cyclam, but it is suitable to fit the data of2,3,2-tet. Fit-
ting the data to the Frumkin isotherm Equation (4) is given in Figure (7). The results show that
this isotherm is not applicable to fit the data ofthe three inhibitors.
The curve fitting for the 2TPSA, cyclam and 2,3,2-tet data to the Flory-Huggins iso-
therm, Equation (5) is given in Figure (8), the data show excellent fit for the three compounds.
The curve fitting for the three inhibitors data to the kinetic model Equation (7) is given in Fig-
ure (9) which shows also an excellent fit for the inhibitors used.
Table (2) records the curve fitting data of2TPSA, cyclam and 2,3,2-tet to the Lang-
muir, Flory-Huggins isotherms and the kinetic model. The table displays the results ofthe
three data treatments when applicable in which the nurober of active sites, 1/y (kinetic
model), the number, x ofwater molecules replaced (Flory-Huggins) and the values ofthe
binding constants, K, are given.
181
3.5 3.5
~::~ 2,3,2 (tetl
-/-Cyclam
3 3
)iE (2 TPSAJ
2.5
CD' 2 2
~ 1.5 1.5
0 0.0002 0.0004 0.0006 0.0008 0.001

[I)
Figure 6. Test of Langmuir adsorption isotherm for the three inhibitors.
3.9
3.7
q> 3 .3
~
CD
.:::;::.3.1 .
Cl
0
...J
2.9
2.7 -
2.5
0.05 0.2 0.35 0.5 0.65 0.8
e
Figure 7. Test ofFrumkin adsorptionisotherm for the three inhibitors.
182
4.5 -r?'---~-----------------------r 4.5
-o- 2,3,2-tet
+cvclam
4 4
* 2TPSA
3.5 3.5
3 3
2.5
2 2
1.5 1.5
1
-0.62 -0.57 -0.52 -0.47 -0.42 -0.37 -0.32 -0.27 -0.22 -0.17 -0.12 -0.07 -0.02
Log 11-81
Figure 8. Test ofFlory-Huggins adsorptionisotherm for the three inhibitors.
3 ~---~-------------------------------------,3
-" 2,3,2 (tetlj
*
/ Cyclam
(2 TPSA)
2 . --- -------------
2
<D
'
-1 -1
-2~---,----,----,----,----,----,----,----,----,----~-2
-4.5 -4.3 -4.1 -3.9 -3.7 -3.5 -3.3 -3.1 -2.9 -2.7 -2.5
Log [I]
Figure 9. Test ofKinetic-Model adsorptionisotherm for the three inhibitors.
183
Table 2. Test for the adsorption isotherms ofthe three inhibitors individually
onto nicke! in 0.5 M H 2 S04
Langmuir Flory-Huggins Kinetic-thermodynamic

Inhibitor K K X K 1/y
2-TPSA 2698.4 0.999 2627 1.25
Cyclam 1352.9 3.02 1055 1.7
2,3,2-tet 613.7 509 1.843 515 1.28
Inspection of Table (2) shows that 2TPSA offers a higher binding constant to the
metal surface than the other two compounds. However cyclam offers a higher binding con-
stant to the metal surface than the 2,3,2-tet. These results confirms the data obtained from the
percentage inhibition versus the logarithm ofthe concentration ofthe inhibitors which is dis-
cussed in the previous section.
A fairly good agreement between the kinetic modeland Flory-Huggins isotherm is
obtained for the equilibrium constant (K) and for the size parameter x (Flory-Huggins) and
the number of active sites ( 1/y) (kinetic model) for fitting the data ofthe three inhibitors. The
table showsalso that the value of(K) obtained from the application ofLangmuir isotherm is
in a good agreement with those obtained from the application ofthe Flory-Huggins isotherm
and kinetic model for the fitting ofthe data 2,3,2-tet inhibitor.
The foregoing results show that the kinetic thermodynamic modeland Flory-Huggins
isotherm are suitable to fit the experimental data of the three studied inhibitors, however,
Langmuir is suitable only to fit the experimental data of the 2,3,2-tet inhibitor. However,
Frumkin isotherm is not suitable to fit the experimental data ofthe three inhibitors studied.
The Kinetic-thermodynamic model presents a fresh new Iook at corrosion data that
are obtained primarily from a kinetic type experiment. In addition it opens the way to a closer
Iook at the system from a rate law range that could results in various mechanistic interpreta-
tion leading to the design of a better class of inhibitors for a given metaland chemical envi-
ronment.
REFERENCES
I. Reshetnikov, "MetalL Kokskhim", 89 (1986) p. 14.
2. Aramaki, Boshoku Gijutsu, Corros. Eng., 36 (1987), p. 444.
3. Sastry, R. Packwood, werkst, "Korros.", 38 (1987) p. 77.
4. R.Abd El-Gulil, A. Abd EI Fattah, "Corros. Prev. Control, 34 (1987) p. 149.
5. Aramaki, T. Mochizuki, H, H, Nishiha, "I O'h Inter. Congress on Met. Corros., Madras, India, vol. 3 Oxford
and IBH, New Delhi, 1988, p. 2759.
6. Aramaki, Kunit Sugu; Nishihava, Hirdshi (Fac. Sei. Technolo., Keio. Univ, Kokohama, Japan 223). J. Elec-
trochem. SOC. 1987, 134 (5), 1059-{)4 (Eng.).
7. Muralidharan, M. Verashanmugani, G. Kalaignan, Bull. Electrochem., I (1985), p. 373.
8. Fillppo, A. Rossi, M. Spezziga, Proceedings of6'h Europ. symp. on Cornos. inhibit., Ferrara, Ita1y, Univer-
sity ofFerrara, (1985).
9. K. Kishi, S. Lkeda, Application of surface science, 5 ( 1980) p. 37.
10. E1-Awady, B.A. Abd E1-Nabey, S.G. Aziz, M.Khalifa and H.Al- Ghamdey. "International Jour. Chem." vol
1, No. 4 (1990). 169-179.
II. El-Awady, BN.A. Abd-El-Nabey, and S.G. Aziz," Electrochem. Soc." vol. 139 No. 8 (1992).
12. Khamis, F. Bellucci. R.M. Latanision, and E.S.H. El-Ashry "Corrosion" pp. 677-686 (1991).
13. Frumkin, "Z. Phys. Chem.", 116 (1925) p. 466.
14. Dhar. 8. Conway, K. Joshi, "Electrochemica Ata." 18 (1973) p. 789.
15. Al-Andouli, F. EI-Taib, F. El-Nizami and 8. Ateya. ExtendedAbstracts ofthe Electrochemical Society Fall
meeting, Chicago, Illinas, Electrochem. SOC., Pennington, NJ, p. 188 (1988).
184
ADVANCED SPATIAL LIGHT MODULATOR BY USING POLYMER
CELL-WALL TYPE LIQUID CRYSTAL LIGHT SHUTTER
Tadahiro Asada
Department of Polymer Chemistry
Graduate School of Engineering
Kyoto University
Kyoto 606, JAPAN
Tel: +81-75-753-5629, Fax: +81-75-751-2769
INTRODUCTION
So far, many studies have been reported to utilize liquid crystallight shutters for making
Spatial Light Modulators (SLM)1 However, a few have intended to make the best use of the
advantage of non-polarizer usage. One of the reason may be due to difficulty to obtain a
q1;1~ed light shutter witho~t the usage of .polarizers. The abilities of Pol~er Ce~-Wall Type
Ltqutd Crystal (PCW-LC) light shutter which has been developed by us2- are constdered to be
suitable for such applications. This is a kind ofliquid crystal + polymer complexes (LCPCs),
utilizing the light scattering of cholesteric liquid crystals4 A distinctive feature of the PCW-LC
light shutter is very small polymer content (aroundlO%), as the cholesteric liquid crystals
domains covered with thin polymer films, what malres the driving voltage to be very small
(5V/10lJ.). Consequently, this type of light shutter can be useful not only for liquid crystal
display devices but also for other various applications, especially for spatial light modulator.
The advantage for this application is that it becomes easier to combine other components to
construct a spatial light modulator because of the non-polarizer usage_ In this work, more
advanced application of PCW-LC light shutter to a spatiallight modulator will be introduced_
Polymer Cell-Wall type Liquid Crystal (PCW-LC) light shutter will be briefly introduced
at the beginning. Then, the application of the light shutter to malre an advanced spatial light
modulator and the new type spatiallight modulator will be described_
POLYMER CELL-WALL TYPE LIQUID CRYSTAL LIGHT SHUTTER

Polymer-dispersed liquid crystals (PDLCs) and liquid crystal + polymer complexes
(LCPCs) have been a great interest for display applications, since they have a lot of
advantages, such as non-polarizer usage, easy fabrication and manufacture of large area
display devices6 7 However, there remain problems in the threshold-voltage, response time
and transmittance8 To malre improvements on these points, the Polymer Cell-Wall Type
Liquid Crystal (PCW-LC) Light Shutter has been developed by us3-4 utilizing the tremendous
light scattering of polydomain focal conic texture of cholesteric liquid crystals(ChLCs)- Some
attempts have been reported for developing a light shutter using this propertY _
Science and Teclmology of Polymers and Advanced Materials

Edited by p_ N. Prasad et al., Plenum Press, New York, 1998 185
G
Figure 1. Schematic representation of a Polymer Cell-Wall Type Liquid Crystal Light Shutter.
(A) : No voltage is applied (Off state).
(8) : A voltage is applied (On state).
G : ITO coated glass plate
Construction of PCW-LC Light Shutter

The time for polydomain texture reformation should be controlled to improve the quality.
One way for this is to improve the cholesteric twisting power, and another is to introduce the
wall effects. The attempts were reported 3"5 previously, that were done to improve the turbidity
and decay-time of LCPC films by Controlling the cholesteric twisting power and the polymer
wall effect We would rather call PCW-LCs mainly because the polymer thin films coat the
cholesteric liquid crystal grains in our system3 4 The ratios of ChLC, NeLC [a cholesteric
liquid crystal obtained by mixing ChLC + nematic liquid crystal (NeLC)] and prepolymer were
selected by comparing many experimental results 3-5 A homogeneous solution of liquid crystal
(LC) and prepolymer was firstly sandwiched between the two ITO-coated glass plates with a
spacer of thickness (7.5-12.5Jlm), and then was polymerized by irradiating UV light for 5-6
min. The solution could become a two phase system. The polydomain ChLCs gradually
appeared during the polymerization. Thus, the very small size particle-like LC grains covered
with thin polymer ftlms were formed within the cell. The thickness of the cell introduced here
is lOJlm.
The sehemarle illustrations of a PCW-LC light shutter is shown in Figure 1.
The Electro-Optical Properties of PCW-LC

The electro-optical properlies of PCW-LCs were investigated using OS-6411C Digital
Storagescope (Iwatsu Co. Ltd.) with He-Ne laser or white light sources. The sehemarle
illustration of the apparatus for the measurement of electro-optical properlies of PCW-LCs cell
is shown in Figure 2.
It is well known that when a small amount of pure ChLCs is added to NeLCs, the mixed
LCs will become ChLCs. As the nematic component 5-CB (4-cyano-4' -pentyl biphenyl) was
used for all experiments reported here, because of the quick response for orientational change
of molecules to applied electric field. MC-15 (biphenyl type, Merck) was used as the
cholesteric component, because this type of ChLC was proved to be suitable for our purpose
taking into account experimental results4 "5 As an example, in Figure 3, transmittance and
voltage curves for two cases were compared when cholesteral acetate was used as the
cholesteric component and MC-15 was. It is also interesting to know what happens when
186
JJetector
Slit
Conduotiv~
Coating Digital Storagescape
Glass
Plate = =
LCPC
Voltaga
Generator
Light
Figure l. Schematic diagram of tbe apparatus for tbe measurements of tbe electro-optical properties of a LC +
Polymer cell.
100~~~--~~--~~~~
90 O:A MC-15 0.35%

80 ~:8 Acetat 0.40%
~70
CD
g 60
0
~50
~ 40
~ 30
20
6 8 10 12 14
Votlage / Vrms
Figure 3. Cbanges of lransmittance and response time of case A and case B against applied voltage at 500 Hz.
100~--~~~--~~--~~
90
80
~ 70
~ 60
c
~ 50
~ 40
c
~ 30
I-
20
10
0 4 6 8 10
Vollage / Vrms
Figure 4. Cbanges of lransmittance against voltage at 500 Hz for case C and case D.
187
chiral smectic LC is added to the cholesteric LC systems. Chiral smectic LC are also known to
form focal conic textures. Combination of the cholesteric focal conic texture and Smectic C*
focal conic texture are interesting. The chiral smectic LC used are Merck ZLI4237 and
ZLI4655. They have opposite helical senses to each other; ZLI4237 has (-) and ZLI4655 has
(+). The experimental results are shown in Figure 4 C. Figure 4 D shows that additions of
chiral smectic (ZLI4237) improve the Transmittance-Voltage properties, that is, the threshold
voltages become lower and the transmittances at 6 V increases very much ( more than 75%).
On the other hand, additions o( chiral smectic (ZLI4655) do not make the threshold voltage
lower (See Figure 4 D). Moreover the additions of ZLI4655 malre the transmittances at 0 V
(oft) higher. After all, additions of ZLI4237 improve the properties, but ZLI4655 do not.
Concerning response times 't, + 'td the additions of chiral smectic make the time longer,
especially in the case of additioning ZLI4655 (See Table 1 and Table 2). For both cases
(additioning ZLI4237 and 4655), 'td becomes longer. In conclusion, the effect of additioning
chiral smectic LCs on electro-optical properties are good (ZLI4237)and bad (ZLI4655).
It has been found that the effect of additional chiral smectic LCs to the above components on
electro-optical properties are very good, when the helical sense of smectic C* coincides with
that of cholesteric LCs4 5
As evidently shown in Figure 4 C, the PCW-LC film using combination of Cholesteric
LC and Smectic C* has a very low driving voltage, very quick response time and also high
contrast ratio for electro-opticalapplication, as shown in Table 1. The electro-optical properties
ofPCW-LC are greatly affected by twisting power of cholesteric liquid crystals and polymer
wall effect. It is clear that one can develop various kinds of LCPC films which have different
driving voltage, response time and contrast ratio for light shutter and display applications by
controlling polydomain textures of LCs and polymer wall effect in LCPC' s films. Besides, it
was found that the temperature during polymerization would greatly affect the turbidity of
PCW-LC films after polymerization, which will be reported in near future.
A Voltage-Transmittance curve of a PCW-LC cell is shown in Figure 5, as for example.
Though not evidently seen from Figure 5, the transmittance belowthreshold voltage is Ca.0.5-
0.55%. It is clearly seen from the Figure 5 that the transmittance at the steady state is attained
at Ca.5(V). The components and properties of this cell are shown in Table 3.
Application ofPCW-LC for display devices is considered mainly in 3 ways: The first is a
usual display systems which are commoruy used like twisted nematic display devises.
Advantage for the use of PCW-LC is to be used without polarizers. The second is reflection
type displays which do not need backlight is an energy saving type and is also good for eyes.
The third is a projection type wide-display to which spatiallight modulator will be introduced
here later, will be utilized.
Table 1. Response times and voltage for sample C.
vrnul -r. (ms) td (ms) T (%)

0 - - 0.72
5 7.0 10.0 76.0
6 7.0 10.5 77.0
Table 2. Response times and voltage for sample D.
V,lllS 't. (ms) td (ms) T (%)

0 - - 1.30
6 15.9 19.9 45.5
10 11.5 30.0 72.6
188
100.-~.-~~~~-----.
90
80 E
~ 70
~ 60
c
,g 50
-~ 40
c
e
I-
30
20
10
0 6 B 10
Valtage /Vrms
Figure S.Cbanges of ttansmittance against applied voltage at 500 Hz for Case E.
Table 3.PCW-LC (E) Components and Properlies

Components Properties
Materials Name Contents volt:;: 5-6V
NeLCs 5-CB 90.00% t, * 3-7ms
ChLCs MC-15
(Merck)
0.30% *
td 8-llms
T::i: 75-78{%)
Materials ZLI4237 0.20% Cont.:!;: 150
(Merck)
Prepolymer a kind of 9.50%
Acrylates
SPATIAL LIGHT MODULATOR USING PCW-LC
Construction of a Spatial Light Modulator
The constructi.on of the spatiallight modulator is as follows : transparent conducti.ve glass

plate + PCW-LC + dielectric mirror + light absorber + photo conductor plate + transparent
conducti.ve glass plate. The schematic illustration of a Polymer Cell-Wall Type Liquid
Crystal Spati.al Light Modulator is shown in Figure 6.
Test of PCW-LCs for a Spatial Light Modulator
At frrst, many PCW-LCs were tested to select the best compositi.on-sample for using
Spati.al Light Modulator. A special apparatus was constructed for the testin1f. The essential
parts of the SLM ( Spatial Light Modulator ) are the photo conductor and PCW-LC which are
sandwiched by the two transparent conductive plates. The construction of the cell is :
transparent conducti.ve coated glass plate + PCW-LC + photo conducti.ve plate + transparent
conducti.ve coated glass plate. When a light beam for writing light irradiates to photo conductor,
the opening and closing of the PCW-LC light shutter is controlled by the light intensity of
writing light ( here used a green light ) . The light beam from a light source ( red ) passes
through the PCW-LC cell when writing intensity is strong enough. When the light is irradiated
on photo-conducti.ve plate, the resistance of the photo-conducti.ve plate "is reduced and the
electric voltage is applied to PCW-LC. Then the light shutter will be open, and the reading light
can pass through. The light intensity passing through the PCW-LC cell is controlled by writing
light intensity.
189
4
Writing Recording
beam beam
2
8
Figure 6. Schematic representation of a Polymer Ceii-Wall Type Liquid Crystal Spatlai Light Modulator.
(a): No writing beam, (b): lradiating writing beam.
I : Polymer cell-wall type liquid crystal
2 : Lightabsorber
3 : Dielectric mirror
4 : Photoconductor
5 : Glass plate
6 : Antiretlective coating
7 : Transparent electrodes
8: Voltage source ( Function generator ).
I
I
0
Flgure 7. Scbematic diagram of tbe apparatus for tbe testing of a SLM (Spatial Light Modulator) unit usirig
Polymer Cell-Wall Type Liquid Crystal (PCW-LC) Light Shutter.
LS: Laser light source (He-Ne)

S: Siite
F I : Fliter(6328A)
D: Detector for Iaser light intensities
LSW: Light source of coodensed light for open shutter
F 2 :Filter to get monochromatic light
L: Leus
G: ITO coating glass plates
PC: Photoconductor
PCW-LC: Polymer cell-wall type liquid crystals
FG: Function generator.
190
100
rJP
Q)
60V
u
....
r
lU
+I 50
+I
.-l
e
Ul
s::
lU
~
E-<
Power (uW/cma), Irradiated Light

Figure 8. Transmittance against in'adiated power
As for an example, it was tested for the case that the thickness of photo-conductor BSO-
crystal plate and PCW-LC were, respectively, 2mm and lOJ.lm. Voltage between conductive
plates were kept 30, 40, 50, 60, 70(V). Then the relation between the Power of irradiatedlight
(J.1W/cm2 ) and Transmittance of reading light have been examined. The results tells that applied
voltage 50V is best for this case.
Taking into account such results, a spatial light modulator was constructed and the
sehemarle illustration of the Spatial Light Modulator is shown in Figure 6. Piease note this is a
sehemarle illustration and actual thickness of PCW-LC is 7-lOJJ.m and the Photo-conductor
plate of thickness 2mm is used. Because of dielectric mirror is placed between PCW-LC layer
and Photo-conductor, the constant applied voltage should be kept much hlgher than that for
testing case. The relation between the power of irradiated light and the intensity reflected light
(reading light) is sigmoidal and the shape of the curve is similar to that obtained for the test
case. We must improve the mirror for our purpose because the thinner is better for efficiency
but is lost the toughness.
ACKNOWLEDGMENT
The support of Kansai Research Foundation for Technology Promotion Foundation is
greatly acknowledged for this research.
REFERENCE
1. L.M.Blinov. Electro-optical and Magneto-optical Properties ofliquid Crystals , John
Wiley & Sons, New York (1993).
2. P.Jiang, and T.Asada, Chemistry Express.6:1005 (1991).
3. P.Jiang, and T.Asada, Mol.Cryst.liq.Cryst.222:81 (1992).
4. T.Asada, and S.Tang, Chemistry Express.8:665(1993).
5. T.Asada, and S.Tang, MoLCryst.Liq.Cryst.282:355(1996).
6. J.W.Doane, A.Galemme, J.L.West,J.B.Whitehand, JR, and B.G.Wu, MoLCrys.
Liq.Cryst. 165:511 (1989).
7. M.Kunigita, Y.Hirai, Y.Ooi, S.Nirayama, T.Asakawa, K.Masumo, H.Kumai, M.Yuki,
and T.Gunjima, Soc.for Information Display Digest. (1990).
8. J.W.Doane, MRS Bulletin. 16:22 (1991).
9. H.Fujikake,K.Maruyama, T.Kuriyama, andH.Ogawa, Abstract liq.Cryst.Meeting,Japan.
16:124 (1990).
191
EFFICIENT FULLCOWUR LIGHT-EMITTING DEVICES
AND LASERS WITII POLYPHENYLS
G.Leising 1, F.Meghdadi \ S.Tasch \ C.Brandsttter \ W. Graupner 1,
S. Hampel 1, J.W.E. List 1, F. Stelzer 1, B. Winkler 1, C. Zenz 1, P.

Schlichting 2, U. Rohr 2, Y. Geerts 2, U. Scherf 2 and K. Mllen 2
*Institut fur Festkrperphysik, SFB Elektroaktive Stoffe, Technische

Universitt Graz,Petersgasse 16, A-80 I 0 Graz, Austria
**Max-Planck-Institut fur Polymerforschung, Ackermannweg 10, D-
55128, Mainz, Germany
ABSTRACT
Soluble and stable polyparaphenylene-type ladder polymers with an extraordinary high

degree of intrachain order and exceptionally low concentration of defects in the electronic
structure belong to the dass of best defined conjugated low-dimensional organic
semiconductors currently available. Parahexaphenyl, the highly stable oligomer of
polyparaphenylene, can be synthesized in the form of single crystals, disordered thin films
and highly ordered epitaxially grown thin films. We present and discuss results on the optical
and optoelectronic properties ofthese polyparaphenylene systems.
We demonstrate the fabrication and characterization of highly efficient red-green-blue
(RGB) and white light emitting devices with these electro-active materials. This RGB-
devices are fabricated based on a new technique, which allows the realization of fullcolour
flat panel displays. The brightness of such RGB emitting devices is higher than 1000 cd/m2
(for the green device), comparable tothat offluorescent tubes. Using this new technique, we
are able to produce devices having any desired emission colour in the visible and near
infrared spectrum.
A high photoluminescence quantum yield and a good environmental stability of the
active oligomer or polymer materials, besides many other device parameters, are very
important to achieve competitive operation lifetimes of these new organic
electroluminescence devices.
Photoexcitation experiments on polyparaphenylenes reveal their high photo-
luminescence quantum yield and the perspective for being true candiates as solid-state
polymer-laser materials due to their pronounced signature ofblue-green stimulated emission.
We present blue-green Iaser action in polyparaphenylene-type ladder polymer.
Scier1ce and Techno/ogy of Polymers and Advanced Materials

Billted by P. N. Prasad et al., Plenum Press, New York, 1998 193
INTRODUCTION
Organic light-ernitting diades (OLEDs) are based on the principle that electrons and
holes are injected into the organic semiconductor from opposite electrodes, when an external
bias (usually between 5 and 20 V) is applied [1-6]. The electrolurninescence (EL) ernission is
observed, when the combination of oppositely charged carriers Ieads to the formation of
excited states (singlet excitons), which then decay radiatively. OLEDs are very suitable
materials for application in flat-color-panel-displays due to the high [7-9] achievable
lurninance (> 10000 cdlm2 [10,11]), the high EL efficiency (up to 4% [12-15]) and the low
driving voltages (<I 0 V) of organic thin film devices.
We show how self-ernissive displays and also efficient white OLEDs for usage as
backlight source liquid crystal displays (LCD) can be produced based on blue OLEDs using
external and internal color conversion techniques.
Due to their high photolurninescence efficiency (>30%), high environmental stability
and the good charge transport properties the derivatives of poly(paraphenylene) (PPP), as
the laddertype PPP (LPPP) and the oligomer hexaphenyl (PHP), are very suitable materials
to realise efficient, stable, !arge area blue organic light-emitting diades (OLEDs) (s. Fig.l).
The emission ofblue OLEDs can be efficiently converted into all other emissioncolorseither
by an extemal color conversion technique (ECCT) or an intemal color conversion technique
(ICCT) and hence are very interesting for a number of display applications:
Firstly, we demonstrate the realisation of efficient red-green-blue (RGB) ernission
colors (representing the RGB-pixels in a multicolor display) by an ECCT. In this case the
blue EL device is covered with highly fluorescent dye/matrix layers, which are excited by the
blue ernission and emit photoluminescence light in a lower energetic range.
Secondly, a new method for producing efficient white light-ernitting polymer diodes
(which are interesting for e.g. backlight sources in liquid crystal displays) based on a blend of
two polymers by an ICCT is presented: a blue light-emitting methylsubstituted laddertype
PPP (m-LPPP) and a red-orange emitter poly(perylene-co-diethynylbenzene) (PPDB). The
red-orange ernission is created within the EL device by an excitation energy transfer from m-
LPPP into the energetically lower lying states of PPDB. This internal excitation energy
transfer is very efficient, so that only a concentration of0.05 weight% PPDB in the polymer
blend is required in order to obtain white light emission.
I. Polyphenyl-type Materials for Blue LEDs
m-LPPP tagether with the conjugated oligomer PHP belong to the most favourable
candidates for the fabrication of blue OLEDs [ 16-18], which are of special interest for the
realisation of multicolour emission.
By incorporating the PPP into a rigid backhone the LPPP (s. Fig.l), a polymer of a
defined effective conjugation length with a low defect concentration is obtained [19]. The
LPPP of the highest and most uniform conjugation length and the best environmental
stability is the m-LPPP with a methyl group on the methin bridge (s. Fig.I). The high purity
ofthe polymer is also reflected in a high photoluminescence (PL) quantum efficiency, which
is up to 100% in solution and 30% in thin filmsandin a very low sub gap absorption (<X.mm<
12 cm-1) for a conjugated polymer.
The PHP layers (for synthesis see [18]), which are produced via a molecular beam
deposition technique, are polycrystalline, when the substrate is at room temperature. At
higher substrate temperatures, PHP films with steadily increasing order are formed, where
the oligomer chains tend to arrange themselves near normal to the plane ofthe substrate (the
angle between the chains and the surface normal is araund 20) as X-ray studies confirm
194
[20]. The shape of the absorption spectra for PHP films - produced at various substrate
temperatures- can be attributed to the degree of order in the PHP films [21] (s. Fig. 4). The
PL quantum efficiency in the solid state is around 30 % [22].
Figure 1. Chemical structure of a Parahexaphenyl (PHP) and b methyl substituted laddertype

poly(paraphenylene) (m-LPPP)
II. Color Flat Panel Displays based on OLEDs
The single layer EL devices ITO (Indium-Tin-Oxide)/PHP/Al emit blue light (Amax =
425 nm) with a luminance of around 300 cd/m2 under cw-operation (s. Fig.3). In this air
stable configuration, considerably high EL quantum efficiencies (measured with a calibrated
photo-diodeinan integrating sphere) for blue LEDs between 0.1 % and 1 % are observed.
An improvement of the performance of the EL devices is obtained, when highly oriented
oligoazomethine (OAM - s. Fig.2) [23] is used as the hole-transport layer HTL.
H,N**NH,
1 2
F F F F
F F F F
Figure 2. Chemical structure of 1 OAM and 2 DOB
In ITO/OAM/PHP/Al devices, the electric field required for the onset of the current in
the forward direction (ITO as anode) is decreased to values around 0.4 MV/ern compared to
0.8 MV/ern obtained for single layer PHP devices, independent ofthe thickness ofthe PHP-
layer (s. Fig. 4). The electric field usually determines the onset ofthe current and the EL, as
the field induced tunneling of the charge carriers via a potential barrier, which is present at
the interfaces between the electrodes and the polymer, is the dominant injection mechanism
at higher applied voltages (see also Ref.[24]). The application ofOAM as the HTL, Ieads to
a reduction ofthe barrier height at the interface anode/PHP, so that the onset ofthe current,
which is mainly dominated by holes (positively charged polarons) as in most organic devices,
decreases. The increased EL quantum efficiency (up to 2%) and luminance (up to 360
cd/m2), which is observed for ITO/OAM/PHP/Al devices, can be attributed to reduced
quenching effects and more balanced charge injection compared to the single layer devices.
Quenching decreases, as the OAM prevents that electrons (negatively charged polarons)
195
reach the ITO electrode without recombining with holes and as the lower driving electric
fields also cause a reduction ofthermal and field-induced quenching mechanisms.
The stability of the EL devices is significantly improved by applying a
diaminoctofluorobiphenyl (DOB) layer (s. Fig. 2,3) at the interface to the Al electrode,
which acts as transport-layer for electrons. The observed degradation processes at the Al
electrode, which are mainly caused by high local temperature effects are reduced as for the
multilayer devices the emissive zone is located at the PHP/DOB interface - in contrast to
single layer devices, where the emissive zone is near the cathode. The EL quantum
efticiency, the luminance and also the onset electric field (s. Fig. 4) ofthe ITO/PHP/DOB/Al
devices are comparable to that of single layer PHP devices.
As expected, the best stabilities are achieved for ITO/OAMIPHP/DOB/Al
multiheterolayer devices. The values for the threshold electric field in this multilayer
configuration are lower than the values obtained for ITO/OAM/PHP/Al devices (s. Fig. 4).
:i m
.!. PHP(25") r-
ge
CD ('\.
~
I \ ;ll
.!... \ 'ii'
0 i:::
.! \ .:....
<
200 250 300 350 400 450 500 550

Wavelength [nm]
Figure 3. Absorbance for different substrate temperatiires. PL (--) and EL (-) spectra of PHP.
2.0
... .. 1.0
...........
.. .

.....
10.8 Cl
Cl
< 1.5 'C 0.6

Cl
--
Cl
~
... .
:I 0.4
E
0 0.2
... .. .
r::::
1.0
~ 0 5 10 15
::::J
... .. ......
ce Bias (V)
0 c
0
0.5
.. ... ~
....
Cl
ITOIPHP/AI
ITOIPH PIETL/Al
ITOIHTUPHPIAI
ITOIHTUPHPIEn/AI
0.0
0.0 0.4 0.8 1.2 1.6
Field (MV/ern)
Figure 4. Current vs. electric field characteristics for PHP single- and multilayer EL devices (inset
current vs. bias voltage).
196
The possibility of producing !arge area, flat devices with a high brightness (comparable
to fluorescent tubes) makes the OLEDs promising candidates for the application in color flat
panel displays (CFPD). The realisation of color dots (pixels) building up a CFPD based on
organic EL devices can be achieved via: (i) blue, green and red OLEDs, (ii) OLEDs tuneable
from blue to red emission controlled by the valtage [ 12,1 5,26], current, local temperature or
another device parameter, (iii) large area EL devices with a spectrally broad white emission,
covered with red, green or blue absorption filters, (iv) blue !arge area EL devices covered
with dye/matrix layers, which are excited by the blue light and subsequently emit
photoluminescence light in a lower energetic range [27,28] (s. Fig.5).
In this chapter we focus on the last method . We show that by an ECCT, based on blue
OLEDs, bright multicolor emission can be achieved in a very simple way and hence this
method represents one ofthe most promising techniques for realising CFDPs.
We present the realisation of bright red, green and blue emission colors by an all
organic ECCT using an EL device of the organic semiconductor Parahexaphenyl (s. Fig.1)
tagether with suitable matrix dye layers and dielectric filters.
A fundamental advantage of the deep blue PHP emission light (CIE coordinates x =
0.1 5, y = 0.06 [29]) is that it can be converted into any other visible color, e.g. with the
ECCT introduced above, since the blue emission is located at the high energy side of the
visible spectrum. To obtain a certain emission color the light can be spectrally purified (with
a minimal intensity loss) by using a suitable dielectric band pass filter. Such interference
filters were produced by subsequent evaporation of high and low refractive index materials
Ti02 and MgF2 of defined thickness.
tf::_;::::':;:}L filtc r
red dye
Figure S. ECCT based on a blue OLED: glass
/transparent electrode ITO/hole-transport-
layer(HTL)/PHP/electron-transport-layer
(ETL)/Al. The blue PHP emission light is
converted by covering the PHP OLED with a
green dye layer ( ~green color) and a red dye
layer together with a suitable dielectric filter
(~red color)
Applying this all organic ECCT, emission colors (as green, yellow, orange, magenta
and red) throughout the whole visible range were produced by covering the EL devices with
dye layers of different concentration, and if necessary, with suitable dielectric filters .
Regarding to the realisation of CFPD the efficient production of the two other basic
colors (besides blue) green and red is of great interest. With this all organic color conversion
technique RGB-emission colors with CIE coordinates (green: x = 0.27, y= 0.62; red: x =
0.65, y = 0.34) similar to the basic colors which are used in commercial color TVs were
produced (s. Fig.6) [28].
In detail the green and red light emission is produced as follows :
bright green emission is obtained by using a layer of the dye Coumarin 102 in
poly(methylenemethacrylate) (PMMA) ofa high optical density (>3). The Coumarin 102 is a
very suitable dye for the color conversion due to the strong overlap between the Coumarin
absorption and the PHP EL emission spectrum and due to its efficient green PL light
emission. The absolute external conversion efficiency from the blue PHP EL emission into
the green was recorded to be around 40% [28]. The green emission (luminance ~1100
cdlm2) is araund three times brighter to the human eye than the blue pumping light from the
197
....... r-....
0.8
I
0.7 I,.. r-....
I"" ~
0.6
[1!1,.
,, .. ['-,.
~
0.5
_\ ,,
, .
1"-.
["...
.......... ~-----------------------,
>- 0.4
\ , -~ ~
:::l
.'\
"1' 't..;. z. I" l.
0.3
,' C> 'iii :
I
\.
,, ,' / I-""
cQ) : ..,
0.2
\i ... , ,,
1.--' 'E I
:
."\...,
,~., #
1.--' 3w
0.1
'\ #
V I ""
0.0 ~
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 400 500 600 700
X Wavelength (nm)
Figure 6. CIE-graph containing the CIE Figurc 7. Normalised spectra of the electrolum-
coordinates ofthe produced RGB-colors (Squares) inescence of the PHP OLED (--), the green (-)
compared to RGB-colors used in cathode ray and the red (-"-) emission produced by ECCT.
tubes (circles) (the dashed lines mark the area of
colors, which can be produced by the RGB colors)
PHP (360 cd/m2), which is due the fact the human eye sensitivity is much higher in the green
spectral range than in blue (s. Fig. 7).
The red emission, which is more difficult to achieve, can be obtained by covering the
Coumarin/PMMA layer with a Jayer of the red dye Lumogen F300 in PMMA. This red dye
strongly absorbs in the green spectral range and therefore converts the green excitation into
redemissionvia PL emission. To obtain an emission color, which is located in the pure red
spectral region (x = 0.65, y = 0.34- s. Fig.6,7) the spectrum can be purified with a band pass
filter (s. Fig.S).The conversion efficiency from the blue (via the green) to the red was
determined to be 10% [28]. The observed intensity Iosses is mainly due to waveguiding
within the red dye layer, but also due to reflection Iosses at the filter.
The external conversion efficiency can be significantly increased, when the index
matehing of the dyelmatrix layers to the EL devices is improved, so that reflection and
waveguiding Iosses are reduced. When the small airgap between the color conversion films
and the EL device are eliminated, e.g. by depositing the color-conversion layer directly onto
the device, the quantum efficiencies for color conversion from the blue into the green can be
improved to about 90% and for the blue into the red of 8 conversion efficiency 80% is
obtained [30).
m. Efficient Wbite OLEDs

The production ofwhite OLEDs is difficult, since no single active material is known up
to now, which produces white light (although the emission of most of the light-emitting
organic semiconductors is spectrally very broad). There have been several concepts
presented in order to achieve white light emission with OLEDs based on thermally vacuum
deposited organic metal complexes:
(i) using an OLED consisting of two or more active layers, where the emission is a
Superposition of the EL emission spectra of these light-emitting layers [31-34]. The
198
recombination zones in these OLEDs are spatially controlled by the application of hole
blocking layers [32-34].
(ii) white light obtained by spectral filtering of the emission light of a suitable broad
emitter [35].
(iii) white light can be produced by the Superposition of red-green and blue OLEDs.
RGB-LEDs based on organic materials have been presented in Ref [27,28,36].
We present the realization of stable and highly efficient white polymer LEDs based on
an ICCT in a blend of two polymers: the blue-light emitting m-LPPP (s. Fig.l) and a new
red light emitting poly(perylene-co-diethynylbenzene) (PPDB) (for synthesis see Ref [37]).
The spectrally broad blue m-LPPP emission spectrum (CIE coordinates x=0.24, y=0.3) in
combination with only one red-orange light emitting component (PPDB) (x=0.6I, y=0.39) in
a polymer blend enables us to realize white light emission (s. Fig.8,9) [38]. In cantrast to the
various concepts presented above, the red-orange component in the emission spectrum is
generated by an excitation energy transfer from the m-LPPP polymer chains into the
energetically lower lying states of PPDB [39]. One important technological advantage of
these efficient white OLEDs compared to other LEDs, is the ease of their production by a
solution casting process ofthe active layer.
According to colorimetry, the coordinates of a color, which is produced by mixture of
two colors, can be found on the connecting line between the coordinates of the two colors in
the CIE graph (s. Fig.8), where the exact position is determined by the quantitative
composition. It is obvious from the position of the CIE coordinates of the m-LPPP and
PPDB emission, that a mixture of m-LPPP and PPDB emission colors can produce white
light emission near the equi-energy white point (x=l/3,y=l/3). In OLEDs various color
compositions can be realized, when the active layer is built up by a blend of different light
emitting polymers [40]. In the m-LPPP/PPDB blend a very efficient transfer of electrons,
holes or excitons from m-LPPP into the energetically lower lying PPDB-states occurs. For
PPDB concentrations above 3 weight% the emission stems exclusively from PPDB and the
m-LPPP emission component vanishes [39].
We obtained a white OLED, by using a 80 nm thick active layer of a m-LPPP/PPDB
polymer blend containing 0.05 weight% PPDB. These OLEDs emit stable white light to the
human eye Independent on the bias voltage. However, in the EL spectra an increase of the
emission coming from PPDB can be observed, when the applied extemal electric field is
exceeding values of2.5 MV/ern. The extemal EL quantum efficiency ofthe white OLED is
around 0.8%.
We further increased the efficiency ofthe OLED without loosing the advantage ofthe
simple processing ofthe OLED by introducing poly(methylenemethacrylat) (PMMA) in the
polymer blend, which acts as a charge carrier-blocking material (instead of using suitable
electron- or hole transpoft layers, which require a thermal evaporation). In this case the
efficient energy transfer from the blue to the red is partly hindered by PMMA, so that the
concentration ofPPDB in the blend has tobe increased in order to produce white OLEDs.
For a polymer blend containing around I 0 weight% PMMA, the PPDB concentration has to
be 0.08% to obtain pure white light emission (CIE coordinates x=0.31, y=0.33) (s. Fig.8,9).
The 1/V characteristics of the white OLEDs containing PMMA reveal two important
advantages compared to those without PMMA: (i) the current flow below the threshold
electric field (leakage current) is reduced to values in the I 0" 8 A-range (ii) the threshold
electric field is significantly lowered and occurs at values below I MV/ern [39]. The
maximum external EL quantum efficiency of this white OLED containing PMMA is around
I.2 %. There is no significant dependence of the EL spectra of the white OLED containing
PMMA on the applied bias voltage.
199
0.8
I """ !--..
0.7
" r-...
0.6
""
0.5
-,
1 ' """ PPDB= ' -
~
\
""
""...
>- 0.4
:".--
0.3
0.2
-l
\
m-LPP
\
""... ~
1.---'
v~-"'" [).
0.1
l---
1\ ~
V
0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0. 7
X
Figure 8. CIE coordinates of the EL of m-LPPP
(x=0.31, y=0.33), the PL of a PPDB (x=0.53,
y=0.46) and of the white PLEDs operated at 30V
(x=0.31, y=0.33).
-
.. ..
~
c !'J.
:I
..ci
....
~
c
.Q
'
<f)
.!!.!
E
UJ
700
Wavelength (nm)
Figure 9. EL (-) spectrum of m-LPPP (dm.
LPPP=IOO nm), PL spectrum of PPDB-solution
(Squares) compared to EL spectra of the white
OLED ITO/m-LPPP:PBD/Al (thickness of active
polymer layer is 80 nm) recorded at 30V (circles)
200
IV. Polyphenyl-type materials for Iaser applications
Conjugated polymers show narrow linewidth light with high quantum yield emission
under high excitation density conditions and hence are interesting for Iaser applications [41-
47]. m-LPPP is a representative of these polymers due to its excellent film forming
properties, low defect concentration and high photoluminescence quantum yield (PLQY) of
30 % in films and low absorption coefficient
[48] (see above). In addition, in m-LPPP there
is no absorptive competition for
photoluminescence by excited states [49]. 1.0
a}
=!CU 0.8
;v
The optical quality of the active material
plays an important role for Iasers. Using
conjugated polymers the required quality can
o.a E 0
ii) 0.4 0
only be obtained in thin films. Considering the ~ 0.2

..__..... ex / 0
.. . .....

~
~
.
definition of LASER as light amplification by 1-
~ 0.0
stimulated emission of radiation, it is vital to 3o~o,...,3=-=5:::-0"74~oo::--4~5:-:::o--=57
oo=-5=:5~o:-:e=-=o-='o
have a strong interaction of the propagating WAVELENGTH [nm]
light with the inverted medium in order to
achieve a high gain. In conventional Iasers
mirrors are used to reflect the propagating
light into the active material, formed as bulk
material, to achieve the amplification. The
mirrors also provide an optical feedback
resulting in a better definition of the properties
of the emitted radiation such as linewidth,
directionality and coherence.
The following strategies, leading to lasing
in conjugated polymers, are known: a
longitudinally pumped microcavity [41], the
introduction of scattering particles to lengthen
the optical path [47], waveguiding in the active 1.0 c) fi.\
polymer film [43]. We present an alternative
~ ~-: _,.~r
route to build an optically pumped Iaser based
on conjugated polymers. Waveguiding along a
thin polymer film is limited by its residual
optical absorption and Ieads to strong ffi 0.2
1-
diffraction at the emitting surface. Applying the ~ 0.01------.....-
polymer film onto a substrate with a higher 470 475 480 485 490 495
refractive index ( n ),
which acts as a
Figure 10.
waveguide, Ieads only to a coupling via the (a) Absorption (dotted) and photo
evanescent wave [50]. These problems are Juminescence emission spectrum at low
solved by using a substrate with an identical (dashed) and high excitation densities (solid)
refractive index as m-LPPP, resulting in a of a m-LPPP Iaser CJ. LAS); excitation (A.EXc) at
refractive index matched composite waveguide 444 nm. (b) Photoluminescence below
(IMCW), which prevents reflection of (dashed) and above (solid) lasing threshold,
temporally integrated spectra). (c) Single shot
propagating light at the polymer/glass interface spectra of the Iaser lines (please note the
resulting in an optimum gain. different wavelength scales).
The IMCWs are built by spincoating or drop casting m-LPPP from toluene solution
onto reetangular shaped glass substrates of a thickness of 0.15 or 1 mm and a width of 7
201
POLYMER LASER
EMISSION
CYLYNDRICAL LENS
IMCW
EXCITATION
SUBSTRATE
m-LPPP
Figure 11. Schematic representation ofthe experimental setup ( IMCW, glass substrate, polymer film,line
focus)
mm. The indlces ofrefraction for the emitting polymer layer ( ~ = 1.58) [51] and the glass
substrates ( n = 1.52) are ideally suited to form an IMCW.
The excitation source was a Nd:YAG-pumped dye Iaser with a pulse duration of 6 ns at
a repetition rate of 10 Hz and a pulse peak power of 170 kW at 444 nm . The vertically
polarised beam was focused by a cylindrical Jens to a 7 by 0.2 mm area using calibrated
neutral density filters for attenuation. The optical pumping by a line focus provides the
necessary gainlength for lasing and also minimises the thermal stress on the polymer layer in
contrast to a point focus. The emission spectra were detected using a grating spectrometer
equipped with an intensified, thermoelectrically cooled CCD detector.
Operating the IMCW (for the experimental setup see Fig.ll) under the previously
described conditions at low excitation densities results in an emission spectrum as depicted
in Fig.l O(b). The spectrum matches the conventional photoluminescence emission of m-
LPPP. The observed output shows weakly polarisation and only very low directionality.
Increasing the excitation density Ieads to a highly directional output, which can be seen
as an elliptical blue-green spot on a screen. The output is completely linear polarised. The
orientation of polarisation depends only on the orientation of the IMCW and does not
correlate with the polarisation of the pump beam. We did not observe any influence of the
film producing process on the lasing properties of the built devices. A variation of the
excitation length has shown, that only 3 mm are sufficient to obtain an operating Iaser.
Further investigations of the optimum parameters of an IMCW will be published elsewhere
[52].
The spectra of the radiation are recorded by temporally integrating the emission within
one second, which corresponds to 10 Iaser shots. The corresponding spectra are displayed in
Fig.lO (b) and yield an apparent linewidth of 3nm. These lines are observed between 483
and 492 nm, which corresponds to the inhomogeneously broadened 0-1 transition of
spontaneaus emission in m-LPPP. By recording the emission of single shots ofthe polymer
Iaser, we obtained spectra as shown in Fig.lO(c). Here the linewidth has an upper Iimit of 1.7
nm. Therefore we conclude that by integrating over I 0 shots we observe a Superposition of
different Iaser lines due to the dynamic shift ofthe emission with respect to time.
The Iaser characteristics do not change by varying the excitation wavelength between
444 and 454 nm. However when pumping at 454 nm the Iaser lines are accompanied by
additional narrow lines of the same linewidth as the excitation. They are Stokes Rarnan lines
ofthe polymer [53], which correspond to the quantum energy ofthe excitation, displaced by
vibrational quanta corresponding to the aromatic C=C stretching vibrations and CH bending
mode ofthe m-LPPP [54].
202
~I
5g
.-
1/)
.!l!
:

10 1 102 103 104
INPUT POWER DENSITY [kW/cm2)
Figure 12. Input-output characteristics ofthe m-LPPP Laser; the output pulses are quantified by their peak
power.
In order to prove that the index matched waveguiding within the glass/polymer
structure is essential for the lasing mechanism we produced identical polymer films on silicon
and sapphire substrates of the sarne optical quality. as the glass substrates. No Iaser emission
can be detected under these circumstances, since the waveguiding either occurs only in the
polymer film (Silicon) or is restricted to the substrate due to the higher refractive index
(Sapphire).
We measured both the pump and output power with a silicon PIN diode for varying
pump power densities to quantifY the optical input/output characteristics and the operation
regime of the polymer Iaser. The result can be seen in Fig.l2. Laser action is observed for
power densities above 12 kW/cm2 with an efficiency of about 0.2%. The threshold for lasing
in the IMCWs is about the same as reported for waveguiding in conjugated polymer films
[43] and considerably low compared to a value of6800 kW/cm2 for the use ofa microcavity
[41]. The reported value for the inorganic wide bandgap semiconductor GaN is 700 kW/cm2
[55].
The saturation of the output power for high excitation densities is due to heating and
photodegradation of the polymer film. At an excitation density of 50 kW/cm2 we have
operated the polymer Iaser up to a few 10 000 shots, after which the output pulse energy
reaches 50% of its initial value.
CONCLUSION
OLEDs are very promising for future application in various types of displays. Blue
OLEDs are of special interest, since their emission can by converted into any other visible
emission color using either an external or an internal color conversion technique (ICCT). We
have demonstrated the realisation of bright (up to 3900 cd/m2) RGB-emission colors by an
external color conversion technique and the realisation of efficient white OLEDs (up to 1.2
% photons/electron) by an ICCT using the blue light emitting materials m-LPPP and PHP.
We have demonstrated an optically pumped Iaser with a conjugated polymer. Laser
lines can be observed in the blue-green spectral range above apower density of 12 kW/cm2
The Iaser emission shows a narrow linewidth with an upper Iimit of I. 7 nm, high
directionality with a small divergence and a complete linear polarisation. The key to the
observed Iaser action is the combination of the intrinsic emissive properties of the polymer
and the index matehing of the substrate to the polymer, resulting in a index matched
composite waveguide (IMCW) geometry. Comparing the threshold values for optically
pumped GaN and m-LPPP Iasers, we conclude, that the threshold current for electrically
203
pumped m-LPPP with a hetero layer IMCW Iaser diodes should be in the order of 103
A/cm2 . Therefore we propose that the realisation of a polymer Iaser diode in an IMCW
geometry is feasible.
ACKNOWLEDGEMENTS
We would like to thank Dr. Koller (Lambda Fluoreszenztechnik GmbH) for providing
us the pure dye systems for the ECCT experiments and J. Flieser, K. lskra, and T. Neger for
letting us use their Nd: YAG/dye Iaser setup.
The financial support of this research work by the Spezialforschungsbereich
'Elektroaktive Stoffe' and the Jubilumsfond der Osterreichischen Nationalbank (project
Nr. 6433) is gratefully acknowledged.
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205
NOVEL ORGANIC COMPOSITES BASED ON N-SUBSTITUTED
QUINACRIDONE DERNATIVES FOR MOLECULAR ORGANIC LIGHT-
EMITTING DIODES
Hideyuki Murata, 1 Charles D. Merritt, 1 and Zakya H. Kafafi 1
1U.S. Naval Research Laboratory, Washington DC 20375
Author to whom correspondence should be addressed
ABSTRACT
Molecular organic light emitting diodes (MOLEDs) where the active emitting layer
has been doped with quinacridones (DHQ), ethyl (DEQ) and benzyl (DBQ) N-substituted
quinacridones have been fabricated by high vacuum vapor deposition. These very bright
and highly efficient MOLEDs are compared in terms of optimum dopant concentration,
spectral characteristics and device efficiencies. DHQ, DEQ and DBQ aggregates formed
by plane to plane stacking seem to be responsible for luminescence queuehing observed at
high dopant concentration. Intermolecular hydrogen bonding between the N-H moiety and
the carbonyl oxygen does not play a major roJe in the queuehing process for DHQ-doped
AIQ3 composites.
INTRODUCTION
Molecular organic light emitting diodes (MOLEDs) based on films of evaporated

molecular components are of considerable interest in various electronic display
applications. 1 This is partly due to their high efficiencies and bright colors at reasonably
low operating voltage. Tris (8-hydroxyquinolinato) Aluminum (III) (AIQ 3) has been
extensively used as the light emitting/electron transport material due to its ability to form
stable amorphous films, transport electrons and luminesce with moderate efficiency.
Doping AIQ 3 with highly fluorescent molecules has been shown to be a very effective
approach for improving device efficiencies and lifetimes. 1 In addition, device color purity
can be also enhanced by selecting a dye molecule with a narrow emission spectrum.
Hence, by properly selecting a suitable dopant molecule, one can develop long-living,
bright and efficient AIQ3-based MOLEDs that are color tunable from the green to the red.

Recently, Wakimoto et. a/,2.3 and Shi and Tang4 significantly improved device efficiency
by doping AIQ3 with quinacridone derivatives. They attributed the enhancement in
electroluminescence (EL) to the high fluorescence quantum yield of the dopant. Frster
energy transfer from host to guest molecules was suggested as the dominant EL
mechanism. 2.3 Replacing the parent quinacridone compound as a dopant with quinacridone
derivatives that have methyl-substitution on the terminal phenyl rings or naphthyl-
substitution gave rise to very bright and efficient devices. For instance, in a four-layered
MOLED that consists of two hole transporters, doped and undoped AIQ3 , a maximum
luminance of 104,800 cd/m2 was achieved with a luminous power efficiency of 10.8 lm/W
reported at 300 cd/m2 ?3 It was further shown that methyl Substitutionon the heterocyclic
nitrogen resulted not only in improving device efficiency but also in proionging its
lifetime. 4 Substituting a methyl group for the hydrogen improved the luminance half-life by
a factor of 15 for a device operating at 200 A/m2 . 4 The improved stability in the devices
where methyl N- substituted quinacridone was used as the dopant was attributed to the
absence of nonradiative quenching centers which can be formed as a result of
intermolecular hydrogen bonding between neighboring quinacridone molecules. In the
present study, MOLEDs, where the emitting AIQ3 layer has been doped with
quinacridones (DHQ), or ethyl (DEQ) and benzyl (DBQ) N-substituted quinacridones, are
compared in terms of optimum dopant concentration, spectral characteristics and device
efficiencies. The roJe that hydrogen bonding plays with respect to spectral characteristics
and luminescence quenching, and its relationship to device performance are ex:plored
further.
EXPERIMENTALSECTION
Composite films of quinacridones doped into AIQ3 with varying dopant

concentration (0.1 to 10 mol %) were prepared on silica for spectroscopic
characterization. AIQ3 and quinacridones were evaporated from resistively heated cells.
They were deposited onto silica substrates mounted on a rotatable wheel in a vacuum
chamber with a base pressure of 5 X 10"8 Torr. The deposition rates ofthe guest and host
molecules were measured by a quartz crystal microbalance placed on the wheel. Film
thickness versus deposition rate was calibrated using a surface profilometer.
Photoluminescence (PL) spectra of the composite films were measured in-situ using the
325 nm output of a HeCd Iaser and a Y4 m spectrograph with a liquid N2 cooled CCD
detector. Subsequently, the samples were removed, and optical absorption spectra were
measured using a Perkin Eimer Lambda-9 spectrophotometer. For the fabrication of
MOLEDs, substrates with patterned ITO stripes (Planar Arnerica) were used with typical
thickness. and sheet resistance of 160 nm and 10 n/square, respectively. Consecutive
deposition of a 50 nm hole transpoft layer (HTL) of N, N' -Bis-(3-methylphenyl)-N,N'-
bis(phenyl)-benzidene (TPD), and an emissive layer of quinacridone-doped AIQ3 was
followed by an electron transpoft layer ofundoped AIQ3. The overall thickness of doped
and undoped AIQ3 filmswas maintained at 50 nm. A Mg:Ag ( 10-15:1 by weight) alloy
top layer was deposited through a shadow mask forming metal stripes perpendicular to the
ITO stripes. Four devices with 2x2 mm2 active areas were fabricated on each substrate.
Characterization of MOLEDs were carried out in a dry nitrogen atmosphere inside a
glove box. Current and luminance measurements as a function of voltage were made
using a Keithley 238 source measure unit and a Minolta LSllO luminance meter.
Electroluminescence (EL) spectra were recorded by collecting the emitted light with a
fiber optic link from the glove box to the Y4 m spectrograph.
208
Q 0
Q-0-0p
CHa H3C
(HTL}
+
cq \ .0
'
.~.
o-:~1-{J"N \ I
(ETL, HOST}
N 0 I
~
0 ~
Transparent
Substrate
---
~ (GUEST)
I 0
R
(a) (b)
Figure La) Device structure; b) Molecular structures ofhole and electron transporters, and host and guest
molecules.
Figure 1 shows the molecular structures of the hole and electron transporters, and
guest and host emitters used in this study. The device structure is also depicted in the
same figure. Figure 2 illustrates the optical absorption spectra of films of doped AIQ3 as
a function of dopant concentration, and compares them to the solid state spectra of the
pure dopant molecules. The spectra of the solid composite films are very similar to the
liquid solution spectra of the dopants (not shown) which indicates that the dopant
molecules are well-dispersed in the host matrix. This is further supported by the dopant
concentration dependence where the absorption bands associated with the guest molecule
increase monotonically as a function of its concentration. A linear relationship between the
absorbance at A",.,. and dopant concentration was observed for DHQ, DEQ and DBQ
which indicates that Beer's law is obeyed, and the composite films are well-behaved solid
solutions. The solid state spectrum of the unsubstituted quinacridone shows a large red
shift relativetothat ofthe composite films, (see Fig. 2a). In contrast, no shift is observed
between the solid state spectra of ethyl and benzyl N-substituted quinacridones, and those
oftheir solid solution spectra, (see Fig. 2b and 2c). In fact, the solid state spectra ofDEQ
and DBQ are quite similar to their liquid solution spectra. The red shift in the spectrum of
solid DHQ film has been explained in terms of intermolecular hydrogen bonding between
the N-H moiety and the carbonyl oxygen of a neighbor molecule. 5'6 This intermolecular
interaction Ieads to molecular aggregation and has been thought to be responsible for
:fluorescence quenching observed at high concentration. 4 Additionally, intra- or inter-
molecular hydrogen bonding has been shown to promote rapid radiationless decay of
excited states. 8
209
(a)
0.08 [DHQ%]
0.06 -----100
--2.09
0.04 --1.0
0.02
-o
-m !\
(b)
-
: i 0.24 [DEQ%]
,., I \ ---1oo----1.o
GI
u 0.18
c i
i V \
\
---9.2 ----0.7
ns ----5.7 -o
...0
.a
-
...--...' '
\ ---- 2.7
! 0.06 -..........._____-------------
<
(c)
0.12 [DBQ%]
---100 . -2.1
--12.6 0.93
---- 4.3 -----0.4
./\' -- 3.2 -o
~. --.... '-.:..
......1 :"\\_
0.03
-;;::-~---------------
400 450 500 550 600 650 700 750 800
Wavelength {nm)
Figure 2. Optical absorption spectra of composite films of a) DHQ-, b) DEQ- and c) DBQ-doped Al(b as a
function of molar concentration of dopant.
The photoluminescence (PL) spectra of composite films of AlQ3 with DHQ, DEQ
and DBQ as a function of dopant concentration are depicted in Fig. 3. Unlike the spectral
features ofundoped AlQ3 they are narrow and sharp, and their position and line shape are
characteristic of the dopant. The fact that emission arises only from the dopant molecules
indicates efficient energy transfer from host to guest. The spectral intensities are also
enhanced relative to that of the host, and at high concentration PL queuehing is observed.
Figure 4 depicts the enhancement in PL intensity for each DHQ, DEQ and DBQ doped
AIQ3 composite as a function of dopant concentration. It is clear that queuehing occurs at
a more dilute concentration for the unsubstituted DHQ relative to that of N-substituted
quinacridones. For DBQ, queuehing occurs at a molar concentration that is an order of
magnitude larger than observed for DHQ. This may be explained in terms of the bulky
benzyl substituent group which may cause some steric effects for dimer and higher
aggregate formation. In the case of DHQ at least two types of interaction for dimer
formation can be envisioned. One involves hydrogen bonding between the N-H moiety and
the carbonyl oxygen of a neighbor molecule. '6 A secend type of interaction may arise
from intermolecular interactions caused by plane to plane stacking, frequently observed in
aromatic molecules. 7 Only the latter interaction can occur in N-substituted quinacridones.
210
0.8 t\
I I
,,..~
0.6 ., \!
II''\\1
0.4 ..,,:,: .. .
'\""
--~
-~
0.2
--~
{b)
~ 0.8 [DEQ%]
~
~ 0.6 . -9.2 --1.0
'iii ..... 5.7 --0.7
c
.!! 0.4 ..... 2.7 -o
.5
...1 0.2
0.
(c)
0.8 [DBQ%]
0.6 13 --2.1
.. -4.3 -o
0.4 --3.2
0.2
400 450 500 550 600 650 700 750 800

Wavelength (nm)
Figure 3. Photoluminescence spectra of cornposite filrns of AlOl doped with a) DHQ, b) DEQ and c) DBQ
as a function of dopant concentration.
-
c
CD
E
CD
4
3
-+-DHQ
-0-0EQ
-D-OBQ
u
c
as
.c
c
w 2
..J
a.
1
0
0 2 4 6 8 10 12 14
Dopant Concentration (mol%)
Figure 4. Photoluminescence quantum yield enhancement of cornposite filrns of AlOl doped with DHQ,
DEQ and DBQ as a function of dopant concentration.
211
"
f'A (a)
0.8
/'' \, [DHQ%]
I\

0.6
0.4
0.2

1''"\I
-; 0.8 (b)
~ [DEQ%]
~ 0.6
-
rn
c . -8.9 --1.0
CU 0.4
..5
...1
w 0.2
(c)
0.8
[DBQ%]
0.6
--2.1
0.4 --1.3
-o
0.2
400 450 500 550 600 650 700 750 800

Wavelength (nm)
Figure 5. Electroluminescence spectra of composite films of AIQ3 doped with a) DHQ, b) DEQ and c)
DBQ as a function of dopant concentration.
Figure 5 shows the EL speetra as a funetion of dopant eoneentration in three triple-

layered MOLEDs where DHQ, DEQ and DBQ were used as the dopant. The relative
heights of the peak near A......x are scaled to match the relative extemal quantum efliciencies
of each device determined at 100 A/m2. The EL and PL spectra are quite similar, which
indicates that the radiative decay occurs from the dopant singlet excited state. The
maximum EL enhancement was achieved at 1 mol % ofDHQ and DEQ. DBQ showed the
broadest concentration dependenee reaching a peak around 1.3 mol % and then falling
more slowly at higher concentrations. Concentration queuehing of luminescence in N-
substituted quinacridones cannot be attributed to the formation of hydrogen bonding
between the N-H moiety and the carbonyl oxygen of a neighboring molecule. Since EL
concentration queuehing occurs roughly above 1 mol % for the three quinacridones, it is
more likely that the mechanism giving rise to this effect is the same. Hence, we attribute
EL queuehing to quinacridone aggregates formed by intermolecular interactions via plane
to plane staeking, frequently observed in aromatic molecules. 7 Self-absorption of the
emission may also eontribute to the decrease in PL and EL efficieneies with increasing
dopant eoncentration. This is primarily due to the small Stokes shifts between the
absorption and luminescence spectra of these quinacridone derivatives.
Figure 6 depiets the luminous (L.E.) and extemal quantum (llEL) efficieneies as a
funetion ofDEQ concentration. In comparison to the control device, an enhaneement by a
212
4 2.4
-
~
3.5 i-o-LEI
2.2
I
E 2
::::::.
>-
(,)
3 1--a.~
cCl) 1.8
--
0
r::; !
2.5
:eU.l 1.6 0~
1/1
::l 2
0
1.4
e
c
::l
...I 1.5 1.2
1 1
0 2 4 6 8 10
[DEQ] (mol%)
Figure 6. Luminous power and external quantum efficiencies as a function ofDEQ molar concentration in
a three-layered MOLED where the emitting layer is AIQ3:DEQ.
factor of2 in luminous power efficiency is measured for a composite based-MOLED at an

optimum concentration of 1 mol% DEQ. In a separate study, the addition of a second
layer of a hole transporter with an ionization potential closer to that of ITO resulted in a
reduction in the driving valtage and further increase in device luminous power efficiency. 9
In addition, preliminary Iifetime measurements indicate an enhancement by a factor of 15
in the luminance half-life for this MOLED relative to devices based on the parent
quinacridone used as a dopant.
In summary, we have fabricated very bright and highly efficient devices using N-
substituted quinacridone derivatives as dopants. W e have shown that hydrogen bonding
does not play a major roJe in quenching the PL/EL of DHQ-doped AIQ3 composites.
DHQ, DEQ and DBQ aggregates formed by plane to plane stacking, and frequently
observed in aromatic molecules7 may be the cause ofPL/EL concentration quenching.
ACKNOWLEDGMENTS
Financial support from the office of Naval Research and the Defense Advanced
Research Projects Agency are appreciated.
HEFERENCES
1. T. Tsutsui, MRS Bull. 22:39 (1997) and references therein.

2. T. Wakimoto, R. Murayama, K. Nagayama, Y. Okuda and H. Nakada, Appl. Surf. Sei. 114:698
(1997).
3. T. Wakimoto in Organic Electroluminescent Materials and Devices, edited by S. Miyata and H.
Nalwa, p. 289 (1997).
4. J. Shi and C. W. Tang, Appl. Phys. Lett. 70:1665 (1997).
213
5. F. H. Chung and R. W. Scott, J. Appl. Cryst. 4:506 (1971).
6. J. Kalinowski, W. Stampor, P. Di Marco and V. Fattori, Chem. Phys. 182:341 (1994).
7. I .. B. Berlman F/uorescence Spectra of Aromatic Molecu/es, second edition (Academic Press, New
York, 1971).
8. C. Merritt, G. W. Scott, A. Gupta and A. Yavrouian, Chem. Phys. Lett. 69:169 (1980).
9. G. M. Daly, H. Murata, C. D. Merritt, M. Miller, and Z. H. Kafafi, Proceedings SPIE, 3148:393
(1997).
214
PHOTOREFRACTIVITY AND OPTICAL WAVE MIXING EFFECTS IN
NEMATIC LIQUID CRYSTALS DOPED WITH FULLERENE DERIVATIVES
ANDDYES
Brett D. Guenther, M. V. Wood, I.C. Khoo
The Pennsylvania State University, Department ofElectrical Engineering

University Park, PA 16802
INTRODUCTION
The photorefractive effect has been observed and documented for decades 1' 2 . This
effect is typically observed in impurity doped electrooptic crystals. When the crystal is
illuminated, charge carriers are excited from occupied donor states to the conduction band.
These excited charge carriers migrate under the influence of diffusion, and any intemal or
extemal electric fields, until they are trapped by empty donors thereby causing a space-
charge field to be formed within the crystal. The electric field that results from the charge
separation acts to modulate the index of refraction through the electrooptic Pockels effect.
The potential applications which make use of the photorefractive effect are obvious.
Holographie storage, for example, whereby pages of information could be stored within a
photorefractive medium, has been investigated since the early 1970's3' 4 . Much time and
effort has been devoted to this research area5, however for practical devices to be
constructed it is necessary to have a switchable holographic material that permits high
diflfaction e:fficiency, low switching fields, fast response times, broadband response, and is
easy to process/fabricate.
Recently, Khoo et. al. have discovered a new class of photorefractive materials6789 .
Nematic liquid crystals (NLC) doped with easily ionizable materials, such as C60 , have been
shown to possess a photorefractive-like effect in the sense that the index of refraction
modulation is caused by static space charge fields induced by the applied optical and DC
fields. The index of refraction change arises from a reorientation of the uniaxial nematic
liquid crystal molecule, and not by the linear electrooptic effect as mentioned before.
Accordingly, we henceforth refer to this effect as the orientational photorefractive effect
(OPE). This paper will address the fundamental theories relating to this novel phenomenon
and present latest experimental results obtained to date.
Science and Technology of Polymers and Advanced MateTlls

THE ORIENTATIONAL PHOTOREFRACTIVE EFFECT
Nonlinearities in NLC resulting from a reorientation ofthe director axis (i.e. the crystal
axis that characterize the macroscopic alignment of the liquid crystal) under the influence of
an applied intensity pattern were first investigated in the early 1980's10'n. More recently,
researchers found that this effect could be enhanced by doping the liquid crystals with
absorbing dyes. In this case the reorientation was produced by intermolecular torques
caused by the photoexcited dopant6' 12' 13' 14 . Earlier works have also shown that an applied
DC magnetic field or low frequency AC electric field near the Freedericksz threshold (i.e.
the point at which the NLC molecules are just about to rotate with the field) would enhance
these optical filed induced effects 151617 .
Photorefractive effects were observed when an optical field and a DC electric field were
applied to aligned nematic liquid crystals7' 8'18 The optical field liberates charges in the bright
areas which tend to drift and diffuse throughout the medium. The charges are trapped by a
phenomenon known as the Carr-Helfrinch effect. The resulting space charge field, in
combination with the applied DC field, tends to realign the NLC molecules so as to
minimize their free energy. The result of this realignment is an effective index of refraction
change, Lln, between the light areas and the dark areas. In the following subsections, we
will explain and compare each mechanism responsible for the orientational photorefractive
effect.
Photo-Induced Charge Producdon
Studies have shown that the exact mechanism for photo-excited ionic production
depends on the type of dopant used. Ionization of the impurities or dye dopants (e.g., R6G
Iaser dye) is likely due to some dissociation processes 19 . On the other hand, photo-eharge
production in C6o may be due to the formation of charge transfer complexes20'21'22 . The
photo-induced current of a C6o doped homeotropically aligned nematic film as a function of
the incident Iaser power (Figure 1) is exemplary.
3.2
i
2.8
......

~
:J 2.4
"
(.)

2.0
0

1.6
0 10 20 30 40 50 60 70 80
Power(mW)
Figure 1. Photo-induced current of a 25 f.llll Ct;o-doped homeotropically aligned nematic film as a function
ofthe incident Iaser power. Applied voltage: 1.05 volt; llluminated area = 1.2 cm2
216
The dependence of the photo-current on the optical intensity Iop is close to (Iop) 112 for both
C60 and dye doped nematic films. This dependence is consistent with the argument that the
generation ofthe mobile ions arises from dissociation ofthe photo-excited molecules 18 . In
experiments performed to determine the best dopant for OPE observation, various doped
liquid crystal samples were tested for photocurrent (i.e. photo-induced charge production).
Each result was then normalized by the absorptionofthat particular sample. The results are
shown in Table 1:
Table l. Photo-induced current in 100 J.lffi thick homeotropically aligned nematic films
Iaser power= lOmWatt; beam diameter=2mm; DC voltage=1 V; /c=5145 A
DOPANT D2LASERDYE R6G LASER DYE C6o UNDOPED

Concent by weight 0.5% 0.2% 0.05% NA
ldalk (J.LaffipS) 0.035 0.029 0.06 0.005
IIU!ht (J.LaffipS) 0.042 0.130 0.13 0.005
Al (l.mmps) 0.007 0.101 0.07 0.000
a. (cm' 1) 373.2 101.7 30.20 0
!>.II a.(JJ.A cm) 1.88x10'5 9.93x104 2.32x10'3 NA
From these results it can be seen that the C6o dopant is a good choice for the OPE since it
has !arge photacharge production without suffering from a great deal of absorption.
Additional experiments were performed with other dopants to compare them with C60 .
These dopants included Perylene23 . A mixture of C6o+C 70 , and a C60 derivative, C61 (6,6
Pheny-C6l butylmethoxy or PCBM), which is a very new substance24 The results of the
experiment are shown below.
Table 2. Photo-induced current in 25 !J.m thick homeotropically aligned nematic film.

P=20 mW, A.=514nm, D=25 !J.m, dbeam= 2 mm, Voc=l volt
DOPANT C6o c61 C,o+C6o PERYLENE

Concent. by weight 0.05% 0.12% ~1% ~1%
I"""' (J,.lalllps) 0.120 0.3 l 0.74

llwt (J.LaffipS) 0.145 0.315 1.05 0.76
M (J.LaffipS) 0.03 0.015 0.05 0.02
a. (cm1) 4 1.2 4.8 ~
!11/ a.(JJ.A cm) 0.0075 0.0125 0.010 NIA
From the results in Table 2, one can see that C61 (PCBM) is almost 2 times better in
terms of the photocurrent versus absorption than C6o, and the mixture of C70+C 60 also
provided an improvement, in this experiment, over C6o alone. The improved response of
these materials is partly due to their higher concentrations within the NLC.
Ongoing research will hopefully provide answers for the exact nature of the photacharge
production in these dopants, and thereby make the dopant choice for observing the OPE in
doped NLC easy. However, until this is done the choice of dopants relies on the material's
absorption spectrum and efficiency of photocurrent generation. Thus empirical studies like
the ones shown above are absolutely necessary in narrowing down the choice materials, and
217
have been shown to correlate weH with the magnitude of the OPE observed in various
samples.
Space Charge Field Formation
As charges in the sample are liberated by incident light intensity they drift and diffuse
within the NLC until they are trapped thus forming a nonuniform charge distribution, which
in turn Ieads to a space charge field. Suppose two coherent beams overlap and form an
interference pattern, 1", = 1.0 + mcos{q r)J , on a NLC film as shown below in Figure 2.
L1qmd Crystal
- z
Olass shde
Figure 2. Schematic depiction of the interacting fields in a nematic liquid crystal film. E3 and E. are first
order self diffraction beams from the grating generated by the incident E 1 and ~ beams
The photorefractive-like space charge field formed within the NLC can be found to be 18 :
mksT IJ!Jd . r-; -)

E"' = -;;-qv-IJ-sm1q r
(1)
= E~' sinq.;
where k8 = Boltzman constant, cr = illuminated state conductivity, crd dark state

conductivity,
D' -D"
V = (2)
D" +D"
where D+ and n are the diffusion constants for the positively and negatively charged ions,
respectively. Notice that Eph is rr./2 phase shifted from the optical grating function [m is the
modulation ratio in the input optical intensity 1." = 10 (1 + mcos{q r))]. This rr./2 phase shift
is responsible for a two-beam coupling effect reported in previous papers7 .
This treatment of the field in the NLC is not complete. lt was recognized in Khoo's
studies that two other sources of space charge fields also play an important roJe in the OPE.
218
These space charge fields arise form the conductive and dielectric anisotropies of the NLC
in combination with the director axis spatial variation. Such space charge fields were first
analyzed by Helftinch in 196925 . The expressions for the fields are given by:
(3)
(4)
where c1 ( crn) and ci (er i) are the DC dielectric (conductivity) constants for field (current
flow) parallel and perpendicular to the director axis respectively. Notice that these space
charge fields are proportional to the applied DC field (i.e. a !arger applied DC field will
create a !arger space charge field) . Also notice that the magnitude of these space charge
fields are an increasing function of the induced reorientation angle, 0, for small 0. Thus a
small initial reorientation angle and space charge field will reinforce each other, and once
reorientation is established, we can maintain the space charge fields by applying the DC field
only; no optical field is necessary.
A simple schematic of the Carr-Helfiinch effect is shown in figure 3. When a DC
electric field Ez is applied in the z direction it encounters the tilted NLC molecules (the
initial tilt is due to imperfections in the initial alignrnent and/or the photorefractive space
charge field mentioned previously). The field can be decomposed into parallel and
perpendicular components. When summed these field components, and likewise the current
components, give a steady state field and current in the z direction only. This means that
any transverse field component or current component in the +~ direction is exactly canceled
by another transverse field or current component going in the -~ direction. The resulting
transverse current profile Ieads to a localized space charge accumulation which in turn Ieads
to a space charge field which further enhances the tilt of the NLC molecules. The same is
true for the transverse field components; the resultant field profile Ieads to and enhancement
ofthe reorientation ofthe NLC molecules.
+
Figure 3. The Carr-Helfrinch effect.
219
The magnitude ofthese space charge fields EM, EAe, and Ec;_> may be expressed in terms
of the so called Freedericksz transition field (this is the threshold field at which the NLC
molecules align themselves parallel with the applied field):
where K is the effective elastic constant and d is the film thickness. Writing
8(J) ""8. sinq.;, E." ""E!~ sinq.;, and E., ""E!~.> sinq.; we thus have:
(6)
For SCB NLC 23 K-10-6 dyne, Lle--10 we thus have
(7)
where we have used kb = 1.38 X 10"23 X 107 erg/K 0 , T=300, e=1.6 X 10"19 X 3 X 109
Statcoulomb, and m- 0.8.
If Ez=EF then the induced space charge fields E':.> and E~ are given by:
(8)
(9)
where the measured values CT1 ""7.0 x w"-cr' -cm' and CTL ""4.6 x to".cr' cm' were used
(these values are for 25 J.lm C6o doped NLC films which were commonly used in the
experiments). In the observed grating diffi"action experiments the reorientation angle was
calculated to be 8;;:: 2 x I o- rad, whereas qd"" 1t . Thus equations 7, 8, and 9 become:
(10a)
(lOb)
(I Oe)
From equations 7-9 note that the magnitude of E';.> can be larger for a smaller grating
wavelength (i.e. !arger q), also E~> and E~ areproportional to the applied DC fieldas weil
as the reorientation angle (which will evolve and increase in magnitude depending on the
duration ofthe applied fields as we will see in the experimental results). Nevertheless, the
above rough estimates show that these space charge fields could all be comparable in
magnitude for the experimental conditions used in the reported wave mixing results. A
schematic depicting the various parameters involved in the OPE are shown in figure 4.
220
'\ input optical intensity
photoinduced conductivity change
liquid flow velocity and

space charge distributions
~
(\ (\ space charge field distribution

n n (\
Ln ---- ....... ....... ----.. .......
/ 't-- -../'-11.......
--.....
,/
/
-- ,/
,/
director axis distribution - n is nonnal to the dotted line

Figure 4. Schematic depiction of the geometry of the various parameters involved in the orientational
photorefractive effect
Torques And Flows
The dynamics of the director axis reorientation process is governed by interplay among
the various torques produced by the fields present and the elasticity of the liquid crystals.
The principal torques involved are the dielectric torque TJc, the flow-shear stress torque Tflow,
the optical torque Topt, and the elastic restoring torque r. 1 For the geometry depicted in
figure 4, these torques are derived are calculated as follows.
(11)
Where E;; and Ez are the ~ and the z component ofthe total DC electric field E,.:
(12)
Under the action ofthe applied DC field E), the liquid bearing the spatially varying space
charges will flo~ 5 26 ' 27 with a spatial variation (i.e. the flow velocity is ofthe form = v(;)z v
where v( ,;) oc cosq;). The shear stress associated with the flow velocity gradient creates a
reorientational torque on the director axis given by26 27 :
dv(;)
rjlo.=-~[a,cos 8-a,sm
' . ' e) (13)
where a2 and a3 are Leslie coefficients. The elastic restoring torque for the same
interaction geometry is given 829 : bl
221
d28
r., = [K, sin 8+ K, cos 8]-;t;z
2 2
2
+[(K, -K,)sin8cos8]( d8)
dz (14)
2
d 8 and(d8) 2
+... similar _terms_in dc; 2 --;};
Finally, the torque associated with the optical electric field is given b/9 :
(15)
where L1&op is the optical dielectric anisotopy, Eop is the amplitude of the optical field, and
<> signifies the time average. Thus the dynarnics of the reorientation process is dictated by
the torque balance equation:
d8
r,.. +rflo +r,, +r." +r-=O (16)
dt
where y is the effective viscosity coefficient. Even at steady state equation 16 is an

extremely complicated function of B.and cannot be solved analytically. When, however, Bis
very small and flows are ignored, the solution for the reorientation angle can be shown to
be9,3o:
8 = 8, si~;) sin( qc;) (17)
where
D..sE E<') cos

(18)
where K is the effective elastic constant, a3 is the Leslie coefficient related to the NLC, and
172 is a viscosity coefficient for the NLC.
Thus the three mechanisms for the orientational photorefractive effect are summarized
below.
!.Charge generation~ ions drift/diffuse~ charge Separation and space charge field
formation~ director axis reorientation~ refractive index change
2.Charge generation~ ionic conduction plus director axis reorientation~ space charge
field formation through dielectric and conductivity anisotropies~ further director axis
reorientation~ refractive index change
3.Charge generation~ material flow~ velocity gradient & shear stresses~ director axis
reorientation~ refractive index change
222
EXPERIMENTAL WAVE MIXING RESULTS
To examine the orientational photorefractive effect wave InJxmg experiments were

performed. Figure 2 shows the typical molecular and optical/electrical field configuration
involved in most of the optical wave mixing experiments. In a typical experiment, doped
pentyl-cyano-biphenyl (5CB) nematic liquid crystal (the concentration of the dopants used
are listed in tables 1 and 2), was sandwiched between two ITO/surfactant coated glass
slides, which were held apart (typically 25 J..Lm) by means of a plastic spacer. Two writing
beams (typical beam diameters were 2 mm) emanating from a linearly polarized CW argon-
ion Iaser operating at 514.5 nm were overlapped to form an intensity grating within the
sample. The diffraction efficiency from the generated phase grating was probed with a
linearly polarized CW HeNe Iaser propagating along a direction close to k2 Experiments
using this set up have been used to examine the dynamic response of the gratings, coupling
effects, the dependence on the grating constant, wavelength, incident angle, applied voltage,
the effects of different dopants, and the effects of different film's thickness7' 8' 9' 3031 . The
effects of AC+DC fields in planar aligned samples were also studied32 .
Dynamics Of Grating Diffraction
Ifthe incident Iaser power is low (a few mW) and the illuminationtime is less than a few
seconds, then the induced index grating is transient in nature. In this regime the
reorientation angle f) is very small and the dominant contribution to the space charge field
and reorientation effect comes from the photorefractive like space charge field, E~) . Upon
application of the optical and DC fields the first order diffraction beam builds up in ~ 1
second to a quasi-stationary value. When the writing beams and/or the DC field are turned
off, the grating decays to a vanishing value in about 0.5 seconds. For transient gratings the
decay time constants have been found to follow weil known orientational relaxation
dynamics. 2829 The orientation decay time constant, -r" is given by:
-r ., r (19)
' [?t'd' 4?t'
K-+-
A'
]
where y is the viscosity coefficient and K is the elastic constant. For d = 100 J..l.m and
A=57J..l.m, K = 0.5x10-6 dyne, y=0.15 P, 'tr = 0.25 sec which is in good agreement with the
experimental observation.
If the writing beams are kept on after the initial quasi-stationary is reached, it is
observed that the probe diffraction slowly but steadily increases in magnitude, before
settling down to a final steady state value after a few minutes. If the writing beams are
turned off before the final steady state is reached, while the DC field is kept on, it is
observed that the probe diffraction drops (in a second or so) to a lower but finite value. In
this state the diffraction persists as long as the DC field is on (for tens of minutes). If the
DC field is turned off, then the diffraction decays to an even lower persistent value
depending on the illumination time. At this stage the reorientation angle f) has acquired a
sufficiently large magnitude after prolonged optical illumination and applied field. The DC
applied field dependent space charge fields E." and E .. (equations 3 and 4) have become
substantial. Since these fields depend on the reorientation angle and the DC field and not on
223
the optical field (like Eph) it makes sense that the OPE can be sustained by the DC field with
the writing beams tumed off.
At the final stage of grating formation, strong diffuse scattering and high order
diffractions are observed; the diffraction efficiency is more than an order of magnitude
!arger than the initial quasi stationary value observed in the transient stage. If all extemal
applied (DC and optical) are tumed off, a persistent grating remains. In R6G dye-doped
film, the grating decays in a couple of hours. On the other hand, in Fullerene C6o-doped
sample, the grating persists indefinitely. Such persistent gratings are due to an irreversible
perturbation of the surface director axis alignment by the current and nematic flows under
prolonged application ofthe optical and DC fields. It is also possible that the photo-excited
charge carrying dopants are deposited on the cell walls, which permanently change the
surface anchoring condition. This, however, remains to be quantitatively ascertained.
An interesting and useful feature ofthese persistent holographic gratings isthat they can
be electronically tumed on and off, as the director axis of the liquid crystal responds to an
applied AC field through the usual electro-optical effece9 . A high frequency (>200 Hz)
high valtage (greater than the Freedericksz transition valtage for the NLC) field will
completely realign the whole sample (i.e. turn off the grating) with a response time of less
than a rnillisecond. The grating can then be restored, with a recovery time of about 20
rnilliseconds, by removing the AC field.
The OPE's dependence on the grating constant, A, is different for transient and
persistent gratings. In the transient case, when Ois small, only the photorefractive like space
charge field is expected to contribute (i.e the 0 dependent terms in steady state torque
balance equation can be ignored). In this case {:t can be shown tobe ofthe form930 :
(), oc [:tr'-+q'
q ]
(20)
d'
where q is the grating wave vector.
2:tr 2:tr ._(

q=-;::=~2siu\2' "'~a
a) 2:tr
for small a (21)
Equation 20 is maximum when q = %, that is when the grating constant A~ = 2d. The
diffraction efficiency versus grating constant for a transient grating was measured for a 25
IJ.m C60 doped NLC sample and is shown in figure 5a. The observed maximum
A"::_""" "'60 IJ.m is very close to the theoretical value A";;"' =50 IJ.m
Under prolonged exposure the 0 dependent terms in the steady state torque balance
equation contribute significantly. In this case l:t can be shown tobe ofthe form30 :
() oc q (22)
0 [;,', +q']
where d' = f.fi. Equation 22 is maximum when q = %, that is when A...". = l414d. The
diffraction efficiency versus grating constant for a persistent grating was measured for a
251J.m C6o doped NLC sample and is shown in figure Sb. The observed maximum
A"::_""" "'40 IJ.m is very close to the theoretical value A'';; = 351J.m.
224
2 12
Transient (left axis)

Permanent (right axis)
10
8 ~
()' >.
u
c
cQ)
u Q)
u
~ 1 6 ~
c c
0 0
n ti

~
<11
:t= 4
0
0 0
0 50 100 150 200 250

Grating Constant II (J..lm)
Figure 5. First order diffraction efficiency dependence on the grating constants for a 25 1-1-rn C60-doped film
(a) transient (b) permanent E 1 bearn power= 10 mW, E 2 bearn power= 7.6 mW
Holographie Grating Recording Sensitivity and Wavelength Dependence
To compare the OPE observed in doped NLC with that of the photorefractive effect
observed in various crystals an estimate of the sensitivity of the effect was made. The
nonlinear sensitivity defined in literature33 is given by:
s = t.n (23)
F
Where Fis the energy per unit area. Since the diffraction efficiency (ofthe first order beam)
for a thin grating is given by:
(t.nmi) "' -t.nmi)'

1J =J, - 2 -
2
(
2 - for our case (24)
which for the case of a permanent grating can be seen from figure 5 to be -1 0% at Amax-
Thus for ...1.=514 nm and d = 25 ~m, Lln=2 x 10-3 . The energy per unit area for this
experiment was (0.01 Watt) x (600 sec)/(0.3cmf = 60 J/cm2 . Therefore the nonlinear
sensitivity for the experiment shown in figure 5b is approximately 3 x 10-5 cm2/J A table
comparing this result with typical photorefractive crystals is shown below.
225
Table 3. Comparison ofthe nonlinear sensitivity ofvarious materials
MATERIAL NONLINEAR SENSITIVITY (cm21J)

C6o Doped NLC 3 X 10"5
C6o+C1o Dooed NLC 1.8 X 10-4
C6t Doped NLC 2.4 X (Q-4
LiNb03 2xl0-4---+ 2x10"5
Ge02 dooed Silica Glass 2 X 10"5
Bulk Silica Glass -10-9
Thus the doped nematic liquid gives nonlinear sensitivities which are comparable and in
some cases better than their crystalline photorefractive Counterparts. Clearly the dopant
(both type and concentration) within the liquid crystal affect the nonlinear sensitivity. These
dopants also affect the OPE's wavelength dependency.
As can be seen from Figure 6, di:ffiacted intensity (i.e. the magnitude ofthe orientational
photorefractive effect) increases by a factor of 3 as the wavelength of the Iaser is varied
from 514.5 nm to 457 nm. These results are well correlated with the absorption spectrum
ofthe C60 dopant. That is as the wavelength is tuned to the higher absorbency region ofthe
dopant there are more charges liberated, and thus there are greater space charge fields
created with the film. The larger space charge fields Iead to a more pronounced modulation
ofthe doped NLC's index ofrefraction, which in turn Iead to a higher diffiaction efficiency.
60
3.0
C&O
55
r-D
' '
50
~
; 45 ! 1.0
~
c: 40
0
'B .o
!!! 300. - - !1110.. - - 700. 81111. 11110.
!E 35 wa".length (nm)
0
:
'E 30
0
~
: 25 !
20 !!
15 !
10
450 460 470 480 490 500 510 520
Wavelength (nm)
Figure 6. Dependence of the 1' order diffraction (E3 & E4 beam) on the wave1ength. lncident 1aser power;
1
Et beam =18 mW, ~ beam =18 mW. 25 J.I.IIl thick C60-doped samp1e.V =1.5Volts
226
Pump
Figure 7. Planar aligned NLC in a wave mixing experiment
40
__..._ Vdc = 1.0V
- Vdc= 1.25V
35 ......,._ Vdc = 1.5 V
--e- Vdc =1 .75 V
-e- Vdc=2.0 V
30
>.
u
c: 25
Q)
"
!E
UJ
c: 20
0
+=>
u
CO
:i= 15
i5
10
0
0 5 10 15 20
Vac (Peak to Peak Volts)

Figure 8. Diffraction efficiency versus voltage for a 25 J.!ffi planar aligned K15+C60 NLC. P~o,=40 mW,
A.=5l4nm
227
Planar Aligned Sampies
Recently the effects of both AC and DC fields have been examined on planar aligned
samples as shown below.
Planar aligned samples have a practical advantage in that they would be easier to fabricate in
an optical system than the tilted configuration shown in figure 2. In these samples, the "tilt"
in the sample, which provides high index modulation, is achieved electrically through the use
ofthe AC field. The AC field (above the Freedericksz threshold) holds the nematic liquid
crystal molecules in a tilted position. In this alignment the sample is, for all intents and
purposes, in the same configuration as in figure 2, and the OPE with the DC field works in
the same fashion as discussed before. However, ifthe AC field is too small then there is no
tilt of the NLC molecules and there will be almost no modulation of the index via the OPE,
and if the AC field is too large then the NLC will become "locked" in place and cannot be
reoriented by the DC and optical fields. A family of curves which demoostrate this effect is
shown below in Figure 8.
CONCLUSION
In conclusion, DC field assisted photorefractive-like nonlinear electro-optical effects

have been observed in nematic liquid crystal films. This, so called, orientational
photorefractive effect (OPE) gives a nonlinearity which requires much Iower optical power
and has much lower absorption loss than many of the purported highly nonlinear
photorefractive crystals. A nonlinear coefficient on the order of 10"3 cm2/W or larger has
been observed. This OPE allows two-wave mixing, energy coupling, and phase conjugation
and can be made permanent under prolonged illumination.
Since liquid crystals are very broadband, relatively inexpensive, and easy to work with a
practical device making use of the giant nonlinearity is a future possibility. However, the
physics behind this effect are extremely complicated, and although much work has been
performed there is still much which can be done. More detailed studies of the physical
processes involved in these nonlinear electro-optical effects, including research on the
underlying mechanism behind photo-induced currents and ionic transpoft in the presence of
the DC field and the photochemical dynamics occurring in the photoexcited dopants and
their interactions with the nematic host, must be further studied to fully understand this
novelphenomenon.
ACKNOWLEDGMENT
The authors would like to thank Min- Yi Shih and Pao Chen for their help in data
collection, and the Air Force Phillips Laboratory for their supportoftbis reasearch.
REFERENCES
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228
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229
A MODEL FOR SINGLE-MOLECULE INFORMATION STORAGE
Christopher B. Gorman *, Brandon Parkhurst, Kang-Yi Chen, Wendy Su,

Michael Hager, and lgor Touzov
North Carolina State University
Box 8204
Raleigh, NC 27695-8204
INTRODUCTION
As computing elements become smaller and smaller, we must devise ways to encode
information in smaller spaces.l At least as far as strictly spatial encoding is concemed, the
two most obvious schemes for nanoscale information storage are (a) continued
miniaturization of known microscale elements to approach the nanoscale or (b) tailoring
existing nanoscale objects (e.g. molecules) so that they can function as information
bearing units (IBUs).
The frrst scheme can be pursued without necessarily losing any of the existing
paradigms for device fabrication, but it is not clear that it will work. Every indication is that
photolithography may have been pushed to its Iimit and is unlikely tobe a method for
producing structures with < 100 nm features.2,3 Mechanical encoding with a scanning
tunnellin~ microscope (STM) or atomic force microscope (AFM) tip (e.g. nanolitho-
graphy)4- or charge encoding (e.g. trapping space charges in thin oxide layers)8,9 may be
valid extensions of this paradigm to the nanoscale. Perhaps more important is the chemical
and physical stability of nanoscale metallic or semiconductor features. For example, metal
pits or mounds of ~ 10 nm size can flll in or spread out at room temperature over the period
ofhours.I0-12
The potential for use ofmolecular IDUs seems equally good.l3,14 Molecules are
autornatically in the right size range, thus obviating the challenges in nanoscale fabrication
based on microscale technology. Moreover, molecules are uniformly sized (in fact, identical)
units. Manipulation of individual atoms has been demonstrated by the work of Eigler et. al in
which "ffiM" was spelled at 4K with xenon atoms.l5 Use of stronger molecule/surface
interactions permitted Hosoki et altoperform similar experiments at room temperature.I6
Information can thus be stored by position. Several basic issues seem to be unaddressed at
this time, however. They include:
Efforts to control molecule/surface interactions have not progressed significantly.

Virtually none ofthe obvious interactions (e.g. hydrogen bonding, metal-ligand
coordination, but particularly covalent organic interactions) have been exploited.
Construction of a model system in which molecules are moved about on a surface

that is arnmenable to STM under ambient conditions would be desirable but has little
precedent. Such a model system would permit a significant step in moving such
studies from ultra-high vacuum physics laboratories into those of physical and
synthetic chemists.
Science and Techno/ogy of Polymers and Advanced MateTlls

Use of molecular state rather than just position has not been exploited. In the field of
molecular electronics it has been suggested that many types of molecules can exist in
two stable states (e.g. conformational states, protonation states, oxidation
states).l7,18 An information storage scheme that encodes information in those states
has not yet been demonstrated. Encoding of information at the molecular Ievel should
fundamentally be able to work. Few efforts have been reported, however, that
consider both switchability and addressability.
In this paper, macromolecular objects will be described that are tailored to serve as
switchable, addressable, and organizable IBUs. lt will be argued that only such a system in
which all of these items have been considered will be suitable for use in nanoscale
information encoding schemes. A number of challenges are encountered when considering
the use of molecular units. Some appear to be imminently solvable with existing
technologies. Some may require substantial additional technological development. They
include:
Control of IBU/surface interaction- Simply having bistable (or multi-stable)

molecular units is insufficient to reliably store and retrieve information. In order to
address encoded information, one must be able to direct IBUs to defined places in
space and to hold them in that space. Pattemed self-assembled monolayers (such as
the system based on organothiols on gold)l9-22 and the marriage of nanolithography
with self-assembly should be useful here. Clearly, one needs methods in which
IBUs can be assembled on a surface (using some form of nanometer scale
lithography to direct this assembly) and held tenaciously to the surface (where their
position is their address and this information is not lost due to diffusion or migration
on the surface). This areaisstill new. Adhesion forces between an AFM tip
derivatized with avidin and agarose beads functionalized with biotin appear to be
quantized in multiples of the force expected for individualligand-receptor binding. 23
Analogous control of forces between a molecule and a surface should be possible. A
surface that presents a uniform, well-defined organic functionality is acheivable using
self-assembled monolayers. 24-26
Positioning IBUs- Scanning probe microscopy has emerged as a useful technique

for spatial addressing at the nanometer length scale. STM-based lithography has
already been explored to write information on a surface using the tip as an electron
beam source or as a nanoelectrode in fluids.27 Such methods are, however, currently
considered to be slow because it takes some time to raster the tip across the surface.
However, new, parallel technologies may circumvent this problem. Already, micron-
sized arrays of STM's can be fabricated on a chip, and schemes for massively parallel
readlwrite o~rations (sort of an STM-based dot-matrix printer/reader) are under
development.28 With IBUs, severallikely schemes can be envisioned in which the
tip is used to position molecules on a surface. Here, it will be argued that more gentle
STM-based "lithographies" (explained below) should be developed to change the
chemical functionality on a surface rather than just to etch the surface. By changing
the chemical functionality presented by a surface, the IBU/surface interaction can be
varied from weak to strong.
Reading/Writing IBUs- As mentioned above, many schemes have been explored

for the synthesis of switchable, bistable molecules. Probably the best prospect is
redox switching as the nature of each of the states is relatively easy to define and may
be possible to probe for individual molecules. One might detect differences in redox
state due to differences in the charge on the molecule (and thus the local electric field
in its vicinity) and also luminesence from one state, but notanother (now documented
using near field optical microscopy).29-33
Isolation- Placing IBUs in close proximity to each other invites such processes as
electron or energy transfer, thus losing any information encoded by differences in
these states. 1t will have to be determined how close one can place a unit in the " 1"
state with respect to a unit in the "0" state and still expect them to reliably hold this
information. This process will require application of what has been leamed about
232
through-bond electron transfer - molecular topologies in which this process is
altemately facile and attenuated have been described.34-38 For now, it is a reasonable
assumption that electron transfer through 35-40 A of a saturated organic assembly
will be much less facile than between two electroactive systems in more intimate
contact.
SYNTHESIS AND CHARACTERIZATION OF ENCAPSULATED

ELECTROACTIVE MOLECULES
Although a number of molecules which are "switchable" have been discussed in the
literature, isolation of information, assembly, and addressing of individual molecules have
received much less attention. A multifunctional molecule will be necessary if it is, for
example, going to be a redox switch and simultaneously have a tailored interaction with a
surface. It was decided to pursue this scheme using an encapsulated electroactive unit.
To this end, a series of molecules were prepared that consist of an inorganic duster
surrounded by a dendrimeric coating (Figure 1). The electroactive core will facilitate the use
of the molecule as a redox switch. The organic coating is designed to isolate the information
held by the redox state of the core. In the molecules discussed here, the coating is a dendron
Iigand containing one to four branch points. The synthesis of these ligands39 and of the
hybrid organic/inorganic molecules have been described in detail. 40
Figure 1. A 3rd generation encapsulated electroactive cluster. Molecules containing similar dendran
Jigands with 1-4 branch points have been prepared.
The electroactive core in this molecule is an iron-sulfur cube. This species is related
to the redox center found in several electron transfer proteins including ferredoxins and
rubridoxins.41 Derivatives have been reported with various alkyl and aryl thiols as the four
peripheralligands on the irons. 42 All of these clusters are extremely stable upon oxidation
and reduction - ideal, reversible electrochernical behavior has been observed for them
233
(e.g. for Fe4S4(SPh4), E112 for the 2-/3- couple@ -1.04V (SCE), Epa-EPc =72 mV and
E112 for the 3-/4- couple@ -1.75V (SCE).43 They are synthesized easily in basic methanol
by mixing an iron salt, sodium hydrogen sulfide and an organic thiol under inert
atmosphere.42 In this fashion, they are synthesized as dianions and crystal structures of
several thiol-derived clusters in combination with tetraalkyl ammonium cations have been
reportect.42
The iron-sulfur core was chosen for several reasons. lt is easy to synthesize, and it
has been shown that derivatives containing a variety of functional groups can be prepared.
The conditions for thiol substitution reactions around the core have been described,44 and
other thiols have been placed around the core in this manner.45 The electrochemical behavior
observed indicates that the core can exist in several, stable redox states. Moreover, the
electrochemical behavior of any new derivatives can be profitably compared with that of
Fe4S4 clusters found in both biological and non-biological systems. Finally, the tetrahedral
disposition of the four ligating points on the cluster is an ideal geometry for the synthesis of
spherical, dendron-capped clusters. A distribution of dendrons with the highest global
symmetry possible will most effectively encapsulate the core. lnorganic clusters and this
cluster in particular offer higher symmetry than is conveniently accessed using electroactive
organic compounds (which tend tobe planar).
lt was sought to show that the rate of electron transfer to and from the core could be
attenuated with the bulky dendrimeric ligands. This behavior was illustrated by performing
cyclic voltammetry of the different molecules and comparing both the thermodynarnic
reduction potential (E 112) and the difference in applied bias between the maximum current in
the reduction and return oxidation waves (Llli). Table I contains these values, and they
indicate that, as the number of branch points in the ligand increases, the molecule becomes
both kinetically (as evidenced by the values of Llli) and thermodynarnically (as evidenced by
the values of E 112) more difficult to reduce/reoxidize. The molecule containing ligands of the
fourth generation did not display a clear retum oxidation wave. This behavior is expected as
the kinetic difficulty of re-oxidation increased through this series of molecules.
Table 1. Electrochemical data for
molecules of the general structure shown
in Figure 1. 1
Branches in E112
&Jgand
0 -970 130
1 -1000 250
2 -1030 340
3 -lp80 i70
4
From cyclic voltammetry in dimethyl
forrnamide solution, 100 mV/sec scan rate,
nBu4N PF6 supporting electrolyte, Ag/AgCI
reference. Ths molecule contains ligands of
the structure -S-p-(C6H4)-CON(CH3) 2. 3The
reduction wave was shifted ca 50 mV more
negative compared to G3. No clear return
oxidation wave was discernable.
In addition to these results, work has progressed to illustrate the effect of molecular
size and degree of encapsulation on both the diffusion constant and on the heterogeneous
electron transfer rate. Such experiments push the limits of cyclic voltammetry for these
quasireversible systems. However, quantitative data have been obtained for the single-
branched molecule shown in Figure 2 using a combination of normal pulse voltammetry and
cyclic voltammetry at different sweep rates. Further experiments that quantitate these
parameters for larger molecules are underway.
234
Normal Pulse Voltam.metry Cyclic Voltammetry
15r---~--~r---4----4----~
14~--~--~----+---~~~
12
10
8
6
4
-10
2 =
k" 2.2 :t 0.2 x 10"3 cmlsec
-15+----+--__,r--4----+---+
0~~~----~--~--~----~
-500 -700 -900 -1100 -1~0 -1500 -500 -700 -900 -1100 -1300 -1500
V (mVvs.Ag/Ag+) V (mV vs. A!ifAg'")
Figure 2. Results of normal pulse voltammetry and sweep-rate dependent cyclic voltammetry give the
diffusion constant and heterogeneous electron transfer rate constant for the molecule shown at top.
In addition to the electroactive nature of the core, it is also paramagnetic - formally it

is a mixed valence species with an overall pararnagnetic moment of 1 BM. It was discovered
that this feature influences the longitudinal (T 1) relaxation times of protons in the dendrimeric
Iigand. lt was hypothesized that the change in relaxation time would monotonically scale
with the distance between the nucleus and the core and that changes in the conformation of
the dendrimer would result in changes in the relaxation time for a particular proton. Figure 3
shows initial results of a systematic study of this phenomenon. Here, relaxation times for
dendrimers of similar shape containing a diamagnetic core were found to uniformly be Ionger
than those containing the paramagnetic Fe4S4 core. A quantitative treatrnent of this data that
includes an account of all possible nuclear relaxation mechanisms and that illustrates the
relative influence of the paramagnetic core on the overall relaxationrate in each of these
molecules is underway.
235
1100
~~6~\70
~0~0 ~

!"~~ ~-;.
"'
"
d:
~ 1590
6~
9-
\:...:(._0
1
"" 0 "' 0 430 0 ...... ,
5 o~ ~~.. ~,[~()~I
Fe,, s '/ \
Ni9
510&810,,f/,d
_ ,-;.
~I
P"
..,.. I N Fe ...
~ o J s' - 1
~o 0

~I - o 06
!\
~0 _rj"""'
(
@
6
500 & 61Y.
6~" G3, .. ~ @-<!?>) i<~"?Os~
~: ~- 0"~\- ~0~-, ~--:)
340
~
-o _190 o '/ \ s:r;~"

~0
N I~ ""Q
@-o.... (I

G3, Dia.
:.
~ 0
v-{j-;.
,~
.. -
0
'/~~
,_.._}"-0-.t;e<~~s~ I o~" J.. 0
if~ ,/'s- ~"@ .. . ., ~

IJWD O@ 1;.
Xd 0
@
N _ IR\
'Cf'
~1
"' 550 & 860 o-{}J
3670 oJf)
(1
.
\.
Gl,Para. 1
J0-o~-,
o"d... -~
}:J :1
@-o . . ( GI, Dia. ) 0
'f)
Figure 3. Relaxation times (in ms) for aromatic pratons in two dendrimers containing paramagnetic
cores and two analogaus dendrimers containing diamagnetic cores. In each case, the relaxation time is written
next to the associated protons in the structure. The symbol "D" denotes other dendran ligands of identical
structure to those drawn out for each molecule (e.g. each molecule contains four identical dendran ligands).
SCANNING TUNNELING MICROSCOPE AND ATOMIC FORCE

MICROSCOPE TIP-INDUCED STRUCTURAL REARRANGEMENT AT THE
NANOSCALE OF ALKANETHIOLATE SELF-ASSEMBLED MONO LA YERS
ON GOLD
In the scheme outlined in the introduction of this paper, a well-defined surface is

necessary to array and manipulate the positions ofthe IBUs. Self-assembled monolayers
(SAMs) formed from the reaction of organothiols with a gold surface provide a system with a
number of convenient features. Large (100 nm x 100 nm) Au(lll) surfaces with a minimal
number of step defects can be prepared by evaporating gold onto preheated rnica or by
melting gold wire in an oxyacetylene torch followed by annealing and electrochernical
polishing.lO Organathiol SAMs can be formed reproduceably on this surfa~e as well-ordered
quasicrystalline monolayers with a variety of functional groups at the monolayer
terrninus.46-53 Typically, deposition of an alkanethiolsuch as decanethiol (which is
illustrated here) from the vapor phase onto a freshly prepared Au( lll) surface results in !arge
(ca. 50-100 nanometer) regions of hexagonal eh X '\13 R30) lattice. Interestingly' this
lattice appears to be metastable as it can be converted under the influence of a scanning
tunneling rnicroscope (STM) tip to a c(4x2) superlattice as described below. This process
was previously observed to occur upon thermally annealing the sample at temperatures of
approximately 100 oc.47,50 Given these initial observations, it was sought to deterrnine the
range of structures that could be induced and observed as the result of a scanning probe tip.
236
By scanning with STM at low (< 2 pA) setpoint current, the hexagonal
--J3 x --J3 R30 lattice could be imaged reproduceably (Figure 4A). Using a STM at a slightly
higher (6 pA) setpoint current, this --J3 x --J3 R30 lattice could be converted to a c(4x2)
superlattice, probably as the result of the force of the tip pressing upon the surface during
scanning (Figure 4B). This result led to the conclusion that the c(4x2) superlattice structure
was energetically more stable than the hexagonallattice. In the process of this
transformation, a metastable intermediate of p2 symmetry was induced and observed (not
shown). Using an AFM tip (data acquired in lateral force, e.g. friction force mode, FFM),
this c(4x2) superlattice could be observed on a thermally annealed sample, although pressing
upon the surface with this particular tip did not Iead to this lattice structure.
2.50
..-.::~--.....tJJ..._ _ _...__....__ r 0
A B o 2.50 5.00
OM
Figure 4. Scanning tunneling microscope (STM) images at 2 pA setpoint current of (A) a ..J3 x ..J3 R30
lattice of decanethiolate on Au( 111) and (B) a c(4x2) superlattice of the first image after scanning with the tip
at a higher setpoint current of 6 pA.
Pressing with a FFM tip induced two intermediates starting from the hexagonal,
--/3 x --J3 R30 lattice (Figure SA). The firstintermediate (obtained at a setpoint force of 8.7
nN, Figure SB) had p2 symmetry as did the intermediate observed transiently by STM. The
second intermediate (obtained at a setpoint force 80 nN, Figure SC) had pl symmetry and
was formally a p(3x 1) superlattice of the original hexagonal alkanethiolate arrangement.
These intermediate structures were not reported in previous work on similar samples
subjected to thermal annealing cycles. These FFM tip-induced intermediates most probably
involve perturbation of the alkanethiolate tail conformations and/or orientations. Because the
p(3xl) arrangement can be converted to the c(4x2) arrangement by thermal annealing, this
former lattice is concluded to be thermodynamically less stable than the latter.
The exact structure ofthe c(4x2) superlattice is not established by this or previous
experiments. lt is likely that the STM experiment is mostsensitive to the positions of the
sulfur and first layer(s) of gold atoms and that the STM-induced Iransformation to a c(4x2)
superlattice involves rearrangement of both the alkanethiolate tails and the sulfur and top layer
or two of gold atoms when compared to the hexagonallattice. However, by comparing the
structures obtained by interaction of the sample with both a FFM and STM tip, it is clear that,
even at low tunneling currents (6 pA), the STM tip interacts considerably with the sample.
The exact mechanism of interaction is not completely definable, but simple notions suggest
that a dominant mechanism is via the force of the STM tip pressing upon the sample. These
data indicate that the result of interaction of the STM tip with the sample is at least as great as
that of an FFM pushing on the surface with a 80 nN setpoint force.
Ultimately, we feel that this description of the nanoscale placement of thiols on a gold
surface will be important in interpreting the results of further model studies and in studies in
which organothiolate SAMs are used to control molecule/surface interactions at the
nanoscale.
237
10.0
A 7 .5
5.0
2.5
0
0 2.5 5.0 7.5 10.0 nM
10.0
B c
7.5
5.0
2.5
0 2.5 5.0 7.5 0 2.5 5.0 7.5

nM nM
Figure 5. FFM images ofthe (A) hexagonal, (B) p2-symmetry and (C) pl-symmetry c(3x l) structures of
a decanethiolate SAM obtained as discussed above.
ACKNOWLEDGMENTS
This work was supported in part by NC State Start-Up Funds, by the U. S. Army Research
Office under grant nurober 34422MS-YIP and by the Air Force Office of Scientific Research
MURI Program in Nanoscale Chemistry.
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240
CLUSTER SIZE EFFECTS AS A BRIDGE TO MOLECULAR ELECTRONICS
Joshua Jortner
School ofChemistry, TelAviv University,

TelAviv 69978, Israel
INTRODUCTION
Molecular electronics 1 3 constitutes a multidisciplinary research field with dual goals:

(I) Providing molecular materials for electronic and optoelectronic applications.
(II) Utilization of single molecular systems, e.g., a molecule, supermolecule, molecular
aggregate or duster for the processing of optical, electrical, magnetic, chernical or
biological signals.
The distinction between dasses I and II is both practical and conceptual. Molecular
materials for electronics (dass I) are already widely utilized. These indude organic
photoconductors in xerography, organic liquid dusters displays, and organic photoresistors.
More esoteric materials for electronic applications, e.g., organic superconductors, organic
transistors, rectifiers, light ernitting diodes, hole burning memories and sensors, have all
been demonstrated. On the other hand, the utilization of a single molecular scale system
(dass Il) to process signals is still in the conceptual, speculative, tantalizing stage and has
not yet been realized. The outstanding goal of molecular electronics pertains to the
perspective utilization of synthesis, assembly and rniniaturization on the molecular Ievel to
accomplish a huge density of devices, e.g., molecular wires, rectifiers, optoelectronic
triggering switches, transistors and memories. Most of the potential application notions of
dass II emerged from attempts to replicate standard electronic devices on the molecular
level. 1-3 Unique applications in which only molecular systems can be used, e.g., molecular
recognition-based sensors, self-assembled molecular systems, molecular pattemed growth
or molecular interfaces with biological systems, are still in embryonie stages and deserve
active exploration. The outstanding challenges of molecular electronics pertain to the
advancement of molecular and biophysical microscopic systems to reproduce the
characteristics of microfabricated electronic devices and, even more interestingly, to strive
towards unique applications of molecular scale systems. In this context of unique
applications, duster systems for electronic applications constitute a bridge between
microfabricated systems (with silicon devices at the upper Iimit of their size domain) and
molecular and biophysical systems (Fig. 1). This brings up an implication of the central
concept of duster size effects: 36 the characteristic dimension at which the molecular,

electronic, optical or transport behavior converges to the limiting behavior of the bulk is
property specific and depends on the constituents of the cluster. The exploitation of the
discrete electronic Ievel structure of finite systems will result in novel electrical and optical
phenomena. Finally, the characteristics of small size and low dimensionality in charge and
energy transport provide a rich set of novel phenomena and, in particular, opening avenues
for the optimization of transport properties in finite systems. These constitute some of the
central themes of current research of cluster size effects as a bridge to molecular
electronics.
BIOLOGICA~ M Ol_~_CU U~!!_ MICROFABRICATED

S. CLUSTER
SIZE
!Al
10 5 I TRANSISTORS
10 4 I BACTERIUM SEMICONDUCTOR
I--- GATES
ELEMENTAL HETERO
0 TOBACCO MOLECULAR
10 3 MOSSAIC VIRUS AND MET AL
CLUSTERS
STRUCT~SI_r3r~A:::R:~Ts
ODNA STRANDS ~ LIMIT LITDGRAPHY
OPHOTOSYNTHETIC RC BRIDGED DAI RESOLUTION
ATOMIC
OHEMOGLOBIN ~
OINSULIN 0 HC13N I~NOWIRES 1 STM RESOLUTION
10 0 Cso
0 BENZENE t TUNNELING BARRI ER
JOSEPHSON JU NCTION
0 C-C BOND
LENGTH
Figure 1. Relative size of molecular systems relevant for molecular electronic devices.
GENESIS OF CLUSTER RESEARCH
The bridge between molecular, surface and condensed matter chemical physics is
provided by clusters, i.e., finite aggregates containing 2-109 particles. 3~ The genesis ofthe
development of cluster science can be traced to the work of Mie in 19087 on the optical
properties of small particles, while the work of Kubo in 19628 pioneered the exploration of
the electronic structure of small metallic particles, addressing the important issue of the
nonmetal-metal 'transition' in finite systems, which can be realized when the thermal energy
exceeds the energy gap. Subsequently alternative mechanisms for metal-nonmetal
transitions in clusters, e.g., the closure ofan electronic band gap, 9' 10 were advanced. During
the 1970s, a wealth of information emerged on electronic transport and optical properties of
metal clusters embedded in insulators, e.g., granular metals11 and metal-rare gas mixtures, 12
where intercluster interactions can be described in terms of the percolation theory and
tunneling effects. 13 Concurrently, studies of electronic, optical and catalytic properties of
clusters supported on surfaces emerged. 14 An additional dimension to the exploration of
clusters originated in 1977 with Friedel's emphasis4 ofthe properties of 'clean and isolated
clusters', which rested on the generation of cluster beams/ 516 on structural concepts for
close packing of hard spheres 17' 18 in conjunction with direct experimental structure via
electron diffraction studies, 19 on spectroscopic and dynamics studies of van der Waals
molecules20' 21 and on studies of excess electron localization in supercritical polar fluids. 22
An arsenal of experimental, computational and theoretical methods23"26 is currently applied
to the study of clusters. While the exploration of isolated clusters in supersonic jets
substantially contributes to the conceptual framework, studies of systems based on clusters,
242
e.g., embedded dusters in the bulk, 27 supported dusters on surfaces, 28 packed quantum dot
solids29 and duster ensembled structures, 30 will provide potential materials understanding
and devices for molecular electronics.
CLUSTER SIZE EFFECTS
A key concept for the quantification of the unique characteristics of atomic and
molecular dusters pertains to size effects? 133 These involve the evolution of structural,
thermodynamic, electronic, energetic, electromagnetic, dynamic and chemical features of
finite systems with increasing duster size (Fig. 2). Cluster size effects fall into two distinct
domains: 31"33
"LARGE" "SMALL"- n
x(n)
BULK
VALUE
x(oo)
Figure 2. The duster size dependence of a duster property :;.:(n) on the number n ofthe duster constituents.
The data are plotted vs nP where s: 0. "Small" clusters reveal specific size effects, while "!arge" clusters
are expected to exhibit for many properties a smooth size dependence of z(n), which converges for n ~ oo to
the bulk value x(oo).
1. Specific size effects. In the "small duster" size domain an irregular size dependence
of the relevant duster properties :x.(n) (where n is the number of units) is exhibited.
This irregular pattern is manifested most dramatically in the existence of "magic
numbers" in :x.(n) vs n, which reflect shell closure effects. Typical examples involve
the structural dosed shells of Mackay isosahedra17' 18 in dusters of rare-gas atoms 19
and of spherical !arge molecules, 34 the enhanced energetic stability and increased
ionization potentials for electronic dosed shells in meta! clusters,35 and the expected
increased stability ofthe Fermion dosed shell structure in eHe)N dusters. 36
2. Smooth size effects, for "!arge" clusters. In this size domain a quantitative description
(Fig. B 1) was advanced for the "transition" of energetic, electronic, spectroscopic,
electrodynamic and dynamic attributes of clusters to the infinite bulk system in terms
of duster size equations (CSEsf 1"33
243
x(n) = x(oo) + An" ' (I)
where Ais the constant and ( :<! 0) is a positive exponent.

CSEs, which are quantified by Eq. 1, can be traced to two distinct physical origins:
duster packing and exduded volume effects. These two categories will now be considered.
Size Effects Originating from Cluster Packing
These pertain to the consequences of the large surfacelvolume fraction of dusters.

For sufficiently large dusters, the fraction of surface atoms is given by F = cxn113 A
Straightforward utilization of this result pertains to the description of extensive variables Y,
e.g., the intemal energy, entropy or magnetization, ofthe duster. Viewing the duster ofn
units as a composite system consisting of surface and volume subsystems, the value of the
extensive variable Y(n) is obtained from a subsystem additivity rule
Y(n) = n(1-F)yv + nFy. , (2)
where Yv and y. are the corresponding variables (per unit) for the bulk and for the surface,
respectively. The total value ofthe variable per unit y(n) = Y(n)/n is
(3)
Eq. 3 constitutes a simple application ofthe liquid drop model ofnudear physics.
Size Effects Originating From Exduded Volume Contributions
A multitude of energetic and spectroscopic size effects can be described in terms of

the infinite system observable, corrected for the exduded volume contribution. The CSE,
Eq. 1, then assumes the generalform
x(n) = x(oo) + C(n) , (4)
where
(5)
is the exduded volume correction term. C(n) accounts for the modification of the bulk
value for the observable in the duster, due to the exduded volume outside it (i.e., the range
R: to oo). R: is the duster radius, which is related to the radius Roof a single constituent by
R: = Ron" 113 Accordingly, the exduded volume can be expressed in the alternative form
(6)
The CSE, Eq. 4, is better than it appears at first sight for the quantification of physical
observables. All the short-range contributions to x(n), which are usually difficult to
evaluate, are incorporated in x(oo), which is often taken from experiment. What is explicitly
evaluated is the correction term C(n) arising from the excluded volume contributions. These
are determined by long-range effects, which are amendable to reliable calculation. Weshall
now apply exduded volume effects to the energetics and spectroscopy of clusters.
244
Exduded Volume Effects on Cluster Ionization Potentials
The CSE was successfully applied to a multitude of energetic size effects. 31"33 For the
size dependence of the duster ionization potentials (IP) and electron affinities (EA) the
exduded volume contribution originates from the charging energy. The application of the
continuum dielectric model to C(n) results in
(2Z + l)e2 f( )
IP(Z;R,) IP(oo) + E:o,E:oo
2R 0
(7a)
(2Z-1)e2
EA(Z;Rc) = EA(oo) + f(e:o,e:oo) (7b)
2R 0
where Z is the duster initial charge and e:0 and Eoo are the static and optical (high frequency)
dielectric constant, respectively. The function f(e: 0,e:oo) depends on the nature of the
ionization or electron attachment, being
f(e:o,Eoo) = (1-1/e:o) (8)
for the adiabatic ionization potential and electron affinity, while
f(e:,,e:oo) = (1-2/e:o+ 1/e:oo) (9)
for the vertical ionization potential and electron affinity. IP(oo) and EA(oo) are the
ionization potential and the electron affinity of the corresponding macroscopic system.
Accordingly C(n), Eq. 5, is characterized by = 1/3. This situation is realized for the
vertical ionization potentials of rare-gas dusters, 31 the vertical ionization potentials of
microscopically solvated anion dusters, 37.3 8 and the vertical binding energies of interior
excess electron states in large (NH 3 )jj dusters. 39 The exduded volume contribution of an
impurity in a heteroduster depends on the location ofthe impurity. The distinction between
surface and interior impurity states is of interest in the context of anion solvation in water
dusters, e.g., x-(H20)n (X= F, Cl,Br,I) 38 and of rare-gas heterodusters. 33 A theory of
site-specific cluster ionization potentialswas developed. 40
The ionization potentials and electron affinities of meta! dusters are of importance for
molecular electronics, being given from the charging model by e: ~ oo, where IP(oo) is the
work function (or band energy) of the (macroscopic) metal and EA(oo) is its bulk band
energy. Theserelations account weH for the smooth duster size dependence ofthe electron
affinities ofsufficiently !arge metal dusters (Fig. 3), which faithfully follow the artist's view
of size effects (Fig. 2). Cluster size effects can provide a link between electrical properties
of mesoscopic systems41 ' 42 and of dusters, with the issues of Coulomb blockade and
Coulomb staircase41 "44 providing a pertinent case.
CONFINEMENT
The interaction of the boundary of a duster with an electron or hole will result in their
localization (confinement) within the duster, provided that this interaction is repulsive.
Such a situation prevails for semiconductor4549 or rare gas (e.g., Ne and Ar)3149 clusters.
For the case of a single charge carrier, duster boundary scattering effects on either coherent
245
n
IX) 1000 100 30 10
7r---~~---r----.-----~----~
00~--~--~~~~~~--~~
I I I I
0.0 0.1 0.2 0.3 0.4
1/Rc(- 1)
Figure 3. The dependence of the energies of the ns and nd bands of Cu;; (n = 1-411) clusters. (0.
Cheshnovsky, K.J. Taylor, J. Conceicao, andRE. Smalley, Phys. Rev. Lett. 64:1785 (1990)). The electron
afiinities of the negative clusters reveal the CSE behavior for n > 60, converging to the corresponding buik
energies (marked by solid bars).
or incoherent motion will be exhibited. Cluster boundary interactions are manifested by the
confinement of large radius Wannier-Mott excitons (i.e., electron-hole pairs) in such
dusters. In this context one encounters an interesting quantum mechanical problem: the
interplay between the attractive two-body electron-hole interaction and the one-body
interaction exerted by the duster boundary. 4549 Consider a Wannier exciton 12 characterized
by the binding energy
(10)
and a principal quantum number N and a radius
(11)
where e is the (optical) dielectric constant and J.t the effective mass (i.e., J.t.1 = m;I + mh1
with llle and mh corresponding to the effective mass ofthe electron and hole, respectively).
Two limiting situations can be realized4549 for such an exciton with increasing duster
size (characterized by the duster radius R,).
1. Strong confinement R, << rN. The situation corresponds to the individual
confinement of the electron and the hole within the potential weil, with negligible
spatial correlation. The energy of the lowest excited state was inferred from an
electrostatic model
(12)
with the first term corresponding to quantum localization of both electron and hole
within a spherical box and the second term representing the interaction between them.
2. Weak confinement, R, << rN. Now the characterization of the exciton as a
pseudopartide is preserved, being confined in the duster. The energy EN of the Nth
246
hydrogenic exciton state is4549
(13)
where the exciton energy in the infinite system is
(14)
with EG being the band gap. The second term in Eq. 13 represents the confinement of
the pseudopartide in a box. Eq. 13 constitutes31 a CSE ofthe interesting form EN(n)
= EN(oo)+a.n-213
Exciton confinement brings up a unique feature of cluster boundary effects. The
spectroscopic manifestations of exciton confinement were established.3149 Of considerable
interest are the effects of confinement on the exciton dynamics, e.g., transport and thermal
ionization. In the realm of molecular electronics one should explore ways to overcome
confinement of electrons, holes and excitons via appropriate molecular circuitry.
THE UNIFIED DESCRIPTION OF CLUSTER SIZE EFFECTS
The description of "smooth" duster size effects, which originate either from cluster
packing or from exduded volume contributions, results in the quantification of the gradual
"transition" from the large finite duster to the bulk systems. The CSE, Eq. 1, provides a
unified description for the energetic, quantum, electronic, spectroscopic and electrodynamic
size effects. 31 33 TableI provides an overview of the parameters ofthe CSEs for several
physical attributes, specified in terms of the exponent. Table I also shows the validity
conditions for the applicability range of these CSEs, specified in terms of the minimal
number n. of units for the onset of bulk properties (B). From the data of Table I, i.e.,
distinct CSEs (with different values of and n.) for different physical properties, it is
apparent that the duster size effects are not universal.
The CSEs provide the quantitative answer to one of the centrat questions in the area
of duster chemical physics: 31.33 What is the minimal duster size for which the duster
Table I. Estimates of"critical" dusters sizes for the attainment ofbulk properties.
n_ (a) Ilc (b)
Observable Alx.(oo)l
Cohesive energy of alkali clusters l/3 5 1 106
Ionization potentials of rare-gas clusters l/3 20 0.1 103
Ionization potentials and electron aff'mities
of metal clusters l/3 60 0.7 3105
Photoionization ofr (H20h l/3 125 1 106
Photoionization of (NH 3 )~ l/3 150 3 HO
Collective vibrational compression modes
ofAI. 1/3 20 5 108
Confined Wannier excitons in rare-gas clusters 2/3 700 I 103
Dispersive spectral shift, MAn cluster 1 10 7 710'
Dispersive spectral width, MAn cluster 3 10 1 7
<> Rough estimates for the minimal cluster size (n > n_) for the applicability ofthe CSE.
(bl Relative deviation of physical property from bulk value S: 1%.
247
properties become size invariant and do not differ in any significant way from those of a
macroscopic sample of the same material? According to the CSE, the relative deviation
from the bulk value for a specific physical property x(n) will be
lx(n)-x(oo)l I lx(oo)l = INx(oo)lnP . (15)
Defining somewhat arbitrarily the realization ofbulk properties for n 2! Ilc, where the relative
deviation is S 1%, one estimates the number ofunits, Ilc, in the "critical" cluster size tobe
(16)
Table I provides a compilation of the values of INx(oo)1. The catalogue of 11c values
(Fig. 4) reveals a variation of 11c over eight orders of magnitude for various physical
properties. The largest value of 11c corresponds to electromagnetic interactions (e.g., the
Einstein coefficients for spontaneaus and stimulated emission) which are characterized by
the dimensionless size parameter (2nRo/A.)n1, where A. is the wavelength oflight. 31 On the
other extreme, dispersive interactions result in the lowest values of 11c. From the foregoing
analysis we condude that the CSEs provide a unified (but not universal) description for the
merging between the properties of microscopic !arge finite systems and those of the
macroscopic bulk material. The nonuniversality of duster size effects implies a wide
variance of different properties (e.g., optical and electrical) of a finite system from the
corresponding bulk values.
DIMENSIONALITY SCALING OF CLUSTER SIZE EQUATIONS
The preceding analysis of duster size effects mostly focused on the usual physical situation
when both the finite duster and the corresponding reference bulk material are three
LIMITING CLUSTER SIZES

Cl)
er
w
(.!)
1- Cl) 1- c u
zcn z cn~ j:
~Cl)
...
- Ir 0
Zw ~0
WCI)
~~.~
0"'
:I:O::
cn w"'
..Jt-erx
1- ..J N
U:x;
c-
..,
~ z z
~0
<1:~
O..J
::iU
ct~WW~
er..JI-erw
2' ... X
z 2 -<t
otio
w c: t-U"'wt- er ~z
Cl)
z erc:~:O
t-erO
z<t u c3-"' LIJ er~ 0
uw
:i~
w<tuz~
a. z..J 1- Wt- j:.
<ll::::!"oo<tu Cl) Zct <t ~ 1- II
..J w!:::!
~ w~..<
LIJ LIJ ct3: !:::!
> > 1!10 (/) u zZ z
i i ww<t ..J ~~ 0
crzt!l
Ir
LIJ
0::
loJ <1: iL w i:!loJ
:x;O
U)0
Wl- 1-
Q_ Q_
o:zo: :::E ox
0
"'
-
Ul :I:
a.o<t a. ua. a.
0 .... uo:
I I j_ I I I I
I 10 10 2 10 3 10 4 10 5 10 6 10 7 108 10 9
nc
Figure 4. An overview ofthe 'critical' cluster size (n.) for the attainment ofbulk properties for energetic,
spectroscopic and electromagnetic observables.
248
dimensional (D = 3). Cluster chemical physics in low dimensionalitl 3' 50 is of interest,
pertaining to the following physical situations.
1. Lower geometrical duster dimensionalities. These may involve finite "duster wires"
converging to an infinite wire (D = 1), or planar dusters converging to an infinite
plane (D = 2) for supported "islands" on a substrate.
2. Fractal dusters. These are characterized as Hausdorf dimensionality D, which
satisfies two conditions:
(i) The correlation length for the (self similar) fractal structure is smaller than the
duster radius.
(ii) With increasing duster size, the duster converges to the macroscopic fractal
structure.
Examples offractal clusters include clusters of porous materials and some clusters
deposited on surfaces.
3. Dimensionality scaling due to duster packing. The fraction of the surface atoms in a
a
duster ofHausdorf dimensionality D is F = n- 1/D, where ais a numerical constant.
These heuristic relations constitute the generalization of the liquid drop model for D
dimensions. A more careful examination of the dispersion relations for elementary
excitations in fractal clusters is still required.
4. Dimensionality scaling of excluded volume effects. We consider now the situation
when the duster and the exduded volume are characterized by a common
dimensionality D (;t; 3). The extension ofthe CSEs just requires the replacements of
the excluded volume corrections C(R:), Eq. 5, by contributions over a D dimensional
space. The packing ofthe constituents is given by setting Re oc n11D. The excluded
volume contribution for the ionization potentials is now C<D>(R:) oc Rp-4 and C<D>(n)
oc n(D-4YD.
Such CSEs, originating from dirnensionality scaling will be of interest for the
ionization, spectroscopic reponse and dynamics of clusters of lower (D = 1 and D = 2)
dimensionality and of fractal clusters. The dimensional features of duster behavior are
particularly relevant to molecular systems, since molecules are generally not spherical
(excluding esoteric cases such as fullerenes and cage compounds). Indeed, quantization
effects perpendicular to the transport direction are crucial both in mesoscopic devices and
molecular wires.
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250
ELECTRIC FIELD EFFECT ON FRENKEL-WANNIER-
MOTT EXCITON STATES IN ORGANIC-INORGANIC
SEMICONDUCTOR QUANTUM WELLS
S.Jaziri
Departement de physique,
Faculte des sciences de Bizerte,
Jarzouna 7021 Bizerte Tunisie.
INTRODUCTION
Organic and inorganic semiconductor nanostructures are the subject of many recent
investigations. The ability, in the near future, to synthesize composite organic/inorganic
semiconductor heterostructures is of crucial importance not only in the development of novel
nanostructured materials for electronics, optics, transport ... , but also for understanding their
size-dependent physical properties. Recently 1-3 a new type of elementary states generated by
optical exicitation are hybrid excitons which can be obtained from the resonant mixing of
Frenkel-Wannier-Mott excitons in organic/inorganic quantum wells. This novel system, the
hybrid excitons localized in organic/inorganic semiconductor heterostructure, is expected to
show characteristic physical properties and also provide a basis for new electrooptic
technology. The hybrid excitons acquire the properties of both types of excitons. They have
very strong oscillator strength like Frenkel excitons. They are delocalized and possess a large
size like Wannier-Mott excitons, then they aresensitive to extemal pertrubations, namely
electric and magnetic field effects.
The effect of an electrostatic field on the electron-hole states and on the confined exciton
states, referred to the quantum confined Stark effect (Q.C.S.E), has received intensive
discussions in inorganic semiconductor low-dimensional structures 4 -6 . The Q.C.S.E has
increased the interest in inorganic semiconductor quantum well electro-optics. The major

results are that the energy for peak optical absorption exhibits a red shift and the amplitude is
little dereased when the electric field is increased. For good device performance, it is necessary
to have large electo-optical effects with a small reduction of the exciton oscillator strength and a
large excitonic stark shift. Most of the previous studies use a reetangular quantum weil
structure. However, recent development of epitaxy technology makes it possible to grow
quantum wells with different forms : parabolic, step-like, triangular... Several types of such
structures have been made successfully to study electro-optical effects.
In the present work, we consider an organic-inorganic semiconductor system which
consists of (2D) organic monolayer juxtaposed to an inorganic semiconductor quantum weil.
We consider a graded parabolic semiconductor quantum-weil system. This structure has the
interesting feature that the ground state sees a wider barrier than the excited states due to the
shape of the potentical. Thus it is possible to populate the ground state without producing an
appreciable leakage current due to tunneling under an applied electric field.
In this theoretical study we discuss the external electrostatic field effects on the hybrid
Frenkel-Wannier-Mott exciton states in the interface of organic and inorganic quantum wells.
THEORY
We study the heterostructure which consists of an inorganic parabolic quantum weil and
an organic monolayer placed at distance z0 . We consider the inorganic quantumweil with the
parabolic confinement for electrons and holes having the different quantization energy 11 0 e
and flOh respectively 7 . The dimension R0 of the parabolic quantumweil is defined by the
electron "magnetic" length and we suppose the electron and hole ones to be the same: R0
-v'+.
=- .- ~
;e--oe=-v ~-
We consider this heterostructure under a uniform applied electric
field F perpendicular to the welllayers (along the z-direction). We neglect the electrostatic field
effect on the organic monolayer, because the Frenkel excitons are more localized on the
molecular site. The inorganic quantum weil is significantly and more affected by this electric
freld perturbation. Under the electric field effect, the wave functions of the electron and the hole
forming the Wannier-Mott exciton are those of the displaced harmonic oscillators which are
shifted in opposite directions. The effective-mass approximation is assumed tobe valid. We
ignore the band non parabolicity. The constant dielectric in the weil and in the barrier is the
same. The effect of the distorsion due to the image potential effect on the binding energy of the
Wannier-Mott exciton issmall because the small probability to fmd the electron and the hole in
the barrier. The constant dielectric of the organic monolayer is taken equal to the unity. We
restriet ourselves to the lowest quantized states of the Frenkel and Wannier-Mott excitons in
the z-direction.
With these assumptions the total hamiltonian of the Frenkel-Wannier-Mott exciton is
given by:
252
(la)
HFE =I. EpE(k)A + (k)A(k) (lb)

k
+
HWE (F)=L EwE(k,F)B (k)B(k) (lc)
k
H. t(F) = L V(k,F) [ B+(k)A(k) + A+(k)B(k)] (ld)

m k
Where Frenkel-Wannier-Mott interaction under the electric field effect V(k,F), in the low
density limit, is the dipole-dipole interaction, calculated according to the equations (13-21) of
ref 1.
+
In the expression of the Frenkel hamiltonian HFE, A(k) (A (k)) destroys (creates) a
Frenkel exciton of energy EFE(k). We assume this energy EpE(k) tobe independent of the
two dimensional wave vector k in the plane of the wells.
+
In eq.(lc) B(k)(B (k)) destroys (creates) the Wannier-Mott exciton of energy
calculated by solving the eigenequation of HwE (F) subjected to the electric field effect,
given by:
(2a)
The hamiltonian for an electron (hole) with effective mass me (mh) localized in the parabolic
quantum well under the electrostatic field F of absolute strength in the z-direction (merely
change F into- F for a hole) is described by:
(2b)
(x,y) are the relative coordinates of the electron-hole pair in the (2D) plane of the inorganic
quantum well with conjugate momentum Px and Py and exciton reduced mass J.l,
e2
--;:::::========== is the Coulomb potential between the electron and the hole, finally
E~ p2+{ze-zh)2
the center- of mass motion is free in the (2D) plane.
To solve the schrdinger equation (2a-b) we introduce the plane Coulomb protential with the
parameter A. 6 in order to split ~ (F) into two parts:
253
(3a)
(3b)
The first one Ho should be analytically solvable while the second one H 1, expected tobe
small, will be treated by first order perturbation calculus on the eingenstates of Ho The
unknown parameter A. in eqs (3b) is determined by requiring that the first order energy shift
<'I' AI H 1 1'I' A> vanishes, where the 'I' A. is the ground state of H0 . The zeroth order
wavefunction and energy of the ground state of Ho are determined exactly. This is possible
because the unperturbed eingenfunctions are separable and analytically expressed as :
(4)
where the ftrst term in (4) is the exciton center-of-mass wavefunction. and the last terms
correspond to the 20 exciton relative motion, 'lf(p ). The extension of the exction is the 20
wannier exciton Bohr radius which is given by azo =i~ where a3o is the (3D) Bohr
radius.
We can solve for the wave function in the z-direction which gives the displaced harmonic
oscillator stength given by:
(5)
ll>e(ze) and Pb(zh) with corresponding Ee,z and Eh,z ll>h is obtained by interchanging Ze
eF eF
by - zh; where Ze = - -2 and zh = - - 2 and the energies
mene mhnh
(6)
and the total energy:
254
(7)
where EwE (0) is not significantly affected by the electric field effect for narrower inorganic
well. Using the product of the displaced harmonic oscillator corresponding to the wave
function for the confinement electron hole factor under the electric field effect. W e estimate the
interaction parameter r given in eq. (26) of ref. I and calculate it by the same procedure. The
interaction parameter r decreases expotentially with the Separation zo. It has its maximum
values in the Brillouin zone with small wave vectors; this it is due to the parabolic shape of the
well. The dependence of the interaction parameter on the electric fteld is evaluated analytically
from cl>e and cl>h which are hermite Gaussian functions displaced in opposite direction. Thus,
it is clear that the r is a gaussian function of the electric field.
The Frenk:el-wannier- Mott hybrid exciton in presence of static electric field is then
described by the coupfing states IFE,k> and IWE,k> :
\jl(k) =A(k) IFE,k> + B(k) IWE,k> (Sa)
r
with A(k) =---;========- (Sb)
~(EFE (k)-E (k)) 2+r2
r
and B(k) = E (k)-EwE (k) A(k) (Sc)
The EFE(WE) (k) are the energies of Frenkel (wannier-Mott) excitons and the energy E(k)
of the hybrid exciton is given by:
The parameters, we use here for the heterostructure (ZnSe/ZnCdSe)/ Anthra-

cene under an electrostatic field F follow those in ref. [1,2], expect some of these: Ille=
0, 16m0 , y1= 3.77 and Y2= 1.27 8.
At zero-field (F=O), we consider the case corresponding to the interaction between exciton
states with crossing of their dispersion curves in fig. (1). We have tak:en a shift
255
between Wannier- Mott and the bare
Frenkel exciton at k=O:
EFE (0)-EWE (0)= 4 meV.
The upper hybrid exciton branch shows a

parabolic behavior and is a Wannier-Mott
like in the region far from ko=
2M[EFE(0)-EwE(0)]/rf!. The lower
branch tends to Frenkel exciton energy
for large k. In the resonance region at
k=ko the hybridization effects are
important and the hybrid exciton in this
region can interact actively with light Figure 1: Dispersion relation of Frenkel-
because the interaction parameter r is Wannier-Mott exciton for (ZnSeJZnCdSe)/Anthracene.
effective for small wave vectors k. This

coupling term is strong when the
energies of Frenkel and wannier-Mott
excitons are in resonance:
I EFE (k)-EwE (k) 1- r. In this case
the exciton states tend to wannier-Mott -F-okV/cm
exciton, then they possess the larger ----F-s&#/cm
....F150kV/cm
radius typical to wannier-Mott exciton.
This property induces a high sensitivity
of the hybrid exciton states to electdc
field effects 1.
In order to clarify the dependence of the
effect, we present the results on hybrid
exciton with different values of electric
field: F=O, F=50 kV/cm, 150 kV/cm
in figure (2). It is seen that, at
relatively weak field F< 100 kV/cm the
Figure 2: Dispersionrelation of Frenkel-Stark
hybrid exciton energies are stable for
each value of kRo The energy shift is Wannier-Mott exciton for (ZnSeJZnCdSe)/Antbracene
larger for larger wave vectors. for three different values of the electric field F.
The figure (3) shows the behavior of the weights IAul 2 and IBul 2 of the upper
energy state. Near the zero wave vector, the weight corresponding to the Frenkell Aul2 part
is predominant and decreases for large k. In the resonance region, the size of the hybrid exciton
is comparable to the wannier-Mott exciton. For strong electric field this region is shifted to
larger wave vector values. The upper energy of the hybrid exciton is shown in fig. (4) as a
256
0.8
0.8
0.4
0.0 _,____--r"_,....:....,r--..---r-..,.-""T"""-1
0.0
Figure 3: The weigbts I Au1 2 and IBul 2 of the upper hybrid Frenkel
-Wannier-Mott exciron energy state for three different values of the electric field F.
-lcRo-0
10 - lcRo-0.4
+- lcRo-0.8
Figure 4 : The upper energy of dispersion relation for hybrid

Frenkel-Wannier-Mott exciton as a function of three different values of kRo
function of the applied electric field for three different wave vectors. The energy, decreases
quadratically with the applied field. We note that the hybrid excitonic shifts to become more
pronounced with increasing wave vector value. Drastic change in the energy at F -100 kV/cm
is understood in term of the strong coupling of hybrid exciton near the resonance region.
257
In conclusion, concerning the shape of the parabolic inorganic quantum well in
comparison with the square one 12 the hybridation is effective for exciton with small wave
vectors. In the square quantum weH, the coupling of Frenkel and Wannier- Mott excitons tends
to zero for small two-dimensional exciton wave vectors.
We have calculated the Stark shift of the hybrid Frenkel-W annier-Mott exciton. It can
be seen that the Stark shift decreases to the lower energy side with an increase of the applied
electric field. We found that the larger electric field induces a larger Stark shift and the
parabolic inorganic quantum well exhibits quadratic Stark shift
REFERENCES
1. V.M.Agronovich, R.D.Atanasov, F.Bassani, Solid State Commun. 92,292 (1994).

2. AD'Andrea, R.Muzi, Solid State Commun. 95, 493 (1995).
3. V.I. Yudson, P. Reineker and V.M. Agranovich, Phys. Rev. B 52, R5543 (1995).
4. G. Bastard and J.Brum, Electronic states in semiconductor heterostructures, IEEE J.
Quantum E1ectron. Q-E 22,1625 (1986).
5. Chen and T.G. Andersson, Semicond. Sei. Techno!. 7, 828 (1992).
6. S.Jaziri, Solid State Commun. 91, 171 (1994).
7. N.F. Johnson and M.C. Payne, Phys. Rev.l.ett. 67, 1157 (1991).
8. P. Lawetz, Phys. Rev. B 1, 3460 (1971).
258
CHIRALITY EFFECTS IN SECOND-ORDER
NONLINEAR OPTICS
Martti Kauranen, Thierry Verbiest, Sven Van Elshocht, and Andre Persoons
Laboratory of Chemical and Biological Dynamies and Center for Research

on Molecular Electronics and Photonies
Katholieke Universiteit Leuven
B-3001 Heverlee, Belgium
INTRODUCTION
Second-order nonlinear optical processes are forbidden, in the electric-dipole ap-

proximation, in centrosymmetric materials. 1 For organic materials, noncentrosymmetry and
significant second-order response (first molecular hyperpolarizability) is relatively easy to
achieve on the molecular Ievel by connecting donor and acceptor groups by a conjugated
Jr-electron system. 2 However, the macroscopic noncentrosymmetry of such materials is
usually achieved only by aligning the molecules in an electric field. In polymeric materials,
the alignment can be frozen by cooling the material below its glass-transition temperature
while the field is applied. Unfortunately, this poling process results in a thermodynamically
unstable material whose nonlinearity tends to relax with time. 3
Chiral molecules are potentially interesting materials for second-order nonlinear op-
tics. Such molecules possess no mirror planes and occur in two enantiomers that are mirror
images of each other. Hence, chiral molecules are necessarily noncentrosymmetric with a
nonvanishing electric-dipole-allowed molecular hyperpolarizability. 4 In addition, isotropic
solutions of a single enantiomer of a chiral molecule are also noncentrosymmetric and pos-
sess a nonvanishing macroscopic second-order susceptibility. 5 For example, sum-
frequency generation from a sugar solution was observed already in the early days of non-
linear optics. 67 Although this particular process cannot be phase-matched, the result is sig-
nificant because the thermodynamical stability of the material was not sacrificed. How-
ever, second-harmonic generation from isotropic chiral solutions is forbidden in second or-
der but becomes allowed in fourth order.S
Symmetry properties of magnetic-dipole and electric-quadrupole interactions are dif-
ferent from those of electric-dipole interactions. Consequently, second-order nonlinear
processes in which a magnetic-dipole or electric-quadrupole interaction occurs in place of

one ofthe electric-dipole interactions9 10 can be allowed in centrosymmetric materials. 11 14
This is particularly interesting because magnetic interactions can be significant in chiral
media. 15 For example, second-harmonic generation through a magnetic nonlinearity has
been observed from a racemic (50/50 mixture ofthe two enantiomers) and centrosymmet-
ric crystal of chiral molecules. 16
In linear optics, chiral molecules are known for their optical activity, e.g., optical ro-
tation and circular dichroism. 17 These effects arise from the different interaction of chiral
molecules with left- and right-hand circularly-polarized light. For isotropic bulk samples of
chiral materials, such circular-difference response is due to the contributions of magnetic-
dipole interactions to the linear optical properties of the medium. 17 The circular-difference
response changes sign between the enantiomers of a chiral molecule. Optical-activity ef-
fects are therefore important in, e.g., biochemistry and pharmacology, because the physio-
logical and pharmacological effects of the enantiomers can be very different. 18 Nonlinear
investigations of chiral materials are important also in this context, because they can Iead
to new and ultrasensitive techniques to distinguish the enantiomers from each other.
Up to date, there have been relatively few experimental investigations of nonlinear
properties of chiral materials, although theoretical studies suggest that chirality should lead
to interesting effects in the nonlinear response. 1922 In this Paper, we review our recent
work on second-order properties ofthin films of chiral polymers. We show that the effi-
ciency of second-harmonic generation from chiral films with in-plane isotropy is different
for the left- and right-hand circularly-polarized fundamental light. 23 28 Chirality of the
nonlinear film also gives rise to other easily observable effects in second-harmonic gen-
eration.2931 All these effects can occur already in the electric-dipole approximation. 3234
However, our detailed studies of chiral polymer films indicate that the magnetic interac-
tions contribute significantly to their nonlinear response. 3536 We also emphasize the im-
portance of in-plane isotropy of the sample by showing that anisotropic achiral films can
give rise to effects that can not be easily distinguished from chirality. 37 Finally, we show
that chiral isotropic bulk materials possess a linear electro-optic response, which chal-
lenges common beliefs about the general properties of nonlinear optical processes. 38
SECOND-HARMONIC GENERATION FROM CHIRAL SURFACES
Themy
We consider a schematic experimental configuration ofFig. l. A laser beam at frequency m

is incident at angle (} on a sample with isotropic surface symmetry. The symmetry of such
a sample is broken in the direction of the surface normal (z direction). For a chiral surface
( CXJ group ), the only symmetry operation is arbitrary rotation about the surface normal.
For an achiral surface ( Coov ), reflection in a plane containing the surface normal is an ad-
ditional symmetry operation.
We assume that the second-order nonlinearity of the sample is localized to a thin sur-
face layer between the two surrounding bulk media. Such samples can be prepared by ad-
sorbing or depositing nonlinear molecules on an isotropic substrate. We assume that the
muttipole contributions of the bulk media3942 are negligible but allow the possibility that
the nonlinearity of the surface layer has contributions beyond electric-dipole approxima-
tion. We also assume that the nonlinear layer is sufficiently thin that its linear optical activ-
ity can be neglected.
260
reflected
Figure 1. Geometzy of second-harmonic generation z 20J

from a thin film of chiral molecules. A Iaser beam at
frequency w is incident on the surface at angle () and
second-harmonic fields are generated in the reflected y-~~~~~~---x
and transmitted directions. The surface normal is
....Jsubstrate
along the z direction and the non linear film is
assumed isotropic in the plane (x-y) of the surface.
Also shown are the p- and s-polarized unit vectors for
each field. transmitted
up to hrst order in the magnetic-dipole and electric-quadrupole interactions, the non-

linear polarization at the second-harmonic frequency is5, 9,10, 41
(l)
where E and B are the electric field and the magnetic-induction field and summation over
repeated indices is implied. The superscripts in the susceptibility tensors associate the re-
spective subscripts with electric-dipole (e), magnetic-dipole (m) and electric-quadrupole
(Q) interactions (two subscripts are associated with the quadrupole interaction). The re-
sponse at the second-harmonic frequency includes also a nonlinear magnetization
(2)
and quadrupolarization
(3)
The nonlinear polarization P(2w) , magnetization M(2m) , and quadrupolarization

Q(2w) act as sources of second-harmonic radiation. The dependence between the electric-
field amplitude of the second-harmonic field and the three different sources is linear. In
addition, the magnetic field B(m) and the gradient VE(w) depend linearly on the electric
field E(w). Consequently, the relation between the amplitudes of the fundamental and
second-harmonic fields remains quadratic.
Due to the surface geometry, the fundamental and second-harmonic fields are most
conveniently analyzed in terms of their p- and s-polarized components and the quadratic
dependence can, in general, be expressed in the form
(4)
where the nonlinear expansion coefficients fi, hi, and gi (i = s,p) are unique to each
component of the second-harmonic field. The coefficients depend linearly on the compo-
nents ofthe various susceptibility tensors that characterize the interaction. 34
By considering the symmetry properties of the five susceptibility tensors, 31 we find
(Table I) that the nonlinear expansion coefficients /p, g P , and hs are achiral in the sense
261
that they are nonvanishing for alt isotropic surfaces, whereas the chiral coefficients hp,
fs, and g 9 are nonvanishing only if the surface is also chiral. Change in the handedness of
the sarnple corresponds to a reflection in a plane containing the surface normal. The achiral
expansion coefficients maintain their sign under this symmetry operation, whereas the chi-
ral coefficients reverse their sign. Note also that the coefficient g 9 vanishes in the electric-
dipole approximation. These results are equally valid for the second-harmonic fields gen-
erated in the reflected and transmitted directions.
With the exception of g 9 , alt expansion coefficients depend on the components of
zeee. Consequently; chiral effects in surface second-harmonic generation can occur al-
ready in the electric-dipole approximation. 2432-34 In addition, there is no direct relation
between chiral effects and higher multipole contributions in the nonlinear response. The
measured second-harmonic signals and their chiral features can therefore always be ex-
plained in terms of the expansion coefficients.
For developing new materials for nonlinear optics and analyzing their properties, it is
important to understand the details of the nonlinear interaction. Such understanding can
only be obtained by considering the dependence of expansion coefficients on the various
susceptibility tensors. However, before the relative magnitudes of the multipole contribu-
tions can be estimated, it is first necessary to determine the values of the expansion coeffi-
cients for various second-harmonic signals. Hence, accurate determination of the coeffi-
cients is the key to any further analysis of the nonlinear properties of the sarnple. In the
present paper, we assume that the higher multipole contributions have the magnetic-dipole
character. This assumption provides the simplestand mostnatural extension to the electric-
dipole approximation, because the importance of magnetic interactions in linear optics of
chiral media is well established. lt can be shown that, for isotropic surfaces, the general
symmetry properties of the quadrupole contributions are very similar to those of the mag-
netic ones. 31 On the other hand, in our experiments we have obtained additional qualitative
evidence that indicates the predominance of the magnetic contributions. 35
Table 1. Classification ofthe nonlinear expansion coefficients as achi-

ral and chiral and their dependence on the independent nonvanishing
components34 oftensors xeee. xeem. and xmee. The chiral coeffi-
cients reverse their sign as the handedness of the sarnple is reversed,
whereas the achiral coefficients keep their sign. The transformation
x ~ x, y ~ - y, z ~ -z is a proper rotation under which all tensors
transform similarly. Consequently, flipping the sarnple over changes
the relative signs of the electric and magnetic tensor components in
each coefficient.
Coefficient Chirality Components Components Components

classification of i'ee of;fem of i"ee
lp achiral ZZZ,ZXX,XXZ xzy, zxy xyz

gp
hp
achiral
chiral
=
xyz
xyz, zxy
ZZZ, ZXX, XXZ, XZX xxz
fs chiral xyz xzx ZZZ, ZXX', XX'Z
g,
hs
chiral
achiral xxz
xxz
xyz, xzy
=
xyz
262
Experimental Procedure
The values of the nonlinear expansion coefficients are determined by polarization meas-
urements. The fundamental output ofan Nd:YAG Iaser (1064 nm, -10 ns, 50 Hz) is firstp-
polarized with respect to the sample. The polarization of the incident beam is then continu-
ously varied by a rotating quarterwave plate. Such measurements have been shown to
uniquely determine the relative complex values ofthe expansion coefficientsf, g, and h for
each signal. 35 43 44 The measured polarization lineshapes are fitted to the model of Eq. (4)
to determine the complex values of the expansion coefficients for the reflected and trans-
mitted p- and s-polarized second-harmonic signals. In principle, any of these measure-
ments is sufficient to determine whether the sample is chiral. However, to assess the rela-
tive importance of electric and magnetic contributions to the nonlinear response, we repeat
the measurements for the case in which the fundamental beam is applied on the substrate
side instead of the film side. The change in the orientation reverses the relative signs of the
electric and magnetic tensor components and thus decouples them in each expansion coef-
ficient (Table 1). 2835
Results on Chiral Polymers
The material system we have studied the most consists ofLangmuir-Blodgett films of
a chiral polyisocyanide (Fig 2). 3035 43 The polarization lineshapes of the measured p- and
s-polarized second-harmonic signals are shown in Figs. 3 and 4, respectively. These par-
ticular results were obtained using a sample with 18 polyisocyanide layers. All measured
signals exhibit several features that arise from the chirality of the sample. First, chirality
gives rise to a different efficiency of second-harmonic generation for left- and right-hand
circularly-polarized fundamental beams. From Eq. (4), the intensity of the second-
harmonic fields for the two circularly-polarized components, E p(w) = iEs (w), is
(5)
The circular-difference response therefore arises from interference between quantities

g - f and h, i.e., from interference between the chiral and achiral expansion coefficients.
However, a circular-difference response can only occur if a phase difference between the
achiral and chiral expansion coefficients exists. Another signature of chirality in Figs. 3
and 4 is the asymmetry ofthe lineshapes for the negative and positive rotation angles ofthe
quarterwave plate. 31 Such "left-right" asymmetry ofthe lineshapes can occur only for chi-
ral surfaces and is independent ofthe relative phases ofthe achiral and chiral coefficients.
As already mentioned, the issue of chirality is separate from the relative values of the
electric and magnetic contributions to the nonlinearity. Evidence ofmagnetic contributions
can be obtained in various different ways. Fora given orientation ofthe sample, the differ-
Figure 2. Structure ofthe chiral polyisocyanide.
263
0.5
0.5
0.0
-180 -135 -90 -45 0 45 90 135 180 -180 -135 -90 -45 0 45 90 135 180
waveplate rotationangle rp (degrees)

Figure 3. Normalized Iineshapes ofthe p-polarized second-harmonic signals from a chiral polyisocyanide
film. The rotation angles of 45 (-135) 135 (-45) correspond to the two circularly-polarized components
ofthe fundamental beam. Film-side incidence reflected (a) and transmitted (b) and substrate-side incidence
reflected (c) and transmitted ( d). The dots correspond to experimental data and the solid lines to fits to Eq.
(4). Note the circular-difference response and the asymmetry ofthe lineshapes for the negative and positive
values of the rotation angle.
-180 -135 -90 -45 0 45 90 135 180 -180 -135 -90 -45 0 45 90 135 180
waveplate rotation angle rp (degrees)

Figure 4. As Fig. 3 but for the s-polarized second-harmonic signals. The difference in the reflected and
transmitted signals for each orientation ofthe sample implies that the results can not be explained in the
electric-dipole approximation.
ence in the normalized lineshapes of the reflected and transmitted s-polarized signals (Fig.
4) can occur only if magnetic contributions are present. 26 This follows from the fact that
only the y component of the nonlinear source can contribute to the s-polarized signals in
the electric-dipole approximation. However, such evidence is only qualitative and does not
allow estimating the relative magnitudes ofthe electric and magnetic contributions.
264
Figure 5. Structure ofthe chiral polythiophene.
The relative magnitudes of the electric and magnetic contributions to the nonlinearity
can be quantified by considering the eight measured second-harmonic signals simultane-
ously.2835 The cleanliness ofthe experimental results ofFigs. 3 and 4 is important to our
procedure, because it allows the determination of most expansion coefficients to better
than 2% accuracy. Our results for polyisocyanides indicate that the largest components of
the tensors Xeem and Xmee are of the order of 20% of those of the tensor Xeee . Further-
more, the largest components ofthe magnetic tensors are only allowed because of chirality.
For the case of polyisocyanides, evidence of contributions beyond electric dipoles is
obtained from a detailed comparison of several second-harmonic signals. However, evi-
dence that is more direct can be provided by the expansion coefficient g., which vanishes
in the electric-dipole approximation. Unfortunately, in the polyisocyanide samples this ex-
pansion coefficient is too small to be determined reliably. On the other hand, we have re-
cently also investigated thin films of a chiral polythiophene (Fig. 5). 36 This polymer is dis-
tinctive because of its extremely strong linear optical activity, 45 which indicates that the
predominantly electric-dipole-allowed n ~ 1r * transition also supports strong magnetic
interactions. An example ofthe polarization lineshape ofthe measured s-polarized second-
harmonic signals is shown in Fig. 6. This lineshape can be fitted to Eq. (4) only by using a
nonvanishing value of gs. This coefficient was found tobe ofthe same order ofmagnitude
as the dominant coefficient hs .
Our results suggest that the relative magnitudes of the magnetic nonlinearities in
polythiophenes are even higher than in polyisocyanides. This difference is most likely due
to differences in the structures of the two polymers. In the polyisocyanide (Fig. 2), the
nonlinear response arises from achiral chromophores attached to the helical backbone, i.e.,
::t
V) -180-135 -90 -45 0 45 90 135 180
waveplate rotation angle qJ ( degrees)
Figure 6. Normalized lineshape ofthe transmitted s-polarized second-harmonic signal from a chiral poly-
thiophene film and substrate-side incidence. The rotation angles of 45 (-135) 135 (-45) correspond to the
two circularly-polarized components ofthe fundamental beam. The dots correspond to experimental data and
the solid and dashed lines to fits to Eq. (4) with g nonvanishing and vanishing, respectively. The solid line
has been obtained by the relative values ofthe fit coefficients of f= -0.055- i0.098, g = -0.378- i0.300,
and h = 1. The results imply that the magnetic contributions to the nonlinearity are essentially comparable to
the electric contributions.
265
chirality occurs only in the secondary structure of the polymer. On the other band, in the
polythiophene (Fig. 5), the response is due to the helical conjugated backhone and the
1r ~ 1r * transition corresponds to the displacement of charge along the helical backbone,
which is expected to give rise to a large magnetic response. In addition, the structure of the
polythiophene is more centrosymmetric than that of the polyisocyanide, which tends to
suppress the electric-dipole-allowed nonlinearity.
OPTICAL ACTIVITY DUE TO ANISOTROPY
Theory
The above results on chiral polymer films have been explained under the assumption that
the samples are isotropic in the plane of the surface. Isotropy is very important, because
anisotropic samples possess more nonvanishing tensor components than isotropic ones. Al-
ready within electric-dipole approximation, these additional tensor components can con-
tribute to the chiral expansion coefficients even if the sample itself is achiral.
The chiral effects due to the anisotropy of the sample can be shown to arise from the
chirality of the experimental setup. The setup is chiral if it is described by three non-
coplanar unit vectors, which defme a handedness for the setup. 46 For the case of surface
second-harmonic generation, the three unit vectors can be chosen to be the direction of
propagation of the incident Iaser beam, the surface normal, and the in-plane anisotropy axis
of the sample (Fig. 7). The chiral effects are expected to change sign as the handedness of
the setup is reversed. Wehave developed a detailed theory of second-harmonic generation
from anisotropic achiral surfaces to show that the chiral effects due to anisotropy satisfy
these properties. 47
The lowest achiral symmetry group for surfaces is c,h . The theoretical results for the
nonlinear expansion coefficients for this group are found to depend on the angle of inci-
dence (} and the in-plane azimuthal rotation angle tfJ of the sample. The coefficients for the
p-polarized second-harmonic signals satisfy the symmetry properties
(7)
The transformations of Eqs. (6) and (7) correspond to the two possible ways of changing
the handedness of the experimental setup. The relative signs of the achiral and chiral ex-
surface z
normal
Figure 7. Geometry of second-harmonic generation from an
achiral but anisotropic surface. The surface normal is along the
z direction and x specifies the in-plane anisotropy axis of the
sample. The orientation of the sample in the setup is
characterized by the angle of incidence () and the in-plane
azimuthal rotation angle t/J The setup is chiral for azimuthal
rotation angles different from 0 or 180.
266
(b)~
~ (
dipping
)
Figure 8. 2-docosylamine-5-nitropyridine (a) and its structure in Langmuir-Biodgett films (b). The bilayer
shown is the repeating structure in multilayers.
pansion coefficients are seen to reverse under both ofthese transformations. Consequently,
any chiral effects in the nonlinear response will change sign as the handedness is reversed.
Experiment
Experimentally, we have investigated Langmuir-Blodgett films of 2-docosylamino-5-

nitropyridine (DCANP, Fig. 8). 48-50 This material forms films ofthe achiral C1h group, in
which the molecules are predominantly aligned along the dipping direction of the sample.
The experiments were performed using the same arrangement as in the measurements on
the chiral polymer films and detecting p-polarized second-harmonic light in transmission.
The polarization ofthe detected second-harmonic light is important, because detection in a
direction that mixes the p- and s-polarized directions also makes the setup chiral. 51 This is
because the role of f, g, and h as achiral and chiral coefficients is reversed for the p- and s-
polarized second-harmonic light.
As is evident from Eqs. (6) and (7), the chirality and handedness of the setup can be
varied by rotating the DCANP sample about the surface normal. For the case in which the
in-plane anisotropy axis is in the plane of incidence ( (J = oo, 180), the setup is achiral and
.. .. .. ..
.M . !'.. "..... f"',
.. : . .. .
1.0
!
""...
; I"' ~
I :
I :
0.5
.. .. . . . .
.... . ...
i (a) v .. .. . .i (b) ;;V
.. . 'Ir
"
\
0.0 V
~
1.0
I"'\.
. .:JNI..... .. .
~\ .!"\. . . ..."'"'..
. .. . .
0.5
. . . . .. .
. .. .'V. ."V .~- : (d) v .. ..;.
.; (c) 'W
o.o
~--L--L~~~~--~~--~
1
"
-180 -135 -90 -45 0 45 90 135 180 -180 -135 -90 -45 0 45 90 135 180
waveplate rotationangle ({J(degrees)

Figure 9. Normalized lineshapes ofthe p-polarized transmitted second-harmonic signals from an achiral an-
isotropic DCANP film. The waveplate rotation angles of 45 (-135) and 135 (-45) correspond to the two
circularly-polarized components ofthe fundamental beam. The angle ofincidence () and the azimuthal rota-
tion angle~ are (a) ()= -43, ~= -90, (b) ()= -43, ~= 90, (c) ()= 43, ~= -90, and (d) ()= 43, ~= 90.
Note the circular-difference response that changes sign as the handedness of the setup is changed.
267
no circular-difference effects are observed. On the other hand, for the angle of incidence
of -43 and azimuthal rotation angles of 90, which correspond to opposite handednesses
ofthe setup, the circular-difference response is found tobe equal in magnitude (-7%) and
opposite in sign (Fig. 9). The circular-difference effects also change sign for the incidence
angle of 43 o ( f/J = 90), which corresponds to the other way of changing the handedness of
the setup. It is also interesting to note that circular-difference effects, which imply a phase
difference between the achiral and chiral expansion coefficients, were observed although
the principal absorption band of DCANP occurs at a wavelength shorter than that of the
second-harmonic light. We believe that experimental techniques of this type can be used to
advantage in accurate determination of the nonlinear properties of thin films of different
symmetry groups.
ELECTRO-OPTIC EFFECT IN CHIRAL BULK MEDIA
Basic Theory
The linear electro-optic effect arises from an additional source polarization in the
wave equation of the form
(8)
where the subscripts refer to Cartesian coordinates in the laboratory frame and surnmation
over repeated indices is implied, Xijk is the electric-dipole-allowed second-order suscepti-
bility tensor, E(w) is the optical field at frequency w, and E(O) is the static field. Common
electro-optic crystals support two linear eigenpolarizations with i = j. 52 In lossless media
with a real susceptibility, the additional source is real and the electro-optic response Ieads
to index modulation of the two eigenpolarizations. Under near-resonant conditions, the
susceptibility is complex and absorption modulation occurs due to the out-of-phase part of
the source. The connection between the real (imaginary) part of the susceptibility and the
refractive index (absorption) is therefore analogous to that in linear optics and third-order
nonlinear optics. We challenge the generality of this connection by showing that in chiral
isotropic media the roles of the real and imaginary parts of the second-order susceptibility
are reversed.
In isotropic chiral media, the second-order polarization is necessarily of the general
vector form 5-7
P(w) = x(w,w,O)E(w) X E(O) , (9)
where the effective susceptibility is
N
X =6 (m + m + m - m - m - m) . (10)
Here 1, 2, and 3 refer to the molecular frame and N is the number density of the molecules.
The relevant components of the hyperpolarizability tensor reverse their sign under re-
flection in plane and under inversion and vanish for achiral molecules. In addition, the sign
268
of the susceptibility is different for the two enantiomers of a chiral mo1ecule and the sus-
ceptibility vanishes for a racemic mixture ofthe enantiomers.
lt is generally believed that, in isotropic media, no electro-optic effect exists, i.e., that
the susceptibility x vanishes. 1753 54 However, such results have always been obtained only
for lossless media. It has also been suggested that the electro-optic effect should exist in,
e.g., conducting55 56 or absorbing 56 media. However, there are no detailed investigations of
these effects. Our approach is to focus on the roJe of damping in the quantum-mechanical
expression for the hyperpolarizability, which is certainly important in absorbing media.
When material damping is neglected, the hyperpolarizability possesses full permutation
symmetry, i.e., uk = /3.iik and the susceptibility [Eq. (10)] vanishes. 5 However, in the pres-
ence of damping, this and other arguments for a vanishing susceptibility fail.
We first investigate the consequences of a nonvanishing susceptibility in the geometry
of Fig. 10, in which the optical field is taken to be a plane wave propagating in the z direc-
tion. In linear optics, chiral media support circular eigenpolarizations. Modulation is there-
fore possible only in the circular basis and we consider the two circular polarizations sepa-
rately. The optical field is expressed as
(11)
where E is scalar amplitude and e are the circularly-polarized unit vectors. Eq. (9) im-
plies that for a transverse nonlinear source, it is necessary to apply the static field along the
z.
z axis so that E(O) = E 0 The nonlinear polarization is found to be
(12)
This result shows that the circular polarizations remain eigenpolarizations in the presence
of the static field, which makes electro-optic modulation possible. The response reverses
sign when any of the following quantities is reversed: 1) the static field, 2) the sense of cir-
cular polarization, 3) the enantiomer ofthe molecule.
The imaginary unit as an overall factor in Eq. (12) reverses the roles of the real and
imaginary parts of the susceptibility. Index (or phase) modulation in chiral isotropic media
is therefore due to the imaginary part of the susceptibility. Similarly, the real part is respon-
sible for electroabsorption. Hence, there is no fundamental connection between the real
(imaginary) part of the susceptibility and phase (absorption) modulation in second-order
Figure 10. Longitudinal electro-optic configuration

in chiral isotropic media. The static field is applied
along the direction of propagation of the optic field.
Circular polarizations remain eigenpolarizations in
the presence of the static field.
269
nonlinear optics. The connection is broken because of the symmetry of chiral isotropic me-
dia that Ieads to the vector relation ofEq. (9). The fact that this connection is maintained in
traditional electro-optic crystals is then only due to their particular symmetry groups and
experimental geometries used in the implementation of electro-optic modulators.
The second-order susceptibility is expected to be essentially real when the optical fre-
quency is detuned far from material resonances. Eq. (12) then suggests, rather surprisingly,
that it is possible to design a nonresonant experiment where the optical field experiences
gain. However, as we will show, such completely nonresonant gain does not actually occur.
Quantum-Mechanical Result
The above results have been derived assuming that the susceptibility is nonvanishing.
To verify that this is indeed the case, we start from the quantum-mechanical expression for
the hyperpolarizability ifk that properly includes damping 57 and calculate the isotropic av-
erage ofEq. (10). The result is nonvanishing only in the presence of damping and only ifat
least three states of the molecule are considered. Within the three-level model (Fig. 11 ), the
essential features of the result can be expressed in the form
(13)
where %o is the susceptibility for a process that does not rely on damping (e.g., sum-
frequency generation67) and accounts for the transition moments and usual resonance fea-
tures of the susceptibility, Yc and mc are the characteristic damping rate and resonance
frequency ofthe ground-to-excited state transitions. The prefactor ofthe last term is
_ Y MN - Y MG - Y NG
K
NMG- . ' (14)
{J)MN - {J) -lYMN
where G refers to the ground state of the molecules and N and M refer to the two excited
states. Only the ground state is assumed to be initially populated.
Equations (13) and (14) show that the electro-optic effect relies on damping. How-
ever, the two terms in Eq. (13) are fundamentally different. The first term is always non-
vanishing in the presence of damping. The factor KNMG in the last term, on the other hand,
vanishes in a purely lifetime-broadened material. In the presence of dephasing, this factor
is nonvanishing and contains a resonance when the optical frequency is close to the energy
difference between the two unpopulated excited states. Such dephasing-induced reso-
nances5859 are weil known in third order but have received less attention in second order.
Note that when the optical frequency is detuned far from any material resonances
(Fig. 11a), including those between the two excited states, %o is real and the damping rate
YMN can be neglected in the denominator of Eq. (14). The susceptibility% is then purely
imaginary. This result in combination with Eq. (12) implies that only phase modulation is
possible through completely nonresonant interactions. In this respect, chiral media are
similar to traditional electro-optic media.
Resonance Structure
We next consider the resonances that can occur in the susceptibility % (Fig. 11 ). When
no dephasing-induced resonance occurs, only the first term in Eq. (13) contributes. The
270
----M
(J)
M
:w
I
M
----N N i N
Figure 11. Resonances of the susceptibility X

responsible for the electro-optic effect in
chiral isotropic media. (a) Completely
nonresonant excitation. (b) Resonance - - "Xm- _
between the ground state G and the excited 1 0
----L--G
state M. )c) Dephasing-induced resonance
between the two excited states M and N. (a) (b) (c)
factor (yeI me) is then a scaling factor that accounts for the fact that X relies on damping.
When the optical frequency is on resonance with the G --+ M transition Xo becomes
imaginary and X real. Eq. (12) then implies that, close to this resonance, the electro-optic
response leads to absorption modulation and can give rise to gain for the right choice of
experimental parameters. However, this gain is only differential since the G --+ M reso-
nance implies a linear background loss.
The situation becomes considerably more interesting when a dephasing-induced reso-
nance between the excited states occurs. lt is then possible that the optical frequency is far
detuned from resonance between the ground state and both of the excited states (Fig. 11 c).
In this case, the material is essentially lossless for linear light propagation and Xo is real.
On the other band, a resonance between the excited states ( m = mMN) makes KNMG imagi-
nary and the second term in Eq. (13) real. Eq. (12) then implies that the optical field can
experience gain due to the electro-optic response. This result is quite surprising since it re-
lies only on resonance between the unpopulated excited states. More detailed investiga-
tions are necessary to understand the origin of this gain mechanism.
Magnitude of Effect
To estimate the magnitude of the susceptibility x that can be achieved in chiral mate-
rials, we note that Xo is proportional to linear optical activity of chiral media. 6 Results on
sum-frequency generation67 show that Xo oftypical chiral media with rotational strengths
of 100-1000 deg dm- 1 g- 1 cm3 can exceed 10-10 esu. When resonances between excited
states do not contribute, the scaling factor is (reime)= 1/(meTz). The dephasing time Tz
for condensed-matter systems at room temperature can be of the order of 100 fs or
shorter. 6061 For an optical frequency (m = 1015 s- 1) the scaling factor is then -1/100. Recent
developments in the synthesis of chiral materials have produced rotational strengths ex-
ceeding 105 deg dm- 1 g- 1 cm3 45 The nonresonant susceptibility for such materials could
then be 10-10-10-9 esu, i.e., comparable tothat ofKDP. On the other band, for a dephasing-
induced resonance the factor KNMG is of the order of unity and the susceptibility of even
more traditional chiral materials could be of this same order of magnitude.
CONCLUSIONS
We have discussed several second-order nonlinear effects that can occur in chiral materials.
Second-harmonic generation from thin films of chiral molecules with in-plane isotropy has
271
different response to left- and right-hand circularly-polarized fundamental beams. This and
other chiral effects can occur in the electric-dipole approximation. However, detailed ex-
perimental results on thin films of chiral polymers indicate that magnetic contributions to
the nonlinearity can be comparable to the electric-dipole-allowed response. Achiral but
anisotropic thin films can also Iead to chiral effects if the orientation of the sample in the
setup makes an otherwise achiral experimental arrangement chiral.
We have also predicted that isotropic chiral bulk media possess a linear electro-optic
response. The response is nonvanishing only if material damping is properly accounted for.
The response includes dephasing-induced resonances between two unpopulated excited
states, which can Iead to gain for the optical field. We estimate that the electro-optic re-
sponse could be comparable to that of KDP in several chiral materials.
ACKNOWLEDGMENTS
We acknowledge the supportoftbis work by the Belgian Government (IUAP-16), the Bel-
gian National Science Foundation (FKFO 2.0103.93), and the University of Leuven
(GOA/95). M. K. acknowledges the support of the Academy of Finland. T. V. is a post-
doctoral fellow ofthe Fund for Scientific Research- Flanders (FWO). Chiral materials for
the experiments have been provided by M. N. Teerenstra, A. J. Schouten, and R. J. M.
Nolte as well as B. M. W. Langeveld-Voss and E. W. Meijer.
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273
ffiGHLY ORIENTAHLE LIQUID CRYSTALLINE POLYMERS FOR
QUADRATIC NONLINEAR OPTICS
C. Noe1' and F. Kajzar2
'ESPCI, 10, rue Vauquelin, 75231 PARIS Cedex 05, France

2
CEA-DT A, LETI, DEIN/SPE
91191 GIF SUR YVETTE CEDEX, France
INTRODUCTION
During the last decade it was recognized, that some organic materials may exhibit second
order nonlinear optical (NLO) properties which are much more pronounced than those of
the conventional inorganic materials, provided timt the arrangement of the
noncentrosymmetric molecular units in the macroscopic structure is noncentrosymmetric 1.
The molecular, non-centrosymmetric, charge lransfer (Cf) constituents can be considered as
molecular diodes with enhanced polarizability in the CT direction. 1n consequence the first
molecular hyperpolarizability tensor ijk has a component (~m enhanced along the CT axis
(z). Such CT molecules consist of a conjugated 1t - electron core, terminated by an electron -
donating group and an electron - withdrawing group. In such systems, the NLO response of
the bulk material, which is important for device applications, is determined by the ptical
nonlinearities of the constituent molecules through their ensemble addition. 1n the simples!
case of a single crystal the macroscopic second order NLO susceptibility x121uK in the
Iabaratory reference frame (IJK) is related to the molecular first hyperpolarizability ijk
describing the second order NLO properties of a given molecule in the molecular reference
frame (ijk). Neglecting intermolecular interactions, x121uK is determined by the summation
over independent molecules. Local field factors must also be included to account for the
effect of the dielectric environment on the electric field strength at the molecular site. For a
three photon proceSS (0>3 = 0>1 + 0>2) X( 2)JJK Can be expressed then by
where N<n> is the number density of molecular species (n), a's are the Wigner rotation
matrices and fs are local field factors at the indicated frequencies. For small molecules r~<
is weil approximated by the weil known Lorentz-Lorenz equation
(n)a> 2
f(ll)aJ= 6 + (2)
3

where &1"1"'= (n<nlm)2 is the dielectric constant and n is the refractive index. at the optical
fi"equency m.
The oriented gas model has been extended to the generat case of non crystalline
materials which may, or not, possess innate axial order. This includes the cases of electric -
field poled polymers, Langmuir-Biodgett films and nematic as weil as srncctic liquid crystals.
In these cases, the second order NLO susceptibility implies an averaging over all molecular
orientations and is given by
(3)
Thus the optimization of the second order NLO response will require the optimization of
poling induced molecular alignment.
The interest in polymers for second-order NLO processes became clear in the late
seventies and early eighties when the electric field poling of guest-host systems was first
demonstrated 2, 3 . In this first approach, a film consisting of a dopant chromophore dissolved
in a glassy host polymer was subjected to an extemal DC field at a temperature higher than
the glass transition temperature Tg where segmental mobility in the polymer was significant.
Subsequently the film was cooled to room temperature under the applied electric field.
During this process, dipolar species in the film could orient and a net polar alignment was
then retained. Since that time a variety of guest-host systems have been developed 4' 5 .
However only low concentrations of active NLO molecules could be incorporated in
polymeric matrices because of aggregation effects due to strong dipole-dipole interactions.
Moreover, a plasticizing effect was also observed which lowered the glass transition
temperature of the host material. In order to overcome these adverse loading effects, the
NLO chromophores were incorporated as a part of the polymer structure 1' 6 . This was
accomplished either by grafting the active chromophores on polymer backbones or by
copolymerizing monomers containing active molecules and monomers known to yield
polymers with high Tg The resulting materials are typically amorphaus isotropic polymers.
They present several important advantages with respect to single crystals such as: low cost,
good optical quality, high optical darnage threshold, mechanical, chemical and thermal
robustness, adhesion to a variety of materials, processability into films, fibers, waveguides,
and large-area structures, and integration with electronics (detectors and sources).
Recently some speculations were reported that particularly !arge second-order NLO
effects could result from the combination of polymer and liquid crystal properties in one
molecule3,6-9. As already mentioned it is however necessary to achieve a high degree ofpolar
order alignment of the NLO mesogenic groups to maximize the second order NLO
properties (cf Eq. 3). Hence, the key to designing new NLO side chain liquid crystal
polymers (SCLCP's) is a better understanding ofthe effects of extemal electric fields on the
material and how they vary with temperature.
In this paper we review and discuss the results we have obtained on a series of
SCLCP' s. The principal aim of these studies was a careful characterization of the molecular
mechanisms responsible for the establishment and the decay of the NLO activity with time
and temperature as weil as a better understanding of the influence of a number of parameters
such as the molecular architecture, the poling temperature. the poling time, the glass
transition temperature, etc. on the extent and the stability of the induced axial order and
polar alignment.
ORIENTATION MODELS
Order parameters
The ensemble average value of any physical property depending on orientation of the
molecules (vectorial or tensorial) can be obtained through the orientational distribution
276
Z Poling tield Ep
l\1olecular
axis
Figurel. Schematic representation of molecular axis

orientation with respect to the extemal poling field EP.
function G(0,,'I') giving the probabilitr density of finding a molecular axis in the solid
angle element dO.. around n = {0, , 'I' J. Consider a liquid crystal composed of rod-like
molecules which are oriented with their long axes more or less parallel to a particular
direction referred to as the director and repre -sented by an apolar vector n (see Fig. 1).
Assurne that in addition the orientational distribution function is cylindrically symmetric
about this reference axis as for uniaxial nematic or smectic A (SA) phases. In this case, the
orientational distribution function depends only on the angle 0 which gives the deviation of
the long molecular axis from the director n. It can be expanded in terms of Legendre
polynomials P1(cos 0):
G(0) = :L--
" 2/+1
1~o 2
< J;(cos0) >J:(cos0) (4)
where the expansion coefficients <P1(cos 0)> = <P1> are defined as order parameters. They
are given by the following expression
"
<Pr>= 2nJ G(0)J:(cos0)sin 0d0 (5)
0
The odd parameters <P2k+I> characterize the polar order, while the even order parameters
<P2k> give the degree of axial order. Usually the two order parameters <P2> and <P4> are
sufficient to describe the state of axial order in the uniaxial nematic (N) and smectic A (S:..)
phases. They are given by
I
< P, >=- < 3cos2 0-1 > (6)
- 2
and
I
<I~>=-< 35cos~ 0-30cos2 0+3 > (7)
8
According to the Maier-Saupe theory 10"11 the order parameters and change
discontinuously from zero at the isotropic/nematic transition to 0.429 and 0.120,
respectively. However, Luckhurse 2 has shown that the Maier-Saupe theory results in an
overestimate of about 25% and 40% in :r-.1 and <P4>NI, respectively. In addition,
comparison of the temperature dependence of <P2> for liquid crystal monomers and
corresponding side chain polymers has clearly demonstrated that the absolute values of <P2>
277
related to the reduced temperature T/T NI are always lower for polymers. At the
nematic/isotropic transition an average value of <P2>NI would appear to be approximately
0.3 for side chain polymers 13 .
Linear and second order nonlinear optical properties of poled polymers
Assuming there is only one molecular species, we have for poled polymers with point
symmetry (oomm) the following expressions for the two different linear susceptibility tensor
components:
iii (-w; w) = NF < a"" + ( a,z - a"" )cos2 0 > (8)
and
i.ii(-w;w) = ii} (-w;w) = NF < axx +(a"- a,")sin 2 0> (9)
where a.xx = a.yy and a.zz are the molecular linear polarizability components, the principal
axes being perpendicular and parallel to the symmetry axis, respectively.
Similarly, for poled polymers functionalized with 1-D CT molecules (.wt'O) and
with point symmetry (oomm), it follows from symmetry considerations and Kleinman
conditions (x<2>1JK equal for all permutations of IJK) that there are 2 non-zero x< 2> tensor
components: x< 2)zzz and x<2>zxx (where z is the poling direction assumed tobe perpendicular
to the thin film surface) which are given by
and
(11)
where F is the local field factor. For the second harmonic generation (SHG) process
(12)
with f"'<lro) given by Eq. (2)
Statistical orientation models
Four different models have been proposed for calculating the electric - field induced order
parameters intervening in expressions for <cos30> and <sin20 cos0>. These are:
- The isotropic model
- The Ising model
- The Singer-Kuzyk-Sohn model 7
- The extension ofthe Maier-Saupe theory 10"11 by Van derVorstand Picken8' 9' 14
The orientational averages of any angle dependent function, F(0) is given by
" (13)
< F(0) >= 2nJ F(0)G(0)sin0d0
278
A Gibbs-Boltzmann distribution is usually assumed for 0(0):
e-U(S)IkT
G(0) = _ 1 t_ _ _ __ (14)
2nJ e-u<eJtkT sin0d0
0
where k is the Boltzmanrt factor,T the absolute poling temperature ofthe system and U the
mean-field thermodynamic potential energy of the molecule in the presence of the electric
field. This energy can be expressed as:
(15)
where the ith term is proportional to the ith power of the electric field. In the simplest case,
U(0) is the energy ofthe permanent dipole ~in the poling field Ep:
(16)
This is the dominant energy term, which is taken into account by all four models. Other
energy terms as weil as computational approximations used in specific models will be
discussed below.
Isotropie model. It assumes no initial axial order at zero field strength (<P2> =
<P4> = 0). The potential energy is given by Eq. (16) and the diagonal and offdiagonal
components of x<2> can be directly calculated from Eqs. (10)-(14). The averages <cos30>
and <sin20 cos0>/2 are given in Table I together with the order parameter <P2>.
Ising model. In this model a perfect axial order is assumed (<P2> = I) and two
molecular orientations are allowed (0 = 0, 1t), each with a maximum amplitude of<cos30>,
but with opposite signs (I). At Ep=O, both states are equaliy populated so their
contributions to <cos30> cancel completely. However, in the presence of an electric field,
the corresponding energy Ievels are split up and are far apart. The lower lying state with
0 = 0 is more denseiy populated than the higher one with 0 = 1t, thus resulting in a larger
value for <cos30>. It follows that only the diagonal component of second order NLO
susceptibility is non-zero
(17)
whereu=~T.
Singer, Kuzyk and Sohn (SKS) modei. Singer et al7 consider the effects of
preexisting axial ordersuch as found in LC's and described by the order parameters <P2>
and <P4>. In this model, the axial order is assumed to be fixed and independent of the
applied electric field. Singer et al7 expressed the molecular energy in by Eq. (14) as the sum
oftwo terms
(18)
where Uo(0) describes the tendency of rod-like molecules to have their long axes more or
less parallel to a preferred direction. It should be noted, however, that they did not introduce
any explicit analytical expression for the term U0(0). Instead, they assumed that the axial
order of the LC host is transferred to the NLO guest moiecuies. In this model, the
279
Table 1. Orientational averages of <cos30> and <sin 20 cos0>/2 in four statistical models
(for details see text).
Model <cos 39> <sin29cos9>/2 <P2>

Ising u 0 1
Isotropie u/5 3 u/15 ""U 2/15
SKS 1 4 8 1 1 8 b)
u(- +- +- )
4
u(-+-<P2 >--<P4 >)
5 7 2 35 15 21 70
No analytical formulac No analytical formulac
MSVP c)
a)u= ~pikT
b) The order parameters <P2> and <P4> are assumed to be independent of the electric field strength and are
to be determined before the poling field has been applied.
c) The order parameter <P2> has to be determined selfconsistently by using numerical methods. This value,
injected into Eq. (19) allows to determine the orientational averages <cos3E>> and <sin2E> cosE>>/2.
dipolar energy is first expanded into a Taylor series up to first order in the poling field Ep.
Then, the Gibbs-Boltzmann distribution is expanded in terms of Legendre polynomials (cf
Eq. (4)) with <P1> coefficients given by Eq. (5). In this case, the configurational average
values of <cos30> and <sin20 cos0>/2 (cf Table 1) are linear functions of the poling field
strength through the term u and depend on the intrinsic axial order of the LC through the
microscopic order parameters <P2> and <P4>.
MSVP model. In the SKS model, the transfer of axial order from the mesogenic
rods to the NLO molecules assumes implicitly the existence of latent mesogerne properties in
the NLO molecules. In the MSVP model, the intrinsic mesogenic properties of the NLO
molecules themselves are taken explicitly into account.
The natural tendency of rod-like molecules to align mutually parallel can be described
by the effective single particle energy Uo (0), introduced originally by Maierand Saupe 1011
(19)
where l;; is a parameter describing the strength of the anisotropic interactions. It takes a
constant value for a given liquid crystal. In the Maier - Saupe theory this parameter is
proportional to the clearing temperature Tc (at zero field strength) through the following
relation
kTc =:0.22( (20)
Van der Vorst and Picken8"9' 14 extended this model to poling of single rod systems. In
addition to U0(0) and U 1(0) they introduced an extra term in the molecular potential
energy. This describes the energy ofthe linearly induced dipole moment in the poling field
(21)
where ~a. is the anisotropy ofmolecular linear polarizability ofthe rod-like NLO molecules.
The resulting orientational averages <cos39> and <sin29cos9>/2 are given in Table 1.
280
EXPERIMENTAL PART
Molecular design
This review narrows consideration to polymers containing 4- cyanobiphenyl based side

groups. The 4- cyano-4' -biphenylyl group was chosen because it has two important
advantages over other mesogenic groups possessing NLO properties themselves: a wide
transparency range (cf. Fig.2) with absorption cut-offat about 340 nm and a noticeable first
hyperpolarizability = 16-20 xl0-30 esu. This mesogen has been attached to various polymer
backbones with increasing stiffiless: polyepichlorohydrin (PECH}, poly-bis
chloromethyloxetane (PBCMO), polyacrylate (PA), polymethacrylate (PMA), poly-p-
chloromethylstyrene (PCMS), polyvinylazlactone (PVAz) and polymaleimide (PM) (for
details on synthesis and physico-chemical characterization the reader is referred to recent
articles 15-24). The thermotropic behavior and the glass transition temperature, T8, could be
controlled by varying the stiffuess of the polymer backbone, the length and the flexibility of
the spacer and the mesogen concentration. A common type of transition temperature vs
degree of substitution plot is shown in Fig. 3. The chemical structures of the investigated
functionalized polymers are shown in Fig. 4 whereas their physical properties are listed in
Table 2.
Tecbniques
Poling. The corona poling apparatus, shown in Fig. 5, was used for chromophore
orientation. The polymeric film was deposited on a slightly conducting substrate (the electric
conductivity of the BK7 glass is quite sufficient) and heated to a given temperature Tp. A
corona discharge was then applied. The charges deposited on the thin film surface created an
intense electric field across the film giving rise to the chromophore orientation. The kinetics
of orientation was monitored bv linear optical absorption measurements ( development of
axial order). These measurements do not allow to determine the polar order.
Stark Effect
- - before polarization
..............._. after polarization
>.
:t::
IJ) =11.58
c: l
2; 0.75
~
'5. 0.50
0
0.25
0.00
270 2BO 300 310 320 330 350
Wavelength (nm)
Figure 2. Optical absorption spectrum of a thin film with before and after poling for polyacrylate P A3.
281
150.
Nematic
100 Isotropie
(.)
0
l-
50
0
Glassy State
-50 L-~--~--~--~~--~--~--~--~~
0 50 100
Oegree of substitution \ o/o)

Figure 3. Transition temperatures vs degree ofsubstitution for PECHsystem (from Ref. 18).
~~J.
x = 0.3 PECH 0.3
x = 0.55 PECH 0.55
x = 0.8 PECH 0.8
mole ratio x/1-x
n
mole ratio Xolx1/x2
Xo = 0.59 Xt =0.35 x2=0.06 PBCMO 59/35/6
Xo = 0.14 X1 =0.43 X2 = 0.43 PBCMO 14/43/43
Xo = 0. Xt =0. X2 = 0.06 PBCMO 100
Figure 4. Chemical structures of the different functionalized polymers investigated.
282
X=H m=J PA3
X=CH3 m=3 PMA3
Hl
o-Q-0-cN
H-/:o - -
W[.l'-ca.... CHz
~H('tH{ \j \}
yHz
{ l-x)
I #
1 CH2
\ j CN
/o-Q-0-j
x =0.5 : PCBMS - co - PM3
x:::! 0.5 : PS - co - PM3
PVAz: x=l :t=0.92

P(Vaz- co- .MMA): x=0.78 :t=0.79
P(Vaz- co- .MMA): x= 0.47 : t=0.92
Figure 4. (Continuation) Chemical structures of the different functionalized polymers investigated.
283
Figure 4. (Continuation) Chemical structures of the different functionalized polymers investigated.
Table 2. Physical properties of side chain polymers with cyanobiphenyl chromophore

synthesized for second order NLO applications
Compound Transition
polymer backhone Mn Mw Ref
Abbreviation temperature (C)
PECH 0.30 G-23-1 21
PECH0.55 polyepichlorohydrin Gb-56-1 11910 17020 19
N-[40-56]"-I
PECH0.80 G-79.5-N-146-1 13040 18640 19
PBCMO 59/35/6 poly-bis- G-63-1 5120 7560 20
PBCMO 14/43/43 chloromethyl G-106-N-126-1 6662 10740 20
PBCMO 100 oxetane G-135-N-155-1 3750 4910 16
G-152-N-172-I 12310 40930 16
PA3 polyacrylate G-51.5-N-90-I 3790 6000 19
PMA3 polymethacrylate G-97-1 22800 66850 19
N-[70-90]"-1
d
PCBMS poly-p-chloromethyl G-132-1 ld
styrene
PM2c polymaleimide G-150-S" 0 10
d d
PM3 G-130-S-190-N-
>260-I
PCBMS-co-PM3 poly(p-chloromethyl G-142-N-220-I
styrene-co-
maleimide)
PS-co-PM3 poly( styrene-co- G-130-1
maleimide)
PVAz poly(2-vinyl-4,4- G-132-1 8690 31750
t=0.92 dimethyl-5-
oxazolone)
P(VAz-co-MMA) poly(2-vinyl-4,4- G-125-1 120000 295000
78/22; t=0.79 dimethyl-5-
P(VAz-co-MMA) oxazolone-co- G-127-1
47/53 t=0.94 methylmethacrylate)
a) G- glassy state, S- smectic state, N- nematic state, I- isotropic state

b) T8 was recorded as the temperature ofthe onset ofthe endothermal increase in heat capacity observed in
the DSC curve of the sample
c) square brackets indicate a virtuai nematic phase transition temperature obtained by extrapolation from
isobaric binary phase diagrams 18 The polymer has a potential or latent ability to give the nematic form, but
this cannot be observed because the temperature of the transition from the isotropic liquid to the mesophase
lies below the normal glass transition.
d) polymer insoluble in THF
e) degradation above ca. 280C.
284
l
--HV
e~-----1 NE EDLE
r8
ELECTRODE
METALLIC
GRID
--HV ++++++++++++++++++++++++++
THIN FILM ELECTRODE
~--;-----~--------7
SU~B~S~T~RA~T~E~------~
HEATING BLOCK
Fig. 5. Schematic representation ofthe corona poling system.
Second barmonic generation. The two non-zero second order NLO susceptibilities
were detennined by comparing the SHG intensity obtained for a given poled film with that
obtained for a reference under the same conditions. An a.-quartz single crystal was used as
reference (d 11 = 0.5 prnN25 ). The SHG experiments were performed at a fundamental wave
-length of 1. 064 J.lm with a Q switched Nd: Y AG Iaser Operating at 10 Hz repetition rate
with 13 ns pulse duration. The incident fundamental beam polarization was varied by
rotating half waveplate (cf. Fig. 6). The SHG intensities were collected as a function of
incidence angle by rotating the sample around an axis perpendicular to the beam propagation
direction for a given fundamental-harmonic beam polarization configuration. The SHG
coefficients d31 (d31 = x<2 >3,/2) and d33 (d33= x< 2>JJ/2) were deduced from the s-p and p-p
configuration experiments, respectively. The experimental curves were fitted using equations
given in Ref. 26.
The same experimental set-up was used for in situ SHG measurements. The sample
cell was mounted on a rotatable heating stage for control of the incidence angle of the Iaser
beam. The film was heated by a built-in foil heater with an open hole at the center and its
temperature was controlled with 0.3C accuracy. The angle between the Iaser beam and the
normal to the thin film surface was fixed at about 50. The corona discharge (voltage 7 kV)
was generated by a tungsten needle held normal to the film at a distance of about 20 mm and
the SHG intensity e"'was recorded as a function of time.
For studying the relaxation process, the polar order of the sample was initially fixed
by poling at different temperatures over a long period of time (ca. 2 hrs). The fi1ms were
then cooled under the applied field to T8-25C. The field was switched off and the SHG
decay was recorded as a function oftime.
Development of axial order
The order parameters <P2> were derived from the linear absorption variation (cf. Fig. 2)
using the following relation
Ap
< P2 >= 1--- (22)
Ao
where A., and Ao are the absorbances of poled (p) and unpoled (o) films, respectively.
Figure 7 shows a typical growth ofthe order parameter <P2> as a function ofpoling time, tp.
This can be weil described by a mono-exponential function
(23)
285
Nd:YAG
FILTERS
C=~=:::J FILTERS
C~~::::J LENSE POLARIZER

REFERENCE
HALFWAVE
PLATE
FILTERS
LENSE
ROTATION
STAGE
FILTERS
ANALYZER
BOXCAR
INTEGRATOR PMT
Figure 6. Schematic representation ofthe in situ second harmonic generationexperimental set up.
0.35
0.30
0.25
').. 0.20
't: 0.15 0 130 oc
0 134 oc
0.10
I> 144 oc
0.05
0.00
0 10 20 30 40 50
t (min)
Figure 7. Temporal growth ofthe order parameter <P2> for PCBMS at three different poling temperatures:
l44C (triangles), l34C (squares) and l30C (circles). The solid lines show a fit of Eq. (23) to
experimental data (Vp = 7k:V).
where <P2> "" is the saturation value of orientation and t is the time constant of the process
In situ sec:ond harmonic generation experiments
A number of amorphous isotropic polymers doped or functionalized with NLO
286
Figure 8. Schcmatic representation of molecular motions involved in the dynamics of polyacrylate liquid
crystals.
chromophores have been examined using in situ SHG to provide a better understanding of
chromophore orientation dynamics during poling and relaxation phenomena. Here we will
focus on polymers exhibiting either a thermodynamically stable or a virtual nematic phase.
Indeed, the dynamics of SCLCP' s combine a number of features characteristic for low molar
mass LC's and conventional polymers6' 27 . Flexible spacers ensure freedom for the
mesogenic units to perform all reorientations characteristic of low molar mass LC's.
Therefore in the liquid crystalline phase the rotational dynamics of these units should
resemble those of monomer LC' s. The only significant differences should arise from the fact
that the mesogenic units are anchored to the main chain since this couples their dynamics to
the motion of the polymer backbone. At low temperatures, only secondary relaxation
processes (noted , y, .. ) involving local motions of dipoles on the side chains are observed
(cf Fig. 8). Above the static glass transition temperature, T8 , two additional processes
occur: the a-process so characteristic of polymers and associated with the segmented
motion of the main chain and the o-process assigned to the reorientation of the mesogenic
units about the polymer backbone, the end-over-end reorientation so characteristic of low
molar mass LC's. The a-process involves both the longitudinal and the transverse
components ofthe dipole moment ofthe mesogenic group while the o-process involves only
the motions ofthe longitudinal component ofthe dipole moment. In contrast with low molar
mass LC's, for SCLCP's the o-process is highly cooperative and exhibits a non-arrhenian
behavior. The slowdown of the reorientation rate, increase of the energy activation and the
distribution of the relaxation times reflect the presence of the anchoring, the different
environments and the dynamics that a mesogenic unit experiences in the liquid crystalline
phases formed by SCLCP's. There is clear evidence of a significant degree of cooperation
between the end-over-end reorientation of the side mesogenic groups and conformational
motions of the main chain.
Induction of polar order. The polar order has been determined by in situ SHG mea
surements. Figure 9 shows a typical temporal growth of SHG signal. This growth can be
described by a triexponential function
287
250
-
Ci)
c:
:J
200

......,
CO 150
~
-
"iii
cQ)
100 Signal
-~ 1 exponential
(.!)
2 exponentials
:c 50
(/") 3 exponentials
0 -
0 1000 2000 3000 4000 5000 6000
time (s}
Figure 9. Temporal gro\\th ofthe SHG intensity for PAJ. Dotted, dash-dotted and solid lines have been
computed using a one, two or three exponential function. respectively.
(24)
where I is the thin film thickness, 1:'s are the time constants and P's are the maximum
contribu -tions of the different mechanisms taking part in molecular orientation process,
respectively. The sum ofthe poling saturation Iimits: P =Pt + P2 + P3 represents the overall
poling efficiency under the experimental conditions (temperature, geometry, poling field,
atmosphere). The superscripts p and r in Eq. (24) refer to polymer thin film and reference
harmonic intensities, respectively. Equation (24) has been least squares fitted to
experimental data. The fitted values are listed in Tables 3 and 4 for PMAJ and PAJ,
respectively.
Decay of polar order. In all experiments the decay ofthe SHG signal (see Fig. 10)
could be described by the following biexponential function
1
_![/fm(t)]2 = R (1-e_,;,, )+~(1-e_,;,, )+C (25)

I I;"'(t) 1
Table 3. Parameters derived from a triexponential fit to the SHG intensity growth for PMAJ
at different poling temperatures (after ref 21).
Poling pl 't!(S) p2 1:2(s) p3 1:3(s) p

temperature
ec)
82 207 2.3 297 589 169 4801 673
92 292 1.1 304 516 444 4003 1040
97 600 3.2 153 349 277 3633 1030
102 553 2.4 785 336 1338
107 1069 4.7 389 187 1458
112 724 25.4 550 235 1274
117 634 6.2 158 224 792
288
Table 4. Parameters derived from a triexponential fit to the SHG intensity growth for PA3
at different poling temperatures (after ref 21).
Poling PI 't!(S) Pz 'tz(s) p3 't3(s) p

temperature
I (oc)
26.5 74 37 77 1387 130 11850 282
41.5 82 30 76 1002 213 6376 371
46.5 206 40 44 910 662 3843 913
51.5 203 43 293 288 568 2834 1064
56.5 426 38 230 306 255 2559 910
61.5 245 5 189 117 467 1592 900
71.5 337 7 186 182 377 1082 900
76.5 522 12 0 0 386 584 908
81.5 331 8 0 0 556 372 887
Table 5. Parameters derived from a biexponential fit to the SHG intensity decay for PMA3
at different temperatures (after ref 2 I).
Temperature ( oq R1 't!(S) Rz 'tz(s) R

82 0.32 80 0.16 690 0.52
92 0.26 17 0.18 1643 0.56
97 0.19 39 0.24 844 0.57
102 0.23 47 0.13 2726 0.65
112 0.17 48 0.23 3550 0.61
117 0.11 80 0.17 6361 0.72
Table 6. Parameters derived from a biexponential fit to the SHG intensity decay for PA3 at
different temperatures (after ref 21 ).
Temperat R1 't1(s) Rz 'tz(s) R

ure C
26.5 0.28 85 0.55 ll66 0.17
31.5 0.34 193 0.41 1643 0.25
51.5 0.19 249 0.25 4150 0.56
where C is a constant characterizing the residual orientation at the experimental time scale
which is important for practical applications. The fitting parameters of Eq. (25) to
experimental data are listed in Tables 5 and 6 for PMA3 and PA3 polymers, respectively.
Figure 10 shows an example ofthe temporal decay ofthe measured and fitted with Eq. (25)
SHG intensity for PA3.
Second order nonlinear optical properties
The SHG susceptibilities d31 and d33 for a number of poled polymer films are given in Table
7. They show two interesting features:
(i) large values of second order NLO susceptibility d3 3 = x< 2 l33 /2 for materials with a large
289
240
2
c: 220 Signal
:J I exponential
-
.ri 2 exponentials
.....
tU
200
~
c;;
cCl)
~ 180
(.!)
J:
(/)
160
0 1000 2000 3000 4000

time (s)
Figure 10. Temporal decay of SHG intensity for PA3. Dash-dotted and solid lines have been computed using
a one and two exponential function, respectively.
Table 7. Orderparameter <P2> and second order NLO coefficients d33 and d31 for selected
corona - poled films.
Polymer Wavelength <P2> d33 d31 a=d33/d31 Ref

jlm prnN prnN
PECH0.55 0.777 0.45 14.6 1.33 10.97 19,24
1.064 0.45 7.9 0.7 11.2s
PECH0.8 0.777 0.57 32.7 1.8 18.16 19,24
1.064 0.57 17.8 0.97 18.3s
1.064 0.62 23.4 1.65 14.ls
PBCMO 1.064 0.19 20 2.2 9.1 20
14/43/43 1.064 0.31 31 2.7 11.4s
1.064 0.32 29.8 2.2 13.6
PBCM0100 1.064 0.28 24.9 2.0 12.4s 16
1.064 0.37 27.1 1.7 15.9s
PA3 1.064 0.47 30.4 2.17 14 19
1.064 0.57 35.6 2.1 16.9s
PMA3 1.064 0.45 33.5 3.3 10.1 19
transparency window (cf Fig. 2). Values of d33 up to ca. 36 prnN were measured at 1.064
!J.m fundamental wavelength.
(ii) !arge ratios d33/ d31 LC materials. Values ofup to 183 were observed with PECH 0.8,
which explains the !arge x< 2>33 value determined for this polymer.
DISCUSSiON
Development of axial order
For the isotropic polymers PCBMS, PS-co-PM3, PVAz and P(VAz-co-MMA)

alignment could not be reached on a reasonable time scale at temperatures more than 20C
290
below T8. However. the axial order was< ound to develop rapidly at and above Tg, the
kinetic constraints on polymer mobility being relieved. Clearly, as the poling temperature
increases. the viscosity of the melt decreases and the rate of orientation increases. The order
Ievels toward a maximum value of 0.3-0.35 at temperatures close to T8 (Tp- T8 "" 20C}. At
higher temperatures, <P2>"' decreases. Such a behavior is expected from the consideration
of equilibrium between the competing rates of alignment due to the directing electric field
and thermal randomization.
It should be noted that the as-spin coated films prepared from the nematic polymers
appeared completely dark between crossed polarizers. thus indicating that these polymers
were frozen in a metastable isotropic state. This results from the rapid removal of solvent
from the isotropic casting solution. Refractive index measurements also supported the
conclusion that the macroscopic orientation in the unpoled films is ne~gible: the
birefringence values were much lower than those usually found for LC materials 8 . For these
nematic polymers, t and <Py"' vary more rapidly with the temperature between T8 - 5C
and T8 + 5C than for the isotropic systems (cf. Fig. 11). Roughly speaking, t decreases by a
factor of approximately 3 and <P2>"' increases by a factor of about 4 with increasing
temperature. This can be explained by a transition from the metastable isotropic state, in
which the polymer is frozen at the end of the spin-coating process, to the thermodynamically
stable nematic state. Heating as spin-coated films above T8 relieves the kinetic constraints on
the cooperative motions ofthe polymer chains (a.-mode) and side chains (8-modet27 (see
Fig. 8), thus allowing the nematic order to develop. In the presence ofthe applied directing
field, the nematic phase is formed aligned and thus free from domain-induced light
scattering. The data obtained for the functionalized polymaleimide PM3 clearly showed that
it is much more difficult to induce a transition from the metastable isotropic phase to the
smectic state than to the nematic state.
While microscopic order parameters up to 0.55-0.65 were observed for PA3,
PECH80, PCBMS-co-PM3 and PM3 systems, the maximum orientation obtained in
PBCMO 14/43/43 and PBCMO 100 filmswas 0.4-0.45 16 . This is due to the narrower range
ofmesophase thermal stability (AT= TNI- T8 = 20C} exhibited by PBCMO derivatives. As
shown both theoretically 10 12 and experimentally13 , the perfection of orientational order in a
nematic phase decreases with increasing values ofthe reduced temperature r = Tpi'TNI. As
poling experiments are performed usually a few degrees above T8 to allow the nematic order
to develop while minimizing thermal fluctuations, SCLC polymers with a narrower range of
mesophase thermal stability will correspond to higher values of r = Tpi'TNI., and as a
consequence to smaller values of <P2>"'. Clearly, the NLO properties of SCLCP's primarily
related to cooperative motions, such as the rate of development of axial ordering, must be
scaled relative to Tg, while physical properties which are primarily determined by the
orientationally anisotropic interactions, like <P2>"' , must be scaled by the reduced
temperature r = Tpi'TNI.
Interestingly, it was found that the plateau value <P2>"' is sensitive to the strength of
the poling field used, i.e. it increases with increasing field strength. This is due to the fact
that, as predicted by the MSVP model8' 9' 14, the actual clearing temperature ,TNI, in the
presence of a field will be larger than the temperature at which the discontinuous
nematic/isotropic phase transition takes place in the absence of a field. The higher the
electric field strength, the broader will be the thermal stability range of the nematic phase.
This will correspond to lower values of r = Tp("" T8)/TNI, and as a consequence to larger
values of <P2>"' .
In PECH0.55 and PMA3, which are isotropic at rest but exhibit a virtual nematic
phase, the axial order is continuously induced from T8 - 20C to T8 + 5C21 (cf. Fig. 11 ). At
this temperature, the <P2>"' values (0.45 - 0.55) are larger than those obtained in the present
studies for PCBMS. PS-co-PM3 and PVAz systems and reported in the Iiterature for
isotropic functionalized polymers. Again this result can be explained by considering the
291
0.6
PA3
0.5
,..
 at saturation
0.4
 for 15 minutes
AN
~ 0.3

0.2
0.1
0.0
-20 -10 0 10
Tp- Tg (OC)
0.5 PMA3
0.4
<P2> at saturation
0.3
<P2> for 15 minutes
..
AN
~
0.2
.t,'
0.1
0.0

-40 -30 -20 -10 0 10
Tp- T 8 COC)
Figure 11. Development of axial order with poling temperature in P A3 and PMA3 at different poling times:
<P2>1s n.m (triangles) and < Pz
>,., (squares). Dashed and solid lines are goides for eyes.
effect of the poling field on the TNI temperature. As already discussed, the strong DC electric
field causes a shift in the nematic/isotropic tmsition to higher temperature. As a
consequence, during poling PECH 0.55 and PMA3 can be pulled through the transition
because TNI becomes equal to or !arger than T8 and the poling temperature. 1t should be
noted, however, that the thermal stability range of the induced nematic phase is quite
narrow.
Poling dynamics
Dynamics of tbe rise of tbe induced noncentrosymmetry. The following

conclusions can be drawn from the values ofthe fitted parameters given in Tables 3 and 4:
292
1. The initial rapid growth of SHG signal is characterized by a time constant 't1 of a few
seconds. This corresponds to the short period of time required to allow the surface charge
density to build up in the corona poling set-up. During that time the system can be
considered as an isotropic medium . The molecular energy depends only on the dipole
orientation with respect to the directing electric fi.eld. Accordingly, this rapid step-growth of
the SHG signal can be attributed to the fast reorientational response of the uncorrelated
polar side chain chromophores which are free to rotate. This process is mainly governed by
local non cooperative motions ofthe side groups (sub-Tg relaxation modes, cf Fig. 8). lts
contribution to the SHG signal depends on three factors:
(i) the size ofthe local free volume around each chromophore
(ii) the degree of decoupling between the chromophore and the polymer backhone
(iii) the poling temperature deterrnining the thermal fluctuation energy.
The subsequent growth of the SHG signal (with time constant 1:2) is due to an
improved alignment of chromophores under the quickly established, constant electric fi.eld
and to the deve -lopment ofnematic order. Now, the energy ofthe system depends not only
on the orientation of the molecular dipoles relative to the electric fi.eld direction, but also on
the tendency toward mutual axial alignment experienced by the active mesogenic groups.
For LC polymers in which the mesogenic groups are attached to the polymer backhone via
short spacers, only a partial decoupling of the main chain and side chain motions is
obtained. Hence, the side chain order influences the polymer chain contour. The antagonistic
effects of the nematic field and the inter - nal entropy of the chains are resolved by a
distortion of chain statistics. The orienting electric field , while leading to an alignrnent of the
active mesogenic groups, also causes the backhone units to change their conformation
locally to adapt to the anisotropic orientation distribution of the poled chromophores. The
polymer backhone adopts progressively a non spherical confor - mation, the anisotropy
defi.ned by the ratio R.t!R 11 of gyration radii being Iarge enough to be measured by the small
angle scattering methods28 .Therefore, the polarization growth process with the time constant
t2 can be associated with the reorientational motions of both the polymer backhone chain
segments (a. - relaxation mode, Fig. 8) and the side chains. lts maximum contribution
depends on the polymer segmental mobility and the degree of decoupling between the
polymer segments and the chromophores.
The slowest SHG signal growth process, characterized by time constant t 3 , which is
not observed with amorphous isotropic polymers, may be ascribed to a peculiar feature of
the molecular dynarnics of SCLCP's, namely the reorientational motions of the
chromophores about the polymer backbone. These motions give rise to the so-called o -
mode (cf. Fig. 8), controlled by free volume effects 27 It should be noted, however, that this
process is highly cooperative and requires more free volume than that characteristic of the
main chain segmental motions. What is interesting and obviously argues in favor of a high
degree of cooperation between the main chain and the side chains in their dynarnics is partial
parallelism of the temperature dependence of the t 2 and t 3 time constants, observed weil
within the mesomorphic state. For PMA3, the thermal stability range of the mesophase
developed under the poling field is rather small and this slow step-growth is absent from the
SHG signal as soon as the poling temperature is a few degrees above T8. For PA3, at a
critical poling temperature {T8 + 25C), the poling mechanisms 2 and 3 tend to merge. This
effect could result from the coupling between the different relaxation modes.
Note that a noticeable enhancement of polar ordering can be induced by using
SCLCP's instead of isotropic polymers. As shown in Table 4 for PA3, the overall poling
efficiency, P, is increased by a factor of ca. 2.5 (from 370 to 910) at the transition from the
metastable isotropic state to the stable nematic state, in agreement with the predictions of
the SKS 7 and MSVP 8914 models.
Relaxation processes. The dynarnics of the decay of the induced

noncentrosymmetry was studied for the same polymers PA3 and PMA3 21 . Briefly, the initial
293
drop of SHG signal with a characteristic time of a few minutes (Tab1es 5 and 6) corresponds
to s1ow 1eakage of the surface charge density after the field is switched off. lt can be
associated with the capability ofthe chromophores to rotate freely. The long term loss with
a characteristic time varying from several minutes to hours depending on how the samp1e
was poled, may be ascribed to the relaxation of the polymer backhone toward its normal
random coil conformation and the disalignment of correlated chromophores via the -
process. Since both the cooperative motions of the chain segments (a. - process) and the
reorientational motions ofthe chromophores about the polymer backhone (- process) are
extremely restricted in the glassy state, a residual SHG signal is observed when the
relaxation processes are recorded below T8 . It is therefore ex.pected that SCLCP's with
Tg> l30C will exhibit reasonable temporal stability of their second order NLO properties
since both the a - and - processes cease to exist at temperatures more than ca. 50C below
Tg.
Two findings argue in favor of the proposed mechanism for the slow decay of the
SHG signal. First, cooling the polymers at the end of poling from their nematic phases to the
glassy state in the presence of the electric field succeeds in freezing in the axial
alignment, <P2> remains constant. Secondly, the decrease ofthe polar order parameter 
as a function of time, which was recorded using Fabry Perot interferometry under oblique
incidence, minimies the decay of SHG signal29 .
Second order NLO properties.
It was found that over a wide range of processing conditions d33/d31 ,., 3 for the
amorphous isotropic PVAz polymer. For the maximum orientation, <P2> = 0.28, the values
of d33 and d31 were determined to be 9.91 and 3.30.4 pm/V. Different results were
obtained for the amorphous isotropic PCBMS polymer. Forthis polymer, at the plateau Ievel
of orientatlon (<P2> ,., 0.3), the average values for d33 and d31 were 12.8 and 2.1 pm!V,
respectively, but the ratio of d33/d31 was found to be 6, thus exceeding the theoretical value
of 3 predicted for isotropic systems. The restricted motion of the NLO side groups during
po1ing provides a possible exp1anation for this discrepancy. In fact, this polymer should be
considered to be po1yethy1ene with the benzyl ether of 4-hydroxy-4 '-cyanobiphenyl as the
chromophore unit attached directly to the backhone and not as polystyrene with the 4-
cyanobipheny1 unit 1inked to the backhone through a -O-CH2 spacer. Bearing in mind that
poling has to be performed at a temperature close to T 8 in order to keep the ionic
conductivity within a tolerable range and to minimize the thermal randomization, one might
expect the polymer backhone to be still ~uite rigid, restricting the motion of the
chromophore side groups. Herminghaus et al 0 considered the effects of conformational
constraints on chromophore ordering by introducing a restriction parameter v (O<v<1) and
developed a model that can account for d3id31 ratios ranging from 3 to 6. If all the dipoles
participate in the poling process (v = 0), the value d33/d31 = 3 ofthe simple theory is retained.
As v ~ 1 only those dipoles rotating about an axis perpendicular to the applied electric field
(i.e. parallel to the film surface) are involved in the poling process with the result that d3Jd31
= 6, a value earlier obtained by Robin et al31 with a simpler model. Preliminary results
obtained for PS-co-PM3 suggest that the insertion of a spacer of three methylenie units does
not completely decouple the chromophore side groups from the rigid poly(styrene-co-
maleimide) chain. Again the ratio d33/d31 is close to 6.
In Figures 12 and 13 the diagonal term of second order NLO susceptibility d33 and
the ratio d3Jd31 are plotted as a function of the order parameter <P2>, respectively, for
polymers exhibiting thermodynamically stable or virtual mesophases and poled over a wide
range of temperature and time conditions. The salient conclusions of the results are the
following:
(i) Again, the initial1y (as spin-coated) isotropic samples do not behave according to the
294
--
. ---
..,,.., ...... -
........,.-'
... .
30 -+:~--,--,
,'
I
,'
: *
..
..
I
20 I
' ~.
*
.
el
,
,, '
. ..
10 ,.,~''
,.,~"'
,' --
_,.-~-/
0~--~--~~--~----~--~----~
o.o 0.1 0.2 0.3 0.4 0.5
Figure 12. Variation of d33 with the axial order parameter <P:z> for polymers exhibiting thermodynamically
*
stable orvirtual nematic phases: PBCMO 14/43/43, Tp = 105-109C, - PBCMO 100, Tp = I26-165C,
.l- PECH 0.55, Tp = 57C, *--PECH 0.80, Tp = 81C. PA3, Tp = 5PC, - PMA3, Tp = 97C.
isotropic model at low . They exhibit ratio values of 5-7 in agreement with theoretical
predictions30,3 1 for side chain polymers with incomplete decoupling of the motions of the
main chain and side groups. As soon as the isotropic/nematic transition takes place (i.e. as
soon as <P2> exceeds a value of ca. 0.3), the ratio d33/d31 increases drastically as predicted

*
... lt
-+:

.6

10
-+:

-fr

...................................... r.- The Robin model
5
Isotropie model
Figure 13. Variation ofthe ratio d3Jd31 with the axial order parameter <P2>. * PBCMO 14/43/43, -
PBCMO 100. .l PECH 0.55, *--PECH 0.80, - PA3, - PMA3
295
by the model developed by Van derVorstand Picken8' 9' 14 even though this model refers to
equilibrium values of <P2> that are reached after a long annealing time.
(ii) Similarly, the diagonal term of second order NLO susceptibility d33 increases with the
orientational order parameter <P2>. Clearly, the field induced folar term <cos30> is
enhanced by the presence of axial order, thus confirming the SKS and MSVP89 14 model
predictions. The nonlinearities in LC systems are determined by the order imposed by the
poling field as weil as the order arising from anisotropic intermolecular forces.
(iii) The observed difference ofbehavior between PBCMO 14/43/43 and PA3 or PMA3 is
likely due to the higher functionalization Ievel in the former. Using a polymer with larger
chromophore content results in a proportionally larger SH coefficient d33 in agreement with
Eq. (10). One would expect higher d33 values for PBCMO 100 which contains exclusively
twice-functionalized structural units. Clearly however, the covalent attachment of two NLO
mesogenic groups to each structural unit through spacers of only one methylenie unit results
in an increase in the rigidity of the system and important steric hindrance effects, preventing
a favorable alignment of chromophores within the film for SHG. It can also be noted that the
PBCMO 100 films were poled at much higher temperatures (TP = 126-165C, depending on
the molecular weight of the sample16' 22 ) than P A3 films (TP = 59C 19). The thermodynamic
1/kT effects are expected to account for a decline in d33 from Tp = 57C (330 K) to Tp =
160C (433 K) by a factor of 1.31. The lower d33 values obtained for the PECH derivatives15
may be partly responsible for the difference in the observed NLO responses. In these
polymers the strong antiparallel near - neighbor correlations result in the formation of
antiparallel interdigitated dimers which have no net dipole moment and do not contribute to
the poling process, thus leading to a reduction in the effective number of polarized dipoles.
All these results provide guidance for realizing SCLCP's with sufficient optical
nonlinearity for NLO applications.
CONCLUSIONS
The results ofthe present studies demonstrate that real time in situ SHG experiments
provide a powerful tool for investigating poling dynamics and relaxation processes in NLO
SCLCP's. The analysis of the SHG signal growth shows that during poling the polymer
backhone changes locally its conformation to adapt to the anisotropic orientation of the
chromophore. As a resukt, a local uniaxial environment is created that allows further
alignment of the NLO groups. Such a poling mechanism, which involves both main chain
segmental motions (a- mode) and reorientational motions of the whole chromophore side
groups about the backhone ( - mode) differs from that reported for amorphous isotropic
polymers. This differing behavior is likely due to the effects of nematic ordering on the chain
shape and the specific features of the dynamics of LC's, namely the existence of the -
mode. Clearly, the poling efficiency is enhanced by the cooperative axial order present in
nematic phases.
Data analysis of the relaxation processes shows that if the polymer chain contour
undergoes a significant distortion from its normal random coil conformation during poling
(samples poled above T8 for a long time), then the subsequent relaxationwill take a long
time. Since both the chain segment mobility and the end-over-end reorientation of the
chromophore side groups about the backhone are highly cooperative and become sluggish in
the glassy state, the disalignment of the chromophores will be incomplete below T8, thus
resulting in a residual SHG signal. lt is worth noting that for SCLCP's the temperature at
which both motions cease to exist at a human time scale has been estimated tobe T8 - T0(a)
::::: 36 K and T 8 - To()::::: 56 K27 . Hence, poled SCLCP's are expected tobe quite stable if
used at temperatures about 80C below T8 . This is observed for LC PBCMO systems which
exhibit lifetimes Ionger than two years with only 15% decay in SHG coefficients at ambient.
The second order NLO suseptibility d33 of the investigated SCLCP's increases with
the orientational order parameter <P2> showing that as predicted by the SKS7 and the
296
MSVP8' 9' 14 models, the field induced polar order term <cos30> is enhanced by the presence
ofxial order. At high <P2>, this Ieads to d33 values of30-35 pmN at 1.064 IJ.m (50-60 pmN
at 0.777 IJ.m for given the effect of wavelength dispersion24) which really exceeds many
previously reported for off resonance SHG measurements on isotropic NLO polymers
containing chromophore side groups of larger hyperpolarizability32. They exceed also those
of other materials suitable for blue conversion such as potassium titanyl phosphate (KTP)
and are approximately equal tothat of Iithium niobate (LiNb03)26 . Further development in
this field would be the improvement of the temporal stability of the polar order at high
temperature by synthesizing SCLCP's with higherglass transition temperatures.
Acknowledgements
This work was supported in part by the lndo French Center for the Promotion of Advanced
Research (IFCP AR Research Project n 1008 - 1).
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Lightwave and Integrated Optics: Technology and Applications , L. A. Hornak Ed.,
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6. D. Gonin, C. Noel and F. Kajzar, Liquid Crystalline Polymers, in Organic Thin Films
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7. K. D. Singer, M. G. Kuzyk and J. E. Sohn, J. Opt. Soc. Am. B, 4, 968(1987)
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13. H. Finkelmann and G. Rehage, Adv. Polym. Sei., 60-61, 99(1984)
14. G. R. Mhlmann and C. P. J. M. V an der Vorst, Side Chain Liquid Crystal Polymers
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15. S. Piercourt, N. Lacoudre, A. Le Borgne, N. Spassky, C. Friedrich and C. Noel,
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16. B. Guichard, V. Poirier, C. Noel, D. Reyx, A. Le Borgne, M. Leblanc, M. Large and F.
Kajzar, Macromol. Chem. Phys.,l97, 3631(1996)
17. B. Guichard, Gangadhara, D. Reyx and C. Noel, Development of Side Chain Liquid
Crystal Polymers for Nonlinear Optical Applications. I. Molecular Design, Synthesis and
Characterization, In Proc. STEPI 4, Polyimidesand High Performance Polymers, M. Ahadie
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18. D. Gonin, B. Guichard, C. Noel and F. Kajzar, Highly Efficient Liquid Crystal
Polymers for Quadratic Nonlinear Optics , in Polymers and Other Advanced Materials :
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York 1995, pp. 465-483
19. D. Gonin, B. Guichard, C. Noel and F. Kajzar, Macromol. Symp., 96, 185(1995)
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21. T. Dantas de Morais, C. Noel and F. Kajzar, Nonlinear Optics, 15, 315(1996)
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ofNonlinear Optical Physics and Materials, 5, 735(1996)
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Commun., 13, 537(1992)
25. M. Choy and R. L. Byer, Phys. Rev. B, 4, 1693(1976)
26. J. Swalen and F. Kajzar, in Ref 5, pp. 1-44
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Collyer Ed., Elsevier Applied Science, London 1992, Chapter 4, pp. 143-236
28. L. Noirez, P. Kellerand J. P. Cotton, Liquid Crystals, 18, 129 (1995)
29. R. Meyrueix and C. Noel, tobe published
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31. P. Robin, P. Le Barny, D. Broussoux, J. P. Pocholle and V. Lemoine, in Organic
Molecules for Nonlinear Optics and Photonies , J. Messier, F. Kajzar and P. N. Prasad,
Eds., Kluwer Academic Publ., Dordrecht 1991, p. 481
32. M. A. Firestone, J. Park, N. Minami, M. A. Ratner, T. J. Marks, W. Lin and G. K.
Wong, Macromolecules, l8, 2247(1995)
298
SOLUTION PROPERTIES OF CONDUCTING POLYMERS
Jae Yoon Lee and Hoosung Lee

Department of Chemistry, Sogang University,
1-1 Shinsoo Dong, Mapoku, Seoul 121-742 Korea
INTRODUCTION
Very often, the scientific data about conducting polymers appearing in

the Iiteratures deviate significantly from author to author. Even in the
same laboratory it is not unusual to get data significantly different from the
ones obtained previously. One of the reasons for such poor reprocucibility of
data is in the lack of ability to reproduce the sample in a well-defined
state. In order to prepare samples in a well-defined state, knowledge on
the molecular properlies, such as molecular weights and their distribution,
degree of chain expansion in solutions, and interactions with the dopant
molecules, etc., is essential. However, the understanding on the molecular
properlies of conducting polymers has been greatly bindered by their
inherent insolubility. Attempts have been made to solubilize these polymers
by incorporating alkyl-substituted monomers in the polymerization1- 7.
Recently, scientists found new methods for dissolving polyaniline (PAN) and
polypyrrole (PPy) without applying substituted alkyl groups8- 13.
It has been known that the electrical conductivity of polyaniline can be
enhanced several orders of magnitude by secondary doping 14 This
phenomena is understood to originate from the attainment of the expanded
molecular structure due to interactions of the conducting polymer molecules
with the secondary dopant molecules 14 It is natural to expect that the
physical properlies, such as electrical and magnetic properlies of solution-
cast PPy film will also depend on the properlies of the solution from which
the film is cast. The purpose of this research was to investigate the
solution-properlies of PPy and to correlate the solution-properlies to the
physical properlies of PPy film cast from the solution. Investigations on
the polymerization conditions for the synthesis of soluble PPy has been
performed as weiL

Editedby P. N. Prasadetal., Plenum Press, New York, 1998 299
EXPERIMENTAL
PPy was polymerized by oxidizing the distilled monomer in aqueous

solution with ammonium persulfate15 DBSA (dodecylbenzenesulfonic acid)
was used as dopane 5. DBSA-doped PPy was precipitated by adding
methanol into the reaction mixture. PPy obtained in this way was
separated by filtration, washed several times with methanol, dried in an
oven at 50"C for a day, and ground into fine powder. The synthesis of PPy
was performed using various oxidantimonomer (0/M) and dopant/monomer
(D/M) ratios. Approximately 3%-solution (by weight) of PPy was prepared
by dissolving the powder in m-cresol or NMP followed by filtering off the
insoluble residues. For film casting, the solution was spread on a glass
plate and the solvent was evaporated at 50 c for 2 days. PPy film obtained
in this way had dark color and very shiny surfaces.
Viscosity was measured using an Ubbelohde viscometer in an oil bath
thermostatted at 25 0.1 "C. Electrical conductivity of the film and pellet
samples were measured by four-line probe and van der Paw methods,
respectively. The doping level of PPy was determined from the
sulfur/nitrogen mole ratio obtained by eiemental analysis. EPR spectra were
measured using a Bruker (ER 200 E-SRC) EPR spectrometer. UV-Vis-NIR
spectra were measured using a Shimazu UV -3101 PC spectrophotometer.
Two different reaction temperatures, i. e. room temperature and 0 c,

were used in the polymerization of pyrrole. PPy synthesized at 0 c always
showed higher conductivity than the one synthesized at room temperature,
as shown in Table 1. The inherent viscosity of PPy synthesized at 0 c
also showed higher value than the one synthesized at room temperature.
This is a good indication that the oc -sample has higher molecular weight.
It is expected that, when polymerized at lower temperature, PPy molecules
with higher molecular weight with lower degree of branching are obtained.
Table 1. Physical properties of PPy synthesized at room temperature

and at oc (0/M = 0.1, D/M = 0.75). The inherent viscosity, ~nh, was
measured for the solution in m-cresol.
Conductivity of the Conductivity of the

Temperature pelletized powder solution-cast film 71inh (dL/g)
(S/cm) (S/cm)
0 'C 1.7 X lO~z 6.0X 10~.< 0.21
room temperature 1.8X 10- 4 1.6 X 10~ 4 0.099
The physical properties of PPy synthesized with various 0/M ratios are
shown in Table 2. When 0/M ratio is greater than 0.2, PPy obtained was
insoluble in any of the solvents used. Thus the conductivity was measured
only for the pellets for those samples. When synthesized with 0/M =0.5, it
300
was impossible to pelletize the powder due to its non-adhering property.
The appearance of PPy obtained with this 0/M ratio was most shiny. PPy
synthesized with higher 0/M ratios showed higher electrical conductivity.
The electrical conductivity of the pellet synthesized at 0/M=0.2 was greater
than that synthesized at 0/M=O.l by a factor of more than 1000, while for
the solution-cast film, the faCtor was less than 100. It is believed that,
with higher 0/M ratios, PPy obtained has not only higher molecular weight,
but also higher oxidation states. The viscosity and electrical conductivity
data in Table 2 also support this argument. The degree of doping
increased with 0/M ratio. This also supports the argument that PPy with
higher oxidation state is obtained at higher 0/M ratios. It should be noted
that 0/M ratio plays the most important role in determining the solubility of
PPy. The physical properties of PPy synthesized with various D/M ratios
with a fixed 0/M ratio of 0.2 are listed in Table 3. With this particular
0/M ratio, the highest solubility was obtained when D/M ratio was 0.5,
while insoluble PPy was obtained at D!M> 1.0. However, this number
varied with 0/M ratio.
Table 2. Physical properties of PPy synthesized with various 0/M

mole ratio with a fixed D/M ratio of 0.75. The inherent viscosity, ~nh,
was measured for the solution in m-cresol.

0/M mole ratio pelletized powder solution-cast film ~nh (dL/g)
(S/cm) (S/cm)
0.1 1.8 X 10 4 L6x w- 0.099
0.2 0.30 1.1 X10-z 0.23
0.5 a
1.0 0.19
a; impossible to pelletize due to non-adhering character of the powder
i; insoluble in solvent
Table 3. Physical properties of PPy synthesized with various D/M

mole ratio with a fixed 0/M ratio of 0.2. The inherent viscosity, ~nh,
was measured for the solution in m-cresol.

D/M male ratio pelletized powder solution-cast film ~nh (dL/g)
(S/cm) (S/cm)
0.5 0.013 a 0.025
0.75 0.12 5.6X 10 6 0.11
1.0 0.26 1.7X10 l 0.11
1.5 059
2.0 0.43
a; Film was too brittle to measure the conductivity.
i; insoluble in solvent
301
The peak width (AHw) of the EPR spectra of PPy powder increased
with 0/M ratio, showed a maximum between 0/M = 0.4 and 0.5, then
decreased slightly as 0/M ratio increased as shown in Figure 1. However,
AHPP showed a monotonaus increase with D/M ratio as shown in Figure 2.
On the other band, the spin concentration in the powder decreased with
OlM and D/M ratios as shown in Figure 3 and Figure 4. The conductivity
of the film increased with decrease in spin concentration. This confirms
that the major charge carriers are bipolarans in the PPy film 16 These
results indicate that not only the 0/M ratio but also the D/M ratios
influences the oxidation states of PPy. It is interesting to note that, at
0/M = 0.2, AHPP jumped up by a factor of more than four times while spin
concentration decreased rapidly with 0/M ratio. Remernhering that, in Table
2, 0/M = 0.2 was the border line between soluble and insoluble PPy
formation, it is evident that soluble PPy consists more of polarans than
insoluble PPy, i.e. oxidation state plays an important role in dissolution of
the polymer. It is also believed that the abrupt increase in AHPP is
associated with localization of the polarons, presumably due to branching
and crosslinking of the polymer chains. Apparently, solubility of PPy is
determined not only by the molecular weight, but also by the oxidation
state, and the degree of crosslinking.
PPy used in the measurement of UV-Vis-NIR spectra in solution was
synthesized with 0/M = 0.1 at room temperature. PPy was more soluble in
m-cresol than in NMP and the film cast from NMP solution was more
brittle than that cast from m-cresol, presumably because the polymer chains
have more expanded structures in a better solvent. UV-Vis-NIR spectra
(Figure 5) of PPy solutions in m-cresol and in NMP were quite different
from those of the corresponding solid17- 19 As the solvent was changed from
NMP to m-cresol, the broad peak at ca. 420 nm (2.95 eV) increased at the
6 soluble
<- --+ insoluble
5
Ii)
Ul
::J
CU
4
.9
a.
a. 3
:::c
-<1
2
o~~~~~~~~~~~~~~~~~~
0.0 .2 .4 .6 .8 1.0 1.2

Oxidant I monomer molar ratio
Figure 1. Variation of llHpp with oxidantimonomer (0/M) ratio. Solubility of PPy
decreases as 0/M ratio increases and totally insoluble PPy is obtained when 0/M > 0.2.
302
5
4 soluble
<--
insoluble
~

Ci)
(/)
3

::J
rn
E?
a.
a.
2

I
<I
o~~~~~~~~~~~~~~~~~~~~
0.0 .5 1.0 1.5 2.0 2.5

DBSA I Monomer Molar Ratio
Figure 2. Variation of llH"" with dopant/monomer (D/M) ratio. Solubility of PPy decreases
as D/M ratio increases and totally insoluble PPy is obtained when D/M > 1.0.
.010
-
-
Cl
c
c .008
( /)
c
a.
.!!!.,
c .006
0
-
~
rn
....
c .004
Q)
u
c
0
(.) soluble
<-- ~insoluble
c .002
a.
Cf)
0. 000 ~-'--'--.l.-..J--'--'-..J...._J...-I._._....J__.__....._._--~...._.__.J..--L-L-l-_.__l.......J
0.0 .2 .4 .6 .8 1.0 1.2
Oxidant I monomer molar ratio

Figure 3. Variation of spin concentration with oxidantimonomer (0/M) ratio. Solubility of
PPy decreases as 0/M ratio increases and totally insoluble PPy is obtained when 0/M >
0.2.
303
.010 I
C>

c
--
;::
1/1 .008 -
c
a.
~

c
0 4

-
:;::::;
.006 -
....
nl
c
Q)
CJ
c
0
(.)
.004
soluble insoluble
-
c
a. ~ -4
Cl)
I l _l
.002
0.0 .5 1.0 1.5 2.0 2.5
DBSA I Monomer Molar Ratio
Figure 4. Variation of spin concentration with dopant/monomer (D/M) ratio. Solubility of
PPy decreases as D/M ratio increases and totally insoluble PPy is obtained when D/M >
1.0.
expense of a sharp peak at 475 nm (2.61 eV). It 1s expected that, in an

acidic solvent such as m-cresol, PPy can be doped more favorably with an
acidic dopant, including DBSA. On the other hand, in a basic solvent such
as NMP, PPy is presumably in the undoped neutral state. Therefore, the
sharp peak at 475 nm and the broad peak at 420 nm correspond to Jt-4Jt*
transitions in the neutral and doped forms, respectively. The conductivity
data also support this argument. PPy film cast from NMP showed very low
conductivity ( -10- 10 S/cm) while the film cast from m-cresol showed a
conductivity of 1.3 x 10-4 S/cm. The peak absorption at 933 nm (1.33 eV) is
believed to arise from the transition between defect states 16. It is known
that Jt-41t* transitions have very high molar absorption coefficient, namely
around 104 L cm-I mor 1. The molar absorption coefficient of the sharp
peak at 475 nm was 2000 L cm -I mor 1. This can be compared with Soret
( -400 nm) band of porphyrin which is also due to the Jt-47r* transition 20.
The UV-Vis-NIR spectra of PPy solutions synthesized under various
oxidizing conditions are shown in Figure 6. As indicated in the figure
caption, the electrical conductivity of the films cast from these solutions
increased in the order of (a) < (b) < (c). For the same 0/M ratio, PPy
synthesized at OOC showed higher conductivity than that synthesized at
room temperature. At room temperature, PPy synthesized with 0/M = 0.2
showed higher conductivity than that synthesized with 0/M = 0.1. In
Figure 6, one can notice that the absorption peak at around 933 nm consist
of two peaks, i. e. a sharp absorption peak at 933 nm overlapped on top of
a broad absorption peak at 950 nm 0.31 eV). It is interesting to note that
as the conductivity increased, the broad absorption peaks at 420 nm, 660
nm, and 950 nm increased at the expense of the sharp peaks at 475 nm and
933 nm. Thus the conducting form is responsible for the broad absorption
peaks at 420 nm, 660 nm and 933 nm.
304
The UV-Vis-NIR spectra also affected by the addition of extra dopant,
DBSA, into the solution as shown in Figure 7. PPy shown in this figure
was synthesized with 0/M =0.2 at room temperature and was dissolved in
m-cresol. With the addition of extra dopant, the sharp absorption at 475
nm disappeared completely and free carrier tail appeared. The appearance
of the free carrier tail upon addition of the extra dopant indicates that the
individual chain of PPy molecule is metallic. This does not seem to be due
to the intrachain interactions because the free carrier tail was absent before
the addition of extra dopant. The electrical conductivities of PPy films cast
from the solutions used for the UV-Vis-NIR spectra in Figure 7 are plotted
as a function of extra D/M ratio in Figure 8.
The conductivity increased with the extra D/M ratio and the highest
conductivity was obtained when the extra D/M ratio was 0.5. Such a
phenomena is very similar observed with polyaniline when doped with
DBSA 40. It is believed that, as the D/M ratio increases in the polymer
matrix, the polymer chains tend to have expanded structures as a result of
association with the dopant ions. This Ieads to higher conjugation length
and higher conductivity. However, if there are too much of dopant
molecules in the film, the conductivity decreases again due to interchain
separation.
CONCLUSION
The solution properties of polypyrrole (PPy), such as inherent viscosity and

solution spectra were measured. Conditions required to make soluble PPy
.--..
::J
~
Q)
u
c:
t1l
.0
.....
0
1/)
.0
<(
400 600 800 1000 1200 1400

Wavelength (nm)
Figure 5. UV- Visible spectra of PPy solution, (a) in m-cresol, (b) in NMP. The electrical
conductivities of the films cast from these solutions were 1.3 x 10- 4 and -10- 10 S/cm,
respectively.
305
G.l
()
c:
(0
.c
.._
0
1/)
.c
<(
400 600 800 1000 1200 1400

Wavelength (nm)
Figure 6. UV-Visible spectra of PPy solution in m-cresol. (a) 0/M molar ratio = 0.1,
(polymerized at r. U, o (cast film) = 1.6X 10 4 S/cm. (b) 0/M molar ratio 0.1,
(polymerized at O,C ), o (cast film) = 6.0 x 10- 3 S/cm. (c) 0/M molar ratio = 0.2,
(polymerized at r. U, o (cast film) = 1.1 X 10- 2 S/cm.
was investigated. The electrical, thermal, and other physical properties of

solution-cast PPy films was investigated in conjunction to the solution
properties. Inherent viscosity and conductivity values of PPy indicates that
higher molecular weight polymer is obtained with higher oxidantimonomer
ratio. Conductivity and EPR data indicates that soluble PPy consists more
of polaronic forms than insoluble PPy, i.e. oxidation state plays an important
role in dissolution of the polymer. Apparently, solubility of PPy is
determined by the molecular weight, oxidation state, and degree of
crosslinking.
It was found that m-cresol is a better solvent than NMP and the film
cast from NMP solution was more brittle than that cast from m-cresol,
because the polymer chains have more expanded structures in a better
solvent. The conductivity data also support this argument. PPy film cast
from NMP showed very low conductivity ( -10- 10 S/cm) while the film cast
from m-cresol showed a conductivity of 1.3 x 10- 4 S/cm. From
spectroscopic studies, it is concluded that the individual chain of PPy
molecule is metallic and the polymer chains tend to have expanded
structures as a result of association with the dopant ions. This leads to
higher conjugation length and higher conductivity. However, if there are
too much of dopant molecules in the film, the conductivity decreases again
due to interchain separation. In the UV-Vis spectra of the solutions, the
sharp peak at 475 nm and the broad peak at 420 nm were assigned to the
n-->n* transitions of the neutral and doped forms, respectively. The peak
absorption at 933 nm (1.33 eV) seems to arise from the transition between
306
(d)
- ::J
(c)
-i
Q)
u
c:
ro
..c
....
0
(/) (b)
..c
<(
400 600 800 1000 1200 1400
Wavelength (nm)
Figure 7. UV- Visible spectra of PPy in m-cresol. (a) No additional DBSA added. Extra
DBSA added in the solvent to make DBSA/Py unit ratio = 0.48(b), 0.97(c), 1.60(d).
-E
u
..._ .10
(/)
.._.
~
:;
u::J
1:J
c: .05
0
u
0.0 .5 1.0 1.5

Molar ratio of extra-DBSA units to Py units
Figure 8. Conductivity of PPy film cast from the solutions shown in Figure 7. The
highest conductivity is obtained at excess D/M ratio = 0.5.
307
defect states. The conducting form is responsible for the broad absorption
peaks at 420 nm, 660 nm and 933 nm.
Acknowledgements: This work has been supported by Basic Science

Research Institute Program, Ministry of Education, 1996, Project No.
BSRI-95-3411 and by the Korea Science and Engineering Foundation
(Project No. 95-0501-01-01-3).
HEFERENCES
1. R. L. Elsenbaumer, K. Y. Jen, and R. Oboodi, Synth Met., 15; 169
(1986).
2. ]. P. Aime, F. Bargain, M. Schott, H. Eckhardt, G. G. Miller, and R. L.
Elsenbaumer, Phys. Rev. Lett., 62; 55 (1989).
3. ]. Mrdalen, E. ]. Samuelsen, 0. R. Gautun, and P. H. Carlsen, Solid
State Comm., 80; 687 (1991).
4. M. Angelopoulos, G. E. Asturias, S. P. Ermer, A. Ray, E. M. Scherr, A.
G. MacDiarmid, M. Akhtar, Z. Kiss, and A. ]. Epstein, Mol. Cryst. Liq.
Cryst., 160; 151 (1988).
5. S. B. Rhee, M. -H. Lee, B. S. Moon, and Y. Kang, Korea Polymer ],
!; 61 (1993).
6. C. Lee, S. B. Rhee, K. ]. Kim, and H. -]. Joo, Polymer(Korea), 19; 692
(1995).
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Prest, A. G. MacDiarmid, and A. ]. Epstein; Synth Met., 55-57; 977
(1993).
8. Y. Cao, P. Smith, and A. ]. Heeger, Synth Met., 48; 91 (1992).
9. Y. Cao, and A. ]. Heeger, Synth Met., 52; 193 (1993).
10. Y. Cao, G. M. Treacy, P. Smith and A. ]. Heeger, Appl. Phys. Lett., 60;
271 (1992).
11. H. Y. Hwang, S. W. Lee, I. W. Kim, and H. Lee, Synth Met., 69; 225
(1994).
12. I. W. Kim, ]. Y. Lee, and H. Lee, Synth Met., 78; 177 (1996).
13. ]. Y. Lee, D. Y. Kim, and C. Y. Kim, Synth Met., 74; 103 (1995).
14. A. G. MacDiarmid and A. ]. Epstein, Synth Met., 65; 103 (1994).
15. ]. Y. Lee, "Synthesis of Soluble Polypyrrole and Their Properties",
Thesis for MS Degree, Sogang University, 1997.
16. ]. L. Bredas and G. B. Street, Ace. Chem. Res., 18; 309 (1985).
17. ]. L. Bredas, ]. C. Scott, K. Yakushi, and G. B. Street, Phys. Rev. B,
30; 1023 (1984).
18. P. Pfluger, G. Weiser, ]. C. Scott, and B. Street, in "Handbook of
Conducting Polymers", T. A. Skotheim, ed., Marcel Dekker, Inc., New
York, p1369 (1986).
19. ]. H. Kaufman, N. Colaneri, ]. C. Scott, and G. B. Street; Phys. Rev.
Lett., 53; 1005 (1984).
20. ]. L. Soret, Campt. Rend., 97, 1267 (1883).
308
HIGH-SPEED PROTONICS POLYMER -TRANSMISSION AND DISPLAY
Takaaki Ishigure, 2 Akihiro Horibe, 1 Eisuke Nihei, 1 and Yasuhiro Koike 1' 2
1Faculty ofScience and Technology, Keio University

2Kanagawa Academy of Science and Technology
13-14-1, Hiyoshi, Kohoku-ku, Yokohama 223 Japan
2 1-1-1, Fukuura, Kanazawa-ku, Yokohama 236, Japan
INTRODUCTION
Recent developments in the personal computer technologies have greatly expanded the
range of the broadband network applications. Some applications are greatly demanding
high-speed data transmission in the order of mega bit per second (Mb/s) even in the
premise network. We believe that the technologies required in the future broadband
network can falls into following three categories: information "conversion" to digital signal,
high speed "transmission" ofinformation and its "display."
With the growing interest focused on the broadband network systems, optical fiber
network for high speed telecommunication will be required even in such premises area.
Silica base single mode fiber is an ideal medium for long distance communication because
of its high transparency and high bandwidth, while its transparency is minor advantage in
the short distance network. As lots of data distributions or fiber connections are required
in the premises wiring and LANs, low coupling and distribution Iosses must be key issues.
Therefore, we have proposed a large-core, high-bandwidth graded-index polymer optical
fiber (GI POF) for high speed data "transmission" medium, and we succeeded in several
gigabit transmission in 100m GI POF link 1' 2 However, as the GI POF was composed of
poly (methyl methacrylate) (PMMA), its high attenuation of transmission limited the GI
POF link length to approximately 100 m. Recently we proposed the low-loss
perfluorinated (PF) polymer base GI POF 3 which enables more than 300-m transmission
with maintaining high data rate.
Breakthroughs in the bandwidth and attenuation of the GI POF have allowed a new
possibility ofPOF application in broadband network. Display technique is also one ofthe
important technologies for the broadband network systems. We proposed a new brighter
backlight system of the liquid crystalline display (LCD) adopting the highly scattering
Sdence and Teclmology of Polymers and Advanced Materials

5000 .........""""T'"-.-.,......,I""'"T-~r"II"""''I""""'"'"""'T""rr-Tr""l--rT"""""':'
4500
4000
PMMA base
PD polymer base
--.
]'3500
;:o 3ooo
~~=
:::s
5 1500
;:::
< 1000
500
0~~~~~~~~~~~
0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4
Wavelength (!Am)
Figurel. Experimental attenuation spectra ofGI POFs.
optical transmission (HSOT) polymer developed at Keio University4 ' 5 This polymer
material is made of PMMA resin and contains a small amount of other resin consisting of
specified microscopic heterogeneaus structure inside the polymer. Therefore, the incident
beam is efficiently converted to the homogeneaus illumination from the surface of the
HSOT polymer by multiple scattering due to such heterogeneaus structures.
This paper focuses on the transmission and display technologies for the broadband
network systems by newly developed photonies polymers as high bandwidth POF and
HSOT polymer.
GRADED-INDEX POLYMER OPTICAL FIBER
Attenuation of Light Transmission
The attenuation of light transmission is one of the important properties of the optical
fiber. In the case of the silica base single mode optical fiber, less than 0.2 dB/km is
achieved which allows more than hundred kilometers transmission with no repeaters.
However, such low attenuation of single mode silica fiber conies to a minor advantage in
the short distance optical network system because its small core diameter causes serious
coupling loss without accurately fabricated fiber connectors, as mentioned above. On the
other hand, it has been recognized that the attenuation of POF is much higher than that of
silica fiber. The use of PF polymer for fabricating GI POF is one of the solutions of the
high attenuation problem. The attenuation spectra of POFs fabricated by PMMA,
310
perdeuterated (PD) polymer, and perfluorinated polymer are shown in Fig.l. Minimum
attenuation of PMMA base GI POF is 150 dB/km at 0.65-!!ffi wavelength, and several
absorption peaks due to the carbon hydrogen Stretching vibration increase the attenuation at
near infrared region. On the other hand, no such absorption peaks exist in the attenuation
spectra of the PF polymer base GI POF. And it is quite noteworthy that approximately 50
dB/km is achieved at 1.3-!!ffi wavelength, which is much lower than that of PMMA base GI
POF (higher than 10000 dB/km). Decrease in the attenuation of POF at 1.3-!!ffi
wavelength compared to that of PMMA base GI POF suggests the compatibility of the
existing silica fiber and POF networks.
It is already reported that6 the intrinsic scattering and absorption Iosses of PMMA Iimit
the attenuation of PMMA base POF as high as 110 dB/km at 0.65-!!ffi wavelength. We
investigated the theoretical attenuation Iimit of the PF polymer base POF with using the
thermally fluctuation theory and Morse potential energy theory to approximate the inherent
scattering and absorption losses, respectively.
The theoretical scattering loss of the PF polymer was calculated by using the thermal
fluctuation theory which was written as 7,
(1)
where aiso is the isotropic scattering loss (dB/km), o the wavelength of light in vacuum, k
the Boltzmann constant, T the absolute temperature, n the refractive index, and the
isothermal compressibility. In order to estimate the scattering loss by Eq. (1), we propose
the following relationship for calculating the isothermal compressibility at the glass
transition temperature Tg of amorphous polymers.
1) Relation between the intrinsic molecular volume and actual molecular volume.
2) Relation between actual molecular volume and molecular weight between chain
entanglements.
3) Relation between the number of chain atoms between physical entanglements and the
cross-sectional area per polymer chain.
4) Relation between the cross-sectional area per polymer chain and the isothermal
compressibility at a liquid-liquid transition temperature.
Therefore, combining the above relations, the isothermal compressibility f3 at liquid to
liquid transition temperature Tu can be calculated from the intrinsic molecular volume Vint
(Vintis calculated from atomic radius and bond length of constituent atoms.) In order to
estimate the light scattering loss at glassy state, the isothermal compressibility f3 at Tg of
polymer was estimated by using the empirical relation between Tu and Tg (Tu=Tg+76 (K)),
and the value (ll at ru)(dldT) = 4.8xl0"3 K- 1 at Tg<T<Tu). Table I summarizes the
calculated isotropic light scattering loss of the amorphous PF polymer compared with
typical transparent amorphous polymers (PMMA and polystyrene ).
The molecular stretching vibration absorption and electronic transition absorption are
the inherent absorption loss factors. Considering the near infrared use, the effect of the
311
Table l. Calculated isotropic light scattering loss of amorphous polymer glasses at various
wavelengths.
isotropic scattering loss (dB/km)

at 0.65 fA.lTl at 0.85 fA.lTl at 1.3 fA.lTl at 1.5 fA.lTl
PF Polymer 4.2 1.45 0.26 0.15
PMMA 8.8 3.01 0.55 0.31
poly styrene 18.3 6.26 1.14 0.65
electronic transition absorption can be negligible. The molecular stretching vibration

absorption loss was calculated by using Morse potential energy theory8' 9 The energy Ievel,
G(v), belonging to the vibrational absorption between two atoms can be written as
2
G(v)=v 0(v+ 112)-vox(v+ 112) (2)
where v=l,2,3 .. .is the quantum number, x the anharmonicity constant, and vo the original
vibration between only two atoms. Then the v-th harmonic vibration, Vv, becomes
(3)
Here, V1 denotes the fundamental vibration in real polymer and v1 = vo when x = 0. The
value of X for carbon-hydrogen (C-H), carbon-deuterium (C-D), and carbon-fluorine (C-F)
vibrations are 1.9 X 102, 1.5 X 102, and 4.0 X 103, respectively. Therefore, the original
vibrations peaks of C-H, C-D, and C-F bonds in real polymerexistat wavelengths of 3.390,
4.484, and 8.000-f..Ull, respectively. Subsequently, the overtone positions of C-H, C-D, and
C-F Stretchingvibrations are calculated by Eq. (3). Absorption Iosses of these overtones
in the amorphous polymer were calculated by the Groh's method 10 where the empirical
result of 3000 dB/km for 5 th overtone of C-H bonding in PMMA was used. Figure 2
shows the calculated absorption loss of the PF polymer due to the C-F stretching vibration
compared with C-H in PMMA and C-D in PD polymer. It is quite noteworthy that the
absorption loss ofPF polymer at less than l-f..Ull wavelength region is almost zero (less than
1o-3 dB!km).
Total attenuation spectrum of the PF polymer base POF was estimated by the
summation of scattering and absorption losses. The result is shown in Fig. 3. lt is
indicated that the attenuation Iimit of the PF polymer base GI POF at 1.3-f..Ull wavelength is
approximately 0.3 dB/km which is comparable with that of silica fiber (0.2 dB/km).
Bandwidth
1t is weil known that the quadratic refractive index distribution enables to decrease the
modal dispersion and that usually an optimal refractive index profile to maximize the fiber
bandwidth depends on the fiber material and used wavelength. As shown in Fig. 1,
312
lxl0 8 I
I
I
2.
V CH V CD
2

,....._
E
lxl0 6 I
I
-- I I e

-
~
lxl0 4
a:l
"'0
c 100
v.m_.; lej
I
0
-~
1 ~ I
::I
ca)
t::
- - -----1- - -
.. 11
I 1
I
L- - - -
I
- - - - -
I dB/km
- - - - -
< I 1 I
0.01 I 1 I
-~ I 1 I e C-H
I 1 I
5l lxl0- 4
.c I 1 I C-D
< I I
I 1
I
I
V CF
IO C-F
lxl0-6 I~ I
I 1 I
I
lxl0-8 ~~~~~.L--~~~~~~~~--~~~~~~~~
0 0.5 1.5 2 2.5 3 3.5
Wavelength (!lm)
Figure 2. Absorption attenuation due to different C-X vibrations vs. spectral overtone positions.
0.1 L-_.____.1_.....__.___._.......___.___._....._....J
0.6 0.8 1.0 1.2 1.4 1.6
Wavelength (!lm)
Figure 3. Calculated attenuation spectrum of PF polymer base POF.
extremely low attenuation of the PF polymer base GI POF in visible to near infrared region
allows to adopt several kinds of light source. Therefore, quantitative investigation of the
bandwidth characteristics of the GI POF is necessary for designing the refractive index
profile. The refractive index profile ofthe GI POF was approximated by the power law
of Eq. (4). The profile of the refractive index was evaluated by the parameter g called
index exponent.
313
(4)
(5)
Here, n 1 and n2 are refractive-indices at center axis and cladding of the fiber respectively,
"a" is radius of the core, g is index exponent, and A is relative difference of the refractive-
index.
Optimum refractive index profile was numerically investigated by considering not
only the modal dispersion but also the material dispersion. The material dispersion of the
POF was estimated by measuring the wavelength dependence of the refractive index of
polymers composing both core and cladding. Measured indices are fitted by Seilmeier
equation shown by Eq. (6). The material dispersionwas estimated based on Eq. (6) and
(7).
(6)
D = -(."A.)(d'n)L (7)
mit C df...'
where n is the refractive index of polymer sample, Ai is the oscillator strength, Ai the
oscillator wavelength, f... the root mean square spectral width of the light source, ).. the
wavelength of transmitted light, C the velocity of light in vacuum, and d2n/d"A.2 the second-
order dispersion, and L length of the fiber.
10 G
Both modal and material
dispersions were considered.
--..,
:0
CL)
l;:j lG
~
.....
;::a
Only modal dispersion was considered.
100M1
.5 2.0 2.5 3.0 3.5 4.0
Index Exponent g
Figure 4. Relation between the index exponent g and the bandwidth of I 00-m PMMA base GI POF at 650-nm
wavelength. e :Experimental
314
lOOG
(C)
..-..
---"'
.0
Q)
li:i 10 G
~
......
~
lG
2 2.5
Index Exponent g
Figure 5. Relation between the index exponent and possible bit rate of 100-m PF polymer and partially
fluorinated polymer base GI POF link. Source spectral width was assumed to be 2-nm. (A): PF polymer
base GI POF link at 650-nm wavelength. (B): PF polymer base GI POF link at 780-nm wavelength. (C): PF
polymer base GI POF link at 1.3-IJlll wavelength. (D): Partially fluorinated polymer base GI POF link at 650-
nm wavelength. (E): Partially tluorinated polymer base GI POF link at 780-nm wavelength.
Figure 4 shows the relation between the possible bit rate and refractive index profile of
the PMMA base GI POF calculated by the WKB method, 11 ' 12 in which both modal and
material dispersions were taken into consideration at 650-nm wavelength. Here, the light
source was assumed to be an LD with a 2-nm of spectral width. lt is indicated that the
!arge material dispersion of PMMA at 650 nm Iimits the maximum bit rate to
approximate1y 3 Gb/s. A good agreement is shown between the experimental data and the
theoretical curve. On the other band, the relation ofthe bit rate and index exponent ofthe
PF polymer base GI POF with the low material dispersion is shown in Fig. 5 compared to
that ofthe partially fluorinated polymer base GI POF. As the partially fluorinated polymer
also has the low material dispersion, approximately 10 Gb/s can be transmitted in 100 m
link even at 650-nm wave1ength. Extremely low material dispersion of the PF polymer
base GI POF allows higher bit rate transmission than the partially fluorinated polymer base
GI POF. Furthermore, the low intrinsic absorption loss of the PF polymer base GI POF
makes it possible to adopt 1.3-!Jlll wavelength as described before. Since the material
dispersion decreases with an increase of wavelength, the possible bit rate in 100-m link
achieves to 100 Gb/s.
Bandwidth characteristics of the PF polymer base GI POF were investigated by a
time-domain measurement method. A narrow pulse shaped input light signal was injected
to the 100-m length PF polymer base GI POF, and the outputpulse was detected by the
sampling head. The schematic representation ofthe measurement system is shown in Fig.
315
Pulse Generator Lens
HalfMirror N.A.~0.3
"-""'~- ~J+
650nm
780nm
-
850nm
1300nm
rigger
OOS-01
Sampling Oscilloscopc
Figure 6. Schematic representation ofthe time-domain bandwidth measurement system.
6. Used wavelengths were 0.65, 0.78, 0.85, and 1.3 f.llll The result at 1.3-f.llll
wavelength is shown in Fig. 7. Measured index profile of the measured fiber at 0.59-f.llll
wavelength is shown in Fig. 8. Although slight amount of pulse spread is observed,
bandwidth of the GI POF estimated by Fourier transform was approximately 2 GHz at all
wavelengths. Approximated index exponent shown in Fig. 8 is 2.5, which is deviated
from the optimum value of 2.17 at 1.3-f.llll wavelength. Calculated wavelength
dependence of the bandwidth of the PF polymer base GI POF with various index values is
shown in Fig. 9. Experimental values are also plotted in Fig. 9. Little wavelength
dependence ofthe bandwidth was observed, which is weil fitted to theory.
Figure 10 shows the high-speed POF network concept. As shown in Fig. 10, a
required fiber length in the premises area or in buildings may be 300"-'500m. Recently
622 Mb/s data rate which is one of the standards of ATM LAN has been interested because
it is suitable to transmit the information of CATV and clear moving pictures. In Table 2,
we summarized the applicability of several media to the data link in which 622 Mb/s of
data rate has to be transmitted for Ionger than 100 m length. The GI POF could be a
promising candidate for such purposes.
Advantage of Large Core of POF
Compared to the single mode glass fiber, multimode GI glass fiber whose core
diameter is generally 50-65 f.U11 offers high tolerance in such couplings. In the multimode
316
Table 2. Characteristics f propsed physicallayers fr shrt distance network (100-300 m)
in which more than 622 Mb/s data rate is required.
G lass optical fiber POF ' Copper cable

SM GI GI SI twist-pair Co-ax
Attenuation 0 6 0 0
Bandwidth 0' X X 6
Coupling X 6 6
Handling 6 6 6
End termination 6 6 0
EMI 2 X 0
Cost of medium 0 6 6
System cost X X 0 6
Reliability 0 0 0
: Best 0: Good 6: Worse X: Worst
1 Modal noise degrades the bit error rate performance. 2 Electromagnetic immunity
oUlOU
t
nDut
500 ps/div
Figure 7. Pulse spread through IOO-m PF polymer base GI POF at 1.3-[AJ11 wavelength.
317
1.35
~ 1.345
.::
d)
]
~ 1.34
1.335
0 0.5 1
Normalized Radius
Figure 8. Measured index profile (solid line) ofthe PF polymer base GI POF compared tothat approximated
by a power-law equation (broken line).
IOOG
,..-.,
0
e
0
N
::c 10 G
-
'-'
..s::
" '0
~
"'0

CO 1 G
CO
"'0
t""l
I
100 M ........,_._......_......."_._........_......."~........_........._.~_._........._.__,
0.4 0.6 0.8 1 1.2
Wavelength (!ID1)
Figure 9. Wavelength dependence ofthe possible bit rate of I 00-m PF polymer base GI POF link.
e: experimental.
glass fiber link, it was reported that 13 the modal noise suffered the network design. The
modal noise is caused by the interference among the transmitted modes when the light
source with high coherency is used. In order to eliminate the modal noise effect, precise
coupling technology is also required in the multimode silica fiber network, which affects
the total cost ofwhole system.
318
llnri/Cinl.ll ( ahl1 ( .'1111 ml
D
I II - I llllll \I hp
.,,
IOICf'\:Uillli.."Cl io n
MI ibcr
Figure 10. High-speed LAN concept by the GI POF.
10-4
...
u
;::
0::
510- 6
\
0
\
t:
tJJ
iiSI0-7
10-8
10- 9
I

I
10- 10 0
\
10- 11 \ 0
'o- 12 .__~.__.__..._~......_~..._-,..._~_._~\_.__.__J
-26 -24 -16 -14 -12 -10
Receiver Po\\Cr (dBm)
Figure II. Modal noise eiTect on bit crror rate in PMMA base GI POF link.
Misalignment: GI POF e: 0 l1fTl : 100 fllll .6. :200 um GIglassfiber
0: 0 l1fTl 0: I 0 1-1m [JJ : 20 l1fTl
319
It was experimentally confirmed tha~. complete reduction of the modal noise was
achieved in the large core GI POF link. Effect ofthe modal noise was investigated by the
bit error rate characteristics of both multimode glass fiber and GI POF. The result is
shown in Fig. 11. Signal rate was 156Mb/sand the source width was 1 nm. In the case
of the multimode glass fiber, even when a I 0-f..Ull misalignment is caused, bit error rate
degradation is observed. Furthermore, 20-f..Ull misalignment causes a significant
fluctuation of the output signal and consequent bit rate degradation was observed. On the
contrary, in the case of the GI POF with 600-f..Ull core diameter, no degradation of bit error
rate is observed even when more than half of the core diameter is misaligned. This result
is attributed to a !arge number of modes transmitted in the GI POF. The signal to noise
ratio (SNR) due to the modal noise is described by Eq. (8) 14
(8)
SNRmodat = ~(M + 1)___2[_
1-1]
where lJ is the connection loss rate and M is the total mode number as shown by Eq. (9) in
the case ofthe GI POF with power law ofthe form as Eq. (4).
(9)
It was assumed that g = 2, /... = 0.65 f.Ull, n 1 = 1.5, and L\~L\n/n,=O.Ol. Total mode number
M transmitted in the GI POF and subsequent SNRmodal, were calculated and listed in Table 3.
It is noteworthy that the SNR is remarkably improved with increasing the core diameter of
the fiber. Therefore, the modal noise effect can be neglected in the !arge core GI POF link.
These results indicate that a low-cost optical devises such as injection-molded polymer
connector and coupler can be adopted although they can cause 50-f..Ull of misalignment.
Table 3. Relation between the core radius ofthe GI POF and SNR due to the modal noise.
a (fun) M Normalized SNR

50 657 I
500 65700 10
1000 262800 20
HIGHLY SCATTERING OPTICAL TRANSMISSION POLYMER
We have proposed Highly Scattering Optical Transmission (HSOT) polymer as a light

pipe for LCD backlightsY This polymer material contains specified microscopic
320
20mm (J
(a) PMMA
20mm (J
(b) HSOT
Figure 12. Light homogenization effect ofHSOT polymer.
heterogeneous structures inside the polymer. Therefore, incident light is effectively

converted to the uniform illumination from all over the surface of the HSOT plate without
absorption. This phenomenon is based on the multiple light scattering effect in this
polymer material. Figure 12(a) and (b) show cylinder bulks of poly methyl methacrylate
and HSOT polymer to which a Iaser beam is injected. The beam injected to the HSOT
polymer is scattered inside the polymer, and illuminates uniformly from the surface. This
light homogenization effect caused by multiple light scattering phenomenon inside the
HSOT polymer is solved by the HSOT modeling simulation based on the Monte Carlo
method and the Mie scattering theory 15 "16 As the result, illumination property from the
polymer can be controlled by changing the heterogeneous structure inside it.
HSOT modeling simulation
Scattering intensity profile from a single particle is calculated by the Mie scattering
theory. Light scattering intensity profiles of particles with various diameters as shown in
Figure 13 are exactly calculated by the Mie theory.
Multiple scattering phenomenon
In the HSOT polymer optimizing simulation, Monte Carlo method is applied to

calculating routines of the photon path length, scattering angle, reflection and refraction.
The calculation method is shown as follows.
321
Incident SOOnm
I
2000nm 4500nm
I
Figure 13. Light scattering intensity profiles of particles with shown diameter.
(a) (b)
Figure 14. Multiple light scattering. (a):Experimental result (b):Calculated result
Figure 15. Loci ofphotons in 4 inches HSOT polymer backlight
Scattering angle "8 " and photon path length "L " are calculated by the following
equations.
8 = F-' (randoml) (10)
F(8) = k
II
I(a) I (, 11 (11)
322
L = -ln(random2) I nr 2 CK (12)
Here, randoml and 2 are random number, r is particle radius, C is particle
concentration, K and I are scattering efficiency and scattering intensity profile of
one particle respectively, which are calculated by Mie theory.
Probability density distribution function F(e) of scattering angle is defined by the
previous light scattering intensity profile obtained by the Mie Scattering theory. Moving
directions at the each scattering point are determined by using both the function and
random number. Photon path lengths are determined by the scattering efficiency defined
in the Mie scattering theory. Reflectivity is estimated from incident angle of ray and the
refractive index of polymer. Many photons are traced in this calculation. This Monte
Carlo simulation to analyze multiple light scattering phenomenon is applied to examine the
photon behavior inside the HSOT polymer.
Simulation of multiple scattering in HSOT polymer
Figure 14 (a) shows the HSOT polymer (8.4inches, Smm thickness) injected Iaser
beam (f...=632.8nm) from the left side, and (b) shows its simulation result under the same
conditions. In Figure 14 (b ), each dot shows the point where a photon came out from the
HSOT polymer surface. This figure shows a good agreement between experimental and
simulation results.
Application to the LCD backlight
Lower power consumption and higher quality illumination of the LCD backlight are
demanded strongly for the recent portable information terminal with long battery operation
3500
3000
2500 I Calculated
~
,
=
<Ii
...... 2000
8
;
.s
s
1500 -i Experimental
A
~ 1000
'
500 '\\ I
0 ~ ......_ ~ ~
-90 -60 -30 0 30 60 90
Angle I degree
Figure 16. Angular dependence ofluminance ofHSOT polymer
323
time. Therefore, this material which has no absorption inside it and illuminates light
uniformly is applied to the light pipe ofthe LCD backlight Figure 15 shows a calculation
result of the HSOT modeling simulation for 4 inches backlight system. In this figure,
each photon which is injected to the edge in accordance with actual intensity profile of the
lamp comes out from the surface of the backlight through various ways. The circles in the
figure show output points of photons.
In this simulation, not only uniformity but also intensity profile of luminance is
exactly analyzed by summing photons whose number is 10 5 Figure 16 shows the
simulation result. The definition of the angle in the figure is that 0 deg. is vertical direction
to the surface and 90 deg. is a direction parallel to the surface forward. Although previous
LCD backlights were designed based on the empirical estimate, we can control the HSOT
polymer as occasion demands by using this simulation.
LCD backlight system
Figure 18 shows construction;; of the LCD backlight systems. All conventional edge-
light type backlight systems (shown in Figure 17 (a)) have consisted of a transparent
PMMA plate with dot printing pattems as a light pipe and other surrounding Iight-
controlling devices. The purpose of our work is to make a brighter LCD backlight by
film
polymer plate
(a) Conventional Backlight System
Prism film fitted for HSOT light pipe

/OT polymer plate
Lamp
(b) HSOT Backlight ystem

Figure 17. Structure ofbacklight systems.
324
using the only HSOT polymer plate. In the conventional system, the complicated dot
printing pattem is necessary at the bottom of the transparent light pipe to obtain uniform
luminance. Further, a diffuser film is indispensable to hide the dot printing pattem. On
the other hand, the backlight system consisted of the HSOT polymer plate is shown in
Figure 17 (b ). In the HSOT backlight system, although the light contraHing devices for
forming uniform luminance are not necessary, the luminance from all over the surface of
the light pipe is almost uniform. It is suggested that high-order scattering inside the
polymer would make the luminance from the surface uniform. So, the backlight system
can become much simpler by using the HSOT polymer.
The HSOT polymer was commercialized as a backlight of TFT Liquid Crystal
Portable TV from CASIO in November 1996.
The illumination property of the conventional backlight system is shown as Figure 18
(C). That ofthe brightness enhanced type conventional system is shown as Figure 18 (B).
Luminance of our proposed HSOT system (curve (A)) has two times and 50% brighter than
(C) and (B), respectively. As shown in Figure 19 (B), brightness enhanced type
conventional one has hollows (pointed out by arrows) near 40 deg.. lt is confirmed that
the hollows degrade visual quality on the LCDs. The HSOT polymer backlight system
has gently-sloping intensity profile (shown in Figures 18 (A), 19 (A)). Therefore, it is
clear that the HSOT polymer backlight system is suitable for the recent wide-viewing-angle
LCDs. Further, as shown in Table 4, it was confirmed that the illumination intensity is
about 50 % stronger than that of the brightness enhanced type conventional backlight
system. Consequently, the backlight system using the HSOT polymer is superb in terms
of power efficiency.
CONCLUSION
Perfluorinated polymer provided great advantage in the infrastructure of the POF

network. Low intrinsic absorption loss of the PF polymer enab1ed the drarnatic decrease
in the attenuation of GI POF that is as low as 50 dB/km at 1.3-!illl wavelength. The
theoretical attenuation Iimit of the PF polymer base POF was estimated by the aspects of
intrinsic scattering and absorption losses. The minimum attenuation of 0.3 dB/km of the
PF polymer base GI POF indicates that the POF link is possible to cover several kilometers
Table 4. Illumination intensity

Brightness enhanced type
Conventional system HSOTsystem
Illumination intensity 3720 5750
(Iux
Components Prism Exclusive prism
Prism HSOT polymer light pipe
Diffuser Silver reflector
Transparent light pipe
White reflector
325
10000
N
E 8000
.._
-c
.._u 6000
0)
u
~ 4000
E 2000
::I
....l
0
-90 -60 -30 0 30 60 90
Angle I degree
Figure 18. Illumination property in right angle direction to the lamp. (A) HSOT Plate + Special Prism (I
Sheet) (B) Conv. Plate + Conv. Prism (2 Sheets) (C) Conv. Plate + Conv. Prism (I Sheet)
,...,
::> , ........
$
8c:: 0.8 (A)/
"' 0.6
::l
] 0.4
.!:l
~ 0.2
z0 0 ....__-_ _ _ _ _ _ _ _ _ _ _ _ ___..
-90 -60 -30 0 30 60 90
Angle (degree)
Figure 19 Illumination property in parallel dircction to the lamp
without repeaters. With increasing the link length, the pulse distortion due to the material
dispersion comes to Iimit the bit rate of POF link. It was clarified that the low material
dispersion of the PF polymer compared with PMMA and silica allows more than I 0 Gb/s
transmission even in 1 km link. Furthermore, no modal noise effect was observed even
when 200-filll misalignment was occurred at the fiber-to-fiber coupling because a !arge
number of modes are transmitted in the )arge core GI POF.
Illumination principle of the LCD backlight using HSOT polymer was explained in
detail. The multiple scattering of the HSOT polymer was analyzed and optimized by
using the HSOT modeling simulation. For the backlight system with 2.5 inches, the
luminance is two times brighter than that of conventional transparent PMMA plate systems.
Further, surrounding devices such as diffuser film and dot printing pattern which are
indispensable in conventional ones are not necessary in our systems. The backlight
system using the HSOT polymer is superb in terms of power efficiency.
We described the possibility of the application of photonies polymers in the broadband,
multimedia network in this paper focusing on two categories, "transmission" and "display."
We believe that further exploitation of photonies polymer materials becomes more
necessary for realization of such broadband premises network.
326
REFERENCES
1. Y. Koike, T. Ishigure, and E. Nihei, High-bandwidth graded-index polymer optical fiber,"

IEEEJ. Lightwave Techno/. 13: 1475 (1995)
2. T. Ishigure, E. Nihei, S. Yamazaki, K. Kobayashi, and Y. Koike, "2.5 Gb/s 100 m data
transmission using graded index polymer optical fibre and high speed Iaser diode at 650-
nm wavelength," Electron. Lett. 31: 467 (1995)
3. Y. Koike, Progress of Plastic Optical Fiber Techno1ogy, Proceeding of ECOC '96. voLl:
41 (1996)
4. A. Horibe, M. Izuhara, E. Nihei, Y. Koike, Brighter backlights using highly scattered
optical-transmission polymer, J ofSID. 3/4: 169 ( 1995).
5. A. Horibe, E. Nihei, Y. Koike, Bright LCD backlight using high-scauering optical-
transmission polymer, SID 96 Digest: 577 (1996).
6. T. Kaino, M. Fujiki, and K. Jinguji, Preparation of plastic optical fibers, Rev. Electron.
Commun. Lab. 32:478 (1984)
7. Y. Koike, S. Matsuoka, H. E. Bair, Origin of excess light scattering in poly(methyl
methacrylate) glasses, Macromolecu/es. 25:4809 (1992)
8. Y. Koike, High bandwidth, low loss polymer fibers, Proceeding of ECOC'92. Vol.2: 679
(1992)
9. T. Ishigure, E. Nihei, Y. Koike, C. E. Forbes, L. LaNieve, R. Straff, H. A. Deckers, high-
bandwidth graded-index polymer optical fiber for near infrared use, IEEE Photon.
Techno!. Lett. 7:403 (1995)
10. W. Groh, Overtone absorption in macromolecules for polymer optical fibers,
Makromol. Chem. 189:2861 (1988)
11. J. W. Fleming, Material and mode dispersion in Ge02 B203 Si02 glasses, J. Am. Cer.
Soc. 59: 503 (1976)
12. R. Olshansky and D. B. Keck, Pulse broadening in graded-index optical fibers, Appl.
Opt. 15:483 (1976)
13. R. E. Epworth, The phenomenon ofmodal noise in analogue and digital fiber systems,
Proceeding ofECOC '78, 492 ( 1978)
14. A. M. J. Koonen, Bit-Error-Rate degradation in a multimode fiber optic transmission
link due to modal noise, IEEE J. Sei. Ar. Com. 4: 1515 (1986)
15. I. Lux, L. Koblinger, Monte Carlo particle transport methods: Neutron and photon
calculations, CRC Press, New York (1991)
16. G. Mie, Beitrge zur Optik trber Medien, speziell kolloidaler Metallsungen, Ann.
der phys. 25: 377 (1908)
327
HIGH-DENSITY DISC STORAGE BY
MULTIPLEXEn MICROHOWGRAMS
Stefan Diez, Robert Elschner, Rainer Macdonald, Roland Schutz,

Andreas Wappelt, and Hans Joachim Eiehier
Optical Institute of the Technical University of Berlin

Strae des 17. Juni 135, 10623 Berlin, Germany
INTRODUCTION
High capacity storage systems with fast data access are essential prerequisites for
future multimedia services. For many applications, optical memories such as Compact
Discs (CD) or Digital Veratile Discs (DVD) are prefered to magnetic high density
systems due to the low production costs and high portability. However, optical disc
systems store the data two dimensionally and a further increase in the storage capacities
is only expected when blue laser diodes become commercially available and dual layer
systems are developed. On the other hand, three dimensional storage systems have been
proposed on the basis of holographic recording techniques. These systems use either
photorefractive crystal cubes 1 or layers of photopolymers 2 to record complete digital
data pages. Experiments demonstrate that holographic methods allow ultra high storage
capacities but they need complex write and read-out devices, a fact which has up to now
impeded the design of commercial products.
MULTIPLEXED MICROHOLOGRAMS
In cantrast to the formerly discussed techniques, we investigate a holographic

memory that combines the advantages of both the bitwise storage from existing disc
systems and the three dimensionality known from holographic approaches. For this, an
optical disc substrate is coated with a photosensitive material (e.g. photopolymers) and,
instead of storing the information by data pits on the surface, volumetric microholograms
are induced to vary locally the reflectivity of the disc. In order to create the
microholograms, a laser beam is focused within the photosensitive layer - see Figure I. A
Scmce anti Teclmology of Polymers anti Advanced Materials

Iaser ource - - ---j
focussing optics
substratc
Figure 1. Schematic diagram of the setup used for data recording. A focused Bragg grating is inscribed
into the photosensitive material by means of a standing wave. A similar setup (without the reflecting
unit) is used for data retrieval, where the local reflectivity of the disc is probed by a focused read-out
beam. Multiplexing requires different wavelengths and directions of the write and read-out beams.
reflecting unit underneath the disc reflects the bearn and generates a standing wave where
incorning and reflected bearn overlap. As a result an index grating (Bragg grating) is
inscribed into the material.
As shown in Figure 2, the generated rnicroholograrns are strongly confined and
therefore can be arranged very close to one another. The surface storage density S A is
estimated by SA = 1 bit/4 w 2 , where w is the radius of the Gaussian bearn in the focus.
The depth of the holograrn is in the order of twice the Rayleigh length z0 Using
photopolymers (e.g. DuPont HRF-700), reflectivities of about 95% are expected for CD-
like focussing ( 2w = 1.5 1-Jm), if the theory of Kogelnik 3 is applied.
By means of holographic multiplexing, a certain nurober of rnicroholograrns can be
stored at the sarne location in the photopolymer. If m'- different wavelengths and me
different angles are used, the total storage density is given by S = m._ 171e S A However, it
should be noted that the multiplexing rates cannot be chosen freely since an increase of
the surface storage density S A diminishes the achievable multiplexing rates m._ and m 9
Gaussian beam
photosensitive
layer
microhologram - - - -
2w
Figure 2. Schematic diagram of the structure of a focused microhologram within the photosensitive
layer. For CD-like focussing (lateral focus dimension 2W=l.S J.IID), the depth of the hologram is about
7.6IJIII..
330
"'e 60 Wavelength and Angle
e---
:::l.
Multiplexing ~
~ 40
"(ij
c
Q)
Cl
Q)
Cl
~
20
j / Wavelength Multiplexing
0
U5 j j /Angle Multiplexing
0~
0,5 1,0 1,5 2,0
Focus Radius (IJm)
Figure 3. Storage density as a function of the focus radius, assuming a total range for wavelength
multiplexing of 630 ... 700 nm, a total range for angle multiplexing of 80 degrees and an index of the
photosensitive material of W= 1.5 J.llll.
The reason is, that both spectral and angular resolution of the inscribed Bragg gratings
decrease with a reduction of the focus radius. Figure 3 depicts the maximum storage
densities for the different multiplexing techniques as a function of the focus radius.
CONCLUSION
A considerable increase in the storage density can be achieved, if wavelength and

angle multiplexing are employed simultaneously. For a disc the size of a CD, storage
capacities in excess of 40 GByte per disc and data transfer rates of about 50 Mbit/s are
estimated.
REFERENCES
1. J. F. Heanue, M. C. Bashaw, and L. Hesselink, Science 265, 749 (1994).

2. A. Pu, D. Psaltis, Appl. Opt. 35, 2389 (1996).
3. H. Kogelnik, Bell Syst. Tech. J. 48, 9 (1969).
331
POLYMERSAND ORGANIC-INORGANIC HYBRIDS
FOR SECOND-ORDER NONLINEAR OPTICS
Kwang-Sup Lee, 1 Sung-Bae Lee, 1 Kyung-Bok Lee/ Hong-Ku Shim, 2

Ki-Jeong Moon, 2 Han Young Woo, 2 Choon Sup Yoon3 ,
and Yoo Hong Min
1 Department of Macromolecular Science

Hannam University
Taejon 300-791, Korea
2 Department of
Chemistry
.KAIST
3 Department
of Physics
KAIST
INTRODUCTION
Poled nonlinear optical (NLO) polymers have been the great interest for photonies
applicationsY Using such materials, electro-optic modulators with a 100 GHz bandwidth
have already been realized at the laboratory leveV and a number of passive and active
photonie devices also sucessfully fabricated. 4-6 From the beginning stage of the NLO
polymeric materials research in the middle of 1980's, thermal relaxation and low values of
NLO coefficients of chromophores in these systems were the major obstacles for practical
applications. Since then there have been continuous efforts toward reducing thermal
relaxation and increasing NLO activity of the materials. In recent years, in addition to
improving these two fundamental factors, research was also extended to enhance optical
quality, processibility and chemical stability of NLO materials, which are the properties
closely related to those of matrix polymers. 78
Recently we developed new polyurethanes with covalently linked side chain moieties
containing highly active NLO chromophores. The main reason we selected the polyurethane
as the matrix was that an extensive formation of hydrogen bonds between the urethane
linkage is expected, thus increasing the rigidity of the matrix and preventing the relaxation
process of the oriented NLO chromophore dipoles. In addition, we also develcped thermally
stable NLO polyetherimide(PEI) and organic-inorganic hybrid materials with excellent long-
term. stability. In these systems, the NLO chromophores were covalently bonded to PEI or
silica glass matrix with good optical quality due to their amorphous state.
As NLO function units, we took the hemicyanine- or cyanovinylene-type chromo-
phores with high hyperpolarizability. It is well-known that the nonlinear activity of

Edited by P. N. Prasad et al., Plenum Press, New York, !998 333
hemicyanine is strongly dependent on the properties of the counter ions, and it usually
increases when bulky conter ions are used. 9 ' 10 Thus, we have chosen the tetraphenylborate
anion as the counter ion for the hemicyanine-type chromophore. In addition to this,
azobenzene chromophores having cyanovinyl units as a strong electron-acceptor were also
introduced into the polyurethanes or PEI to obtain the high NLO activity materials.
In this article, we report the synthesis and characterization of polyurethane-, PEI-, and
silica-based NLO systems. We also present the details oftheir optical second-order activity
in terms of electric field poling, and temporaland thermal stability.
LINEAR POLYURETHANES
Polyurethanes containing NLO active chromophores were synthesized by the reaction

of diols, which possess azomethine-, stibene- or azo-type chromophores, with toluene-2,4-
diisocyanate or 4,4' -diisocyanato-3,3'-dimethoxydiphenyl. The synthetic routes are descri-
bed in Scheme l.
Scheme 1 OCN~NCO
~H3
HO......_........N~OH
1G-Bct'Cf OMA< or DMSO
PU2
:~..cH~o, : PU1-AZ
X c -CHJ. : PU.CNMS
X -C(CH,), : PU.CNBS
: PU.OCN
The structures of the polymers were confirmed by the conventional spectroscopic

techniques such as IR, 1H-NMR and UV/vis. The results obtained were consistant with the
proposed polymer structures. The UV/vis absorption maxima, A max, due to a 7r - 7r *
transition ofthe samples were found at 459 - 500 nm (Table l). Allpolymers were readily
soluble in dimethylformamide (DMF) and its mixture with cyclopentanone. From DMF/
334
cyclopentanone solutions ofthese polymers, good optical quality fi1ms could be cast on glass
substrates by spin coating.
DSC analysis showed the glass transition temperatures (Tg) in the range between
121 Oe and 159 Oe for the linear polyurethanes. No melting points were detected in these
polymers, which indicates that the polymers are amorphous. Thermogravimetrie analysis
{TGA) results showed the initial decomposition occurring at around 225 - 257 Oe under
N2 atmosphere. The lowest decomposition temperature found insalt-type polymer, PU1-C4B,
is due to the presence of tetraphenylborate conter ion. This result is supported by the fact
that the calculated weight loss corresponded weil with the fraction made by the molecular
weight ofthe polymer structural unit.
In order to determine the macroscopic second-order susceptibility X (2 ) of the
materials, the samples were removed from the poling stage after the poling was completed.
The angular SHG dependence of poled materials was recorded and then compared with the
values obtained from the 1 mm thick, Y-shaped quartz plate (du=0.5 prnN: 0.8 x 1010 esu).
After optimizing the poling conditions, we were able to produce PUl-AZ, PU1-C4B, PU1-
CNMS, PUI-CNBS and PUI-DCN film with x<2l values of20, 128,57,57 and136 prnN,
respecti-vely {Table 1).ll-IS The high x <2l value of PU1-C4B seems to prove the earlier
prediction about a possible enhancement of the nonlinear second-order properties in organic
material;; triggered by utilizing the strong electron-accepting nature of the stilbazolium
salt. 13 Also, very high optical nonlinearity of PU1-DCN comes from the function of
dicyanovinyl group as a strong electron acceptor. The second harmonic generation (SHG)
signal of a poled PU1-C4B, stored at room temperature, was recorded periodically over a
period of 33 days. The decay of SHG signal is negligible within the bounds of experimental
error (Figure 1). Moreover, the poled sample retained almost 70% of its initial optical
activity after being exposed for 100 h to the temperature 100 Oe (Figure 2). This result
indicates the stabilizing function of the hydrogen bonds between the neighboring
polyurethane chains, hence preventing the relaxation of oriented mo1ecular dipoles. Good
thermal and temporal stabi1ities were also observed in the PU-CNMS, PU-CNBS and PU-
DCN samples.
CROSSLINKED POLYURETHANES
In general, for crosslinked polymer systems, the optical Iosses caused by the limited
uniformity ofthe crosslinking reaction are significant. In order to circumvent these problems,
Tab1e 1. Physical data and x <2l coefficients for second-order NLO polyurethanes
X (2)
Sampie Tg A max n{TM)
(prnN) (X 107esu)
PUI-AZ 137 460 1.7013 20 0.5
PU1-C4B 121 484 1.7410 128 3.1
PUI-CNMS 140 476 1.8607 57 1.4
PU2-CNMS 127 490 1.8712 50 1.2
PU1-CNBS 153 459 1.7178 57 1.4
PU2-CNBS 131 500 1.7208 40 1.0
PU1-DCN 159 489 1.7799 136 3.3
PU2-DCN 159 496 1.7572 120 2.9
335
0 3 6 8 11 14 17 19 22 25 28 31 33
Time[days)
Figure 1. Temporal stability ofpoling alignment at room temperature.

5
E
=..
C'1 4
->
...-
~
3 8 0
-
0
0 0
2
E o SG DANS diol
.9: SGMHENS
....~ SGBPTP
o~--~--~----~--~--~----~--~~
0 200 400 600 800 1000 1200 2400 2600
Time (hours)
Figure 2. Temporal stability ofpoling alignment at 100C.
novel crosslinking reaction techniques proposed by Park et al. have been investigated. 16 In
our method a liquid polymer with high flow property, poly[(phenyl isocyanate)-co-
formaldehyde] (PPIF), which has one crosslinking site located at every pher.ylene moiety,
was used in order to improve the uniformity of the crosslinking reaction between the
polymer chains and hydroxy-functionalized NLO chromophores. The synthetic routes of the
crosslinked polymers with three different bonding sites are shown in Scheme 2. Dried
monomers V-OH, P-OH and VP-OH were reacted with the liquid polymer PPICF. The
isocyanate/hydroxy (NCO/OH) ratios were the same. Highly viscous liquid PPICF was
diluted to about 50 wt.% for microsyringe handling. The monomers were dissolved in
solvent (DMF:cyclopentanone = 1:4 by weight) and the diluted PPICF was added and mixed
throughly for 10 min. The resulting mixture was then filtered using 0.45 f.lDI pore size
syringe filter and directly spin-coated at 400 rpm. For PU-VP, the solutions did not exhibit
the flow characteristics due to fast gel formation. The quality of the spin-coated film
improved with cosolvent system compared to when DMF was only used. The films were
directly poled and their SHG signal was measured at the in-situ poling set-up. Here,
thermally-induced condensation reactions of hydroxy functionalities and isocyanate groups
Iead to a hardended lattice during subsequent induction of polar alignment by the electric
336
tield. After the curing process was dorre, a solubility testwas performed in which the films
were dipped into DMF. All cured samples did not dissolve in this solvent, but PU-V and
PU-P systems exhibited some swelling effects.
According to the FT-IR spectra of the three crosslinked systems, a sharp absorption
peak at 1716 cm- 1 due to carbonyl stretching vibration in urethane 1inkage was present. The
absorption peak at 2276 cm- 1 from the isocyanate group of precursor polymer PPIF was not
observed. The Tg of these crosslinked polymers did not appear below the decomposition
temperature of chromophores around 156 Oe.
Scheme2
H~~~OH
V-OH
J. BPh4-
~";4H9
0
PPICF HJC...~CHzCH:z()-~-NH-
PU-P
9<
"'""'*
QBPh4- O
CHzCHzCHzO-~-NH-
0 0
-~'::1'"~~~:~""-
c~:C~4zCHzO-~-NH-
For the measurement of macroscopic second-order susceptibility x (2) upon comple-

tion of poling, the angular SHG dependence was recorded foreachfilm samples removed
from the poling stage. Figure 3 shows the SHG profiles ofthe three different polymers along
with that of 1 mm thick, Y-shaped quartz standard. Relatively high second-order optical
activity was shown for the poled and cured polymer films. The values of x (2) for PU-V,
PU-P and PU-VP were 8.9 X 10-8 (37.4), 4.0 X 10-8 (16.8) and 7.2 X 10-8 esu (30.2 pmN),
respectively. The lower X (2) value of PU-P is indicative of a significant reduction of
parallellocking structure due to crosslinking effects. 17
Figure 4 illustrates the thermal endurance of SHG activity for poled and cured PU-VP,
measured for every twenty minutes at every constant temperature interval during stepwise
temperature increase from room temperature to 150 Oe . Results for all samples are also
tabulated in Table 2. The decay ofthermal stability in PU-VP was minimized due to lattice
hardening of polyurethane with three bonding sites. Also, the SHG intensity does not show
337
3.0
PU-V PU-P PU-VP

2.5 1.51'm 1.51'm 1.51'm
~
:::1
IJ
~
2.0 "'
..
i!:'
'l ~
c: "':::1
2
.f:
1.5 ...
~
"
... ~EE
(ij
c:
rn 1.0 :::1
5 y
(.9 >- .....
I 0.5
(/)
0.0
Rotation Angle (degree)
Figure 3. SHG signal profiles of crosslink.ed polyurethane samples and quartz
l.S ....------.----......----~----.---~
-..!.
::i
25 t: 75 t: 100 t: 125 t: ISO t:
i'c t.o~l:ill~L~r:U!ID
2
....c
;a
...&,
crJ
0.5
::c'-'crJ
0.0 +-~..--~h.-.--.--+~--r--.--l--.-....-~+-~~,.---.j
0 20 40 60 80 100
Time (min)
Figure 4. Thermal endurance of SHG activity for PU-PV
Table 2. Chromophore contents and thermal stability data of x <2l values for crosslink.ed
polyurethanes
Polymersa) Bonding Chromophore x (2) value (prnN)

Directionbl Content
(wt. %) 25 c 75 c 1oo c 125 c
31.8 20.6 4.9
PU-V vertical 69.2 37.4 (85%)") (55%) (13%)
15.0 9.6 3.5
PU-P parallel 68.4 16.8 (57%) (21%)
(90%)
vertical & 30.2 30.2 26.9
PU-VP 69.7 30.2
parallel (100%) (100%) (89%)
a) Sampiefilms were cured at 100 'C for 12 h under vacuurn.
b) Bonding directions indicate approxirnate angle betwe.en dipole of Chromophore and two bonding sites.
c) Retained percentage of initial NLO activity to the corresponding temperature.
338
Schemel
0 0
H3C-N~~H3 conc. HBr

acetic acid
0 0
1
DEAD I PIIJP I THF
PEI.OANS
N~
~ ~~~:t
DEADIPh,ITHF \ \._~N_r~ ~O
HO
r
~ ., PEITH
HO 8
'===' LQ ,_L
lalracyanoethylene
/ OMF
_ CHa
NC
R=~
- '\._f/ ~Ha"==/ -
N~
N
NC
any reduction until the temperature rises to 100 Oe . For temperatures below 100 Oe , the x (Z)
for PU-V and PU-P decreased only to 85-90% ofthe initial value. 18
POLYETHERIMIDES
Despite the excellent thermal stability and mechanical properties of aromatic poly-
imides, the Iack ofprocessability, such as the high temperature imidization process and the
limited solubility due to the chain rigidity, have been the major hurdle to use them as the
NLO matrix materials. However, polyetherimide (PEI) can be prepared without the
339
imidization process and their final polymer structure shows good solubility in common
organic solvents. 1920 Therefore, we employed PEI as the matrix to achieve thermally and
mechanically stable NLO polymer systems.
The synthetic procedures for PEI-based polymers are shown in Scheme 3. The methyl
-protected diimide compound 1 was hydrolyzed by conc. hydrogen bromide in acetic acid
solvent. The resulting tetraacid 2 was so hygroscopic that the isolation to powder form was
performed in a dry condition. The tetraacid was subsequently treated with acetic anhydride
and then gave dianhydride 3. The compound 3 was reacted with urea at 200 C for 2 h
without solvent and then cooled to room temperature. The resulting solid was crushed into a
fine powder and was further reacted at 200 C for 1 h. The purified diimide 4 was obtained
by washing the reaction mixture with water. Two diol monomers 5 and 6 were synthesized
by the Horner-Emmons Wittig reaction between dialkylaminobenzaldehyde and diethyl 4-
nitrobenzyl phosphonate or diethyl thiophen-2-ylmethylphosphonate, respectively. 21
The polymerization reaction between the diimide and diol was executed by the
Mitsunobu reaction using diethyl azodicarboxylate (DEAD) and triphenylphosphine in
anhydrous tetrahydrofuran solvent. The soxhlet extraction in methanol was performed for 48
h to purify PEI-DANS and PEI-TH polymers. The Mitsunobu reaction has been utilized in
various organic syntheses. 22 However, the use of this method to obtain the polymerization
products of PEI has not been attempted in prior to this work. The advantage is that with the
proper application of this method, PEI can be obtained in a single-step reaction. When PEI-
TH was further reacted with tetracyanoethylene in DMF solvent, a blue-colored copolymer
(PEI-Tli-co-PEI-TCN) was produced which in some portions contained tricyanovinyl group.
The structures of the polymers were confirmed by the conventional spectroscopic
techniques such as IR, 1H-NMR, UV/vis, and eiemental analysis. Figure 5 shows the FT-IR
spectra for three polymers. In all cases, strong peaks at 1770 and 1711 cm 1 are attributed to
the carbonyl stretching vibration ofthe imide group. The peak at 1334 cm 1 ofPEI-DANS is
due to the symmetric stretching vibration of the nitro group. For PEI-TH-co-PEI-TCN,
tricyanovinylation of PEI-TH caused a new absorption peak at 2216 cm-I. The weak
-:::s
~ 1"'"1111118"*-------...
lt
nitro group
Q)
(.)
c b
Cil
_:;::;
E
Cl)
c
Cil
~
c
cyano group
3900 3200 2500 1800 11 00 400

Wavenumbers (cm-1)
Figure 5. FT-IR spectra of(a) PEI-DANS, (b) PEI-TH, and (c) PEI-TH-co-PEI-TCN
with KBr pellets.
340
b
'I
::J / \
~ I ' ,... a
Q)
--.1 I I \
1 I
(")
c: iJ \ I I
,,
I
I
..."'0
.c i . \ I
I
1/1
\ II
.c I\
<( \ I \ c
.., I
I
\
,_ - - - -\ - - --------.=-- --=----:.----------
\.
300 400 500 600 700 800 900 1000

Wavelength (nm)
Figure 6. UV/vis spectra ofthe polymers: (a) PEI-DANS <Amax= 441 mn), (b) PEI-TH
(Amax= 365 mn), and (c) PEI-TH-co-PEI-TCN (Amax= 365,669 mn).
intensity of the cyano group indicates that PEI-TH was partly tricyanovinylated. From the
eiemental analysis, tricyanovinylated portion of PEI-TH-co-PEI-TCN was determined to be
26.3 mol %. This result is in good agreement with that from UV/vis spectra shown in Figure
6. The absorption maximum for the 1t-1t transition of the stilbene chromophore in PEI-
DANS is 441 mn. A new absorption maximum at 669 mn for PEI-TH-co-PEI-TCN, which is
not observed in PEI-TH, indicates that NLO chromophore is generated by tricyanovinylation
Also, the absorption maximum at 365 mn indicates that the substitution reaction is not
complete and some portions remains unreacted with the polymer chain.
Molecular weights and Tg values of the three polymers are listed in Table 3. The
number average molecular weights (Mn) ranged between 6,200 - 10,700 (Mw!Mn=l.64 -
1.94) as determined by GPC with a polystyrene standard. DSC analysis showed Tg values in
the range between 144 oc and 157 oc for the three PEis. Flexible ether Iinkage and bulky
chromophores incoporated to the polyimide backhone can be attributed to the low Tg values
Table 3. The molecular weights and T g of several PEis
Molecular Weight"l T g bl
Polymers (OC)
Mn Mw Mw/Mn
PEI-DANS 10,700 17,600 1.64 157
PEI-TH 6,200 12,000 1.94 144

PEI-TH-co-PEI-TCNc) 7,200 13,400 1.86 147
a) Molecular weights were measured by GPC using THF solvent.
bl Tg means a glass transition temperature obtained by DSC analysis (I 0 C/min, N2 atmosphere ).
cl Tricyanovinylated portion ofthe copolymer was determined tobe 26.3 mole% from eiemental
analysis.
341
of the polymers. Both PEI-DANS and PEI-TH-co-PEI-TCN polymers were soluble in
common organic solvents such as cyclopentanone, chloroform, and 1,2-dichloroethane.
Good optical quality films were obtained by the spin coating.
The optically nonlinear second-order activity of the polymer films on the ITO glass
was produced by using a corona discharge induced electric poling. The poling was
performed in a wire to plane geometry under in situ conditions. 23 Directly after the poling
field was imposed across the film at room temperature, a rapid build-up of the SHG signal
was observed for PEI-DANS. However, the build-up ofthe SHG signal for PEI-TH-co-PEI-
TCN appeared at 180 C. When the temperature reached 220 C, the intensity ofthe SHG
signal was maximized. In order to determine the macroscopic second-order nonlinear
susceptibility (x(2 )) of the material after poling was completed, the sample was removed
from the poling stage and its angular SHG dependence was recorded and then compared
with the values obtained from a 1 mm thick, Y-cut quartz plate. The macroscopic x(Z) values
were determined tobe 73 prnN for PEI-DANS and 56 pmN for PEI-TH-co-PEI-TCN.Z4
According to UV/vis absorption spectra, the resonant enhancement effect of x(Z) values may
not be significant in both samples, particulary in PEI-TH-co-PEI-TCN which has a very low
absorption at 532 nm. The NLO coefficient of the copoymer system is not very high
compared to PEI-DANS. However, considering the low degree of substitution of
tricyanovinylene, the x(2l of copolymer is significant. In the present work, some basic
knowledge to increase the Substitution degree up to about 50% by controlling polymer
reactions becames availiable.
-
:::s
tei
0.0 1.0 2.0 3.0

Time (h)
Figure 7. Thermal stability ofpolar alignment in (a) PEI-DANS and (b) PEI-TH-co-
PEI-TCN.
In Figure 7, thermal endurance of SHG activities for poled films of PEI-DANS and PEI-TH-
co-PEI-TCN is presented. The SHG signal was monitored for 30 minutes at every
temperatures during the stepwise increase. Two polymers showed quite different thermal
stabilities against the relaxation of the poled chromophores. lt can be clearly seen that the
intensity of SHG signal for PEI-TH-co-PEI-TCN did not change from its initial value up to
125 C. On the other band, for PEI-DANS, the intensity slowly decreased with the
342
temperature rise for the same temperature range. For the former the SHG signal began to
decrease slowly between 125-150 C. When the temperature reached 175 C, a fast signal
decay set on, causing the SHG signal to disappear within 30 minutes. Such a rapid signal
decay, however, occured at a lower temperature (125 C) for PEI-DANS.
The decay process ofPEI-DANS is similar to those of other side chain NLO polymers
reported. 25 However, much enhanced thermal stability of SHG signal for PEI-TH-co-PEI-
TCN is comparable to that of highly crosslinked NLO polymers. The PEI-TH-co-PEI-TCN
is composed of two chromophores. One is the chromophore which does not have second-
order nonlinearity but is very electron-rich. The other has a high polarizability due to
electron-withdrawing effect of tricyanovinyl group. Hence, the abnormal thermal stability
shown in PEI-TH-co-PEI-TCN may be attributed to an attractive interaction between
nonbonding electrons of thiophene and strongly electron-withdrawing tricyanovinyl group,
through which gives the chain rigidity and thus improved thermal stability.
Scheme4
DANS diol NOt
11 So~Gel Processlng
2 I Poling I Curing
IChromophore I 510 2 hybrid systems
343
SILICA-BASED NLO POLYMERS26 -31
Inorganic glasses like silica or vanadium oxide are excellent photonie media and can
be made into high quality fibers and films with extremely low optical losses. Therefore, if
chromophores can be introduced into inorganic glass, this could be one of the better ways for
obtaining materials with !arge optical nonlinearity and low opticallosses.
Scheme 4 shows the synthetic route to the preparation ofNLO chromophore/Si02
hybrid systems. In prior to the sol-gel process, dye-attached monomer were made by using
the urethane reaction between -NCO ofiP-TEOS and -OH ofchromophores. This coupling
reaction was made to proceed at the temperature of 90 C for 3 h so that almost all
chromophore molecules could be attached to the sol-gel monomer, IP-TEOS. To this
solution, IN HCl aqueous solution and TEOS were added and the viscosity increased rapidly,
attributable to on going hydrolysis and polymerization reactions. This process is a general
methodology which can be applied to various chromophores containing hydroxy functionals.
In the present experiment three different chromophore/Si02 composite films, where
hemicyanine type dye BPTP, MHENS (MMONS) and DANS diol were covalently bonded
to Si atoms, were synthesized. The reason for choosing hemicyanine type dyc is that it has
proven to show a very !arge second order nonlinear coefficient in the crystals and LB
2.0
- - (a) unpoled
-: :I
1.5 - ... -- (b) poled
~
CD
(.)
c 1.0
al
-e0
rn
.0
<(
0.5
,
O.OL.___.._--~..._.....__..L...-_...._..:.::J::=~===..-.=:1
300 400 500 600 700 800
Wavelength (nm)
Figure 8. UV-visible spectra for (a) cured sample and (b) poled sample ofBPTP/Si02
hybrid.
films. 910 DANSand MMONS diols arederivatives ofwell-known chromophore which also
has a large nonlinear optical property. Particulary, MHENS derived from MMONS can be
applicable to second harmonic generation because of its lower cutofT frequency ( A = 500

nm). 3 Figure 8 shows a typical UVNisible absorption spectrum of the cured and corona-
poled BPTP/Si02 films. These were measured between 300 and 800 nm. In the cured sample
(a), the absorptionpeakwas 473 nm and there was no other absorption peak between 700
and 1300 nm frequency range.
In the poled sample (b), The absorption spectrum was lowered than the cured sample.
The curing condition of samples (a) and (b) were the same, so that the observed reduction
344
can be attributed to molecular alignment effect by the corona poling. In this BPTP chromo-
phore of charge transfer structure, the direction of transition dipole moment < 1-l eg> =
< rjJ groundl er 1 rjJ exited> is nearly parallel to the direction of molecular dipole and the
absorbance of light is proportional to 11-l g El 2 . Therefore, if the chromophore molecules
are aligned perpendicularly to the surface by corona poling the value of 11-l g EJ 2 decreases
for the incident light perpendicular to the film and thus the absorption peak becomes
diminished.

5
E 4
::t
~
.....
II
~
Cil
3 08 0
0
~ 2
E o SG DANS diol
Q.
(;) SGMHENS
.....C') SGBPTP
0~--~-----L----~--~----~--~~~~~~.
0 200 400 600 800 1000 1200 2400 2600
Time (hours)
Figure 9. Temporal stabilities ofpolar alignment for several hybrids at room
temperature
Table 4. Linear and nonlinear optical properties of theree different composite films.
Chromophores poling cond n(l.3,um) TJJ(l.3,um) d33(1.3,um)
DANS diol 170 "C /0.5h, 6KV 1.608 3.1 pm!V

MHENS 148 "C /0.5h, 6KV 1.597 3.2 pm!V 14 pm!V
BPTP 160"C/2h, 13KV 1.599 5.0pm!V
The surface morphologies of the cured film and corona poled film at 13 KV taken by
atomic force microscopy. The surface of the unpoled film was very flat. The surface
roughness was lower than 2 nm. In the case of corona poled film, on the surface right
undemeath the probe needle, there exist irregularly dispersed craters of non-uniform shapes
with the size of several hundreds nm radius and 12-26 nm in depth. Further from this area,
the surface was clean similar to the unpoled film. These defects seem to be the surface
damages generated by the bombardment of the plasma in corona discharge. In spite the
345
presence of these surface defects, the short circuit did not occur between the ITO layer and
the Al electrode deposited on the film. Considering the high corona voltage in our
experiment, these results condradict the cases of the organic polymer films where severe
surface damages are made when corona-poled. The endurance of sol-gel film to corona
discharge comes from the strong bond ofthe Si02 matrix.
Linear and nonlinear optical properties of three different type composite films are
sumrnarized in Table 4. The refractive indices were measured by prism coupling method at
1300 nm. The electro-optic coefficient r 33 were measured by simple reflection method and
the r33 ~3r 13 , 11o~11e~n was assumed for the calculation. 32 The second harmonic coefficient
d 33 of MHENS film was obtained by Maker-fringe technique. The measurement was
performed at 1064nm wavelength using a mode-locked Nd:YAG Iaser as the fundamental
light source.
The second harmonic signal from the sample was compared to Y-cut quartz reference. The
relatively small d33 value of MHENS may be due to the fact that the resonant enhancement
effect did not contribute because the second harmonic wavelength il =532nm was located
apart from the absorption region.
Figure 9 shows the temporal change ofthe electro-optic coefficient at room tempera-
ture for the three composite films. For all three samples, decrease of electro-optic coefficient
was not detected within the range of experimental error. The BPTP/Si02 film retained
around 100% ofits original value after 54 days and the DANS diol/Si0 2 film stabilized its
original value after 500 h. As for the MHENS/Si02 film, the electro-optic coefficient,
measured after 105 days, shows similar value to the initial measurement. The good
stabilities may come from the rigid Si02 matrix and the attachment of chromophore to the
Si02 backbone.
CONCLUSIONS
In the present reserch we illustrated how to design and synthesize the highly efficient
NLO active polymers with long-term stability. For this, we have sucessfullv demonstrated by
using both linear and crosslinked polyurethanes induced hydrogen bonding, high Tg PEis,
and silica glass deviced from sol-gel processing as the matrix polymers. Also, for the high
NLO activities we used various azomethine-, stilbene-, or azo-type chromophores having
strong hyperpolarizability. The resulting polymers showed promising features for nonlinear
optics applications.
ACKNOWLEDGEMENTS
This research was supported by the Korea Science & Engineering Foundation and the
Korean Ministry ofEducation. The authors are grateful to Prof. P. N. Prasad, Prof. T. G. Lim
and Dr. J. Zieba for their help in determining the SHG activity of our samples.
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347
RECENT PROGRESS IN NONLINEAR PHOTONIC DEVICES
AND PHENOMENA BASEDON ORGANIC MATERIALS
George I. Stegeman, Akira Otomo:, Mattbias Jaeger,

Christian Bosshardt, Rien Flipse* and Michael Canva
Center for Research and Education in Optics and Lasers (CREOL)

University ofCentral Florida
4000 Centrat Florida Blvd, Orlando, FL 32816-2700, USA
ABSTRACT:
There has been a great deal of activity in the last few years in the application of nonlinear
organic materials to optical phenomena (excluding electro-optics). The goaloftbis paper is to
focus on recent progress.
INTRODUCTION:
The field of nonlinear optics in organic materials started soon after the first discoveries
in nonlinear optics. For example, organic crystals were tested for second harmonic generation
(SHG) as early as the mid 1960s. However, the concept which dominates current strategies for
engineering large second order nonlinearities d<2>s (or x(2>s), i.e. that charge transfer is a very
efficient mechanism, was not identified until the early 1970s when it led to highly nonlinear
materialssuch as MNA and MAP. 1 The field has been developing since then, with progress
towards frequency conversion devices accelerating in time. The current interest in electro-optic
devices is mak:ing available a large spectrum of new materials for SHG and other parametric
effects. 2 This is similar to the scenario under which LiNb0 3 was developed for SHG.
Current Address: AKZO Research Laboratories Ambern, P.O. Box 9300, 6800 SB Ambern, The
Netherlands
t Current Address: Institute ofQuanturn Electronics, ETII Honggerberg, Swiss Fed. lnst. ofTech., HPF E14,
Zurich Switzerland CH-8093
~ Current Address: Kansai Advanced Research Center, CRL, MPT, 588-2 Iwaoka, Nishi-ku
Kobe 651-24 Japan
Sdence and Techrwlogy of Polymers and Advanced Materils

Edited by P. N. Prasad et al. Plenum Press, New York, 1998 349
Organic materials were also among the first to be studied for third order (X(3>) effects such
as self-focusing, stimulated Raman and Brillouin scattering. The nonlinearities, specifically the
intensity-dependent refractive index coefficient n2 (in n = n 0 + n J) were initially modest by
present day standards. The concept of conjugated polymers for 1t-electron delocalization started
in the late 1960s and led in 1976 to the report of very !arge non-resonant nonlinearities in the
single crystal polymer PTS by Sauteret et aJ. 3.4 These are still among the largest reported
coefficients to date. Currently new materials are still being invented and assessed, and a few
applications are slowly emerging.
A previous comprehensive report reviewing the field into the early 1990s was published
in the proceedings of the first Frontiers in Polymers conference. 5 Here we will concentrate on
selected advances since that report.
SECOND ORDER DEVICES
The second order coefficients of organic materials are among the largest obtainable from
any material system, both for single molecules and single crystals. 12 6-9 Values in excess of I 00
prnN arenot unusual in crystals, with the current record being of order 600 prnN. 78 For poled
polymers, magnitudes of I 00 prnN and more have also been reported. 9 The key challenges have
been to extend the limited transparency region allowed by highly nonlinear materials, and to use
them in nonlinear optics devices, for example for generating sources in the blue region of the
spectrurn for data storage. The physical origin ofthis transparency problern isthat the stronger
the charge transfer mechanism (and hence nonlinearity), the !arger the value of }..mruc In fact, no
real solution has emerged and interest in this aspect ofthe problern is waning. However, recently
frequency conversion involving the communications wavelengths of 1300 and 1500 nm have been
explored for applications such as wavelength shifting for WDM networks and all-optical
phenomena via cascading.IO,Il
The principal problern here, as it is for all frequency conversion devices, is of course to
achieve phase-matching, that is to find a geometry in which the phase velocities of the
fundamental and harmonic are matched over centimeter distances. For waveguides, there is a
!arger spectrum of phase-matching techniques available, as shown schematically in Fig. 1. In
fact, all ofthese have been implemented in polymer waveguides, both planar (slab) consisting of
a single or multicomponent guiding film(s) for confinement in one dimension, andin channel
waveguides in which the beam is confined in both transverse dimensions. The propagating fields
areproportional to exp[i(wt-z)] where is the guided wave propagation wavevector. Thus SHG
wavevector conservation typically requires (2w) = 1(w) + 2 (w) where (2w) is the harmonic
wavevector, either guided or parallel to the guiding surfaces, and the i(w) are the fundamental
guided wave wavevectors. Wavevector conservation is required for efficient SHG.
Second Harmonie Generation in Poled Polymers: Quasi-Phase-Matching (QPM)
QPM can be implemented by either modulating the refractive index, the waveguide
thickness or the nonlinearity. Modulating the second order nonlinearity ct<2), as shown in Fig Ia,
350
(ro) (ro ) K=27tfl m>O
(J)
(a) (b)
P(2ro)
(ro) (ro) 2ro
P(2ro)
(c) (d)
Fig. 1 Four schemes for producing wavevector-matching in second harmonic generation in waveguides. (a) shows
quasi-phase-matching in which the nonlinear coefficient is periodically reversed. Alternatively the index can also
be periodically modulated. (b) showsmodal phase-matching utilizing the lowest orderfundamental and higher order
harmonic waveguide modes. (c) shows the generation ofCerenkov radiationout ofthe waveguide and the necessary
wavevector condition. (d) shows SHG by the mixing oftwo counter-propagating guided waves.
results in much more efficient SHG than modulating the linear waveguide properties.12 13 In this
case, (2w) = 2(w) 27t/A. and d(2)(z) = d(2) + d(2)cos[27tz/A.] where A. is the period. 12 That
is, the process must be wavevector-matched in order to obtain !arge conversion efficiencies. Such
a modulation in the nonlinearity is usually much more effective for efficient SHG than a
modulation in the refractive index. 1213 In this Iimit P(2w) =11 Lpm2 P2 (w) where 11 is the figure
ofmerit and Lpm is the effective phase-matched device length. (We use the term "effective" since
loss [usually at the harmonic wavelength] or fabrication tolerances frequently Iimit Lpm to less
than the actual device length L.)The key parameter is notjust the figure ofmerit T), but the Iosses
at the fundamental and second harmonic must also be considered in obtaining a !arge net
conversion efficiency.
An early QPM approachwas to periodically set the nonlinearity of a poled film to zero
in planar waveguides.[Khanarian et al., 1990, Norwood and Khanarian, 1990, Rikken et al., 1990,
Azumai et al., 1991a].14- 17 For example, in Rikken and coworkers, 1991 , 4-alkoxy-4'-
alkylsulfone stilbene molecules were periodically exposed to UV light inside the absorption band
to periodically reduce the second order activity d(2) effectively to zero via trans-cis
isomerizatio'1. 18 Although no conversion efficiencies or Iosses were reported, doubling of 820
nm light was achieved with films exhibiting 9 pm!V activity. In work on DANS, it was found
that the resulting index grating radiated the fundamental out of the waveguide, leading to
unacceptably !arge Iosses of 25 dB/cm at the fundamental wavelength. 19
Khanarian and coworkers were the first to use the QPM concept for SHG in periodically
poled polymers. They fabricated periodically poled films using a ground electrode under the
guiding film, and a periodic electrode deposited on the waveguide surface. 20 Using 4-oxy,4'-
nitrostilbene as the active molecule doped into a methylmethacrilate slab waveguide, a d(2) of
2 pm/V was achieved and a conversion efficiency of 0.01 %/W with a 1340 nm fundamental. The
351
effective QPM distance of5mm was inferred from the spectral bandwidth ofthe SHG conversion
efficiency. One way of reducing the modulation period of the fabricated gmting is to use a higher
grating order, as demonstrated by Azumai et al., 1994, with, however, a subsequent decrease in
the SHG efficiency. 21
Efficient devices require channel waveguides in which beams are confined to typically the
optical wavelength in both beam dimensions. In the first experiments at CREOL, channel
waveguides with DANS, 4-dinitro-amino-stilbene, as the active moiety with side-chain doping
Ievels of 30-40%, were investigated for second harmonic using QPM with input wavelengths
around 1550 nm. 19 The waveguides were defined by photobleaching through a mask used to
define the channels. This process upon illumination with radiation inside the charge-transfer
absorption band not only Ieads to a reduction in d(2) but also to the refractive index at Ionger
wavelengths due to trans-cis isomerization of the molecule. lt was found that poling with
periodic electrodes on top ofthe film led to !arge periodic thickness modulation (>100 nm) due
to capacitive forces and unacceptably !arge propagation Iosses of 40 dB/cm in the fundamental
due to the resulting grating. However, with periodic electrodes on the substrate, the thickness
modulation was reduced to 4 nm and fundamental Iosses to less than 5 dB/cm. In this second
case, an 11 = 0.05o/o/W-cm2 and a phase-matching length of 7 mm was achie~ed. However,
because ofthe detailed field structure in the periodically poled film, a Ad(2) of only a prnN was
induced, leading to the small conversion efficiency.
A totally different approach to fabricating periodic regions with zero nonlinearity has
recently been reported.2223 Using a novel serial grafting technique too complex to describe here,
the authors created in a channel waveguide regions of zero and non-zero nonlinearity without
significant index differences between them. They were able to achieve a figure of merit 11 =
I o/o/W-cm2 , the largest reported to date for QPM techniques.2 3
QPM has also been reported for a quasi-bulk stack of periodically reversed poled polymer
films. 24 First a !arge area film was uniformly poled, the film 'floated off' the substrate and then
was cut into a !arge nurober of small pieces. By placing films one on top of the other, with
altemate films poled in opposite directions, a bulk stack consisting of tens of layers was
fabricated. Light incident at an angle produced a field component parallel to the normal to the
surface and by adjusting the angle of incidence, or wavelength, phase-matched SHG was
obtained. 24
QPM by corrugation of one of the waveguide interfaces has also been demonstrated for
an SiNIMNA crystal channel waveguide by Suhara et al. 1993, as well as periodic Iaser ablation
[Marowsky et al., 1993].25 26 However, in both cases the conversion efficiencies were rather
small.
Second Harmonie Generation in Waveguides: Modal Dispersion Phase Matehing (MDPM)
The usual dispersion in material refmctive index due to electronic resonances in the UV
and blue and due to the normalized waveguide'thickness with wavelength requires that the SHG
signal appears in a higher order waveguide mode than the fundamental if the two are co-polarized.
Co-polarized beams have proven advantageaus because for most materials the diagonal elements
ofthe d(2)ijk matrix are usually the largest. For MDPM,
352
TJ oc f f dxdyd< 2>(x,y)E 2(w,x,y)E(2w,x,y)
where E(w) and E(2w) are the fundamental and harrnonic fields respectively. For higher order
second harrnonic modes, the sign of the field changes one or more times across the waveguide
core region which Ieads to interference effects in the integral, assuming that d( 2) is a constant in
the active region.
Many ofthe early "demonstration ofprinciple" experiments on SHG in slab waveguides
used the MDPM technique. The first experiments [Sugihara et al. and Azumai et al.] employed
relatively simple planar waveguide structures for light confinement in one dimension only. 27 28
The efficiencies were also reduced due to partial cancellation in the overlap integral, as just
discussed. One approach to avoid this cancellation is the placement of the nonlinear material
outside of the waveguide, where the modal fields do not change sign due to their evanescent
(exponentially decaying) nature. This design was implemented by Rikken and coworkers utilizing
a channel waveguide geometry. 29 The confinement in two dimensions enhances the efficiency
significantly compared to a planar guide. Another advantage is that this waveguide design can be
made noncritical with respect to the fundamental wavelength, ensuring a !arge SHG acceptance
bandwidth. 30 On the other hand, evanescent fields tend to have a smaller amplitude than the
guided fields in the waveguide, severely reducing the efficiency.
More recently, excellent progress has also been reported by two groups in thin film
waveguide SHG based on Langmuir-Blodgett films. Pennerand coworkers at Kodak deposited
alternating layers oftwo different molecules, one with a !arge activity (4-[dimethylamino]-4'-
[methylsulfonyl]azobenzene) and the second with no activity, allowing Y-type deposition to build
up a nonlinearity linear in the double layer thickness (20 prnN) with low waveguiding Iosses (0.5
dB/cm) at 633 nm in planar waveguides. 3! By eliminating one passive layer, they were then able
to reverse the direction of the nonlinearity over one half of the film and thus optimize the overlap
integral. 32 . The key concept of using SHG-inactive, or inverted layers was first introduced in
the 1970s by Ito and Inaba. 33 The Swiss ETH group independently followed a similar path using
DCANP (2-docosylamino-5-nitropyridine) Langmuir-Blodgett films to form "herringbone" Y-
type layers resulting in a d(2) in the plane of the surface of 13 prnN and waveguide Iosses of 5
db/cm at the fundamental wavelength. 34 35 They improved the overlap integral by both using a
d(2) = 0 layer as part of the guiding film, and also by inverting the d(2) nonlinearity about halfway
through the guiding film, using phase-matching ofTE0(w) to TE 1(2w) .34 35 The measured
conversion efficiency for the planar waveguides was 0.02%/W. 34 This idea ofusing a non-d(Z)_
active layer to reduce interference effects in slab poled polymer waveguides was reported by
Clays et al., 1994, used a combination of inorganic buffer and polymeric guiding layers. 36
The most recent work has concentrated on incident wavelengths of 1500 nm. It is
noteworthy that a dimensional analysis shows that TJ scales as -4 so that operating at Ionger
wavelengths Ieads to inherently smaller FOM for the same nonlinearity, i.e. the difference
between operating with a fundamental wavelength of 1600 versus 800 nm is a reduction in TJ by
over an order of magnitude. Successive experiments in DANS channel waveguides led to
progressively better optimized overlap integrals. Fora single, d(2)_active, poled film channel
waveguide, the combination TM 00 (w) -+ TM20(2w) produces the best overlap integral. In
DANS, this gave TJ = 1%/W-cm2 with a phase-matching length of at least 2 mm.37
353
The situationwas improved by using multi-layer films. By making the guiding region of
two layers of approximately equal thickness, one DANS and the other polyetherimide (d<2 >=o),
with TM00 (w) -+ TM 10(2w) the interference from one half of the waveguide is eliminated. 38 A
T] = I4%/W-cm2 with a phase-matching length >7 mm was achieved. This approachwas later
optimized by actually reversing the direction of d(2) every time the field of the second harmonic
changed sign so that the product dC2>(x,y)E(2w;x,y) was always positive, hence optimizing the
overlap integral. 39.4 This was achieved by using two polymers with different glass transition
temperatures Tg in alternate layers, the number of layers = n+ 1 corresponding to the number of
times n that the field changed sign inside the active, guiding core. The resulting stack was frrst
poled at the higher temperature for which all ofthe chromophores were aligned in one direction,
and then reverse-poled near the lower Tg where only the lower Tg films were able to reverse their
nonlinearity. For TM00(w) -+ TM20(2w), i.e. three active layers, an TJ = 44o/o/W-cm2 was
achieved for a nominal poling field of 50V/~m with the DRI chromophore. This value is
equivalent tothebest reported LiNb0 3 QPM result41 . However, in this polymer case a.(2w)-
100 dB/cm due to the long absorption tail in DR1, versus a few tenths of dB/cm for LiNb03
which makes the absolute conversion efficiency still far superior in that ferroelectric. Fortunately
polymers are available with Iosses of order I dB/cm at 800 nm and this situation is expected to
improve.
In cantrast to the above work involving normal dispersion in the refractive index, Singer
and his colleagues have been able to use "anomalous" dispersion to directly phase-match the
lowest orderfundamental and harmonic guided modes. 42 This is possible ifthere is a narrow
absorption line between wand 2w so that it is possible to match the refractive indices (and hence
the guided wave wavevectors) for the fundamental and harmonic simultaneously for the lowest
order mode. Using this approach which obviously optimizes the overlap integral, they obtained
TJ = 33o/o/W-cm2 with input wavelengths in the 800 nm range. The Iimitation is the attenuation
which is large on both sides of the absorption peak, limiting propagation to I Os of microns.
Second Harmonie Generation via Cerenkov Radiation
One of the simplest "phase-matching" techniques for guided wave systems is the
Cerenkov approach. Here the second harmonic is radiated out of the waveguide region with the
angle 6 measured away from the waveguide surface given by wavevector conservation parallel
to the surface, i.e. cos = 2(W )/11gub(2w)kyac(2w) where Dsub(2w) is the Substrate (into which the
harmonic is assumed to be radiated) refractive index for the harmonic. Note that this wavevector
matehing automatically occurs whenever 2(w) < llgub(2w)kyac(2w). The figure of merit for this
case varies linearly with the sample length L, [i.e. t]=P(2w)/P2(w)L].
Cerenkov phase-matching has been irnplemented in both slab and fiber waveguides. 43 -4x
The most promising cases have involved single crystal organic materials grown inside the core
of small diameter glass fibers. The crystal orientation in a small fraction of the cases has led to
non-centrosymmetric crystal structures which have led to SHG with good conversion efficiency
with the second harmonic radiationernerging from the fiber cladding in a cone. 43 44 The best
results were achieved with a DMNP [3,5-dimethyl-1-(4-nitrophenyl)pyrazole] crystal core with
a nonlinearity of 90 pm!V (d32). 44 A 840 nm Iaser diodewas doubled with an efficiency of
354
40%/W-cm in a 15 mm long fiber, i.e. the conversion efficiency was 60% per watt of fundamental
input. The 1oss at the fundamental wavelength was on1y 1. 7 db/cm. Similar experiments were
performed on DAN [4-(N,N-dimethylamino)-3-acetamidonitrobenzene] crystal fibers with 1064
nm input wave1ength.4446 Losses were measured at 633 nm (not the fundamental wave1ength)
and found to be 9-13 db/cm. The conversion efficiencies were smaller than for the DMNP case,
ofthe order oflO%/W-cm for 4.7 mm 1ong fibers. Cerenkov SHG with moderate efficiencies has
also been reported from organic crystal waveguides grown in the form of a s1ab. 47
The result obtained in DMNP is the largest efficiency obtained in organic materials to
date. It corresponds to 0.16 mW ofdoubled light for the 17 mW input coupled into the fiber. 43
This extrapolates to 1.4 m W for a 50 m W input, useful for data storage applications. However,
this line ofresearch has been discontinued because oflong-term optical darnage in the fibers.
Both the Kodak and ETH groups have achieved impressive Cerenkov SHG in LB slab
waveguides as precursors to their work on MDPM just discussed above. 48 49 For example, the
ETH group reported a slab figure of merit of 1.4xlo-7 in DCANP. Asai and coworkers
demonstrated Cerenkov SHG in a DCANP film with an inversion ofthe nonlinearity to enhance
the SHG efficiency. 50 However, the overall efficiency in LB films is limited by the difficulty in
achieving confinement in two dimensions.
There has also been work on Cerenkov radiation from poled polymer slab waveguides. 51 -
54 Sato and colleagues have found that they could increase the cross-section for the second
harmonic by using a grating to participate in the out-coupling process. By chirping the grating,
i.e. varying the grating period with distance, they were able to presumably couple to one ofthe
film Fabry-Perot resonances and enhance the SHG signa1. 55 More recently, polymeric channel
waveguides were employed leading to an improvement of the efficiency. 5657 Cazeca et al.
reported a doubling efficiency of 1.4xl0-3 %/W obtained in a channel for the doubling of a
Nd:YAGlaser.
SHG by Oppositely Propagating Guided Beams
The usual way to generate second harmonic or sum frequency light is by mixing two
beams propagating in the same direction, as just discussed above. However it is also possible to
generate sum frequency signals when two oppositely propagating guided waves overlap as
indicated in Fig 1d. When two equifrequency beams mixvia a second order nonlinearity, for
example through d(2)YYY for TE guided waves with electric fields polarized along the y-axis, the
nonlinear polarization
is induced when the beams overlap. Here fy(x) and U are the guided wave field distributions
along the confinement direction (x-axis) and the field envelopes along the propagation axis (z)
respectively. For the polarization at the harmonic frequency, the net wavevector parallel to the
surface is -=O and only radiationnormal to the surface (for which kz = 0) is possible. This
effect has been studied previously in dielectrics and semiconductors, and various applications
such as pulse autocorrelation, spectrometry etc have been reported. 58-60
355
The generation of SHG by two counter-propagating waves has also been demonstrated
in DANS (4-dimethylamino-4'-nitrostilbene) waveguides poled in the plane ofthe surface {i.e.
along the y-axis).61 -63 For a 1064 nm input, a line of green light was observed radiating from the
waveguide. Similar experiments were performed for waveguides made ofDCANP LB films. 64
The signal efficiency surpassed that for a single layer in GaAs.
The SHG signal can be further enhanced by adopting a form of quasi-phase-matching.
The process cross-section ANL is proportional to
I Jftlmdx d;:}(x) J:<x) sin[k_.(2W)] 12
Note that if d(2) is a constant, interference effects occur due to the sin[kx(2w)] term. However,
these interferences can be removed by also modulating the nonlinearity so that the product d(2)
sin[kx(2w)] does not change sign. This was achieved by using alternate layers with d(2)=0. (The
optimum case would be to periodically reverse d(2), but this is difficult for thein-plane poling
required for this interaction). An enhancement in excess of two orders of magnitude in ANL was
achieved by using a five layer stack.6263 One watt on inputpower produced 3mW in green-blue.
SHG of Femtosecond Pulses
The large nonlinearities of organic materials can be useful for ultrashort pulse analysis and
generation. For femtosecond pulses, the group velocity dispersion in most materials Ieads to a
temporal pulse broadening which increases with material thickness. This is also true for SHG
materials used for autocorrelation measurements of pulse widths. Pulse autocorrelation of 200
fsec pulses at 600 nm has been demonstrated with a 1.1 Jlm thick poled polymer film consisting
of disperse red 1 azo dye in a PMMA host. 65 Because the nonlinearity is so large and hence the
film can be so thin, pulse broadening is dramatically reduced. Suchthin SHG film autocorrelators
have 1arge spectral and angular bandwidths. This work has recently been extended to the efficient
doub1ing (0.025%) of 50 nJ, 13 fsec pulses at 625 nm. 66
Optical Parametrie Oscillator
One of the applications of single crystal materials with second order nonlinearities has
been for efficient parametric oscillators. The goal is to use a single input beam to generate
tunable radiation over a useful range of wavelengths. This is achieved by simultaneously
satisfying energy and wavevector conservation, i.e. wp = w 1 + w2 and ~ = k 1 + k2 where the
subscript "p" identifies the input beam and the subscripts 1 and 2 denote the generated signals.
These conditions can only be satisfied at one temperature and one direction in a crystal. By
varying the orientation ofthe crystal relative to the incident beam direction, different frequencies
can be generated. (Alternatively tuning can be achieved by varying the sample temperature.)
Such a device Ieads to a tunable source. If the bandwidth of the crystal is large enough, pulses
as short as femtoseconds can be generated as discussed above.
Zyss and coworkers have used a single crystal material, NPP, with an effective d(2) of50
pmN to implement an OP0. 67 (This is tobe contrasted with the standard OPO material BBO
which has a nonlinearity of only a few pmN.) The crystal used was 1. 7 mm long. OPO output
356
was demonstrated from 900 to 1700 nm with a 593 nm pump. The maximum conversion
efficiency was 4.7% with 1 nsec pulses of0.41 mJ energy.
THIRD ORDER DEVICES
Over the last few years many new materials with interesting nonlinearities have been
reported. Almost exclusively the key parameter is the parameter n2 which quantifies the optically
induced index change An= n2I (Kerr-law case). Unfortunately, rarely have the linear and two
photon absorption coefficients also been reported so that the nonlinear device figures of merit
cannot be estimated and hence the suitability ofmaterials for all-optical devices assessed. 68 The
diacetylenes PTS and PPV are notable exceptions.69-71 For PTS it was found that the non-
resonant n2 = 2.2x1o- 12 cm2/W with no measurable two photon absorption around 1600nm. 72
For PPV, a spectral window was found around 850 nm in which the nonlinearity n2 - 10- 11
cm2/W and the two photonabsorptionwas negligible. 73 74
There has been some interesting progress with these as well as other materials (with !arger
losses) in the last two years. Since the last report, switching with femtosecond pulses in nonlinear
directional couplers, a nonlinear Bragg reflector and various soliton phenomena have all been
investigated.
Nonlinear Directional Coupler
The nonlinear directional coupler is the most widely studied waveguide device for all-
optical switching, logic etc. 68 It consists oftwo waveguides, usually channels, which areparallel
and located close enough to each other so that the waveguide fields of one overlap the
neighboring waveguide. When the waveguides are identical, this overlap Ieads to the transfer of
power from one guide to the other in a periodic fashion with propagation distance. When the
waveguides are sufficiently different, the transfer between the channels is inhibited. Such a
detuning can be induced optically in one channel by injecting a high power beam into it, assuming
that the channel material is nonlinear. That is the index is changed locally by the high intensity
via An = n2I. This Ieads to a power-dependent response for the output of the two channels.
This device has been studied previously in polydiacetylene materials. At 1064 nm, the
responsein poly4-BCMU with psec pulseswas found tobe dominated by two photon absorption,
leading to a non-ideal response. 74 The most recent results were obtained by Sasaki and
coworkers.7 5 This particular device consisted ofthree layers, with the active films being a PDA.
A mode-locked Ti:saphire Iaser operating at 885 nm with 100 fsec pulseswas used arid power-
dependent control ofthe output ofthe two channels was demonstrated. However, the switching
results aredifferent from those expected from a simple Kerr nonlinearity. In that case the outputs
should asymptotically approach either 0 or 1 at high input powers, depending on which channel
is the input channel. This does not correspond to result reported in which the output from he two
channels equalized with increasing power. Further research is probably needed to resolve this
discrepancy.
357
Nonlinear Bragg Reflector
A nonlinear Bragg reflector has been demonstrated using Si-naphthalocyanine as the

nonlinear material. 76 The structure utilizes one of the strengths of spinnable polymers for
nonlinear optics, i.e. appropriate solvents can be found so that altemate layers of different
materials can be deposited. The sample was made by spinning altemate layers of PMMA and
Si-naphthalocyanine on top of each other. The layers were chosen so that the optical thickness
of each corresponds to one quarter ofthe wavelength ofthe incident radiation in the respective
media, i.e. d = 0.25 A.vadn!ayer As a result, the Bragg condition for retroreflection ofthe incident
light is satisfied for normal incidence. The fraction of light reflected depends on the number of
layers, and the refractive index discontinuity between altemate layers.
Increasing the intensity ofthe incident radiation changes the refractive index ofthe Si-
naphthalocyanine layers. This detunes the structure away from the Bragg condition, i.e. a
wavevector mismatch k = kvacn21 is induced and the reflection coefficient is reduced, as was
verified experimentally at A. = 688nm, near the maximum of the resonant nonlinearity in this
material. Note the reflection coefficient ofthe beam decreased with increasing intensity. Such
a device has potential applications for opticallimiting, switching etc.
Soliton Effects
Solitons are wave packets in space or time which propagate without spreading. 77 They
are unique solutions to the electromagnetic wave equation which includes terms in which the
refractive index ofthe medium is modified as some function ofthe light intensity, usually n =
n2I . Normally, a "bright" soliton requires n2>0 and a "dark" soliton n2<0. A bright soliton is a
well-defined maximum in light intensity which decays exponentially, or faster, with distance
from the maximum. Conversely, a dark soliton basically consists of a specially shaped "hole" in
a background of constant illumination with a phase change of n: across the minimum. F or Kerr
media, spatial solitons do not diffract (spread) as they propagatein space, and the pulse envelopes
for temporal solitons do not spread (broaden) upon propagation. These solitons are stable in only
one dimension (lD), which implies fibers or channel waveguides for the temporal case, and a slab
waveguide for the spatial case. However, if higher order nonlinearities, or saturation of the
optically induced index change are present, then solitons are also stable in two dimensions (2D),
for example in bulk media with beams that can diffract with two cross-sectional dimensions. In
all cases, bright, dark etc., the index is higher in the region of the soliton center and hence this
region can be used to guide light of different polarization or wavelength, just like the usual
waveguides which are based on initial index differences between the adjacent media. That is, a
strong beam can be used to form the spatial soliton and a signal beam can be guided by it.
Both lD and 2D bright spatial solitons have been investigated in organic materials. One-
dimensional bright spatial solitons have been identified in PPV slab waveguides.7 8 That is a
power Ievel has been found for which a guided wave beam does not spread with distance. The
nonlinearity was verified tobe self-focusing, presumably Kerr-law. Bright spatial solitons have
also been investigated in bulk, single crystal PTS, allowed by virtue of a higher order negative
nonlinearity, i.e. n = n2I + n3I2 with n2>0 and n3<0. 7279 This combination, to date only found
358
in PTS, Ieads to a stable 2D spatial soliton, i.e. a 2D beam which propagates without diffraction.
However this only occurs for powers up to a maximum value beyond which the soliton becomes
unstable. 80 These stable solitons have been observed experimentally, as weil as their break-up
into a soliton + a ring at 1600 nm in PTS for temporally pulsed Iaser beams. 7981
Dark solitons have been more widely studied because thermal nonlinearities are typically
negative and dominant in most organic materials near their principal absorption features. 82 They
can be easily generated with a phase plate used to introduce a phase shift of 1t across the writing
beam. The properties of dark spatial solitons have been investigated in a series of experiments by
Luther-Davies and colleagues. They have shown the splitting of dark spatial solitons, the number
being generated depending on the phase change across the dip. 83 The interaction between
solitons, their excitation as grey solitons, and their directional control via the phase change across
the minimum. 84 All of these experiments were important in experimentally establishing the
properties of dark solitons.
In similar experiments, dark solitons were written into a DANS solution with an argon ion
Iaser operating at 515 nm using the absorptive thermal nonlinearity ofthe DANS molecules. 85
lt was also verified that a weak He-Ne "probe" beam at 633 nm was guided by the soliton and that
the signal beam's direction in space could be changed by reducing the phase shift across the
middle ofthe dark soliton beam. Subsequently a novel method for producing linear arrays of dark
spatial solitons and their all-optical scanning inspacewas also demonstrated. 8687 A high contrast
interference pattem contains a 1t phase change across its minimum and evolves into an array of
dark spatial solitons in a n2<0 medium. Normally the solitons would further evolve back into the
interference pattem. However "gain" is provided by gently focussing the beam into the medium
leading to a stable array of dark solitons. By varying the intensity of the two beams causing the
interference pattem, an array of grey solitons is formed which sweeps in space as the relative
intensity is tuned. 87 Guiding of a probe beam and its scanning was also observed.
Organic materials have also been used to demonstrate temporal solitons under unusual
circumstances. To date, temporal solitons have been studied cleanly only in fibers with n2>0 and
with GVD (group velocity dispersion) <0. 88 Sasaki's group has recently reported temporal
solitons with nz<O and GVD >0 in planar waveguides made of DRI doped to about 5% in a
PMMA polymer host. 89 They essentially found that over a given range of powers their I 00
femtosecond pulses did not spread temporally in traversing the waveguide. (There was a
significant broadening at low powers.)
SUMMARY
There has been good progress in the development of nonlinear optical devices based on
organic materials. For second order nonlinearities materials with sufficient activities are now
available and the performance of SHG in channel waveguides is competitive with LiNb0 3, at
least in terms of the figure of merit. The challenge is to incorporate new materials with low Iosses
at the harmonic wavelength into device structures and perform the engineering necessary to
improve device performance to acceptable standards. For third order effects, it is still not clear
that good enough materials have been developed. However, the performance of organic materials
is now much more convincing than a few years ago.
The research that was performed at CREOL was supported by AFOSR.
359
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364
NEUTRAL AND DOPED STATES OF POLYMERS WITH AROMATIC
RINGS STUDIED BY RESONANCE SPECTROSCOPIES
S. Lefrant, J.P. Buisson, M. Baitoul, I. Orlon, A. Simonneau and G. Froyer
Laboratoire de Physique Cristalline

Institut des Materiaux*
BP 32229
44322 NANTES Cedex 3 FRANCE
ABSTRACT
In this work, we present spectroscopic studies on conjugated polymers and oligomers

containing phenyl ring, focusing on two farnilies of compounds: PPP and PPV. The
resonance Raman Scattering (RRS) technique has been extensively utilized to characterise the
neutral of doped states of these compounds but also, we have used high resolution solid state
NMR to add information on the nature of the elementary excitations which can appear on
these polymers or oligomers in their doped state.
INTRODUCTION
Polyphenylene-vinylene (PPV) is nowadays one of the most studied polymers for

numerous reasons associated to its potential technical applications. Beyond the property
common to all conjugated polymers which can become conducting after doping, PPV has
attracted attention due to its remarquable ability to ernit light by either photo- or electro-
excitation. Therefore the possibility of making Light Ernitting Diodes (LED'S) in a wide
range of emission is now reality. As a matter a fact, the possibility of monitoring the optical
properties of such compounds by substitution of appropriate organic groups, added to the
easy processability ofthe polymer via a precursor, has made this material of real importance
in new devicesl-3. The use of other polymers like PPP has also been demonstrated to be
important to extend the range of light emission to the violet, achieving therefore some of the
requirements needed for flat screens for example4 ' 5 Both series of compounds contain
aromatic rings, they are more stable that the so-called prototype conjugated polymer, i.e.
polyacetylene, and have a non-degenernte ground state. It remains that most of these
polymers are rather disordered and exhibit a chain length distribution. This was clearly
proved in polyacetylene via Raman measurements6 8 Some experimental data, although not
evidenced by frequency dispersion of some vibrational modes, demonstrate the same
phenomenon in PPP, PPV or others. Therefore, if one wants to optirnize the compounds to

be used in devices, it is important to control their properties in a reliable manner. In order to
do so, different spectroscopic techniques have been used, starting with known samples like
oligomers to provide reference data.
In particular, extensive studies have been carried in Resonance Raman scattering in the
series of phenylene oligomers from biphenyl to polyparaphenylene9 10 As already
demonstrated, the use of so-called model compounds is of prior importance, in particular for
modelization of Raman spectra. Calculations require the introduction of numerous parameters
which are in general in larger number than the experimental frequencies. Performing a
simultaneous fit on the monomer, oligomers or model compounds is a way to increase
drastically the experimental data to be used, leading to more reliable results in both
assignment and calculated frequencies. In this case, the benzene modes (Wilson notation11 )
are in addition the starting point in such calculations. Different assumptions have however to
be introduced. First, we assume that geometry pararneters are identical from one compound
to the other, or have negligible influence on the frequency calculations. Second, the planar
geometry is introduced tobe able toseparate in plane and out-of-plane vibrational modes. It
has been checked that this assumption is reasonable as far as vibrations of the phenyl rings
are concemed, and problems have been encountered in a few cases for a accurate frequency
determination of some modes, but when an H-H interaction is too strong tobe neglected12
In this paper, we have mostly investigated the neutral state of sexiphenyl and PPP, as
weil as PPV together with its oligomers, trans-stilbene (TSB), distyrilbenzene (DSB) by
means of resonance Raman scattering and high resolution solid state NMR. These studies
were achieved to provide reference data for further investigations of these compounds in their
doped state. Previous calculations predict the appearance of a quinoid structure of the chain
backbone, referred usually to localized excitations called polarons or bipolarons. The
occurrence of the quinoid structure has already been put in evidence by changes in the
carbon-carbon force constants in the case of PPP and PPV9 ' 13 Here, we have extended our
spectroscopic investigation to high resolution Solid State NMR in order to confirm Raman
measurements. Once again, the analysis of NMR spectra requires reference data on the NMR
lines coming from known and weil characterised compounds such as oligomers.
RESULTS
1. Phenylene compounds
Extensive studies have been carried out on polyparaphenylene. Different types of

synthesis Iead to polymers whose characteristics are drastically different in terms of
conjugation length for example. In addition, some of them exhibit a rather strong
fluorescence which has been proved to be due to extrinsic defects and therefore not useful to
utilize in applications since these properties are not reproducible. The bestpolymer compound
is achieved by electro-chemical synthesis inducing a polymerisation of dichoro-benzene and
leading to a rather linear polymeric chain. Nevertheless, the obtained compounds are
inhomogeneous in terms of conjugation length. Recently, the development of LED's has
given a renewed attraction for PPP or derivatives due to the basic colours for flat screens4 5
This was achieved for example with derivatives like ladder-PPP which exhibit a flat
structure 14 Also, new studies have been carried out on PPP oligomers such as sexiphenyl
since the synthesis and processing in these fllms are now rather well controlled. For this
reasons, we have undertaken systernatic investigations on this oligomer is both its neutral and
doped states bv using resonance Raman Scattering.
Let reca1l that Raman spectra of doped PPP have revealed new Raman bands which can
be easily interpreted in a valence force-field model by a modification of the main carbon-
366
carbon force constants. As a consequence, the quinoid type of structure can be confirmed in
the frame of this model in agreement with theoretical predictions performed previously 15
The sexiphenyl oligomer (here after referred to as 6-P) has been synthesis in our
laboratory. Details on the preparation are given in ref.16. It consists in a first step in the
preparation and purification of monobromoterphenyl which is then coupled electrochemically
in the presence of a Ni catalytic complex. The obtained 6-P is then carefully purified by
sublimation in a fumace with of several temperature zones.
The Raman spectrum of the 6-P compound has been studied previously since it has
been used as a model compound to modelize the valence a force field in PPP. We will focus
here on the doped state of 6-P. In ordertobe able to achieve the doping, it is necessary to use
rather strong reducing or oxidizing agents, due tothelarge value of the estimated gap (....3.15
eV). In this study, n-type doping has been achieved by using radical-ions in solution in THF
according to a method weil controlled by Fran~ois and Mathis 17 Raman results are those
obtained with naphthalene-sodium used as the radical salt All samples have been handled in
vacuum cells due to the very high reactivity of the materials in air, characteristics of a very
fast dedoping.
In Fig.1, we show Raman spectra of Na-doped 6P recorded at room temperature using

an excitation wavelength in the red range, A.."" =
676.4 nm. Strong modifications are
observed from a so-called weak doping to a strong doping. Some Raman bands broaden or
are shifted, as weH as new doping-induced bands appear in the Raman spectra. These
modifications with respect to the Raman spectrum of neutral 6P can be summarized as
follows:
- the mode initially observed at 1280 cm 1 disappears at the benefit of a new mode
peaked at 1286-1288 cm 1
- the main Raman band of neutral 6P (1592cm- 1) is downshifted and splitted into two
components at 1570 and 1583 cm 1
- new groups of bands appear at 1180-1198 cmI, 1339 cm 1 and 1495-1520 cm 1 All
of them shift downwards when the excitation wavelength is changed form 457.9 nm to 1064
nm. In the case of high doping Ievel, particular Raman bands are strongly enhanced with the
1064 nm excitation, peaked at 1570, 1469, 1339, 1287 and 1192 cm 1
1200 1400 1600

Raman shift (cm-1)
Figure 1. Raman spectra recorded at 20C of sexiphenyl (6-P) with A.exc=676.4 nm doped
at different doping Ievels: a) weak b) intermediate c) strong.
367
Raman shift (cm-1)
Figure 2. Raman spectrum recorded at 20C of sexiphenyl (6-P) with A.exc-=1064 nrn
doped at saturation with Na.
The interpretation of there results is realizable by a modelization of the Raman spectra

shown above on the basis of a valence force field model. As performed previously on a large
number of polymers or oligomers containing aromatic rings, the structure is considered as
planar and only in-plane modes are taken into consideration. In the case of 6-P, this
assumption is rather justified in the sense that the angle between rings is very small due to the
crystalline arrangement, contrary to the free molecule. Let recall that the main carbon-carbon
force constants are F12 and F/ for the ring and FR2 for the inter-cycle bond. The number of
Raman active modes for the 6-P molecules has been determined previously, and if restricted
to in-plane modes, this gives : 7 A8 + 6B38 + 7B 1u + 6B 2 u In the neutral compound, the
modelization which Ieads to a good calculation of IR and Raman frequencies provides the
following values for the force constants :
F12 = F/ = 6.208 mdyn I A ; FR2 = 5,19 mdyn I A
Details of the calculations will be published elsewhere.
The peculiarity oftbis work is to interpret the experimental data obtained in doped 6-P
in terms of localized excitations such as polarons or bipolarons which are limited in length in
this particular case. In fact, calculations have given good results provided the extemal cycles
are treated differently from intemal cycles, i.e. new force constants called F12 1 and F/ 1 have
been introduced for extemal rings. Calculations have been focused on the divalent species 1>2-6
whose Raman spectrum is supposed to be given by the Raman spectrum shown in Fig.2,
with an excitation wavelength at 1064 nm. A good agreement is obtained for all frequencies
and the following values for the main force constants are as follows :
Ft2 =6.76 F/ =5.68 =

FR2 6.23
=
F12 1 6.40 F/ 1 =5.06 in mdynl A
From there values, it appears clearly that the structure is not totally quinoid, since for
example FR2 is still too small tobe characteristic of a double C=C bond. Also, we deduce a
difference of 5 and 11 % for F/ 1 and F/ 1 compared to F/ and F/. If one takes into account
previous results on p-doped PPP, we notealso that the quinoid structure is favoured in the
case of n-doping, in agreement with observations by Froyer et al. 18 that the electrochemical
reduction of PPP produces many more spins that its electrochemical oxidation. Further
results, in particular concerning the behaviour of the cl>\ species in the presence of THF will
be presented elsewhere.
368
2. Polvphenylene - vinylene (PPV)
PPV films have been extensively studied in the past since the discovery that they can be
used in light emitting diodes. Many different derivatives have been synthesised in an attempt
to shift to higher energies their emission for applications in flat screens. A great effort has
also been made in the preparation of different oligomers in order to gain advantages due to
weil ordered materials of known length. As a matter of fact, a good control of the preparation
of the materials can provide real improvement in terms of reproducibility as weil as longevity
of the devices which use such polymer materials. PPV is prepared via a precursor polymer
which is in general thermally converted under vacuum at ca. 300" C. The synthesis conditions
however are of crucial importance since polymers of different conjugation length can be
obtained. This has been observed in various spectroscopic studies such as X-ray diffraction
from which a coherence length can be deduced from the width of the diffraction peak. A PPV
converted at 300"C for example has a coherence length of .., 40 A, whereas another one
converted at 180"C exhibit only.., 30 A for such a coherence length19 In resonance Raman
Scattering also, although no frequency dispersion is observed as a function of the conjugation
length, the triplet of Raman band in the 1600 cm- 1 region, assigned to carbon-carbon
stretching modes in both the vinyl group (1625 cm- 1) and the aromatic rings (1546 and 1582
cm- 1) exhibitrelative intensities which can vary from one sample to the other. In particular, a
great deal of experiments have been carried out in our laboratory to study the conversion of
the precursor polymer into PPV at a much lower temperature (120C) but under U.V.
illumination with a Xe lamp for durations of typically 30 min. It turns out that the optimized
conditions of conversion Iead to a PPV polymer very close to the one thermally converted at
180C. Fig.3 show the Raman spectra obtained in different cases in which the relative
intensity ofthe three Raman lines around 1600 cm- 1 can be determined. A similar behavior
can be obtained also by UV-visible absorption measurements. Great details on the
photoconversion will be presented elsewhere.
900 1100 1300 1500 1700

Raman shift (cm-1)
Figure 3. Raman spectra of PPV: T= 20"C, /..=.=676.4 nm
a) optimized photoconverted film; b) c) and d) thermally converted at 120C, 240C and
300"C respectively.
369
-. (d)
---..:... -
1200 1300 1400 1500 1600

Raman shift (cm-1)
Figure 4. Raman spectra ofPPV: T= 20C, "-..=676.4 nm

a) neutral PPV; b) c) and d) after weak, intermediate and strong doping with Na
respectively.
The main purpose of our investigation in once again to study the modifications which
occur on the PPV chains by doping. Previous experiments carried out on FeCI3 -doped PPV
have revealed strong modifications in the Raman spectra. A preliminary modelization showed
that a quinoid character can be expected, also the model is over-simplified. In this study, we
have undertaken more systematic studies on n-doped PPV, at different Ievels via a vapour
phase procedure. Fig. 4 shows the Raman spectra obtained after a weak, intermediate and
strong doping of PPV, respectively, compared with the Raman spectrum of neutral PPV,
recorded at room temperature with Ar_= 676.4 nm. Different groups of bands (labelled A, B,
C and D) are observed. The relative intensity of these bands is also very dependant on the
excitation wavelength, as an evidence of a strong resonance behaviour. In addition, our
results are close at those reported by Sakamoto et al. 21
Dynamic calculations on neutral PPV have been published previously 13 Let recall again
that among the 43 force constants introduced in our calculations to determine the frequency of
in-place Raman and i.r. active modes (14 Ag+ 12 Bu), we focus mainly on those associated
with carbon-carbon bonds, namely F,2 and F/ for the benzene ring and F/ and F 0 2 for the
single and double bonds of the vinyl group, respectively. The assignrnent of the vibrational
modes of the neutral PPV has been obtained with the following value F,2 = F/ = 6.21 mdynl
A, F/ = 5.15 mdynl A and F0 2 = 7.23 mdynl A, in agreement with the benzenoid form of
the aromatic ring.
Raman spectra of Na-doped PPV are much more complex than FeC1 3 -doped PPV and
therefore, the modelization is not straitghforwards. As suggested2 \ the existence of ionized
species of different length have to be introduced and in fact, our calculations were refined on
PV2 segments composed of three phenyl rings and two vinyl groups 13
370
Table l. Experimental frequencies in neutral and Na-doped PPV.
Neutral ll70 1197 1301 1415 1546 1582 1625

PPV
Na.<Joped 1156 1174 1216 1240 1250 1287 1312 1344 1425 1455 1508 1539 1583
PPV
Label D A c B B c B c D D c B A
In table 2, we have collected the experimental Raman frequencies in both neutral PPV
and Na-doped PPV with the Iabel we have given to the different groups. One can obtain a
reasonable agreement between experimental data and calculations with the following
parameters:
F/ =5.88 F/ =5.55 F 0 2 = 6.65 in mdyn/ A
Details on our analysis based on the modelization of bipolaronic species will be given
elsewhere. One can deduce that the variations on the force constants are clearly consistent
with a quinoid form along the polymeric chain, as put in evidence by an increase in FR2 and a
decrease of F 0 2 , whereas the aromaticity of the ring is modified since F,2 is now stronger than
F/. Further calculations and refinements are in progress in order to identify all the doping-
induced Raman bands, since the calculations presented here arestill preliminary.
3. High resolution solid state NMR results

In order to understand the modifications induced by doping on the HR solid state NMR
spectra of Na-doped PPV, it is necessary to investigate in detail and to assign correctly the
NMR lines to the different carbon sites. To do so, we also investigated oligomers in the
phenylene family, together with polyparaphenylene (PPP). Then, we studied the PPV series,
namely TSB (trans-stilbene), DSB (distyrylbenzene) and PPV. The scheme presented below
(Fig.6) indicates the Iabel of the different carbon sites, tagether with the position of the NMR
0 ,.. 0 ,. 0. 0
.-:"':.::::: .
. . . .. ::::::::
. . . . . . . .:s. :s:o:::: : .. .
.........
~
.. .. :::::::::::r ;:::~: :::::::::::: . ...

I IJ-
!,
150 140 130 120 110

criso I ppm
Figure 5. HR 13C NMR spectra of Na-doped PPV:

a) weak doping; b) intermediate doping; c) saturated doping.
371
lines in the PPV series, and the assignment given to the different carbon sites. In the case of
Na-doped PPV, the 13C solid state NMR spectra are shown in figure 5 for three different
TSB r1, 1b

ti
2'
2
:b
'(
~
i
\
!4
DSB II I I I I
1 2)'
'
c ' ' ' ,,_ 2
PPV I I I I
140 136 132 128 124 120
oiso /ppm
Figure 6 Left side: Iabel of carbon sites; Right side: assignment of HR 13C NMR lines in
the PPV series.
doping Ievels, i.e. weak, intermediate and saturated doping. The main observation is first that
a broad component develops as a function of the doping Ievel together with a decrease of the
carbon lines. Second, a detailed analysis of this decrease indicates clearly that the NMR lines
assigned to the carbon site Iabelied C, decrease more quickly than those associated with the
other carbon sites. Performing HR 23Na NMR provide additional information. Two
resonance bands are observed at 0 ppm and 350 ppm, characteristics of a totally ionic Na
species and a partially ionic one, respectively. This observation is typical of the presence of
"s" electrons on Na nuclei and the observed Knight shift would correspond to a more ordered
Na-doped PPV phase. Furtherdetails will be published later.
CONCLUSION
We have shown in this paper that complementary data can be obtained in the
understanding of conjugated polymers in both their neutral and doped states by using two
spectrospcopic techniques. Resonance Raman Scattering, when performed on neutral
oligomers and polymers, provide information on the changes which occur upon doping in
terms of localized excitations. It remains that refinements in the calculations are needed to
modelize correctly polaronic ob bipolaronic species of different lengths, since our studies Iead
only to qualitative conclusions. Also, the HR NMR experiments tend to comborate our
results, but need to be analyzed and performed further in order to be exploited on a more
reliable manner.
Acknowledgments:
We would like to thank B.Dulieu and Dr. J. Wery for helpful discussions and for the
communication of experimental data prior to publication.
REFERENCES
* The ''Institut des Materiaux" is Unite Mixte de Recherche CNRS/Universite no 6502

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372
3. D. Braun and A.J. Heeger, Appl. Phys. Lett. 58 ( 1982).
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(1991) eds J. Messier et al, Kluwer Acad Publ.
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(1944) eds P.N. Prasad, Plenum Press.
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320 Ilb, 515 (1995).
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(1995).
15. J.L. Bredas, D. Beljonnne, Z. Shuai, J.M. Toussaint, Synth. Met. 43-3, 3743 (1991).
16. A. Simonneau, Ph. D Thesis (1996), unpublished.
17. B. Fran~ois and C. Mathis, Synth. Met. 16, 105 (1986).
18. G. Froyer, Y. Pelous, A. Siove, F. Genoud, M. Nechtschein, B. Villeret, Synth. Met.
33, 381 (1989).
19. B. Du1ieu, and J. Wery, tobe published.
20. J. Bullot, B. Dulieu and S. Lefrant, Synth. Met. 61, 211 (1993).
21. A. Sakamoto, Y. Furukawa, M. Tasumi, J. Phys. Chem. 96, 3870 (1992).
22.1. Orion, J.P. Buisson and S. Lefrant, submitted to Phys. Rev B (1997).
23. S. Lefrant, J.P. Buisson, M. Baitoul and I. Orion, Pure Appl. Opt. 5, 613 (1996).
373
ADVANCED ORGANIC MATERIALS FOR OPTOELECTRONIC
INTEGRATED DEVICES, INTERCONNECTS, AND PACKAGING
Sandalphon, E. Hendrickx, J. Herlocker, G. E. Jabbour, Y. Kawabe,

B. Kippelen, M. M. Morrell, S. E. Shaheen, D. D. Steele, J. F. Wang, and
N. Peyghambarian
University of Arizona
Optical Seiences Center
Tucson, AZ 85721
USA
Organic materials complement many commonly used inorganic materials in

optical devices due to their improved linear and nonlinear optical properties. Research
has progressed on several fronts, investigating the electrooptic, photorefractive, and light-
emitting properties of organic materials, and their mechanical and chemical stability for
commercial applications. We present some of our achievements which demonstrate the
attractive performance of the organic materials, and show that practical optical devices
using organic materials are closer to commercial development.
Photorefractive devices are a promising application for organic materials since the
discovery of high performance photorefractive polymers 1 However, a problern with the
long-term shelf-life of these materials clouded the prospect of their use in commercial
systems. The following section reports on the progress made in understanding the
chemistry and material science aspects of the shelf-life of these materials, and reports
significant progress in extending the shelf-life to several years that make these materials
appropriate for commercially viable devices.
High performaoce photorefractive polymers with loog shelf-life

In these guestlhost polymers a gradual crystallization of the chromophores (50
%wt.) Iimits the shelf-life ofthe samples. The shelf-life ofDMNPAA(2,5-dimethyl-4-(p-
nitrophenylazo )anisole) PVK(poly-vinylcarbazole) ECZ(N-ethylcarbazole)
TNF(trinitrofluorenone) samples with 50 %wt. of DMNP AA was found to vary between
a few hours and a few weeks depending on the starting materials and the processing
conditions. Here we present a new guestlhost photorefractive composite based on
isomeric mixtures ofthe Chromophore NPADVBB (4-(4'-nitrophenylazo)l,3-di[(3"or 4"-
vinyl)benzyloxy] benzene). These composites exhibit a performance Ievel that is identical
tothat of DMNPAA-based samples but have an estimated shelf-life of several years at
room temperature.
The photorefractive properties ofthe sample were tested by four-wave mixing and
two-beam coupling experiments in the tilted geometry described previously 1 The Iaser
source was a HeNe Iaser (633 nm). The steady-state diffraction efficiencies as a function

of applied field in sarnples with composition DMNPAA:PVK:ECZ:TNF (40:39:19:2
%wt.) and NPADVBB:PVK:ECZ:TNF (40:39:19:2 %wt.) were found tobe identical
within experimental error. For both sarnples maximum diffraction efficiency is observt;d
at an applied field ofapproximately 65 V/JJm. The photorefractive origin ofboth signals
was confirmed by two-beam coupling experiments. The dynamics of the build-up of the
photorefractive grating was similar in both sarnples and are sub-second.
To quantify the shelf-life ofthese different sarnples, we studied the crystallization
behavior of the chromophores in the polymer matrix as a function of temperature. The
crystallization was followed by monitoring the intensity of the light scattered from the
sarnple within a fixed solid angle. Crystallization does not start immediately upon
heating: an induction period for the formation of nucleation sites that scatter light is
observed and followed by a period of accelerated crystallization during which the nuclei
grow in radius. This behavior is characteristic of phase separations occurring through the
mechanism of nucleation and growth. The crystals appear as isolated spots in the
composite matrix. Finally, the intensity ofthe scattered light decreases exponentially with
time due to multiple scattering and backscattering. This behavior is typical and very
reproducible within 25% in the sarnples investigated in this study. To quantify the shelf-
life of guest/host photorefractive polymers we define a reference time tref that
corresponds to the intercept of the linear extrapolations of the induction and growth
phases. That reference time corresponds to the first visible appearance of crystallites in
the polymer matrix.
We investigated the crystallization onset as a function of several parameters
including the sarnple composition, sample temperature, plasticizer to polymer ratio
(ECZIPVK), and the nature of the dopant chromophore. The results are summarized in
Table 1. A first factor that strongly influences the sarnple lifetime is the temperature at
which the sarnple is stored. The reference time tref drops drastically upon heating the
samples. Theories developed for crystallization processes usually describe their
temperature dependence by the Arrhenius velocity equation, commonly used for the rate
of a thermally activated process :
.!.. cx: k = Aex~ -~) (1)

tc RT
where tc isatime constant characteristic for the process, k is the rate constant (s' ), R the
Table 1. Dependence ofphotorefractive polymer shelf-life upon chromophore

species, chromophore doping concentration, melting point temperature, ratio of polymer
to plasticizer, and ambient temperature.
Dye(% wt.) TM( 0 C) PVK/ECZ req tref(s)

DMNPAA21% 161 3/2 75 1650
DMNPAA 19% 161 111 75 250
DMNPAA39% 161 2/l 35 94000

DMNPAA39% 161 2/1 45 1200
DMNPAA39% 161 2/l 55 500
DMNPAA39% 161 2/1 65 200
DMNPAA39% 161 2/1 75 110
DMNPAA39% 161 2/1 85 60
NPDAB39% 149 2/1 85 140
NPADVB839% 127 2/1 85 6600
376
gas constant (8.314 J K 1 mor\ A a prefactor, E the activation energy (J mor 1) and Tthe
temperature (K). Our results show that the nucleation period can be described by an
Arrhenius plot. An activation energy of E = 11 4 kJ mor 1 (0.74 eV) can be deduced.
This value is close to the activation energy for diffusion of gases and liquids in polymers,
20-80 kJ mor', and suggests that the speed of diffusion of the polar molecules in the
polymer matrix is the rate-limiting step in the crystallization process.
Table 1 also shows that the reference time frejdepends not only on the nature of
the chromophore and the temperature, but also on the composition of the matrix and in
particular the polymer/plasticizer ratio. This behavior can be seen from the decrease in
lifetime, from 27.5 min. to 4.2 min. at 75 o C, in samples doped with DMNPAA
chromophores when the PVKJECZ ratio is varied from 3/2 to 111. The addition of a
plasticizer to a polymer increases the free volume and the segmental mobility. This
results in an increased rate of diffusion and consequently a lower sample lifetime.
All these measurements were carried out at temperatures that are well above room
temperature, i.e. well above the glass transition temperature which, for composites with
PVKIECZ 2:1 weight ratio, falls in the temperature range of 0 C to 40 C. If we compare
the lifetime ofDMNPAA-samples at 85 C tothat ofPVK-based composites doped with
other dyes at the same temperature, we can see an increase in lifetime upon going from
DMNPAA, to NPDAB (4-(4'-nitrophenylazo)1,3-di(benzyloxy)benzene) and
NPADVBB. The chemical structures ofthese three chromophores are shown in Figure 1.
This increase in lifetime also corresponds to a decrease of the melting point of the polar
dye. Upon going from DMNPAA to NPADB, it can be seen that the extra phenyl
substituents already induce a lowering of the melting point and an increase in the sample
lifetime. For NPADVBB, however, the vinyl bonds on both phenylrings can be either in
the 3 or 4-position. Hence NPADVBB is a mixture of four isomers, with the vinyl groups
in positions (3,3'), (3,4'), {4,3') and (4,4'). As a result the melting point is lowered further
and the sample remains optically clear for 110 minutes at 85 C. From this behavior, we
can estimate a room temperature shelf lifetime of several years for samples containing 40
%wt. OfNPADVBB and with a PVK:ECZ ratio of2:1.
Besides photorefractive devices, light emitting devices provide an application of
organic materials that has stimulated world-wide research efforts over the past several
years. Organic LEDs may be used in display panels involving millions of elements
arranged over a large area. They may also be used as individual light sources grown on
an integrated circuit for optical interconnects, or other optoelectronic devices. The
commercial demand for large area flat panel displays represents a multi-billion dollar per
year market. In the next section we report significant improvements in the performance of
organic LEDs.
Ultra-bright and highly efficient organic electroluminescent devices with Al cathode

We report on devices with an Al/LiF cathode that exhibit luminance in excess of
20,000 cdlm2 and an extemal quantum efficiency of 3 %. The electron injection process
in quinacridone doped organic light emitting devices has been enhanced tremendously by
inserting a buffer layer ofLiF.
We fabricated an ultra-bright and highly efficient organic light emitting device
(OLED) based on an electron transport and light emitting layer of quinacridone (QAD)
doped Alq3, and a hole transport N-N' -diphenyl-N-N'bis(3-methylphenyl)-[1-l '-
biphenyl]-4-4'-diamine {TPD) layer.
Figure 2 shows a typical structure ofthe devices fabricated for this study, and the
chemical structure of the organic compounds. In a vacuum chamber, a 60 nm layer of
TPD was deposited followed by a 50 nm of Alq3:QAD layer with QAD doping Ievel
controlled to be 0.5 %. After the organic layer deposition, a buffer layer of LiF was
deposited, followed by deposition of an Al cathode. The chamber pressure during the
deposition process was on the order of 10-6 Torr.
377
(a)
rn, (b)
0 ......c H r -
CH3
~
~~HrQ
N
~
~
N
N(h ~ N02
(c)
Figure 1. Chemical structure ofthe nonlinear optical chromophores: (a) DMNPAA, (b) NPADB, and
(c) NPADVBB.
Figure 3 depicts the I-V characteristics, luminance, and quantum efficiency of

Al/LiF OLEDs with various thicknesses of LiF layer. Maximum luminance exceeding
20,000 cd/m2 was measured, and about 3 % external quantum efficiency was observed
for devices with nominal thickness of 0.5-0.8 nm LiF buffer layer. Similar values were
also seen for devices with LiF layers ofvarious thicknesses (l-2.2 nm). In each case, the
presence ofthe LiF layer resulted in a shift ofthe operating voltage to a lower value than
that of devices without LiF.
From Figure 3 (b) and (c), the following observations can be made at 12 V: For
the optimum LiF thickness (0.8 nm), the luminance Ievels are lO times higher than those
of devices without LiF. About six times the external quantum efficiency can be seen in
the Al/LiF devices compared with those without the LiF layer, at 12 V.
When driving these devices to the failure point under continuous voltage operation, and
without cooling, very high luminance Ievels exceeding 45,000 cdlm2 could be seen. To
the best of our knowledge, this is the highest value reported for such devices under a
continuous bias voltage operation, at room temperature and without cooling the devices.
378
(a)
0- 2.2nm
50nm
60 nm
120 nm
Glass
(b)
Quinacridone
TPD
Figure 2. (a) Typical device structure ofthe OLEDs. The SiO stripwas used to avoid shorting the
electrodes during testing.
(b) Chemical structure ofthe organic compounds used in device fabrication.
One possible explanation of the mechanism behind the performance enhancement

in our devices is based on tunneling theoryl-6. LiF is an excellent insulator with a large
bandgap of about 12 eV. As illustrated in Figure 4, the presence of the LiF layer allows
for a large voltage drop across it and thus moves the Fermi Ievel of Al to the point where
it is aligned with the lowest unoccupied molecular orbital (LUMO) of Alq3. This results
in more electrons being injected through the insulating layer directly into the LUMO of
the organic layer leading to an increase in electrolurninescence. The increase in
efficiency to 3 % indicates a more balanced injection of both types of carriers which is
not possible in the case of Al only cathode OLEDs. At a given voltage, as the thickness
of the insulating layer increases, the probability of electron tunneling becomes smaller,
leading to a weaker carrier injection, and thus weaker lurninance.
We have seen the remarkable performance of organic materials for the above
applications. However, these materials must lend themselves to industrial fabrication
methods in order to be commercially feasible. In the next section we report the use of
injection molding and extruding techniques for fabricating organic devices.
379
300
(a)
250 r
.r
E 2oo r
~ 150
.5. ~ D
100

~ 0
20k~----~==============~--------~.--------,
(b)
..- 200 D
i3 100
0
0 ".
c
10k i
c
e 0
.:1
(c)
3 ~
2 -
Oo
D
1 -

0 0 o: a
a
D
oa ccc
.. e o o o o o~CbCbD D C
I I I
6 8 10 12 14 16 18 20 22
Bias voltage (V)
Figure 3. Effects ofLiF thickness variation on the 1-V characteristics and electroluminescence of Al
OLEDs: (a) I-V characteristics (I is used forcurrent density). (b) Luminance. (c) Extemal
quantum efficiency. Legend: +
= 0 nm, = 0.8 nm, 0 = 1.2 nm, 0 = 22 nm, all thicknesses
arenominaL
Materials Processing of Optical Polymers

In order to transfer optical polymer technology to industrial applications, it is
necessary to examine and demoostrate material compatibility with common plastic
manufacturing processes. Among the most pervasive commercial plastic forming
techniques is injection molding. The process may be used to form polymer optical
devices, substrates, or packages, as weil as preforms for use in secondary forming
processes. Also, it is possible that integration might Iead to forming objects which
contain more than one ofthese functions simultaneously.
In producing simple integrated optic devices and packaging, one encounters a
number of material processing issues, many similar to those found in semiconductor
integrated circuit manufacturing. Among these are dimensional control, mutual
380
LUMO LUMO
Al
HOMO
HOMO
Alq Alq
LiF
(a) (b)
Figure 4. Energy band model of: (a) Al/Alq layers, (b) AI/LiF/Aiq layers. For simplicity, no band bending
is shown. The TPD/ITO energy Ievels are also omitted.
alignment, input/output routing, and protection of devices from external environmental

agents which influence performance or reliability. There are also problems unique to
polymer processing, such as material shrinkage during processing, temperature stability
of polymer moieties, and the simple ability to release a part from its mold after it is
formed.
Injection molding capabilities are being developed to ensure that such factors are
considered in the design process for optical polymers. By conducting simple pilot
operations, beginning with studies of surface replication, and following through with
more complex designs, such process feedback will be inferred. These Iead to optical
materials which, aside from having the desired optical properties, also have the
appropriate physical and chemical compatibility to industrial processing. These benefits
extend to other common processes such as compression molding and extrusion, since
many of the same factors influence their capabilities.
Current activity in this area involves sample processing of common industrial
plastics to establish process windows, and the construction of molds which enable rapid
prototyping and transcription of optical surfaces. Goals include applying these molds to
replication studies using common optical polymers to gain an understanding of generat
process issues, followed by fabrication of devices important in applications of nonlinear
optical polymers.
Extruding films of the photorefractive polymers allows these materials to be mass
produced for applications such as holographic data storage and time-gated holography for
medical imaging. In the following section we describe a proof of principle experiment
using the photorefractive polymers for time-gated holography.
381
Transillumination imaging through scattering media using photorefractive
polymers
Imaging through highly scattering media using optical radiation has received
particular attention recently due to potential applications in medical diagnostics. By using
optical radiation one can avoid the hazards of ionizing radiation7 while obtaining high
spatial resolution (potentially diffraction lirnited) images, offering a distinct advantage
over current clinical ultrasound techniques. 8 Additionally, spectroscopic techniques may
be employed to discern functional information. However, optical radiation, unlike
ionizing radiation, is heavily scattered in biological tissue by refractive index
inhomogeneities. As a result, the transmitted light consists of photons that have
experienced no scattering events (ballistic light), weakly scattered photons which emerge
almost collinear with the incident radiation (so-called "snake" light), and highly scattered
(or diffuse) photons. 9 These are shown schematically in Figure 5. Ballistic and snake
light provide useful information about absorption centers in the medium. Conversely, the
diffuse light can emerge from the medium in potentially any direction and usually
significantly later than the first-arriving (i.e., ballistic and snake) light. The main
challenge when imaging through scattering media, therefore, is to selectivell extract the
information-bearing ballistic or snake light without imaging the diffuse light.
A variety of methods have been developed to extract the ballistic light from the
background of the scattered light (see references in Gayen and Alfano9). As mentioned
above, the least-scattered light exits the medium at earlier times than more heavily
scattered light, and several techniques have been developed to exploit this characteristic.
Included amongst these is the technique known as the "light-in-flight" or time-gated
holography method. 10 which has been implemented using photographic emulsions, 10
electronics, 11 and even inorganic photorefractive crystals. 12
We have recentll developed the first high-efficiency, near-infrared sensitive
photorefractive polymer 1 and have demonstrated its use as a recording medium for time-
gated holographic imaging through scattering media. 14 This polymer is a composite of the
dye 2, N, N-dihexylamino-7-dicyanomethylidenyl-3, 4, 5, 6, 10-pentahydronaphthalene
(25-wt. %), the polymer matrix poly(vinylcarbazole) (48-wt. %), the plasticizer N-
+------ d - - - - -
Scattering Snake
medium ----- light
I I
r
Ballistic
light
light
Figure S. Possible event outcomes for photons entering a scattering medium.
382
ethylcarbazole (25-wt. %), and the photosensitizer (2, 4, 7-trinitro-9-
fluorenylidene)malononitrile (2-wt. %), and exhibits sensitivity from 700 to 900 nm.13
This falls within the transparency window ofbiological tissue. 15
The experimental set-up can be seen in Figure 6. In this configuration, a hologram
of an object embedded in a scattering medium is formed in a photorefractive polymer by
the temporal overlap of the reference pulse and the first-arriving (least-scattered) light
from the stretched image-bearing pulse. The fittering of the ballistic photons from the
scattered photons is thus achieved in real-time without any need for digital processing.
The image carried by the ballistic light can then be reconstructed in real-time via
diffraction of a probe beam (pulsed or continuous-wave). This points to the possibility to
perform real-time, in vivo imaging by taking advantage of the polymer's ability to serve
as an erasable holographic recording medium.
The scattering media used in the experiments were various suspensions of
calibrated polystyrene microspheres (Polysciences, Inc.). This allowed us to
quantitatively determine the number of scattering mean free paths that we were able to
image throurJt by calculating the scattering cross-section of the microspheres using the
Mie theory. 6 Using the polymer as our recording medium, we were able to image a
portion of a standard Air Force resolution target through 10 mm of a 0.06-vol.%
suspension of0.55-llm microspheres using 150-fs pulses from a mode-locked Ti:sapphire
Iaser. This suspension corresponds to nine scattering mean free paths, or a ballistic light
attenuation of -I 0-4. These results are seen in Figure 7.
Given the inherent flexibility of guest/host photorefractive polymer systems via
molecular engineering, their demonstration of high diffraction efficiencies in thin layers,
their ability to form !arge area thin films, and their low cost, these media offer significant
possibilities to perform in vivo imaging that provides important morphological
information to physicians.
The research projects presented above show that organic materials can be used in
advanced applications involving photorefractivity. And they have considerable promise
for light emitting diodes in flat panel video displays and as optical interconnects on
Mode-Iocked
Ti:Sapphire
Laser 800 nm
').)2
Probe Beam
Reference Arm
.........
Adjustable
Delay
Medium
Figure 6. Experimental set-up. The circled components are rotatedout ofthe plane ofthe page.
PBS = polarizing beam splitter, iJ2 = half-wave plate, CCD = charge-coupled device camera
383
Figure 7. Timegated hologram of a portion of an Air Force bar target through nine scattering mean free
paths using 150 fs pulses.
optoelectronic circuits. In the case of the photorefractive polymers they can be fabricated
using common industrial processes, such as injection molding or extruding. for mass
production. The advantages of the organic versus inorganic materials in terms of their
low cost, !arge area and complex shape forming capability, and the ability to optimize
their optical properties through chemical engineering, may Iead to the use of
photorefractive polymers and organic materials in practical optoelectronic devices.
This work has been ftmded by ONR through the MURI Center CAMP, NSF,
AFOSR, and AASERT student support through BMDO/AFOSR.
References:
1 K. Meerholz, B. L. Volodin, Sandalphon, B. Kippelen, and N. Peyghambarian, Nature 371,497 (1994).
2 A. G. Fischerand H. J. Moss, J. Appl. Phys., 34,2112 (1%3).
3 Y-E. Kirn, H. Park, and J-J. Kirn,App/. Phys. Lett. 69, 599 (1996).
4 F. Li, H. Tang, J. Anderegg, and J. Shinar, Appl. Phys. Lett. 70, 1233 (1997).
5 L. S. Hung. C. W. Tang. and M. G. Mason, Appl. Phys. Lett. 70, 152 (1997).
6 G. E. Jabbour, Y. Kawabe, S. E. Shaheen, J. F. Wang. M. M. Morrell, B. Kippelen and N.
Peyghambarian, submitted to Appl. Phys. Lett. See also, G. E. Jabbour, Y. Kawabe, S. E. Shaheen, J. F.
Wang, M. M. Morrell, B. Kippelen and N. Peyghambarian, CLEO, postdeadline paper #CPD 19 (1997).
7 See, for example, Z.-H. Cho, J. P. Jones, and M. Singh, Foundations of Medica/ lmaging (Wiley, New
York, 1993).
8 W. R. Hedrick, D. L. Hykes, D. E. Starchman, Ultrasound Physics and Instrumentation (Mosby, St.
Louis, 1995).
9 S. K. Gayen and R. R. Alfano, Opt. and Phot. News 1, no. 3, 16 (1996).
10 N. H. Abramson and K. G. Spears,Appl. Opt. 28, 1834 (1989).
11 E. Leith, C. Chen, H. Chen, D. Dilworth, J. Lopez, J. Rudd, P.-C. Sun, J. Vladmanis, and G. Vossler, J.
~t. Soc. Am. A 9, 1148 (1992).
1 S. C. W. Hyde, N. P. Barry, R. Jones, J. C. Dainty, P. M. W. French, M. B. Klein, and B. A. Wechsler,
frt. Lett. 20, 1331 (1995).
1 B. Kippelen, 8 . L. Volodin, D. D. Steele, Sandalphon, E. Hendrickx, H. Rcke!, L. Erskine, S. R.
Marder, and N. Peyghambarian, submitted.
14 D. D. Steele, B. L. Volodin, 0 . Savina, H. Rcke1, S. R. Marder, B. Kippten, and N. Peyghambarian,
submitted.
15 W. F. Cheong. S. A. Prahl, and A. J. Welch, IEEE J. Quant. Elect. 26,2166 (1990).
16 C. F. Bohren and D. R. Huffinan, Absorption and Scattering of Light by Smal/ Partie/es, (Wiley, New
York, 1997). A. Ishimaru, Wave Propagation and Scattering Random Media (Academic, New York, 1978).
384
SYNTHESIS OF A COVALENT SQUARE GRID
Thomas F. Magnera, Jaroslav Pecka, andJosefMichl*
Department of Chemistry and Biochemistry, University of Colorado,

Boulder, CO 80309-0215
INTRODUCTION
For quite a few years, the area of atomic and molecular scale technology has been the
subj ect of intense speculation. 12 There has also been considerable interest in the actual
synthesis ofvarious more or less complex single-molecule devices, both electrical3 (e.g.
switches 4 and wires 5) and mechanical (e.g.,brakes, 6 tumstiles, 7 levers, 8 and even a mouse-
trap9 ). However, it is often not vety clear how any of these devices would be used in practice
when they float about freely in a solution . Some degree of control over their location in space
and absolute orientation w ould appear highly desirable, particularly if several devices are to
worlctogether. Onepossibility is to adsorb them on a surface in an oriented fashion, perhaps
singly for work with an STM tip 10 or in a periodic array dictated by a surface lattice, 11 or
attached to the outside of a self-assembled monolayer. Still, the degree of control over their
locati.on in space and absolute orientation would remain rather limited. Another possibility
is to allow the devices to form a three-dimensionally periodic lattice of a crystal. Usually,
they will then be packed in a manner over which one has limited control, if any. Such
regulararrays could still be quite useful, e.g., as quantum dots, if one had complete control
overthe separations, the nature of the material that separates them, and the geometry of the
lattice. Much progress in crystal engineering has been made by numerous research groups,
and this type of control may be available in the future.
The effort described below is quite different. W e believe that it would be generally
useful to have the capability to position the active molecular devices permanently in space
in any desired fashion with no more periodicity than desired, possibly none at all, at
preselected distances and at preselected orientations, separated by air or another preselected
material. Such capability would permit the design of true molecular machines, mechanical,
chemical (enzyme-like), optical, or electrical. These would then be based on arbitrary
combinations of precisely positioned and oriented active molecular devices that could be
charged, dipolar or multipolar, conducting or insulating, magnetic, light-absorbing or light-
emitting, electron donating or accepting, linearly or non-linearly polarizable, directionally
and selectively bonding, rigidly held or rotatable, etc.
For some time, we have been attempting to use concepts borrowed from children's
construction kits such as Tinkertoys 12 to develop a covalent molecular scaffolding that would

be built layer by layer, with the composition of each layer potentially different and with each
distance between layers potentially different from all others. 13 14 This scaffolding would
serve to cany and orient the built-in active structures. We refer to the resulting, so far
hypothetical, thin-layer material as a "designer solid". Even without functionalization, the
scaffoldings, and the individuallayers, could be of practical interest, e.g., in size-based
Separations or as templates for the growth of arrays of quanturn dots. In this regard, they
would be reminiscent of but much more versatile than layers of S-proteins, 15 since all
distances and separations would be freely selectable. Admittedly, even a designersolid of
the type described here is still far from the ultimate goal, as it would only provide atomic
design freedom in one dimension, and mere periodicity in the other two. The latter
dimensions would have to be pattemed on a different scale by the usual much cruder tools
ofmicrolithography. Still, such designer solids would nevertheless represent a considerable
step forward.
W e emphasize three aspects of our work. One is the conscious effort to make all
procedures as generalas possible, permitting the future choice of any desired dimensions for
the characteristic lengths in the scaffolding, to the nearest A or so, permitting the choice of
square, triangular, or hexagonal stru cture, permitting the use of transparent or absorbing rods
and connectors, perrnitting the use of a variety of coupling reactions, etc. The second feature
of the project is our desire to secure two-dimensional order and crystallinity, with a
minimum number of defects. This distinguishes our effort from prior work mentioned
briefly below, which produced very thin layers of amorphaus polymers in surface or
interfacial regions. The third important aspect is the covalent nature of the desired
scaffolding, which would make i t sturdy, and would permit the covalent addition of new top
layers without any disturbance to the layers already present. W e realize that many
researchers strive for supramolecular assembly, with individual subunits held by hydrogen
bonds orvanderWaals interactions, and although we admit the utility and advantages ofthe
supramolecular approach, we view it as distinct from the project described here. When it is
expedient, we are willing to accept bonds that arenot strictly covalent, such as metal-ligand
bonds, into our final structures, but only ifthey are kinetically stable and sturdy.
The initial phases of our work were characterized by a synthetic effort directed
toward axially functionalized inert rods with small increments 1416171819 and connectors of
various geometries. 20 21 22 23 Since many such building modules are now available due to
efforts in many laboratories, 13 1416171824 we have more recently focused our attention on the
development of assembly techniques that would produce the desired covalent scaffolding.
lnitially, we are attempting to synthesize just the bottarn layer, i.e., a molecular grid.
A1though we have already presented a conferen ce report25 describing an attempt to synthesize
a covalent molecular grid that could serve as a bottarn layer for a scaffolding, at the time we
bad on1y its IR spectrum and no further characterization and thus were not ab1e to claim that
the desiredgiant molecule was actually formed. The present conference represents the first
time that we can confidently claim the synthesis of a molecular grid, since in addition to
grazing incidence IR spectra we now have STM images that prove the overall structure. 26
Theregularity ofthe grid stillleaves much tobe desired, however, and securing long-range
orderwill be ournext goal. Another important task for the future isafurther increase in the
size of these giant molecules. Ultimately, we hope to make the two wide dimensions
macroscopic, i.e., visible to the naked eye, while keeping the thin dimension under 1 nm.
The covalentgrid thatwe haveprepared of a size so far is an ultrathin (0.7 nm x ~ 150
nm x ~ 150 nm) web composed of ~2.5-nm squares with ~ 1.5-nm square voids and
cantairring nurnerous defects. It has been synthesized by two-dimensional cross-linking
polymerization oflanthanum(III)bis[5, 10, 15,20-tetrak.is(4'-pyridyl)porphyrinate] anion with
p-xylylene dibromide, constrained to proceed on a mercury surface under irreversible
386
conditions. The grid was characterized by grazing incidence IR spectroscopy and, after
transfer to the surface of highly ordered pyrolytic graphite, by STM imaging. lt is quite
sturdy and survives boiling in alcoholic HCl.
SYNTIIESIS
Single-layer two dimensionally cross-linked covalent polymers have been generally

identified as desirable synthetic targets, 27 28 and the manipulation of single graphite sheets
has been of considerable interest as well. 29 However, to our knowledge, only one synthetic
covalent grid polymer of Subnanometer thickness has been reported so far. This was
produced on the surface of a gold electrode by oxidative cross-linking of dissolved
porphyrins carrying four dithienyl or trithienyl substituents in meso positions. 30 The grid
was very irregular, similar to ours. No attempt was made to transfer it to another surface.
Much more attention has been paid to multilayers formed by two-dimensional
polymerization in various constrained spaces, but these are only distantly related to our
synthetic objective. Among these, the closest precedents are the polymeric "perforated
membranes" made from functionalized calixarene multilayers, 31323334 and the multilayer
membrane prepared by interfacial polymerization of meso-tetrapyridylporphyrin quatemized
by propargylation. 3536
Cl)
0
c
ctJ

0
r/1
.Q
<(
1600 1400 1200 1000 800

- -1
v/cm
Figure l. Inset A schematic representation of !wo-dimensional cross-linking polymerization. Grazing
incidence IR spectra: (a) n-Bu.N' salt of 1 in KBr pellet; (b) Hg surface with adsorbed 1; (c) Hg surface after
coupling with 2; JJ.., pyridine;..,. ;v pyridiniurn; e,O porphyrin; .,0 p-xylylene (open Symbols: locally
out-of-plane polarized, closed symbols: locally in-plane polarized), +tetra-n-butylammoniurn.
The method of grid synthesis, that we have been developing 2021 2223 but remained
unproven until now, is two-dimensional rigid-rod cross-linking of point or star
387
connectors, 2021 22 mounted on tentacled pedestals, as shown schematically in the inset in
Figure 1. The tentacles are chosen so as to adsorb very strongly on a liquid surface, causing
the pedestals to be oriented and confined to two dimensions, and yet to possess complete
two-dimensional translational and rotational freedom. Wehave selected mercury as the
liquid on whose surface the synthesis is performed. This offers many advantages: the
interface of mercury with organic liquids is very weil defined, providing accurate vertical
positioning of the pedestals, the surface of mercury is easily cleaned and kept clean, its
properties are easily modified by the formation of amalgams, adsorption on it has been much
studied, its metallic nature provides the reflectivity needed for grazing incidence
spectroscopy 21 23 .25 and the conductivity needed for potential control and for
electrochemistry,37 etc. In the present study, we have chosen the sandwich anion
lanthanum(III)bis[5,10,15,20-tetrakis(4'-pyridyl)porphyrinate] (1) as a four-armed star
connector. This sandwich structure is known 23 25 to adsorb to mercury firmly and with
porphyrin ~parallel to the surface, as needed. The pyridine arms of the upper deck serve
as the links for linear coupling and those of the lower deck, which represents the pedestal,
serve as the tentacles. When a monolayer of 1 on clean mercury surface is treated with p-
xylylene dibromide (2) in absolute ethanol, the desired grid is formed.
La
Admittedly, although the coupler 2 is easily available and quite reactive, it is not
ideal. Its two tetrahedral carbon atoms prevent exact linearity and introduce undesirable
mobility. Moreover, under the conditions of the reaction 2 slowly polymerizes. We are
therefore currently examining other types of couplers.
STRUCTURE PROOF
The s1ructure of the grid has been proven by a combination of IR and STM structural
probes. First, all residual1 was removed from the mercury surface bound grid by boiling in
3% HCl in ethanol. The surface was carefully rinsed and dried. Grazing incidence IR
(Figure 1) showed the absenc e of 1, the presence of all the bands expected from the oriented
grid according to conductor surface selection rules, 38 and the absence of in-plane polarized
porphyrin bands. The IR spectrum resembles that of the material obtained by coupling p-
388
xylylene dichloride with a monolayer of perpendicularly stacked free-base 5,10,15,20-
tetrakis(4'-pyridyl)porphyrin attached to a Si(lOO) surface via a silane. 39
Wewere unable to obtain STM images ofthe grid directly on the mercury surface,
as expected from Iiterature reports 40'41 that STM on liquid mercury is very difficult if not
impossible. Wehavethereforetransferred the grid to the surface ofhighly ordered pyrolytic
graphite (HOPG). This was accomp1ished by depositing a thin layer of polystyrene on the
Hg surface by evaporation from a solution in THF, peeling off the resulting polymer sheet,
placing it on a HOPG surface, swelling it with acetone, and dissolving the polystyrene in
THF. Intensities of peaks in IR spectra showed that all of the grid was removed from the
mercury surface, but on1y a fraction was actual1y successfully transferred to HOPG.
Apparently, some of the domains were carried away by solvent in the polystyrene removal
step.
A typical STM image (Figure 2) shows that the transferred grid is about 0.7 nm thick
and consists of- 150 nm x - 150 nm sheets with the expected pattern of hollow squares of
the anticipated size.
W e believe that the imaged grid sheets are the first of a molecular grid that has
actually been transferred from one surface to another. However, they have poor Iang-range
order, contain many local irregu1arities, and are still relatively small. The shortcomings are
attributed to the irreversibility of the coupling reaction under the conditions used, to
imperfect linearity of the coupler, and to darnage caused by the transfer, and they call for
further effort. The irreversible nature of the coupling conditions used is particularly serious,
as it makes any repair of defects by annealing impossible. We are currently experimenting
with "phantom couplers", designed to bind weakly and reversibly, thus perrnitting defect
removal and domain size growth by annealing, and meant to be replaced ultimately by
irreversib1y bound real couplers in a slow gradual process.
0 25.0 50.0 75.0

nM
Figure 2. STM image of a grid formed from 1 and 2 on mercury surface, after transfer to HOPG Ptllr tip,
constant current mode (bias: - 325 m V, current 131 pA).
389
We conclude that the "molecular Tinkertoy" approach to covalent giant-molecule
grids is promising and are encouraged to continue work towards covalent multi-layer
designer solids. Even the single-layer grid sheets may be of some utility, for instance for fast
size-based Separations, 31,32,33,34, 42 for growth of regular arrays of very small quantum dots, 1143
and for other applications.
Acknowledgments. This work was supported by the Advanced Energy Project program of
the U.S. Department ofEnergy (FG03-94ER12141). The STM instrumentwas funded by
NSF grant CHE-9419335.
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AdvancedMaterials, J.F. Rarrod and R.M. Laine, eds., Kluwer, Dordrecht, The Netherland
(1995).
21. U. Schberl, T.F. Magnera, R.M. Harrison, F. Fleischer, J.L. Pflug, P.F.H. Schwab, X. Men1
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119:3907 (1997).
22. R.M. Harrison, T. Brotin, B.C. Noll, and J. Mich!, Organometallics, in press.
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391
NANOSCALE SYNTHESIS AND PROCESSING OF MULTIFUNCTIONAL
POLYMERSAND COMPOSITES FOR PHOTONICS
N. Deepak Kumar, Manjari Lai, and Paras N. Prasad

Photonies Research Laboratory, Department of Chemistry
State University of New York at Buffalo
Buffalo, NY 14260-3000
USA.
INTRODUCTION
Multifunctional composite materials that simultaneously exhibit more than one

property are a new generation of materials which hold considerable promise for
numerous applications in the field of electronics and photonics. Nanosize control of
molecular architecture and morphology provides a powerful approach to control the
electronic and optical properties as weil as to impart processability of this new generation
of materials. In recent years, the design and processing of nanostructured materials has
emerged as a frontier area of research. These materials simultaneously exhibit more than
one property and, in many cases, produce new effects by the combined action of more
than one property. The electronic and photonie properties ofthese materials are strongly
dependent on their bandgaps. This bandgap dependence has been weil documented in the
case of inorganic semiconductors, where the nanostructure control to produce quantum
dots of different sizes has been used to control the electronic, luminescence and nonlinear
optical propertiesY Quantum confined structures(quantum dots and quantum weils) of
inorganic semiconductors such as CdS is an area that has been active for some time. 34 In
contrast, nanoscale polymerization in restricted geometry to produce quantum confined
conjugated polymers and composites is practically unexplored. This paper focuses on
nanoscale synthesis and processing to control band gap and to prepare novel composite
materials for photonies applications.
NANOSCALE SYNTHESIS
We present here, a novel approach of nanoscale polymerization in a controiled

size cavity of a miceile or a reverse miceile (depending on whether the reactants are
hydrophobic or hydrophilic ), which holds a tremendous promise to produce novel
multifunctional polymeric and composite materials.
Our approach towards the nanoscale processing of multifunctional composites
involves nanoscale polymerization and subsequent chemical processing within precisely
size-controiled cavity of a miceile or a reverse miceile to produce novel polymeric and
Science and Teclmology of Polymers and Advanced Materials

composite multifunctional materials for electronics and photonics. This novel approach
has successfully been applied to produce controlled chain length poly-p-phenylene
vinylene (PPV) polymer, a polymer which has drawn considerable attention in the past
for its electroluminescence56 and nonlinear optical properties 7 PPV is the first
conjugated polymer to exhibit electroluminescence, opening a new frontier of research
dealing with polymer LED. Recently, superradiance in the PPV and PPV analogues have
been achieved, suggesting the prospect of polymer semiconductor lasers. 8- 10 PPV also
exhibits a strong two-photon pumped up-conversion emission when excited by near IR
Iaser pulses of 800 nm. This opens up another prospect, that of up-conversion lasing. 11
Unfortunately, the PPV polymer is insoluble and, therefore, not processable in the
final form. Furthermore, the polymerization condition used in the past produces very fast
reaction which is uncontrollable to produce a finite chain length or low molecular weight
polymer. This also causes a problern in exactly reproducing the same polymer (and
polymer properties) from batch to batch. If one intends to make a polymer blend and
composite with another polymer to improve on the electroluminescence property or the
lasing property, the conventional processing using a water soluble precursor creates a
serious problern in the choice of a suitable polymer. Finally, conventionally processed
PPV has been shown to be prone to photo-oxidation. 12
The PPV polymer is traditionally made by a base catalyzed reaction of a water
solublesalt monomer precursor 13 Since the finallong chain polymer is insoluble, one
first produces a water soluble sulfonium salt precursor polymer in which the vinylene
double bond is not yet formed. This precursor is then heated to form the final PPV
polymer. The reaction scheme is shown below:
-t0-scr CH-CH2j_
Jn
~ -fO-cH=CH-t-
0
In this article, we present controlled, nanoscale polymerization of the PPV
monomer conducted within the size controlled cavity of reverse micelles, which yields
processable PPV. Thus, PPV polymers (oligomers in this case) of controlled band gap
can be easily achieved. These PPV analogs (oligomers) can be readily processed through
dispersion to prepare polymer blends. For polymerization reactions which are highly
exotherrnie that Iead to uncontrolled growth, polymerization within a reverse micelle
cavity provides an alternative method to control extent of polymerization.
Reverse micelies are thermodynamically stable aggregates in organic solvents
where the polar heads of the ampiphiles duster to form a micellar core enclosing the
polar fluid; the hydrophobic tails extend into the bulk/continuous organic phase. 1415 The
solute material is dissolved in the polar fluid which is immiscible with the continuous
phase. The reverse micelies have a polar fluid -to-surfactant molar ratio W0 , which can
vary over a range having a maximum ratio that determines the maximum size of reverse
micelles 16 The double chain surfactant Aerosol OT (sodium bis(2-ethylhexyl)
sulfosuccinate) used here, has been extensively investigated for its ability to form reverse
micellar aggregates in nonpolar solvents and to encapsulate relatively !arge amounts of
water. As the molar ratio, W0, increases, the hydrodynamic radius of the spherical polar
miceBar core increases monotonically with W0
Figure 1 shows the schematic representation of nanoscale synthesis of PPV
within the cavity of a reverse micelle system and the subsequent recovery of the
synthesized species from the system.
394
Water-ethanol 1-------1
mixture
Swfactant
......,!+"-_.. contineous
phase
oil
interface
Figure 1 Schematic of the reverse micelle technique for size controlled synthesis of
poly (para-phenylene vinylene)
Reverse micellar solutions were prepared by dissolving appropriate amounts of

AOT in isooctane (2,2,4, trimethyl pentane) and adding specific volumes of aqueous
solution of the base to achieve the desired W0 value. Volume additivity was assumed
in calculating the AOT concentration and the water/AOT molar ratios. The synthesis of
the PPV polymer involved base catalyzed polymerization of the monomer, xylylene
bis(tetrahydrothiophenium chloride), which in the form of ethanolic solutionwas mixed
with the continuous phase i.e. isooctane. Due to interdroplet interaction which arises due
to the Brownian motion of the reverse micellar droplets, the monomer slowly diffuses
inside the base catalyzed core and polymerization occurs within the cavity. The size of
the reverse miceBar cavity as mentioned earlier is govemed by the amount of the
aqueous solution of the base. Light scattering, neutron scattering, viscometric, and
ultracentrifugation measurements of AOT reverse micelies suggest a spherical shape with
15 A radius in the absence of water. 15 As the molar ratio of water to AOT increases, the
hydrodynamic radius ofthe spherical aqueous core increases with the increase inW0 For
the AOT-water-isooctane system, it has been reported that the inner core radius amounts
to 30 A at W0=15. 16 The situation however changes substantially in the presence of a
dissolved reactal;lt. This is explained to be due to the swelling of the aqueous core in the
presence of a dissolved species which can even effect the morphology of the droplet.
Reverse micellar systems with 0.5M [AOT] and W0 varying from 5 to 20 were examined
for UV absorption and fluorescence measurements. On the basis of preliminary mass
spectroscopic measurements of the extracted PPV, the average number of units in the
polymer chain were found tobe six at W0=15.
Figure 2 shows the uv-vis spectra obtained from the in-situ synthesis of the PPV
polymer at various droplet (W0) sizes. As observed at lower droplet size, the uv-vis
spectra shows structured absorption bands around 380 nm with absorption edge at 440nm
indicating that at low droplet size, the polymer has very few repeating units.
With the increase in the droplet size the intensity of these bands increased and
became more broadened at W0 = 20 with an absorption edge at 500 nm indicative of a
more conjugated system . In all the cases , the retention of the structure in the absorption
spectra is due to the conjugated sequences resulting from the chains which are
essentially oligomeric. 13 Also with the increasing cavity size (W0), a shift in the
absorption edge towards Ionger wavelengths was observed. The figure also shows the
395
""':"' 0.4
-
:I
aj
Cl)
(,)
1:
ca
...0
,g
1/)
,g
<( 0.2
400 500 600

Wavelength (nm)
Figure 2 In-situ uv-vis spectra ofpoly (p-phenylene vinylene) synthesized within

the reverse micellar cavities of varying droplet sizes, (a) W0 = 5, (b) W0 =
10, (c) W0 = 15, (d) W0 =20 and (e) PPV extracted from the micellar
system (W0 =20).
uv-vis spectra ofthe PPV film made by extracting the polymer from the reverse micellar
system. The spectra of the extracted polymer (W0=20) shows a bathochromic (red) shift
suggesting that the polymeric chains are free to grow once removed from the reverse
micelle cavity where the growth of the chain length is hindered due to the encapsulation
within surfactant head groups. Also the loss of structured sequence in the absorption
spectra of the extracted polymer indicates that the polymeric chains are no Ionger
oligomeric rather they have grown/interconnected to form Ionger chain polymers. Thus
the degree ofunsaturation (chain length) can be controlled by varying the droplet size of
the reverse micellar system. It should be noted that uv-vis light spectrophotometry
becomes insensitive to increasing conjugation length for more than 6 repeat units. 17
Analysis by infrared spectroscopy of the extracted PPV polymer (from reverse
micelles) showed a very strong absorbance at 966 cm 1 for the trans-vinyl CH out of
plane bending mode, 18 suggesting that the polymerization reaction yielded trans-PPV
exclusively. The peak at 835 cm 1 is consistent with a para-substituted ring indicating that
the phenylene rings are only present in the para-substituted form. The presence of a small
peak in the 2900 cm 1, sp 3 C-H stretch region, indicated a small fraction of uneliminated
units; These, however were of fairly low concentration and were not expected to
significantly alter the properties of the PPV films.
Figure 3 shows the in-situ flourescence spectra of PPV synthesized within the
cavity of a reverse micelle system of different W0. The fluorescence emission from PPV
oligomers of different chain length resembled that of the typical fluorescence spectra of
396
1.2 - , - - - - - - - - - - - - - - - - - - - - - - - - - - - ,
- - reverse micelle (W0 =5)
- - reverse micelle (W0 =8)
pure ppv film from precursor
~c 0.9
2
E
Q)
u
c
2l
(/)
~ 0.6
0
::l
<;::
~
cti
E
~ 0.3
\
\
450 475 500 525 550

"'
575 600
Wavelength (nm)
Figure 3 In-situ photoluminescence (PL) spectra ofpoly (p-phenylene

vinylene )synthesized within the reverse micellar cavities of different
droplet size, W0 = 5, and W0 = 8. For comparison PL spectra of pure PPV
thin film made from the conventional precursor route is also shown.
pure PPV thin film. The PL spectra of all samples showed weil resolved vibronic
structure. With increase in the cavity size, the peak of the fluorescence emission shifts to
Ionger wavelengths. For comparison photoluminescence spectra ofpure PPV thin film is
also shown in the figure 3.
Using an ethanol dispersion film of PPV, produced by the reverse micelle
approach, we have been able to cast this film or blend with another polymer (such as
PMMA, PVK) through solution phase mixing. These blends could be used for
applications in light emitting devices,solid state polymeric Iaser systems and
photorefractive polymeric devices. Therefore, the reverse micelle approach has provided
processability to PPV.
NANOSCALE PROCESSING
The capability to incorporate many materials with different functional properties
in sol-gel processed glass matrix has been explored in making multifunctional composite
materials for photonies applications. The !arge pore volume fraction and the enormous
surface area of the sol-gel glasses enables one to introduce many materials in to them in a
phase separated fashion, were the phase separation is in the nanometer regime. It is
possible to introduce an active material onto the pore surface by solution infiltration and
subsequent removal of the solvent, then the pores are filled with a monomer containing
another active material and the monomer is subsequently polymerized inside the pores.
Using this approach we have developed composite materials for tunable solid state dye
lasing.
Figure 4 shows the schematic representation of a multiphasic nanocomposite, where
different optically active domains are incorporated into a sol-gel derived porous glass
397
Glass
Phase 1
Interface
Phase2
Polymer
Phase 3
Figure 4 Schematic representation of a multiphasic nanostructured composite glass
through nanoscale processing. In the diagram, phase I represents nanoclusters of

innorganic semiconductors which are incorporated into the glass phase during the
formation of the sol-gel glass. Phase 2 represents the interface between the glass phase
and the pores of the sol-gel glass where an organic phase is introduced by solution
infiltration. Phase 3 is generated in the composite by the in-situ polymerization of a
monomer containing an active organic material. In this manner three distinct phases with
different optical functionality can be introduced into the composite.
Hydrolysis and condensation of silicon alkoxide under carefully controlled
conditions followed by partial densification produces porous silica monoliths of
nanoscale pore size. These pores can be successfully used as a platform for loading
organic molecules to form inorganic-organic composite glass. 1921 The silica skeleton of
the composite glass is prepared by a two-step hydro Iysis of tetraethyl orthosilicate. First,
an acid catalyst was used for hydrolysis, which Iead to a high degree of cross-linkage,
followed by a base catalysis to aceeierate the gelation. The resultant product was a
highly porous monolith with small pores. These monoliths yielded high quality porous
glass after a moderate heat treatment. The porous glass was then impregnated with an
organic monomer (such as methylmethacrylate), which diffuses into the pores, and
polymerize in-situ to form a composite glass. The final composite glass consisted of
32% by volume silica and 68% by volume PMMA. 22 Nitrogen adsorption measurements
indicated that the composite glasses are pore free and hence mechanically stable. 23 The
observed density (1.447 g!cm 3) and refractive index (1.472) are in good agreement with
the expected values from the average macroproperties of the separate phases. These
composite glasses exhibit excellent transmission over most of the visible range since the
domains are of nanometer size.
Using the above approach, two different organic dyes were incorporated into two
different phases of the composite glass to achieve tunable solid state lasing from the
composite glass. Organic dyes Rhodamine-6G and a new Iaser dye trans-4-[p-(N-ethyl-
N-(hydroxyethyl)amino)phenylstyryl]-N-(hydroxyethyl) pyridinium iodide (ASPI) were
introduced in to the composite glass by the same approach, where ASPI was deposited
onto the walls of the porous glass and Rhodamine-6G were incorporated in the PMMA
phase.
The multidye solid state tunable Iaser consisted of ASPI, which resides in the
interfacial phase and Rhodamine-6G, which resides in the polymer phase. Figure 5
presents the fluorescence emission of a multiphasic composite glass containing both
398
. \~~----~--------;1.
I
0.9

08
\\ :'! I
~
::i
$ 0.7
f
.2:!
0.6 .
I
.s 0.5 +
~
:; 0.4 i
5 0.3 t
I.
\ ...
\ -..
:Z: I i
v
I'
0 2 i \\
\\
\:..... ..
0.: J........... '...~- I~ -+--~-
. :;:._
-... ....
~
515 565 615 665 715 765

Wavelength (nm)
Figure 5. Fluorescence emission ofRhodamine-6G composite glass (solid

curve, composite glass containing ASPI (dotted curve) and compoposite
glass containing both dyes (dash-dotted curve).
-~-~
,;
,;
0.4
I
I
0.3

I
I
I
0.2j I
I
I
I
I

I
0.1 [ -+-----' -+---1 ,_,_j
550 560 570 580 590 600 610 620 630 640 650 660
Wavelength (nm)
Figure 6. Lasing Tunability ofRhodamine-6G (diamonds), ASPI (squares), and a

mixture ofRhodamine-6G and ASPI (diamonds) all in ethanol.
dyes. For comparison the fluorescence emission of two composite glasses containing
each dye separately are presented as weil. Emission is observed from both dyes in the
multiphasic composite glass with no significant quenching of emission from either dye.
However, a liquid solution of the two dyes, at the same concentration as that of the glass,
exhibits complete quenching of the Rhodamine-6G emission.
399
Tunahle lasing was also observed across the region of the individual dyes. For
comparison the lasing tunability of the dyes in the solution state were also measured.
Tunahle narrow band Iaser outputs were observed in a cavity consisting of a grating as
the back reflector and a - 70 % reflecting output coupler. Figure 6 presents the lasing
tunability of the dyes in the solution state. Three curves are presented: one of a
Rhodamine-60 solution, one of an ASPI solution, and one of a Rhodamine-60/ASPI
solution, each with ethanol as the solvent. It is clear from this figure that in the
Rhodamine-60/ASPI solution the lasing emission from Rhodamine-60 is completely
quenched.
Figure 7 presents the lasing tunability of a multiphasic composite glass containing
both dyes. For reference, figure 7 also presents the lasing tunability of two composite
glasses containing each dye separately. The FWHM of the tunability spectra for the
ASPI composite glass is - 21 nm and that for Rhodamine-60 - 12 nm. For the
multiphasic composite glass containing both dyes it is - 37 nm. From this data it is
evident that the glass containing both dyes is tunable across the range ofboth dyes, (560-
610 nm), where as in the solution state the Rhodamine-60 emission is quenched. 24 We
believe that the quenching in the solution state is a result of Frster energy transfer.
Therefore, due to the extremely large ratio between the specific surface area and the pore
volume, which is- 8.5 x 106, it is possible to separate the two dye molecules, (which
reside in different phases) to a distance where the Frster energy transfer is not effective.
The rate of energy transter between the donor molecu1e (Rhodamine-60) and the
acceptor molecule (ASPI) in the Frster energy transfer mechanism can be described by
the following equation. 25
k = 9(ln 10)K 2QJ (l)
T 1287t 5n4 Na 'td R 6
where K2 is the orientational factor for the dipole - dipole interaction, Qd is the
1.2 ,----~-~----~---~- ~ --------~-------~
.,..
I
1I
,
\
I \
I \
,C0.8 :
=
I I
rl.l I I
I I
~- I -.
... I I
..:: 0.6 I I
I I
"CC I 1 I
~ ' I I
~ 0.4 t + \
~ I ! ~
z 0.2t i \ ~
J
I ....... ,
I I '7...,~.
0 -c __J__-+~ -- --~-+---~---l----~~-~-4- -~ -~~--!----~
555 565 575 585 595 605 615 625
Wavelength (nm)
Figure 7. Lasing tunability ofRhodamine-60 composite glass (diamonds), ASPI

composite glass (squares), and a composite glass containing both
Rhodamine-60 and ASPI (triang1es).
400
fluorescence quantum yield of the donor molecule without the acceptor molecule, n is the
refractive index ofthe medium, N. is Avogadro's number, 1:d is the fluorescence lifetime
of the donor molecule without the presence of the acceptor, R is the distance between the
centers of the donor and the acceptor molecules, and J is the normalized spectral overlap
integral. From equation (1) the rate of energy transfer is directly proportional to the
orientational factor K to the second power and inversely proportional to the sixth power
of the distance between the centers of the molecules. It is these two factors that we
be1ieve are significantly changed in the mu1tiphasic composite glass. By increasing the
distance between the molecules by a factor of 1.6 we have decreased the rate of energy
transfer by more than one order ofmagnitude. 26 Also, in the solution state, the molecules
are free to rotate and sample most if not all of the orientational possibilities during the
excited state lifetime of Rhodamine-60. In the solid state the molecules are effectively
frozen in p1ace with little or no rotation allowed 1eading to a further decrease in the
energy transfer. 26 Due to the increase in the distance between the mo1ecules and the
decrease of the orientational factor, Frster energy transfer (and other potential
queuehing mechanisms) has been prevented in the multiphasic glass. This result
represents another fascinating possibility embodied in the multiphasic composite glasses
for fabricating multifunctional devices for photonics.
CONCLUSIONS
In conclusion, we have demonstrated that nanoscale polymerization can be a

general powerful method to produce multifunctional polymers and composites. This
approach of producing a multiphasic composite can be used to produce n and p type
inorganic:organic semiconductor junctions such as CdS:PPV with nanometer control of
electron transfer. Multifunctional nanostructured composites for photonies applications
have been accomplished through sol-gel processing and the reverse micelle approach.
We were able to incorporate different photonie active materials in sol-gel glasses in
different phases, with phase separation in nanometer scale. Two different dyes doped in
two different phases of a composite glass showed broad band lasing in the gain region of
both the dyes.
ACKNOWLEDGEMENTS
This research was supported by a University of Southem Ca1ifomia MURI

program sponsored by the Chemistry and Life Seiences Directorate of the Air Force
office of Scientific Research under contract number: F49620-96-l-0035.
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14. G. Drefahl, R. Kuehmstedt, H. Oswald, H. H. Hoerhold, Die Macromol.
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17. D. D .C. Bradley, G. P. Evans, R. H. Friend, Synthetic Metals 17, 651(1987).
18. H. E. Katz, S. S. Bent, W.L. Wilson, M. L. Schilling, Solomon B. Ungashe, J.
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19. E. J. A. Pope, M. Asami andJ. D. Mackenzie,J. Mater. Res. 4,1018 (1989).
20. L. L. Hench and J. L. Nogues, Sol-Gel Optics: Processing and Applications, Ed.
by L. C. Klein, Kluwer Academic, Boston, 1993, Chapter 3.
21. L. C. Klein, Sol-Gel Optics: Processing and Applications, Ed. by L. C. Klein
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402
INTERFACE CONTROL OF POLYMER-BASED LIGHT-EMITTING DEVICES
A.J. Epstein, Y.Z. Wang, D.D. Gebier

Department of Physics
The Ohio State University
Columbus, Ohio 43210-1106
ABSTRACT
Bilayer and multilayer polymer structures provide opportunities for new photophysics
and new types of light emitting devices. Photoluminescent and electroluminescent sturlies
of bilayer heterojunctions formed from a poly(pyridyl vinylene phenylene vinylene)
(PPyVPV) derivative and poly(vinyl carbazole) (PVK) show an emission peak which
cannot be ascribed to either the PPyVPV derivative or PYK layer. Through sturlies of
absorption and photoluminescence excitation (PLE) spectra we demonstrated that the
additional feature results from an exciplex at the bilayer interface. The photoluminescence
efficiency of the exciplex is greater than 20%. We also discuss here the fabrication of
color variable bipolar/ac light-emitting devices based on conjugated polymers. The
devices consist of blends of pyridine-phenylene and thiophene-phenylene based
copolymers sandwiched between the emeraldine base form and the sulfonated form of
polyaniline. ITO and Al are used as electrodes. The devices operate under either polarity
of driving voltage with different colors of light being emitted, red under forward bias, and
green under reverse bias.
Conjugated polymer based light-emitting devices 123.45678 have become a topic
of great interest since the report of electroluminescent (EL) properties in poly(phenylene
vinylene) (PPV). 1 A !arge variety of polymers, copolymers, and their derivatives have
been shown to exhibit EL properties, including a relatively new dass: polypyridines, 56
and poly(pyridyl vinylene)s 6 9 The configurations of these devices may consist of a
simple single layer, 12 bilayers, 2 or blends 7 used to enhance efficiency and tune the
emission wavelength, or multilayers that may allow the device to operate under an ac
applied voltage. 6
In single layer devices the low efficiency frequently is due to the imbalance of
electrons and holes. lnserting a hole-transport (electron-blocking) or electron transport
(hole-blocking) layer provides a means to enhance minority carriers and block the
majority carriers and confine them to the emitter layer, which increases the probability of
recombination. 2 Poly(N-vinylcarbazole) (PVK) has been used as a hole transport layer8
and occasionally in blends with the emitter polymerY PVK is a well-studied photo-
conductive polymer which often forms exciplexes with organic molecules, e.g., dimethyl
terephthalate. 10 An exciplex is a transient donor-acceptor complex between the excited
state of the donor and the ground state of the acceptor. 10
403
For most devices the color of the emitted light is fixed once the device is
fabricated. Recently there has been great interest in developing color variable Jight-
emitting devices, i.e., individual devices that can generate two or more colors of light. In
color variable devices based on blends of polythiophene derivatives, different components
in the blend emit different colors of light simultaneously with the intensity of each
component varying with the applied voltage.U Though such devices can emit multiple
colors oflight, they have very limited control of the brightness at a desired color. Color
variable LECs, 12 which emit two independent colors of light, also have been developed.
The two color LECs offer an improved control of the color and brightness: the color is
controlled by the polarity and the brightness is controlled by the magnitude of the driving
voltage. However, due to the involvement of ionic species in the device operation, the
response ofthe devices is intrinsically slow and not suitable for applications that require
rapid switching of colors. More recently, multilayer light emitting devices which generate
two independent colors were achieved at liquid nitrogen temperature by inserting a
blocking Jayer in between two different emitting polymer JayersY The two colors also
can be controlled by the polarity of the driving voltage. Such an approach improves the
device response time. However, it raises the device operating voltage due to the
introduction ofthe charge blocking layer and retains the stability concems of conventional
polymer LEDs.
We discuss here bilayer devices with PVK as the hole transport layer and a
derivative ofthe copolymer poly(pyridyl vinylene phenylene vinylene) (PPyVPV) as the
emitter layer. Absorption, photoluminescence (PL) and electroluminescence (EL) results
demoostrate emission due to exciplex formation at the interface between the PVK and
copolymer. The PL and EL ofbilayer films are dramatically different from that ofa single
layerfilm.
We also discuss a new approach to color variable light-emitting devices which
generates two independent colors of light at room temperatures. The devices consist of a
layer of active electroluminescent polymers sandwiched between two different redox
polymer layers. The redox polymer layers modify the charge injection and transport
properties such that the device can be operated under both forward and reverse bias.
Also, at least one ofthe redox polymers is capable of modifying the emission properties
of the emitting polymers at the interface so that the interface emits different colors of
light than the bulk does. In this approach, the colors of light are controlled by selecting
the desired emission locations which in turn are controlled by the polarity of driving
voltage and the charge injection and transport properties of the emitting polymers. Since
motion ofionic species is not required for device operation a relatively fast time response
is expected, allowing the colors tobe switched rapidly.
Figure 1 presents the chemical structures of PPyVP(COOC 12H 2s)2V and PVK.
Figure 2 shows the PL of a single Jayer of the copolymer, a single layer of PVK and a
bilayer ofPVK and the copolymer. The PL of single PVK layers excited at 3.6 eV has a
peak emission energy at 3.05 eV, similar to previous reports ofthe PL ofPVK? 8 The PL
for single layer copolymer films excited at 3.1 eV shows an emission peak at 2.05 eV.
The bilayer when excited at an energy less than the absorption edge of the PVK, but
greater than the absorption edge ofthe copolymer shows PL peaked at the same energy as
for the copolymer along with a low intensity tail to the blue side. When the bilayer was
excited at energy equivalent to the excitation energy for the single PVK layer (3.6 eV), the
PL emission spectrum contains contributions from both single Jayers (3.05 and 2.05 eV),
as well as from a completely new species, which we identify with an exciplex. To the
low energy side of the exciplex PL is a weak shoulder near the PL energy for the single
404
(b)
Figure I. Molecular repeat unit of(a) PPyVP(COOC 12H25 ) 2 V and (b) PVK.
1.0
,..-.
::i 0.8
.:!
0
c
0
0
.Cii
c::
'\
~ 0.6 0
0
c::
....... 0
"0
Q) o~ :
~
.!:::l
c; 0.4
.. ..
E
....
z0
0.2
0.0
1.5 2.0 2.5 3.0 3.5
Energy (eV)
Figure 2. PL ofPPyVP(COOC 12H25 hV at 2.8 eV excitation energy (-), a bilayer of
PVK and PPyVP(COOC 12H25 ) 2V at 3.6 eV excitation energy (square) and 2.8 eV
excitation energy (0), and PVK at 3.6 eV excitation energy ("'), all on quartz substrates.
layer of the copolymer. Figure 3 shows the PL intensity as a function of both the
excitation energy and the emission energy. At excitation energies above 3.6 eV the PL due
to the exciplex and PVK are apparent, but ifthe excitation energy is lowered below 3.4 eV
these peaks have essentially disappeared. As the excitation energy is further lowered into
the peak absorption of the copolymer, PL from the copolymer strongly predominates
(excitation energy 2.6-3.0 eV and principal emission energy 1.8-2.2 eV).
We fabricated bilayer devices using ITO as the anode and aluminum as the
cathode. The inset of Fig. 4 shows the EL spectrum of a typical device with the PL
spectrum from the same device. The devices can easily be seen in a brightly lit room,
appear bright green to the eye, and have internal quantum efficiencies of -0.1%-0.5%.
Although the PL efficiencies are comparable, the EL efficiency of the bilayer
405
PVK single
layr r peak
Figure 3. PL of a bilayer of PVK and PPyVP(COOC 12H25) 2V as a function of both emission energy and
excitation energy. The 3D plot shows three prominent features: a peak due to the PVK (excitation energy
from 3.6 to 4.2 eV, emission energy from 2.8 to 3.4 eV), a peak due to the copolymer (excitation energy
from 2.4 to 3.0 eV, emission energy 1.8 to 2.2 eV), and the exciplex peak (excitation energy from 3.6 to
4.2 eV, emission energy 2.2 to 2.8 eV).
100
~
0.4 ::i
~
~
c
;;;
80
"'E c::
,....,
E 0.3 ]
<
5
0)
u
c::
60:0
"'e:
~
c
;;;
0)
u
"'"'
c:: 0.2 "'
0)
c::
0)
0
0)
e 40~
c::
c
0) "'
-l c
al
t:
"'
u 0.0 2.0 2.5
Energy (eV) 20
0.0
0
0 5 10 15 20 25
Voltage (V)
Figure 4. Current-voltage (-) and brightness-voltage (square) characteristics of a typical
bilayer light-emitting device. Inset: PL('') and EL(-) of a bilayer light-emitting device.
configuration, -0.1%-0.5%, is much greater than for a single Jayer device which has an EL
efficiency of less than 0.0001%. The similarity between the PL and EL of the bilayer
device demonstrates that the exciplex is responsible for the EL emission. Figure 4 shows
the current-density valtage and brightness-voltage characteristics for a typical bilayer
406
device. The tum-on voltage of the bilayer devices depends on the thickness of the
polymer layers and in this case is -18 V, with the brightness following the current. The
generality of this concept has been demonstrated using several other pyridine-based
copolymers. 14 Through the use of polyaniline network electrodes 15 we have lowered the
threshold voltage to below 10 V while maintaining the same efficiency .16
Thus heterojunctions of PVK and PPyVP(COOC 12H 25 ) 2V show a strong
photoluminescence and electroluminescence feature due to exciplex emission at the
interface. The absorption and PLE spectra have shown that the exciplex is not directly
accessible from the ground state. The exciplex is also the primary species of
electroluminescence emission in the bilayer devices. The efficiency of the bilayer devices
is greatly enhanced over single layer devices due to charge confinement and exciplex
formation and emission at the interface.
Fortwo-color devices presented here, a copolymer of poly(pyridyl vinylene) and
poly(phenylene vinylene) derivative, PPyVPV*, and a copolymer of polythiophene and
polyphenylene derivative, PTP*, were used as the emitting materials; sulfonated
polyaniline (SPAN) 17 and the emeraldine base (EB) form of polyaniline were used as the
redox materials; ITO and Al were used as electrodes. Figures 5 and 6 show the chemical
structures ofthe polymers used and the schematic device structure, respectively. The EB
layer was first spin coated at -3000 rpm from N-methyl pyrrolidinone (NMP) solution
(b)
(c)
'=~~f~~ OCH3
(d)
OCH3
Figure 5. Repeat units of polymers used in this study. (a) PPyVPV* [poly(pyridyl
viylene phenylene vinylene) derivative]; (b) PTP* [poly(thienylene phenylene) derivative];
(c) EB (emeraldine base); and (d) SPAN (sulfonated polynaniline).
407
Al
SPAN
EB;:::::.
Emitter--
ITO----
Giass L---------'
Figure 6. Schematic diagram of the color variable light-emitting device.
4 103
;- 1.2
~ 1.0
3
;?;- 0.8
"i!!
\
0.6
N
E 2 .<!! 0.4
102
E - c 0.2 ~
N
.s< \ ....1
:c
E
--
w 0.0
\
500 600 700 800 ~
?:- Wavelength (nm) ?:-
"(h 0 II 101 "(h
c c
(I)
0 .<!!
-1 E
c ....1
~ w
5 -2 'b
II
0

10
0
0----
0
0 0
-3 '' f
""'
00
-4
0
10"1
-15 -10 -5 0 5 10 15
Voltaga (V)
Figure 7. Current-voltage and light-voltage characterist.ics of color variable light-emitting

devices under forward and reverse bias conditions. The device emits red light under
forward bias and green light under reverse bias. Inset shows the electroluminescent
spectra of such a device under forward and reverse bias conditions.
(concentration of - 5mglml) onto precleaned patterned ITO substrates (with a sheet

resistance of 15 Q/square). The emitting layer was then spin coated over the EB layer
from a blend of PPyVPV* and PTP* (3 :2 weight ration) in xylenes or trichloroethylene
(total concentration -10 mglml). The SPAN layer was subsequently spin coated over the
emitting layer from an aqueous solution. This device differs from the prior SCALE
device 18 in having different polyaniline forms on the two sides of the light emitting
polymer. Figure 7 shows the typical I-V and luminance-voltage characteristics of the
devices configured as in Figure 6. The devices have typical turn-on voltages of -4-8 V
depending upon film thickness and work equally weil under both polarities of driving
voltage as reported earlier for similar symmetrically configured ac light-emitting (SCALE)
devices, with different colors of light being emitted. The light appeared red and green to
the eye under forward and reverse bias, respectively, and was clearly visible under normal
indoor lighting. Interna! device efficiencies of up to 0.1% photons/electron has been
achieved for the initial devices. The EL spectra under forward and reverse bias are shown
in the inset of Fig. 7. The CIE chromaticity x,y coordinates of the two spectra are
408
calculated tobe (0.654,0.345) and (0.471,0.519), respectively, showing both colors tobe
relatively pure. The colors of the devices have been switched rapidly, up to -20kHz,
depending upon device impedance and geometry.
The EL spectra under forward bias is substantially different from that ofthe single
layer devices of either PPyVPV* or PTP*, suggesting that the light is generared from the
interface between the emitter blend and either EB or SPAN under forward bias. The red
light is generated from the PPy VPV* /SPAN interface on the cathode side und er forward
bias. Sturlies suggest the formation of complex species due to the quartemization of the
pyridyl units by SPAN.
The new approach to the color variable light-emitting devices reported here has a
number of important advantages:
(I) The two redox polymers modify the charge injection properties of the
polymer/meta! interfaces allowing the use of high work function metals as
electrodes. This potentially reduces the aging problems associated with reactive
low work function metals.
{2) The introduction of the two redox polymers allows the devices to operate in
both forward and reverse bias. Since no ionic species are directly involved in the
device operation, the colors can be switched very rapidly, in sharp contrast to
intrinsically slow response LECs.
{3) The emitting polymers are protected by the redox polymers against direct
exposure to air, potentially improving the device stability.
(4) ac or periodically reversed operation may retard failure due to migration of
metals from the electrodes into the polymer. Such operation may also dissipate
the buildup of space charges.
In sum, bilayer and multilayer structures show unusual photophysics phenomena
and provide means offabricating unusual devices with new functions.
This work was supported in part by the Office of Naval Research. The authors
thank Nitto Chemical Industry Co., Ltd., for providing the SPAN materials.
REFERENCES
1 J.H. Burrougbes, D.D.C. Bradley, A.R. Brown, R.N. Marks, K. Mackay, R.H. Friend, P.L. Bums, and
A.B. Holmes, Nature (l..ondon) 347:529 (1990).

2 D.D.C. Bradley, Syntb. Met 54:401 (1993), and references !herein.
3 A.R. Brown, D.D.C. Bradley, J.H. Burrougbes, R.H. Friend, N.C. Greenbam, P.L. Burn, A.B. Holmes,
and A. Kraft, Appl. Pbys. Lett. 61:2793 (1992).

4 Y. Yang, Q. Pei, and A.J. Heeger, J. Appl. Pbys. 79:934 (1996).
5 D.D. Gegler, Y.Z. Wang, L.B. Lin, J.W. Blatcbford, S.W. Jessen, T.L. Gustafson, T.M. Swager, H.L.
Wang, A.G. MacDiarrnid, and A.J. Epstein, J. Appl. Pbys. 78:4264 (1995).
6 Y Z. Wang, D.D. Gebier, L.B. Lin, J.W. Blatcbford, S.W. Jessen, H.L. Wang, and A.J. Epstein, Appl.
Phys. Lett 68:894 (1996).

7 B. Hu, Z. Yang, and F.E. Karasz, J. Appl. Pbys. 76:2419 (1994).
8 C. Zbang, H. von Seggern, K. Pakbaz, B. Kraabel, H.-W. Scbrnidt, and A. J. Heeger, Syntb. Met. 62:35
(1994).
9 J.W. Blatcbford, S.W. Jessen, L.B. Lin, T.L. Gustafson, H.L. Wang, T.M. Swager, A.G. MacDiarrnid,
and A.J. Epstein, Pbys. Rev. B 54:9180 (1996).

10 M. Pope and C.E. Swenberg, Electronic Processes in Organic Crystals, Oxford University Press, New
York (1982) p. 739.

11 M. Berggren, 0. Inganaas, G. Gustafsson, J. Rusmusson, M.R. Ansersson, T. Hjertberg, and 0.
Wennerstrom, Nature (London) 372:444 (1994).

12 Y. Yang and Q. Pei, Appl. Pbys. Lett. 68:2708 (1996).
13 M. Hamagucbi and K. Yosbino, Appl. Pbys. Lett. 69-143 (1996).
14 D.D. Gebier, Y.Z. Wang, A.G. MacDiarrnid, D.-K. Fu, T.M. Swager and A.J. Epstein (unpublisbed).
409
15 Y. Yang and A.J. Heeger, Appl. Phys. Lett. 64-1245 (1994).
16 Y.Z. Wang, D.D. Gebier, D.-K. Fu, A.G. MacDiannid, T.M. Swager and A.J. Epstein, Synth. Met.
85:1179 (1997).
17 W. Lee, G. Du, S.M. Long, A.J. Epstein, S. Shimizu, T. Saitoh, and M. Uzawa, Synth. Met. 84-807
(1997).
18 Y.Z. Wang, D.D. Gebier, L.B. Lind, J.W. Blatchford, S.W. Jessen, H.Ll. Wang, and A.J. Epstein, Appl.
Phys. Letter 68:894 (1996).
410
ELECTRICAL TRANSPORT AND MAGNETOCONDUCTIVITY IN DOPED
POLYPYRROLE
M.D.Migahed 1, T.Fahmy 1 and S.Roth2
1Polymer laboratory, Phys. Dept., Faculty of Science, Mansoura Uni.,

Mansoura, Egypt.
2Max-Planck Institute for Festkorperforschung, Reisenberg str.l, 70569-
Stuttgart, Germany.
ABSTRACT
Polypyrrole doped with Toluene-p-sulfonate (PPy (TOS)) has been prepared
electrochemically at different current densities. lt was found that, electrical conductivity (
=
cr) has a great dependence on the current density i.e., (cr 0.17 and 50 S/cm at j= 0.5 and
7.5 mA/cm2 respectively). conductivity has been fitted according to Mott's equation in a
wide range of temperature from 18 K to 200 K with a good agreement in 3D-system. In
addition, it was observed that, polypyrrole samples have a strong positive
magnetoresistance at very low temperatures and it has a quadratic behavior at small
magnetic fields, up to H= ST.
INTRODUCTION
The field of the conducting polymers has been rapidly expanding during the last
two decades or so. 1 Since the discovery of the high conductivity of intrinsically
conducting polymers, a lot of work in research and development on this kind of material
has been carried out. The conductivity of intrinsically conducting polymers is directly
connected with the specific electronic structure of the polymers. The carbon backhone
consists of a chain of strictly altemating single and double bonds, a so-called conjugated
system and, the difference between several intrinsically conducting polymers is produced
by the side groups added to this carbon backbone.
Conducting polymers are also seen as candidates for many important applications.
Polypyrrole (PPy) is an interesting candidate for several applications, as it is
comparatively stable in the atmosphere and also has some interesting optical properties.
PPy can be readily prepared as free standing films since in 1979 Kanazawa and co-
workers2 used an improved electrochemical technique for the synthesis. PPy is normally
made electrochemically, by which method the material is produced in its doped film state.
Science anti Techrwlogy of Polymers anti Advanced Materials

The anion from the electrolyte is incorporated directly into the polymer film. PPy in its
electrochemically oxidized state is often claimed to be relatively stable to atmospheric
exposure. However, it has been observed that degradation of conductivity, as weil as an
optical change, takes place during prolonged storage in air. 3
To describe and explain the transport process of conducting polymers, it is helpful
to distinguish between two different regimes, the first regime being of low and medium
conductivity and second regime of high conductivity. The model of electrical transport in
the regime of low and medium conductivity has been derived from inorganic amorphous
semiconductors. The model of hopping conductivity (Mott hopping)4 is modified to the
model of variable range hopping, conceming low dimensionality and the semiconducting
character of intrinsically conducting polymers. The basic idea ofthis model is a hopping
of charge carriers between defect states that have been created by the doping process. The
hopping probability depends mainly on distance between the defect states (doping
concentration) and on the energetically interval between the states (temperature). Within
the model, the dependence of conductivity on temperature and doping Ievel can be
explained quite reasonably.
As means to know the transport mechanism, we threw our attention to
magnetoconductance at low temperatures. Magnetoresistance has traditionally been a
powerful method to probe the mean spatial characteristics of charge transport and
scattering processes in metals. In this paper we will present the dependence of electrical
conductivity on current density and magnetic field dependence on the low temperature
conductivity ofpolypyrrole doped with toluene-p-sulfonate (PPy(TOS)).
EXPERIMENTAL WORK
The polymerization ofpyrrole monomer can take place electrochemically as weil as
chemically. Chemically, pyrrole monomer can be oxidatively polymerized in both
solution and vapor phase. 3 The most convenient technique to demonstrate the preparation
is to use pyrrole monomer in an aqueous solution in one compartment cell.
We have prepared different polypyrrole samples at different temperatures. Initially
the pyrrole monomer (Fluka) was distilled twice just before the polymerization process
under reduced pressure. The doped polypyrrole films with toluene-p-sulfonate were
obtained by using the electrochemical oxidation of pyrrole monomer on the Pt foil as
anode, with an area of about 6 cm2 ( cathode was also Pt foil) in an electrochemical cell
containing a solution of 0.2 M pyrrole monomer and 0.1 M of tetraethylammonium
toluene-p-sulfonate, C 15H27N03S, (Fluka) and 1% volume of water in acetonitrile (
Merck, Germany) as a solvent at different current densities and temperatures. After
polymerization the free standing films of PPy-TOS with different thicknesses ranging
from 200 11m to 400 11m were peeled off the electrode and washed several times in pure
acetonitrile, then dried under vacuum at room temperature. A cooler (model Julabo F 10, -
50-200 Oe , Germany) was used to prepare different samples at low temperatures.
Electrical conductivity measurements for all the samples were done by using the
four-probe technique in the temperature range from 4.2 K to 300 K, whereas,
magnetoresistance measurements were done, for the polypyrrole sample PPy * which was
prepared at T= 253 K and atj= 7.5 mA/cm2 , in the temperature range from 1.2 K to 4.2 K
by using a 4He cryostat (OXFORD model No:B27016) containing a superconducting
magnet of 12 T. The applied current was lilA which was supplied by a 244 Keithley
programmable current source which was connected to a 196 Keithley DMM system.
412
(a)
..
101
,. ,.
0

0
0
100

. ..
,.
.._
1()-1
E
i. 0 '0
~b 1()-2 ~ 0 0 j= O.SmAJcm2
j= 2.0mAJan2
0 j:: 30mAJan2
1(}3 ... j= 4 OmAian2
... j= 5.0mAJan2
1(}4

liE
j= 6.0mAJan2
j= 7.5mAJan2
0
0 j= 9.0mAJcm2
1(}5
j= 16mAJcm2
0.2 0,3 0.4

T-1/4 (K-114)
(b)
.. --
,. ,. "' )lf ,.
<>oo o- o~
101
............ -... -
........_. - ..
E
0
100
~ ~
----
0 0 0
u;
b
j= 0 SmAJcm2
o j= 2.0mAJcm2
10- 1 j= 3 OmAJan2
"" j= 4.0mAJcm2
iil-_

.,.

j= 5.0mAian2
j= 6 OmAJan2
liE j= 7.5mAJcm2
1 o-2 .___~ _ __.___ __.__..__.....__.......__.___ --

_.__~_....._
....;:,.o _ ____,
0
0
j= 9.0mAJan2
j= 16 mAJcm2
0,0030 0,0035 0,0040 0,0045 0,0050 0,0055
T-1 (K1)
Figure (1): a) Conductivity vs T-l /4 and b) Arrhenious plot for different polypyrrole samples prepared at
different current densities.
413
Electrical Conductivity
The properties of electrochemically-prepared polypyrrole samples are expected to
depend, not only upon the kind of counter-ion, but also upon the preparation conditions,
such as the type of the current density and temperature. Although the counter-ion is
indispensable for the charge compensation of conducting polypyrrole, it behaves as an
obstacle to the carrier path. Therefore, the size and the shape ofthe counter ion are
expected to in:fluence electrical conductivity.
A mechanism very often proposed to explain the electrical conductivity in
disordered and amorphous materials is Mott's variable-range hopping. 4 In the variable-
range hopping model it is assumed that the carriers are quasi-free in thesensethat their
localization length is large enough and electron-phonon coupling is small enough; to
prevent polaron formation, that is self-trapping of the charge carrier in its own phonon
cloud.
According to this model, the electrical conductivity temperature dependence follows
the form4
1/l+d
cr = cr0 exp [-(Toff) ] (1)
where d =I, 2, and 3 for one, two and three dimensions respectively and T0 is the
characteristic temperature.
Figure (1.a) shows the temperature dependence of electrical conductivity of different
polypyrrole samples prepared at different current densities, according to Mott's equation.
The complex morphology of PPy (polymer chains, small crystalline regions, fibrils,
disturbances effected by the anions), makes it difficult to describe the transport properties
by a consistent model within a large temperature range.
However, one can observe that the plots obeyed the Mott equation, in a wide range
of temperature from 18 K to 200 K, with some deviation from the equation below 18 K
and slightly deviation above 200K. This deviation which is observed at high temperatures
may be due to spatial inhomogenties and lower dimensionality. 4 Starting from 200 K and
around the room temperature the electrical conductivity fitted Arrhenius equation better
than Mott equation suggesting nearest-neighbor hopping as shown in Figure (l.b). It was
found that the activation energy decreases as the current density increases until the optimal
Ievel (7 .5 mA/cm2) and then increases again, as listed in table 1. It was observed that in
Mott's plot the deviation below 18 K was smaller as the current density was higher.
Accordingly, for samples prepared at high current densities, the plots were close to the
Mott's equation down to 18 K, suggesting that the electrical conduction is dominated
mainly by the mechanism based on variable range hopping in a wide temperature range.
The 3D Mott's model has now been observed in many conducting polymers. 5
The most interesting observation is the variation of To with the values ofthe
current density, values of T0 ranged from 4.24xi04 to 3.26x107 K relating to different
current densities. In addition, it was found that the room temperature electrical
conductivity increases as current density increases up to some optimal value (cr:: 50 S/cm
at j=7.5 mA/cm2 ) and then decreases at higher current densities. At lower current
densities oxygenation of active sites on the pyrrole ring may occur in preference to the
polymerization reaction, resulting in chain termination and thus a low conjugation length.
lt is also, probable at high current densities that side reactions occur, which result in lower
conjugation lengths and thus higher defect concentration. This Ieads to forrnation of
potential barriers, inhibiting electrical conduction. 6
414
Table (1): Room temperature electrical conductivity cr, characteristic temperature T 0 from Mott's plot
in 3D-system, and activation energy L1E, and initial conductivity cr 0 , from Arrhenius plots at
different current densities.
j(mA/cm2) cr(S/cm To(K) L1E(eV) cro(S/cm)
~---------------------- . ----------..----------------. -------~--------------------------
7
0.50 0.174 3.2x10 0.0471 0.250
6
2.00 0.930 9.2x10 0.030 1.227
6
3.00 4.335 1.2x10 0.017 5.150
5
4.00 7.399 4.3x10 0.014 8.355
5
5.00 14.02 3.4x10 0.011 15.454
6.00 26.297 1.2x105 0.011 29.600
4
7.50 47.619 4.2x10 0.009 50.000
4
9.00 33.072 8.1x10 0.010 36.756
6
16.0 6.480 2.6x10 0.021 7.176
MAGNETORESIST ANCE
The magnetoresistance has been measured for the PPy *-sample, in two different
configurations of the magnetic field to the applied current (transverse i.e., H ..L J and
longitudinal i.e., H II J, where J is the current) in the temperature range 1.2K to 4.2K under
the magnetic fieldranging from H = 0 T to H = 10.3T. Figure 2 shows the transverse and
longitudinal magnetoresistance at different temperatures, respectively. As shown from the
Figure (2a&b), the magnetoresistance increases in the positive direction as the magnetic
field increases and the temperature decreases. Since the contribution from electron-
electron interaction increases at lower temperatures and higher magnetic fields 7 , the
magnetoresistance has a higher value at very low temperatures (t..p/p at H=10.3T,
T=1.2K, = 2.4), where p is the resistivity at zero magnetic field and t..p is the shift in the
resistivity caused by the applied magnetic field. This high value of t..p/p is characteristic
for the insulating regime. Similar behavior has been obtained for doped conducting
polymers. 89
The conduction mechanism in this regime is dominated by VRH, where the
magnetic field may modify the conduction process via a Zeeman shift in the Ievels
relevant to hopping. Electron transfers either between singly occupied Ievels or between
doubly occupied and vice versa are suppressed; this leads to a positive
magnetoresistance. 10 Simultaneously, since the Zeeman shift acts oppositely for opposite-
sense spins the mobility edge is partly lowered, so reducing the localization effect. It was
observed that, the transverse and longitudinal magnetic-field cases are qualitatively similar
415
2.0
1.6
1.2
0.8
0.4 T=
0.0
0 2 4 6 8 10 12
H (T)
(b)
2.0
T=l.6K
1.6
1.2 .OK
0.8
0.4
0.0
0 2 4 6 8 10 12
H (T)
Figure (2a&b): Transverse and Longitudinal magnetores1stancc ~p/p (where p is the resistance at H =
OT and Ll.p is the resistance increament) for sample PPy*, respectively.
416
0.5 (c)
0.4 T= 1.6K
T=l.8
0.3
0.2 T=2.5
T=2.8K
T=3.0K
0.1 T=3.5K
T=4.2K
0.0
0 4 16
Figure (2): c) Dependence ofmagnetoresistance L'ip/p on H2 at small magnetic field
to each other. Hence, the magnetic field is rather insensitive to the field direction. This
indicates that the classical orbital effect is not the principle cause.
A characteristic feature of hopping conduction is the very !arge positive
magnetoresistance caused by the field reducing the overlap of the impurity wavefunction
and which gives rise to quadratic behavior of H2 at small magnetic fields, as shown in
Figure (2c ).
For the sample in the insulating regime, the localization length can be calculated from the
expression of the magnetic field dependence on the resistivity (applicable for hopping
conduction) as follow 11
4 3/4
ln [p(H)/p(O)] =t (Lc I LH) (To /T) (2)
where t = 5/2016 for 3D-system, LH is the magnetic field, Lc is the localization length. By
knowing the value of T0 and slope of Eq.2, localization length can be calculated in the
parallel and perpendicular directions. It was found that the localization length decreases as
the magnetic field increases and are comparable to each other at different magnetic fields
in the two different directions and it has a value in the order of - 45 Aat H= 10 T in both
directions as shown in Figure 3.
CONCLUSION
The study revealed that, the electrical conductivity of PPy samples has a great
dependence on the current density. Conductivity has been fitted with a good agreement to
Mott's equation in 3D-system in a wide range oftemperature. PPy-sample has a strong
positive Magnetoresistance at very low temperatures, with a localization length in the
order of- 45 at H =lOT. Moreover, magnetic field configuration has no roJe on the
behavior of the magnetoresistance .
417
-1:>
......
00
Ho:oOT (b)
e H.,3T 1,01 H3T
100 -1 I
A

Hs4T
H,. GT
(a), e
A
Hs4T
H BT
+ Hs8T -. H 8T
+ Hs 10T I/ ~ 0, 8 + H 10T /./
::::::
0 0,6
E '0:
0 /
g :r:
-
0. ~
//.
c: 0,4
10 / --------
0,2 ~/ / ---------
/._____..
k?/-A~
........~--~-------
0,0 -:::::----~---
0,3 I
0,70 0,75 0,80 0,85 0,90 0,95 0,4 0,5 0,6 0,7 0,8
T-1/4 (K-114) T-3t4 (K-314)
Figure (3): a) p(T) vs T-l/4 and b )in [p(H)/p(O)] T- 314 for sample PPy * in the longitudinal configuration at different magnetic fields.
ACKNOWLEDGMENT
The authors (Migahed and Fahmy) are deeply indepted to Max-Planck Institute
(MPI), Germany for the facilities given during the carrying out ofthe experimental part in
the frame of the Egyptian German channel system.
REFERENCES
I. T.A.Skotheim, "Handbook of Conducting Polymers"(Marcel Dekker, N. Y 1986)
2. K.Kanazawa, A.F.Diaz, P.M.Grant, G.B.Street, G.P.Gardini and J.F.Kwak, "Polypyrrole:
an Electrochemically Synthesized Conducting Organic Polymer", Synth. Met., l, 329
(1979/1980).
3. G.B.Street, J.Clarke, M.Kronubi, V.Lee, P.Pfluger, J.Scott and G.Weiser, "Preparation
!!fld Characterization ofNeutral and Oxidized Polypyrrole Films", Mol. Cryst. Liq. Cryst.
83, 1253 (1982).
4. N.F.Mott and E.A.Davis, "Electronic Processes in Non-Cryst. Mater." Clarendon, Oxford
1979.
5. K.Sato, M.Yamaura, T.Hagiwara, K.Murata and M.Tokumoto, "Study on the Electrical
Conduction Mechanism of Polypyrrole Films", synth. Met. 4!1, 35 (1991 ).
6. M.Satoh, K.Kaneto and Y. Yoshino, "Dependence of Electrical and Mechanical
Properties of Conducting Polypyrrole films on Conditions of Electrochemical
Polymerization in an Aqueous Medium", Synth. Met. JJ., 289 (1986)
7. T.F.Abou-Elazab, M.D.Migahed, H.Park, Y.Park, P.MacNeillis, T.Rabenau and S.Roth,
"Magnetoresistance ofPolypyrrole and Polyacetylene", Synth. Met. :M_, 281 (1996).
8. M.Reghu, Y.Cao, D.Moses, and A.J.Heeger, "Counterion-induced processibility of
polyaniline: Transportat the metal-insulator boundary" , Phys Rev. 847, 1758, 1993
9. A.K.Meikap, A.Das, S.Chatterjee, M.Digar and S.N.Bhattachargya, "Electrical Transport
in Doped Polypyrrole Films at low Temperature", Phys. Rev. ]Jfl, 340 (1993).
10. A.Kurobe and H.Kamimura, "Correlation Effects on Variable Range Hopping
Conduction and the Magnetoresistance", J. Phys. Soc. Jpn. U, 1904 (1982).
11. B.I.Shklovskii and A.L.Efros "Electr. Proper. ofDoped Semicond.", (Springer-Verlag
Berlin, 1984) p.212.
4i9
ELECTRICAL PROPERTIES OF PURE PVC
A.A. Bahgatl , S.M. Sayyah2 and H.S. Shalabil

1 Department of Physics, Faculty of Science, Al-Azhar Univ.,
Nasr City 11884, Cairo, Egypt.
2 Faculty ofScience, Cairo Univ., BenisuefBranch, Benisuef, Egypt.
Electrical properties of PVC are of great interest because of their wide electrical applications, and
which can be considered as one of the easily molded insulators. The electrical properties of PVC
depends not only on the chemical composition and structural features but also on the degree of
molecular order. The dielectric investigations provide a fundamental method for studying the
rotational and hopping of electrons processes involved in materials and account for the dispersion
behaviour associated with molecular configuration and its ordering as it affects the conductivity
behaviour. In the present work the Egyptian brand with K value 67 from AI-Amria Petro-Chemical
Co. is being studied. Dielectric properties and Ioss factors together with electrical conductivity at
different temperatures and frequencies are given.
JNTRODUCTION
The main problern in PVC industry is it's thermal instability. The evolution ofHCl
through thermal degradation of PVC may be one source of environmental pollution.
Acid rain may be caused by the evolved HCl which dissolves in water, and its presence
in air may form hydrochloric acid which harms, in general, the surrounding
environment. In the mid-1980s the world bad indications that global Ozone
concentrations has fallen by perhaps a few percentl. Though chlorofluorocarbons
were suspected of being responsible for the drop, there was no firm evidence to convict
them. Beside CFCs, the evolution of HCl through the thermal degradation of PVC can
play the same effect of significant depletion of Ozone.
Polyvinyl chloride (PVC) is an amorphous polymer , in general, a white powder

ranging from fine dust to sand like particles. The polymer is rarely used in the
uncompounded form, and is normally mixed with stabilizers, lubricants and, in the
case of flexible compounds, with plasticizers. It can also be used in the form of pastes
or plastisols in which the polymer forms the dispersed phase in a liquid plasticizer.
PVC is the most versatile of all thermoplastic materials because of the wide range of
formulations with widely varying properties which can be produced from it. There
are three commercial processes for the manufacture of PVCl-7: 1- Suspension
polymerization, 2- Emulsion polymerization, 3- Mass or bulk polymerization.
Vinyl chloride can also be polymerized in a solvent (i.e. solution polymerization) but
this process has received little commercial exploitation. Most PVC is produced by the

suspension method and a wide variety of polymers is thus available. Emulsion
polymers contain residues of soap and are much finer in particle size than suspension
or mass polymers. Mass polymers are characterized by their regular spherical shape,
open porous structure and high bulk density.
In spite of its enormous technical and economic importance, PVC still has many
problems. Its rather low stability to the influence of heat results in discoloration,
hydrogen chloride loss and serious corrosion phenomena8.
The products ofthermal degradation of PVC are hydrogen chloride and a coloured,
highly conjugated residue which are analogous to those from poly (vinyl acetate).
heat
H2 - CH- CH2 - CH- ~- CH=CH-CH=CH- + HCI

\ \
Cl Cl
Nevertheless the mechanism of degradation of PVC is still not completely

understood in spite of the fact that more research time has probably been devoted to
this polymer than to any other. The rate offormation ofHCI is accelerated by oxygen
and under certain conditions, by radical producing compounds like azo-bis-
isobutyronitrile. It has been claimed that hydroquinone, a radical reaction inhibitor,
slows down the reaction, all ofwhich strongly indicates radical mechanism8.
The stabilization of PVC against heat (i.e. thermal stability), Ieads to the
development of complex stabilizer systems and the production of intrinsically more
stable PVC. Electrical properties of pure PVC is of great interest because it can be
considered as one of the easily molded insulator. The electrical properties of PVC
depends not only on chemical composition and structural features but also on the
degree of molecular order and polymerization. On the other band the dielectric
investigations provide a fundamental method for studying the rotational andhopping
of electrons processes involved in materials and account for the dispersion behaviour
associated with molecular configuration and its ordering as they affect the conductivity
behaviour.
The aim of our present work is to study the Egyptian pure PVC manufactured in El-
Amria Petro-Chemical plant, which to our knowledge is the first one on this product.
This will give us an idea about its potential as an electrical product as a major field of
applications of PVC.
EXPERIMENTAL
In the present work PVC: Suspension polyvinyl chloride resin, K-value 67, a
product of Egyptian Petro-Chemieals Co., Egypt, was used. The films were prepared
by a solvent casting technique. A flat glass plate provided with four leveUing screws
and water balance is used as a base for the glass dishes containing the material to
ensure uniform film thickness. The appropriate weight of PVC (5g) was dissolved in
tetrahydrofuran "analar" as a common solvent (lOOml). This solutionwas poured into
the casting dish whose area was 50 cm2 . The rate of solvent evaporation was not too
rapid and could be controlled by placing an inverted 1000 ml beaker over the casting
dish and allowing 1 cm clearance to permit air circulation. The beaker also prevents
dust from contaminating the sample. The solvent is allowed to evaporate over a period
of 24h. The plastic film adheres to the bottom of the casting dish. ,
A sharp bladed microspatula is used to score the film around its edges to detach it
from the wall of the casting dish. The film is then covered with warm water and after a
few minutes it floats to the surface from where it is gently picked up and lay flat on a
non adhering surface such as apiece ofwhatman Nol Filter paper. The filter paper
422
and film are then placed in an oven to dry for 24h at 40 C under vacuum. The
measured thickness of the film obtained by the above mentioned technique was found
to have a high degree of uniformity.
The thermal stability tester Model 1393 is used to determine the stability of PVC
du ring heating. The parameter for the determination ofthermal stability is the time,
in which the chlorine causes a change in colour of the indicator (congored paper
method). The test is according to the DIN 53 381 standard and the ISO R 182
recommendation. The tester consists of a thermal block heater, test tubes, stoppers
with glass tubes and a stop watch. A test tube is filled with the test material up to a
Ievel of 50mm and gently shacked (about 5 g of the material to be tested). In the
bottom part of the glass pipe in the stopper a folded strip of congored paper is placed.
Both the tube and paper are put into the test tube. The test tubes prepared as
described above are placed into the preheated thermal block of the thermostat, and the
temperature is adjusted to the required test temperature. The test temperature for
unstabilized PVC is 180 C. The time required from the introduction of the test tube in
the meta! block thermostat to the moment at which the indicator paper shows a first
clear change from red to blue is recorded in minutes. The results of this test is
recorded. We observed that pure PVC resin have degraded in only 4.7 minutes.
An air bubbles free, from pure PVC was cut 2.5 x 2.5 cm and cleaned from any
residual finger prints and dust using methanol to assure good ohrnie contact. A
circular area of 3 x1o-4 m2 was coated face to face by silver paste and dried in ambient
conditions. Sampie thickness was determined using a flat pin micrometer, and was on
the average 0.5 0.05 mm thickness. The temperature of the sample was measured
using a Cromel-Aiumel thermocouple calibrated with standard international tables.
Uncertainty in the measured valucs of capacitywas 0.005 pF and in conductance
0.5%. D.C. resistivity was measured in the temperature range 300-373 K, where the
applied voltage shows a linear relation with current, i.e. obeys Ohms law.
The A.C. conductance G and dielectric permittivity E were measured using EG & G
Princeton Appl. Res. Lock-in amplifier Model126, applying the electric circuit shown
recentty9, in the frequency range 102 - 2x104 Hz at room temperature. The same
parameters were measured in the temperature range 300-420 Kat a fixed frequency of
103 Hz. The dielectric permittivity E and the Ioss factor tan were calculated using
the same relations given recently 9.
The conductivity a(co) ofthe test sample is given by:
d
o-(m) = Gx(m)- (.Q-lm-1) (1)
a
where d and a are the thickness and area of the test sample respectively. While the
dielectric permittivity of the test sample is given by:
C
Ii 1 = __x_ ; and C = E -a
c0 0 0 d
(2)
and Eo is the permittivity offree space (8.85 xi0-12 F/m) while the loss tangent:
1
tan o = (3)
OJRxCx
where the angular frequency co = 2n:f, while Rx and Cx are the equivalent resistance
and capacitance of the sample. Corrections of stray conductance and capacitance were
done according to ASTM specifications.
RESUL TS AND DISCUSSIONS
The dielectric permittivity E' of pure PVC measured at room temperature for
423
different applied A.C. frequency in the range from 0.10 up to 20KHz was calculated.
It can be seen that the dielectric permittivity decreases slightly from 3.4 to 3.1 as the
frequency increases. This effect is commonly observed in dielectric materials specially
if the temperature or the applied frequency range are not out of the Debye theory
predictions. This is the normal behaviour for dipolar materials such as PVC.
On the other band Fig. (1) shows the variation of &' as a function of temperature at
a constant frequency of 1.0 KHz. It can be seen that as the temperature increases &'
increases gradually up to 356 K and then slowly decreases. This decrease may be due
to thermal agitation which will not allow the dipole to orient. But at the same time, the
contribution of interfacial polarization giving rise to space charge cannot be ruled out
completely. However, Fig. (2) shows the dependence of the loss tan as a function of
temperature at constant frequency f =1.0 KHz. It is clear from this curve that the loss
has a maximum at 351 K which corresponds to the glass transition ofPVC. Also
Fig.(3) shows the relation between tan and ln f at room temperature in the
frequency range from 0.10 up to 20 KHz.
The observed curve shows the familiar behaviour of dielectric materials, where tan
decreases with the increase offrequency in the range mentioned above.
Fig. (4) shows both A.C. (1.0 KHz) and D.C. conductivity of PVC in the
temperature range 298 up to 383 K. It can be seen that D.C. conductivity is drastically
lower than the corresponding A.C. conductivity. Also the D.C. conductivity is
observed to be insensitive to phase changes around the glass transition T g , while on
the contrary the A.C. conductivity is very sensitive to such phase transition as
indicated by the hump. The thermal activation energy is calculated from the D.C.
conductivity by applying Arrhenius relation:
a = a 0 exp (-AE/kT) (4)
where k is the Boltzmann constant and T is sample temperature, this gives AE= 1.51
eV for pure PVC.
The relaxation times which are necessary to describe the present dielectric loss data
is not only due to a distribution of molecular processes, but arises also from a
cooperative relaxation process in which the motion of a given molecule depends upon
its neighbours. This cooperative process may be treated in terms of a diffusion of
defects to the relaxing species, with relaxation being more probable immediately after a
defect reaches it at an arbitrary time. Hence the relaxation tim es of the system not
only depends upon the cbaracteristic time of the molecular relaxation process but also
upon the diffusion rate of the defects. Consequently, the relaxation temperature or
frequency depends on intra and intermolecular interactions. The greater the
intermolecular interaction, the less mobile are the molecules; and the higher is the
relaxation temperature at which the loss maximum occurs, the Ionger is tbe relaxation
time and the lower is tbe relaxation frequency fm. The usual procedure to calculate
the energy associated with the process of relaxation is to measure the sample at
different fixed angular frequencies <D in a wide temperature range and to find out the
temperature at which the loss is maximum Tm then to plot the relation between In <D
vs. lffm and apply Arrhenius plot to calculate the activation energy Q. This
procedure is quite time consuming, and in the absence of a weil defined loss peak and
whether it is characterized by a single relaxation time or by a distribution of relaxation
times, and uncertainties involved in the subtraction of the D.C. conductivity from the
total conductivity, errors are usually encountered. In the present work an alternative
method given next is applied. This entails performing the experiment at only one
frequency over a wide temperature range where a loss peak is observed as shown in
Fig. (3).
424
0.20
0.15
-
00
r::
ca
0.10
0.05 +++ + +
I I I
300 320 340 360 380 400 300 320 340 360 380 400
Temperature (K) Temperature (K)
Figure 1. Real dielectric permittivity of pure Figure 2. Loss tangent of pure PVC at a
PVC, at a fixed applied frequency of 1.0 KHz. constant applied frequency of 1.0 KHz.
0.045
1.0 KHz
0.040 -20
; ::
sc 0.035
c
...J
-24
0.030
o.c.
-28 -+-~--r--r-.,........,...~-r--.,.--.---f
4 6 8 10 0.0024 0.0026 0.0028 0.0030 0.0032 0.0034
Ln(f) 1/T (K-1)
Figure 3. Loss tangent of pure PVC at room Figure 4. D.C. and A.C. electrical
temperaturein the frequency range 0.1 up to conductivity of pure PVC in the
20KHz. temperature range up to 400 OK.
425
In the Debye approximation, assuming a single relaxation time both the dieleetric
permittivities &' and &" could be given as9:
& = &' + j &" (5)
(6)
(7)
Where the loss factor tau = &" !&' is simply given as:
tan 8 = 2 tan 8 m wr i 2 (8)

1+ {i) T1
where
(9)
,, ~ ft
and
(10)
It is easy to see that tau has a maximum aton = 1. while &" passes through a
maximum at <D't =1. lfwe introduce the notation tan m /tan = r, thenwe have the
solution of the quadratic equation :
mr1 = r Jr2 - 1 (11)
and if we assume that the relaxation time 1 depends on temperature T in

accordance to Arrhenius formula then
(12)
Where 'tr is a constant quantity, k is the Boltzmann's constant, and Q is the energy
of activation associated with the relaxation process, assuming that the ratio 1i'tr is
temperature independent. In order to obtain the value of Q for a relaxation
mechanism, the relation between tan d and temperature for a particular applied
frequency (ro) always shows a maximum tan at a temperature where 't =1/ro and r
=1. On combining relations (11) and (12) at a fixed applied angular frequency ro, a plot
between In 1 and lff is obtained taking the positive root sign for the low temperature
part and the negative root sign for the high temperature part of the curve. This plot
should be a straight Iine if we deal with a single relaxation process of the Debye type.
straight lines will be obtained, each corresponds to a particular relaxation mechanism.
Applying the above procedure to the data extracted from Fig. (4), Tm= 351 K where
<D't1 = 1.0 and r =1.0, the relation between In 't1 as calculated using eq. (12) against
1/T is shown in Fig. (5) It is clear that the curve could be described by one linear
relation having slope Q = 0.88 eV = 20.2 KCal/mol. This is describing the energy
426
associated with dipolar-segmental processes occurring at the glass transition
temperature as weil as molecular dipoles orientations . The former is due to
transition from the glassy to the rubbery state while the later is due to localized
movement of molecules. This result may indicate that the activation energy due to
relaxation is less than the activation energy due to D.C. conduction (AE = 1.51 eV).
Consequently it may be said that A = AE - Q = 0.63 eV is the activation energy
association with conduction due to drift mobility.
-7
-8
-9
-10
-11 -+-----r----~----~----~~~~----~-----r-----r----~
0.0026 0.0027 0.0028 0.0029 0.0030 0.0031
1/T (K -1)
Figure 5. Relaxation time 't1 as a function oftemperature.
Some Electrical Parameters of EI-Amria PVC
T (K) f (KHz) a(S/m ) e' tan

300 0.00 3.44 xlo-14 ---- --
0.10 8.32 xlo-1o 3.4 0.044
1.00 6.42.xto-9 3.3 0.035
341 0.00 1.38 x1o-1o --- ---
1.00 5.oo x~o-8 5.0 0.17
373 0.00 5.6 x1o-9 --- ----
1.00 1.11 x~o-8 10.5 0.09
N.B.
a(ro) = ro e' Eo tan , ro =27tf.
From the above results and discussion the foUowing conclusions can be given:
1- PVC suffers from very low thermal stability: 4.7 minutes at 453 K.
2- There is a single phase glass transition at 351 K.
3- The dielectric permittivity varies from 3.4 to 7.2 in the temperature range from 303
to 423 K with a maximum e' = 10.5 at temperature of 373 K indicating apolar
polymer.
4- The behaviour of the dielectric permittivity at room temperature in the frequency
range from 0.10 to 20 KHz shows the familiar trend of polar polymers, and is in the
range 3.4 to 3.1.
427
5- The D.C. thermal activated energy is 1.51 e.V in the temperature range from 300 to
353K.
6- The A.C. activation energy of 0.41 e.V above 356 K.
7- A single relaxation mechanism is observed and is due to dipolar-segmental processes
occurring at the glass transition temperature with relaxation energy 0.88 e.V.
8- EI- Amria PVC is not a suitable material for electrical commercial applications in its
pure form.
REFERENCES
1- B.G. Levi, Phys. Today, 45(7),17 (1992).
2- A.Tager "physical chemistry ofpolymers" (Pl9) Mir Pulbishers, Moscow (1978).
3- RH. Burgess "Manufacture and Processing of PVC" Applied science publishers
Ltd. London (1982).
4- Breon PVC Resins. BP Chemieals International Limited Devenshire House Mayfair
Place. Piccadilly London (1973).
5- N.J. Mills "Plastics" Microstructure, Properties and Applications. Edward Arnold
(Publishers) Ltd. London (1986).
6- A. Keller "lntroduction to Polymerie structure and Properties" University of
Bristol. England (1987).
7- L.K. Mutreja. "PVC compounding and Processing" By SBP Board of consultants
and Engineers. Delhi. SBP chemical Engineering series No. 60 (1982).
8- A A. Yassin and Magdy W. Sabaa "Degradation and stabilization ofPoly (Vinyl
chloride" JMS-REV. Macromol. Chem. Phys., C 30 (3 4), 491-558 (1990).
9- A.A. Bahgat, Matr. Sei. Eng., B26,103 (1994).
428
EMISSION CHARACTERISTICS OF A NEW CLASS OF STRONGLY
FLUORSCENT PHENANTHRENE AND PHENANTHRENE-LIKE DERIVATIVES
Nahed M. Fathy,' Essam. M. Hassan, 2 and Khaled A. Abou-Zeid2
'Photochemistry Department
National Research Center
Dokki
Cairo, Egypt
2Nationallnstitute of Laser Enhanced Science (NILES)
Cairo University
Cairo, Egypt
ABSTRACT
Fluorescence quantum yield ( cJ>r) of some highly fluorescent phenanthrene and

phenanthrene-like derivatives has been measured using diphenyl anthracene as
reference in ethanol .
The experimental critical transfer distances, Ro , between some of these

compounds and rhodamine 6G, 2,5-Distyryl pyrazine (DSP) and 1,4-Bis (-Pyraidyl-
2-Vinyl) Benzene (P2VB) Iaser dyes have been studied using steady state emission in
0
isopropanol giving values in the range from 29.6 to 57.6 A. The underlying
mechanism of energy transferisthat ofFrster type.
INTRODUCTION
Strongly fluorescent materials find various application in many areas including

the fluorimetric estimation of metal ion, 1 solar concetra-toras,2-5 fluorescent
whitening agents, 6 and as Iaser dyes 7
In the present paper we present the spectral characteristics, emission
efficiencies and energy transfer parameters of a series of phenanthrene and
phenanthrene-like derivatives 89 Some of these derivatives exhibit extremely high
fluorescence efficiencies (close to unity) and this makes them of potential applications
in many research and technological areas.
DISCUSSION
Some members of the present series of compounds exhibit fluorescence

e:fficiencies close to unity (Derivatives 4 7 N, 26 N and 23 N). These dyes emit in the
important blue - UV regions with reasonable absorbances at 337 nm which is the
common wavelength of nitrogen laser as a pumping light source. The laser activity of
one of these dyes (Dye 23 N) was tested using nitrogen laseras a pumping source.
Despite the high fluorescence e:fficiencies ofthe dye and its absorption at the pumping
source, no laser action was detected and this may be attributed to excited-state
absorption phenomena.10-11
This dye, however, act as a donor of excitation energy to several known laser dyes
including rhodamine 6G (R6G), 2,5--distyrylpyrazine (DSP), 12 and 1,4-bis(-pyridyl-
2-vinyl) benzene (P2VB). 12 The energy transfer process undergoes Forster-type
mechanism with critical transfer distances, Ro , largely exceeding those of collisional
mechanism. Energy transfer dye laser (ETDL) systems are important in the area of
laser dyes since they provide a means of better harvesting of pump photons and
broaden the lasing range oflaser dyes.
The presence ofheteroatoms in most ofthe studied dyes makes them possible
candidates to the fluorogenic estimation of metal ions and similar systems. The
extremely high fluorescence e:fficiencies, on the other hand, suggest a possible
application of these dyes as solar collectors in the short wavelength of the solar
spectrum.
EXPERIMENTAL
Laser grade rhodamine 6G (Lambda Physik) was used as supplied, 2,5-distyry1

pyra.zine (DSP) was prepared by the method described by Hasegawa et al. 13
Purification was achieved by recrystallization and column chromatography on silica
gel using methylene chloride as eluent and 1,4-Bis (-Pyraidyl-2-Vinyl) Benzene
(P2VB) was also supplied by Professor Masaki Hasegawa of Toin University of
Yokohama, Japan, and was used without further purification. The solvents used were
spectroscopic grade isopropanol and ethylene glycol. Steady state emission spectra
were measured using a Shimadzu RF 510 spectrofluorophotometer using a reetangular
quartz cell of dimensions 0.4 x 1.0 cm. UV-visible absorption spectra were measured
using a Shimadzu UV-160A spectrophotometer.
The room temperature fluorescence quantum yield <l>r (s) were ca1culated
relative to the fluorescence quantum yield of9, 10-diphenyl-anthracene in ethano1
using the relation1 4 :
The indices s and r denote sample and reference respectively. Integrals

represent the corrected fluorescence peak areas, A and n are the absorbance at
excitation wavelength and the refractive indices ofthe applied solvents respectively.
The use of the squares of the refractive indices (n2) gives about 5 percent higher <l>r
values compared with the values obtained upon substituting for the refractive indices
(n) in the above equation. Correction of fluorescence for machine response was
carried out by comparing the fluorescence spectrum of 1.0 x I0- 5 M anthracene
sample with those published by W. H. Melhuish in absolutes quanta15 .
430
The laser activity of some of these dyes was checked using a nitrogen laser
type 1 M 50 A Lambda Physics, A.ex. = 337.1 nm, pulse duration 5 nm as excitation
source. Unfortunately the investigated dyes gave no laser action.
DSP P2VB
R6G
The electronic absorption , emission, excitation spectra and the fluorescence

quanturn yield (cpf) of new prepared dyes were investigated extensively in ethanol.
These dyes' struCtures and data were tabulated as shown in Table 1-4. The emission
spectra using different excitation wavelengths and the excitation spectra (following
the low-energy absorption bands) are shown in Figures (1-26)
S CN
~ 1JC::l
OJ-
8 ~.,hphOCH3
OJ-
23N 26N
The critical transfer distances , Ra , have been calculated from the emission of
donor and absorption speCtrum ofthe acceptor using the Forster formula. 16
where <Po is the emission quantum yield of donor in the absence of acceptor, n is the
solvent refractive index and the integral is the overlap integral for fluorescence
spectrum of donor normalized to unity (F 0 ) and the absorption spectrum of acceptor
(EA) divided by the fourth power of wavenumber (u). Ra is the distance at which
energy transfer and emission processes are equally probable.
431
ooxphN(CH,l,
S CN
GN-10 GN-7
Table 1 Spectral and cpf data
Code absorption '-(max.) emission A(max.) cp; E

no. maxima (excit.) maxima (abs.) M 1cm 1
X 103
23N 369.5 nm 370.0nm 410.0nm 369.5 nm 0.99 16.70
263.0nm 280.0nm 20.90
222.5 nm 37.50
47N 369.5 nm 372.0nm 435.0nm 369.5 nm 0.98 6.50
278.5 nm 290.0nm 23.20
26N 367.0nm 370.0nm 410.0nm 367.0nm 0.99 17.40
271.0 nm 280.0nm 21.90
224.5 nm 33.50
GN-10 370.0 379.0 412.0nm 370.0nm 0.99 16.10
260.0 290.0 15.17
223.0 29.66
GN-7 381.5 nm 380.0nm 425.0nm 381.5 nm 0.35 14.25
275.5 nm 21.25
227.0nm 22.30
GN-8 374.5nm 375.0 nm 420.0nm 374.5 nm 0.29 15.10
274.0nm 19.10
227.0nm 29.20
*'-= = absorption maxima
432
63-N 64-N
GN-1 145-N
Table 2 Spectral and cpf data
absorption emission

Code (max.) ~max. Q>r E
no. maxima (excit.) maxima (abs.) M- 1cm- 1

X 103
385.5 nm 385.0 nm 430.0 nm 385.0 nm 0.713 17.8
63N 298.0 nm 305.0 nm 18.3
266.5 nm 29.4
242.5 nm 42.9
64N 386.5 nm 383.0 nm 430.0 nm 386.5 nm 0.745 21.1
296.5 nm 305.0 nm 22.5
267.0nm 35.0
243.0nm 50.9
GN-1 387.0 nm 390.0 nm 430.0 nm 387.0 nm 0.6 16.8
296.0nm 315.0 nm 18.6
267.0nm 22.4
241.0 nm 35.2
145N 392.5 nm 390.0 nm 435.0 nm 392.5 nm 0.326 15.9
301.5 nm 310.0 nm 16.1
268.0 nm 22.6
(sholder)
222.0nm 240.3
*.ex. = absorption maxima
433
138N 76N
Table 3 Spectral and <pf data
emission
s
Code absorption Acmax.) Acmax.) <l'r
no. maxima (excit.) maxima (abs.) M- 1cm- 1
x w-3
138N 391.5 nm 390.0 nm 440.0 nm 391.5 nm 0.8 16.2
266.5 nm 270.0 nm 12.8
76N 356.5 nm 352.0 nm 390.0 nm 356.5 nm 0.20 12.9
273.0 nm 285.0 nm 23.2
230.5 nm 16.7
*A.ex. = absorption maxima
GN-5
Table 4 Spectral and <pfdata
s
Code absorption A(max.) emission Acmax.) <l'r
maxima (excit.) maxima (abs.) M- 1cm- 1

no.
x w-3
GN-5 373.5 nm 375.0 nm 420.0 nm 373.5 nm 0.11 28.3
272.0 nm 33.2
228.0 nm 51.0
*A.ex. = absorption maxima
434
0.20
0.00 L__ _ _....___ _ _.J...::=~--.L...-----'
200 .wo 400 500 600

Wavelength
Figure 1. Absorption spectra of 1 x 105 M of 23N in ethanol.
0.30 . - - - - - . - - - - - , . - - - . . - - - - - - . - - - - - ,
~ 0.20

-e
"'
~
~ 0.10
0.00 '-----'----L---.L..---L---= ::::-L-----1

200 250 300 350 400 450 500
Wavelengtlz
Figure 2. Absorption spectra of 1 x 10-s M of 47N in ethanol.
- - Acx:= 369.5 nm
- - - - Aex;: 263.0 nm
excit. specra
-. .. -------................
.
--- ---
----
_
500 450 400 350 300 250

Wavelengtll
Figure 3. The room temperature emission and excitation spectra of 1 x 10-5 M of 23N in ethanol
435
The Ra values are summarized in Table (5). It was observed that the values of
Ra are much greater than the value for the collision energy transfer in the range of 4 - 6
0
A .17 This indicates that the dominant mechanism responsible for energy transfer with
these phenanthrene derivatives to R6G, DSP and P2VB is that of resonance energy
transfer due to long-rang dipole-dipole interaction between excited donor and ground
state acceptor molecules.
Table 5: Summarizes the R. values ofthe phenenthrene derivatives.
Compounds Rn A
R6G DSP P2VB
GN-26 50.4 57.6 41.9
GN-7 29.6 43.3 30.68
GN-1 49.7 45.1 33.3
23N 51.6 57.6 42.9
..
I "'' \ :
I \:
I .
I ~
I :\
I : \
I : I
/ : \
: \
,/
//
..
550 500 450 400 350 300 250
Wave/engtlt
Figure 4. The room temperature emission and excitation spectra of I x 1o-s M of 47N in ethanol
436
0.30
0.20
0.10
0.00 t __ _---.Jl....------L:::::====--... 1.----l

200 300 400 500 600
Wavelengtlz
Figure 5. Absorption spectra of 1 x 105 M of 26N in ethanol.
1.50
..,"'t:
-e<:>
1::1
1.00
"'
><:)
"'(
0.50
0.00 '--------1.-'------~-------J
200 300 400 500
Wavelength
Figure 6. Absorption spectra of 1 x 10-5M of GN-10 in ethanol.
- - Aex;' 367.0 nm
---- Aex= 271.0 nm
........... excit. specra
........ ......................
___ ............. ..... .
500 450 400 350 300 250
Wavelengtlz
Figure 7. The room temperature emission and excitation spectra of 1 x 10-5 M of 26N in ethanol
437
- - Aex:= 370.0 nm
- - - - Aex"' 260.0 nm
excit. specra
\\
...
\/
... '

500 450 400 350 300 250 200
Waveleugth
Figure 8. The room temperature ernission and excitation spectra of 6.7 x 10-5 M of GN-10 in
ethanol
0.00 L------'--------'-=----J
200 300 400 500
Wavelength
0.20 .----,---..------.----,.-------.,
0.00
200 300 400 500 600
Wavelength
438
- - Aex:= 281.5 nm
---- Aex" 275.5 nm
excit. specra
I \
! \
..
--------------...
-.......
550 500 450 400 350 300 250
Waveleugtl:
Figure 11. The room temperature emission and excitation spectraof 6.7 x 105 Mof GN-7 in ethanol
- - Aex:' 374.5 nm
---- Aex;: 274.0 nm
/\
...........
...........
--- 450 400 350 300 250
550 500
Waveletzgtlt
Figure 12. The room temperature emission and excitation spectra of 6.7 x 10-s M of 92N in
ethanol.
439
0.00 L - - - - - - ' ' - - - - - - . _ _ . . . . . : : ._ _ _.___ __,
200 300 400 500

Wavelengtlz
Figure 13. Absorption spectra of I x 10-s M of 63N in ethanot
0.50
0.40
...<>
=:: 0.30
c::s
-e
<:)
~ 0.20
~
0.10
0.00
200 300 400 500 600
Wavelengtlz
440
- - - Acx. J85.S nm
- - - Acx. = 298.0 nm
- - Acx.- 166.5 nm
- - - - -A..cx."' 242.5 nm
, ctcilaelon reclra
.
.
..
550 500 450 400 350 300 250
Wavelengtll
Figure 15. The room temperature emission and excitation speetra of 6.7 x 10-s M of 63N in
ethanol.
441
- - Aex:= 386.5 nm
- - - - Aex"' 296.5 nm
--- Aex"' 267.0 nm
........ A.ex"' 243.0 nm
.. .:
....
550 500 450 400 350 300 250
Wavelengtlt
Figure 16. The room temperature ernission and excitation spectra of 6.7 x 10-s M of 64N in
ethanol.
2.00
.....
;::
1.50
<:s
~ 1.00
..,<:.
oQ
~
0.50
0.00
200 300 400 500
Wavele11gtlz
Figure 17. Absorption spectra of 1 x 10-s M of GN-1 in ethanol.
442
~ 0.20
;::
-ec
<::s
~
~ 0.10
0.00 L----1--~--......J..--....L-........::..__,L__ ___J
200 250 300 350 400 450 500

Wavelength
Figure 18. Absorption spectra of 1 x 10-5M of 145N in ethanol.
/ .....
I \
/ \
/ \ .
",..-
//
. - .-
.-~.
........
\
'
~.
.....
550 500 450 400 350 300 250
Wavelengtlz
Figure 19. The room temperature emission and excitation spectra of 6.7 x 105 M of GN-1 in
ethanol.
443
r\
- - Aex:= 392.5 nm
-- - - Aexo= 301.5 nm
excit. specra
550 500 450 400 350 300 250

Wavele11gtl!
Figure 20. The room tempc;:ature emission and excitation spectra of 6.7 x 105 M of 145N in
ethanol.
0.40
0.30
...,"'
r::
-e..,c:.
~
0.20
>Cl
""'(
0.10
0.00
200 300 400 500 600
Wavelength
Figure 21. Absorption spectra of 1 x 10-5M of 138N in ethanol.
444
0.30
...... 0.20
c:
o::s
1:
c::.
~
~ 0.10
0.00 '-----'-----1--_......__..::.._....L._ __ J
200 250 300 350 400 450
Wavele11gth
- - Aex:= 391.5 nm
- --- Aex:= 266.5 nm
excitation spectra
.. ................... .
--- -----
550 500 450 400 350 300 250
Wavelength
Figure 23. The room temperature emission and excitation spectra of 6. 7 x 10-s M of 138N in
ethanol.
445
- - Ae.r. 356.5 nm
- - - - Aex .. 273.0 nm
- -- Aex., 230.5 nm
....... excit. specra
''
1'
'' ''II
I '
I '
I '
\
'I
'I
I
I
I.
,:
I' '
~
I
J
II""
'
/---.\.,,
/
..../ \.
\ ..
...............
500 450 400 350 300 250
Wavelength
Figure 24. The room temperature emission and excitation spectra of 6.7 x lQ-5 M of 76N in
ethanoL
~ 0.40
;::
-e
o::s
<:I
~
~ 0.20
0.00
200 300 400 500
Wavelength
Figure 25. Absorption spectra of 1 x lQ-5 M of GN-5 in ethanol.
446
_l,ex.=373.)nm
- - -\x. :272.0 nm
excitation s\)Xtra
.....
.
. .
550 500 450 400 350 300 250
Wavelength
Figure 26. The room temperature emission and excitation spectra of 6.7 x 10-5 M of GN-5 in
ethanol.
REFERENCES
L K.Marishige, Anal. Chim. Acta, 121 (1980) 301.

2. W.H. WeberAnd J. Lambe, App. Opt., 15 (1976) 2299.
3. R. Reiseld, M. Eyal, V. H. Ernyak and R. Zusman, Solar Energy Materials, 17 (1988) 439.
4. A.N. Abdel-Rahman and A.F. Mansour, J. Phys. E., 18 (1985) 149.
5. A. Goetzberger, B.K. HeidJer, V. Wittwer, A. Zastrow, J. Bour and E. Sah, Photovoltaic Solar
Energy Conference, Berlin (1979).
6. S. Yonjia and R. Shengwu, Dyes and Pigments, 15 (1991) 157, 183.
7. F.J. Duarte and L. Hiliman (Editors) "Dye Laser Principles with Applications" Academic Press,
New York, London (1990) and references therein.
8. Galal E.H. Elgemeie and Nahed M. Fathy, Tetrahedron, 15 (1995) 3345.
9. Galal E.H. Elgemeie, Adel M.E. Attia and Nahed M. Fathy, Nucleosides and Nucleotides (in
Press).
10. G. Jones II in "Dye Laser Principles with Applications", F.J. Duarte and L.W. Hiliman (Editors),
Academic Press, London, New York (1990).
1l.L.C. Nair, Prog. Quant. Electron, 7 (1982), 153.
12.E.M. Ebeid, M.M.F. Sabry and S.A. El-Daly, Laser Chem., 5 (1985) 223.
13.M.H. Asegawa, Y. Suzuki, F. Suzuki and H. Nakanishi, J. Polum. Sei., Part A-17, 7 (1969) 743.
14.J.N. Demas and G.A. Crosby, J. Phys. Chem., 75 (1971) 1991.
15. W.H. Melhuish, J. Phys. Chem., 64 (1960), 762.
16. G.R. Penzer and S.B. Brown, (Ed.) "An Introduction to Spectroscopy for Biochemists", Academic
Press, London, New York, (1980), p. 86.
17. N.J. Turro, "Molecular Photochemistry", Benjamin, New York, (1967).
447
GELATIN-POLY(VINYL ALCOHOL) BLENDS
AS BIOARTIFICIAL POLYMERIC MATERIALS
Paolo Giusti, Niccoletta Barbani, Luigi Lazzeri, Giovanni Polacco,

Caterina Cristallini, and Maria G. Cascone
Department of Chemical Engineering

University ofPisa
via Diotisalvi, 2
56126 Pisa, ITALY
INTRODUCTION
Polymers constitute one of the widest dass of materials used for biomedical
applications. Both synthetic and biological polymers have been used in this field.
Synthetic polymers are available with a wide variety of compositions, properties and
forms and they may be readily fabricated into complex shapes and structures. Nevertheless,
their interaction with living tissue constituents remains the majorproblern to be solved. On
the other hand, biological polymers show in general good biocompatibility, but their
mechanical properties are often poor, their processability is complicated by the necessity
of preserving biological properties, and their production or recovery costs are very high.
A new dass of polymeric materials, called "Bioartificial Polymerie Materials" (Giusti
et al. 1993, 1994a, 1996; Lazzeri, 1996), was conceived with the aim of realizing
biomaterials that combine the features of synthetic polymers with the specific
biocompatibility properties of biopolymers. The performance of these materials relies on
the relationship between the synthetic-natural polymer interactions and the
biocompatibility of the resulting material. In fact, the biocompatibility of a material is
determined by the interactions, at the molecular Ievel, between the material and the
constituents ofthe living tissues ofthe host body.
The basic idea ofbioartificial polymeric materials is to smooth the interactions between
synthetic and living systems by creating a two-component material inside which synthetic-
natural interactions at the molecular Ievel have already occurred before coming into contact
with the living tissues.
Several synthetic polymers were so far used in preparing bioartificial materials. Among
them poly(vinyl alcohol) (PVA) resulted particularly interesting because it is a Iow cost
polymer showing good water solubility, biocompatibility and versatili':y.
Bioartificial polymeric materials prepared by mixing PVA with different biopolymers
such as collagen (Cascone et al. 1996a, 1996b; Giusti et al. 1994b; Barbani et al. 1995) and
hyaluronic acid (Lazzeri et al. 1994; Sbarbati del Guerra et al. 1994) were studied. More

recently, gelatin was used as biological component in preparing PVA-based bioartificial
materials.
Gelatin was chosen in order to reduce the production costs of collagen containing
bioartificial materials. In fact, gelatin is the denatured form of collagen and it is available at
low cost from several processes involving natural tissues.
Gelatin is a water soluble protein whose structure in aqueous solution, above the
temperature of about 40 C, is that of a random coil. By cooling below this temperature,
fractions of gelatin chains can arrange in segments of triple helix (renaturation) which act as
physical crosslinking sites and Iead to gelation. The triple helices of gelatin are shorter than
those of native collagen and, unlike collagen, do not show the highly ordered supramolecular
structure that is responsible for the formation of fibrils.
In comparison with collagen, gelatin shows a more pronounced glass transition, related
to the random coil chains, and a Iess pronounced denaturation event related to the triple
helix segments.
This paper concerns with the production and characterization of gelatin/PVA thin
films obtained by casting from aqueous solutions of the polymers. The properties of these
materials were studied by thermal, mechanical and morphological analysis, before and after
a chemical (by glutaraldehyde) or physical (by thermal dehydration) crosslinking treatment
performed in order to reduce their solubility in water.
MATERIALSAND METHODS
PVA (MW=I24,000-186,000; hydrolysis degree 93-99%) and gelatin (type B from

calfskin) were supplied by Sigma Chem. Co. (USA), glutaraldehyde (GTA) (8% aqueous
solution) was provided by Fluka Bioehemika (Switzerland).
I% aqueous solutions of PVA and gelatin were mixed in order to obtain gelatin/PVA
blends with different weight ratios. The mixtures were poured into Petri dishes at room
conditions and films were obtained by casting. For each composition, films were prepared
in triplicate to be used either as prepared, or crosslinked by GTA or crosslinked by
dehydrothermal treatment (DHT).
The chemical crosslinking was performed placing the films in a desiccating chamber
with 8% GTA vapour at 37 C for 18 hours.
The physical crosslinking was canied out through two dehydration steps and a final
crosslinking step. First, the films were placed in a vacuum oven at 50 C and subjected to a
vacuum of less than 13.5 Pa for 3 h. Second, the temperature was increased to 90 C and
maintained for 30 min. Finally, crosslinking was achieved by heating at 120 C for 72 h.
Calorimetric analysis ofthe filmswas canied out by a Perkin Eimer DSC7 Differential
Scanning Calorimeter (DSC), in the temperature range 40-250 C at a scan rate of 10
C/min. Two consecutive scans were performed on DHT treated samples.
Dynamic mechanical thermal analysis (DMTA) was performed by a Polymer
Laboratories DMT A analyser, operaring in the tensile mode at a frequency of 1 Hz over a
temperature range from room to 350 C and at a scan rate of 4 C/min. Both elastic modulus
(E') and loss factor (tan) were recorded.
Morphological analysis was carried out by a scanning electron microscope (SEM) Jeol
T300 on samples sputter-coated with gold.
RESULT AND DISCUSSION
Calorimetric Analysis
In fig. I the thermograms related to the first scans ofuntreated gelatin/PVA samples are
450
5
t
0
4
e
"0
Jl d
3 c
bll
~ 2
~
."'
0
!I: a
:I:
0
0 50 100 150 200 250 300
Temperature ( C)
0
Figure 1. DSC thermograrns ofuntreated gelatin!PVA samples: a) 100/0, b) 70/30, c) 50/50, d) 30/70, e)
0/100. (scarming rate 10 C/min)
reported. It ean be observed an endethennie event around 100 oc due to water evaporation.
A seeond endethennie event ean be seen at ab out 230 C. In the ease of pure PVA the latter
is related to the melting of the polymer whilst in the ease of pure gelatin it is related to the
denaturation of the protein. In the ease of gelatin/PVA blends the two phenomena are
superimposed and therefore their enthalpies arenot separately deteetable.
In fig. 2 the total enthalpy (L'1H) is reported as a funetion of gelatin eontent and
eompared with the theoretieal value (L'1Rt) ealculated by using the additivity rule:
L'1Ht = MHpvA +(1-a)L\.Hgelatin (1)
where .1HpvA and L'1Hgelatin are the enthalpies of PVA melting and gelatin denaturation
respectively and a is the weight fraction of PV A in the blend. It can be supposed that the
observed positive deviation of L'1H from L'1Ht indieates the presenee of intennolecular
interaetions, such as hydrogen bonds, between the two eomponents.
The thennograms corresponding to the first sean ofDHT films, reported in fig. 3 show
a trend similar to that of the untreated samples. In addition a third minor event at about
130 C, corresponding to the melting of seeondary PVA crystals fonned during the thermal
treatment, ean be observed.
Fig. 4 shows that L'1H for DHT samples is very close to L'1Ht. This indieates that
thermal treatment induces a phase separation between the two components inhibiting their
interactions. Moreover, like a thermal curing, DHT increases the crystallinity of PVA by
both increasing the size of primary crystals and favouring the formation of secondary
crystals.
DHT seems do not affeet gelatin, in faet both temperature and enthalpy of
denaturation do not differ from those ofthe untreated sample.
The thermograms corresponding to the first scan of GTA treated samples (fig. 5) do
not signifieantly differ from those of the untreated samples. However, a shift of gelatin
denaturation temperature toward higher values can be observed whilst PVA melting is not
changed. This suggests that GTA affeets mainly the biologieal polymer. In fig. 6 negative
deviations of H from Ht ean be observed, indicating that erosslinking by GTA inhibits
the interactions between the two components and disturbs PVA crystallinity.
451
In order to get further infmmation on the entity of gelatin!PVA interactions, second
scans were performed on DHT treated samples. Because gelatin denatures during the first
scan, the endethennie event at about 230 C in the second scan is only due to PVA melting.
This allows the evaluation ofthe thermodynamic interaction parameters as Nishi and Wang
(1975) suggested for amorphous/crystalline polymer blends.
In this case the melting temperature depression of the crystalline component can be
written as follows:
(2)
where the subscripts I and 2 refer to the amorphaus (gelatin) and crystalline (PVA)
component respectively, T~ is the melting point ofthe pure crystalline polymer, Tm is the
melting point of the crystalline polymer in the blend, v is the volume fraction, Yu is the
..... .
.....
80 1()()
gelatin content ( weight %)
Figure 2. Total enthalpy, H (PVA melting + gelatin denaturation), for untreated gelatin!PVA samples as a
function of gelatin content (dashed line: theoretical value, H1).
molar volume of the repeating unit, Miu is the melting enthalpy per mole of repeating unit,
and B is the interaction energy density related to the interaction parameter 12 by: x
B=RT~(X\)u12 ) (3)
where R is the gas constant.

Equation (2) represents a straight line from the slope of which the value of B, and
therefore of X12, can be obtained plotting ~Tm as a function of the blend composition
x
expressed as v~. When interactions occur 12 is negative, and its absolute value is as high as
the interactions between the two polymers are streng.
452
5
f4
0
=
'0
~
~e
u:i
3 d
~
c
l)
~2 b
~
0
tE., 1
:r:
<lJ
~a
0
0 50 100 150 200 250 300
Temperature (0 C)
Figure 3. DSC thermograms of DHT treated gelatin!PVA samples: a) 100/0, b) 70/30, c) 50/50, d) 30/70, e)
0/100. (scanning rate 10 C/min)
70
60 " .....
' '
.. '
.
.....
50 .....
~
.....
~ 40 .....
,
:r:
<l 30
20
.....
.....
.
.....
,
' .....
.....
10 '--...;
0
0 20 40 60 80 100
gelatin content ( weight %)
Figure 4. Total enthalpy, t.H (PVA melting + gelatin denaturation), for DHT treated gelatin/PVA samples
as a function of gelatin content (dashed line: theoretical value, t.H1).
453
5
t4 e
j d
3
c
b
a
50 100 150 200 250 300
Temperature (0 C)
Figure 5. DSC thermograms of GTA treated gelatin/PVA samples: a) 100/0, b) 70/30, c) 50/50, d) 30no, e)
0/100. (scanning rate 10 C/min)
Figure 6. Total enthalpy, Mf (PVA melting + gelatin denaturation), for GTA treated gelatin/PVA samples
as a function of gelatin content (dashed Iine: theoretical value, .1H,).
454
The thermograrns corresponding to the second scans of DHT treated samples are
shown in fig. 7. Water loss is not present, whilst PVA glass transition can be obsetved at
about 70 C. The ATm evaluation Ieads to a value for B equal to -10.13 Jcm"3 (X 12 -.40) =
which indicates the presence of significative interactions.
Dynamic-Mechanica1 Analysis
Fig. 8 shows the viscoelastic spectrum of a pure untreated PVA film. This sample was
analysed starting from -50 C in order to reveal the glass transition that, in the case of
not completely dry samples, occurs at a temperature lower than that (85 C} reported in
Iiterature (Lide, 1996) for anhydrous PVA. The glass transition occurs at about 40 C as
outlined by both a peak in the tanB cutve and a drop in the modulus cutve. Just beyond the
glass transition a slight increase in the modulus can be obsetved. This is due both to an
increase in crystallinity, like in thermal curing, and to a stiffening due to water loss. Over
200 C the modulus dropsdown because ofthe melting ofthe polymer.
The mechanical spectrum of pure untreated gelatin is shown in fig. 9. The modulus
value remains almost constant and higher than that ofPVA until about 200 C; beyond this
temperature the glass transition ofthe protein is clearly obsetved.
In fig. 10 the trend of the modulus values for the gelatin/PVA films is reported. All
samples show a first drop in E' related to the glass transition of PVA and a second drop
related to both gelatin glass transition and PVA melting. In the 40-200 C temperature range
the modulus value ofthe blends is intermediate between those ofthe two pure components.
In particular, it increases by increasing the gelatin content, the protein being in the stiff
glassy state.
Fig. 11 shows the dynamic-mechanical spectrum of a DHT treated pure PVA sample.
Because of a lower water content the glass transition occurs at a temperature (about 60 C}
higher with respect to that of untreated PVA. A second transition, at about 160 C, is
related to the melting of secondary crystals; a third transition, corresponding to the melting,
occurs at a temperature close to that of untreated PVA. With regard to DHT treated pure
gelatin, no significative differences were found in comparison with pure untreated gelatin.
t4
~3 e
d
c
b
0 ~~~~~~~~~~~~~~~~~
0 50 100 150 200 250 300
Temperature eq
Figure 7. DSC themiograms of DHT treated gelatin/PVA samples: a) 100/0, b) 70/30, c) 50/50, d) 3ono, e)
0/100. (second scan; scanning rate 10 C/min).
455
10.0 .45
~~ ,40
9.5
--......: .
....
\
"" +
+
.35
+ .
..
++ .30
,-...
!'I
9.0
._,
Q"
+ .25
+ ~
~
Cl)
Q
8.5 +
+
+
+ \.~
+
+
+
~ +...
+
+
......,...,...., ...... 4
"* +.".iF" .20 S'
t :::1
~;
,.J 0>
.15
8.0
.10
:+ ...._
__.../-- + .05
/
+
-
7.5
\ \+ ~
.00
7.0 ......_. -.05
-50 0 50 100 ISO 200 250 300

Temperature ( 0 C)
Figure 8. Elastic modulus (E' ) and loss factor (tano) for a pure untreated PVA sarnple. (scanning rate 4
C/min, frequency 1 Hz).
10.0 1.8
1.6
9.5 ~"""'""' ''"' ~
-----.
1111 ..... - ............................................. +
1.4
+
1.2
9.0
o;s
Q" 1.0
'-'
~ S'
Cl) 8.5 .8 ::I
Q 00
,.J
.6
8.0
.-

.4
~.-
t
7.5 : .2
~~~~
.............., _....
, ...
, ... fi.IIF
, _ ,....,., .'"'111-. . .. .U.UoltiiH>l>++IIIH>III
. ...
Il'<'111...
l *III++<II++<I'"II"'IU_I....
It# +
''1111 1111+hll 1!1tott-+i+f++
-o
7.0 -.2
r---.----,----,----,---,,---,----.----.----r--~
20 50 80 110 140 170 200 230 260 290 320
Temperature (C)
Figure 9. Elastic modulus (E') and loss factor (tano) forapure untreated gelatin sarnple. (scanning rate 4
0 C/min, frequency 1 Hz).
456
10.0
9.5
,...., 9.0
~
f:.l
~ 8.5
.J
8.0
..
+
7.5 ...

7.0 "+-~--~
~--~----~--~~--~----T----,----~----~--~----~
-50 -15 20 H ~ IB I~ 195 230 265 300
Tempcrature (0 C}
Figure 10. Elastic modulus (E') ofuntreated gelatin/PVA samples: a) 100/0, b) 70/30, c) 50/50, d) 30170, e)
01100. (scanning rate 4 C/min, frequency I Hz).
10.5 .40
10.0 .36
....
9.5 +
....

. .32
+
.28
,...., 9.0
.24
...
CQ
0 8.5 to
f:.l .20 ::I
Oll 01
0 8.0
...l .16
7.5
. 12
7.0
6.5
6.0 .00
-50 0 so 100 ISO 200 250 300

Temperature (C)
Figure 11. Elastic modulus (E') and loss factor (tan) of a DHT treated pure PVA sample; scanning rate 4
C/min, frequency I Hz.
457
10.5
10.0
9.5
9.0
0:
e
~ 8.5
~
Oll
Q
..l 8.0
7.5
7.0
6.5
6.0
-50 -15 20 55 90 125 160 195 230 265 300

Tcmperaturc (C)
Figure 12. Elastic modulus (E') of DHT treated gelatin!PVA samples: a) 100/0, b) 70/30, c) 50150, d)
30no, e) 0/100. (scanning rate 4 C/min, frequency I Hz).
10.5
0:
e 8.5
&:!
Oll
j 8.0
7.5
7.0
6.5
20 50 80 110 140 170 200 230 260 290 320

Tempcrature (0 C)
Figure 13. Elastic modulus (E') of GTA treated gelatiniPVA samples: a) 100/0, b) 70/30, c) 50/50, d)
30no, e) 0/100. (scanning rate 4 C/min, frequency 1 Hz).
458
This indicates that the thermal treatment affects only the properties of the synthetic
polymer, thus confirming the results of DSC analysis. The modulus of DHT treated
gelatin/PV A films (fig. 12) shows the same transitions of the pure components and its value
results intermediate between those of pure gelatin and PVA.
In fig. 13 the modulus curves of the GT A treated gelatin!PVA films are shown. It can
be seen that the curve corresponding to pure PVA is similar to that of pure untreated PVA,
whilst the curve corresponding to pure gelatin shows a glass transition occurring at a
temperature higher than that of the untreated sample. This means that the chemical
treatment affects mainly the biological polymer rather than the synthetic one. With regard
to the blends, it can be seen that, like for untreated and DHT treated blends, E' remains
almest constant between the two main transitions and its value increases increasing the
gelatin content.
Morphological Analysis
The results of morphological analysis, performed on both film surfaces and cross-
sections, showed that the material structure does not significantly vary after thermal or
chemical treatment. lt can be observed (figs 14, 15) that both gelatin and PVA show an
uniform structure whilst the blends, independently on the composition, have a typical
biphasic structure. SEM images of cross-sections for DHT treated gelatin/PVA 70/30 and
30/70 films are reported in figs 16,17. In both cases it is evident a Segregation of the two
components in separate phases. Unlike the sections of pure components, obtained by
cutting, the sections of the blends were obtained by tearing. This allows the two
components to be weil distinguished because PVA has a plastic behaviour whilst gelatin,
being in the glassy state, shows a brittle breaking.
Figure 14. SEMimage ofa pure untreated PVA film (section); bar=lO ~m.
459
Figure 15. SEMimage of a pure untreated gelatin film (section); bar-10 J,Lm.
Figure 16. SEMimage of a DHT treated gelatin/PVA=70/30 film (section); bar-10 J,Lm.
460
Figure 17. SEMimage of a DHT treated gelatin!PVA=30no film (section); bar=10 J.l.m.
CONCLUSIONS
Although composite materials containing a natural component are used in several fields,
true polymer-polymer blends based on synthetic and natural components represent a class
of materials that has received a little attention until now, especially because of the
complexity of these systems. However, the study of the interactions occurring between
synthetic and natural polymers can be useful in order to produce materials with good
biocompatibility properties, thus suitable for applications in the biomedical field .
The examined gelatin!PVA blends represent an attempt aimed to this objective. From
the characterization analysis it resulted that gelatin and PVA are incompatible from a
thermodynamic point of view, in fact the materials obtained by their mixing show a
biphasic behaviour. However, they can be considered as mechanical blends, showing good
mechanical properties in a wide range of temperature.
It can be concluded that these materials are potentially usable for the production of
manufactures tobe employed in the biomedical field. The next step will be the evaluation of
their biocompatibility characteristics by specific in vitro tests.
Acknowledgments
The authors wish to thank Piero Narducci for performing SEM analysis.
HEFERENCES
Brubani, N., Cascone, M.G., Giusti, P., Lazzeri, L. Polacco, G., and Pizzirani, G., 1995, Bioartificial
materials based on collagen: 2. Mixtures of soluble collagen and poly(vinylalcohol) cross-linked with
gaseous glutaraldehyde, J. Biomat. Sei., Polym. Ed. 7 (6): 471.
Cascone, M.G., Giusti, P., Lazzeri, L., Pollicino, A., and Recca, A., 1996, Swface characterization cf
collagen-based bioartificial polymeric materials, J. Biomat. Sei., Po/ym. Ed. 7 (10): 917.
461
Cascone, M.G., Lazzeri, L., Barbani, N., Polacco, G., Pollicino, A., and Giusti, P., 1996, Dehydro-
thennally cross-linked collagen-poly(vinyl alcohol) blends: mechanical, biological and sudil:e
properties, J. Mat. Sei.: Mat. Med. 7 (6): 297.
Giusti, P., Lazzeri, L., and Cascone, M.G., 1996, Bioartificial Materials, in: The Polymerie Materials
Encyclopedia, CRC Press, Boca Raton.
Giusti, P., Lazzeri, L., Barbani, N., Lelli, L., De Petris, S., and Cascone, M. G., 1994, Blends ofnatural
and synthetic polymers: a new route to novel biomaterials, Makromol. Chem., Maeromol. Symp. 78:
285.
Giusti, P., Lazzeri, L., Oe Petris, S., Palla, M., and Cascone, M. G., 1994, Collagen-based new bioartificial
polymeric materials, Biomaterials 15 (15): 1229.
Giusti, P., Lazzeri, L., and Lelli, L., 1993, Bioartificial polymeric materials: a new method to design
biomaterials by using both biological and synthetic polymers, TRIP 1: 261.
Lazzeri, L., 1996, Progress in bioartificial polymeric materials, TRIP 4 (8): 249.
Lazzeri, L., Barbani, N., Cascone, M.G., Lupinacci, D., Giusti, P., and Laus, M., 1994, Physico-chemical
and mechanical characterization of hydrogels of poly(vinyl alcohol) and hyaluronic acid, J. Mat. Sei.:
Mat. Med. 5: 862.
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Sbarbati del Guerra, R. Cascone, M.G., Barbani, N., and Lazzeri, L., 1994, Biological chaicterization rf
hydrogels ofpoly(vinyl alcohol) and hyaluronic acid, J. Mat. Sei.: Mat. Med. 5: 613.
462
PRODUCTION OF POLY(3-HYDROXYBUTYRATE)
BY RECOMBINANT BACTERIA
Sang Yup Lee*, Jong-il Choi, and Fulai Wang
Department of Chemical Engineering and BioProcess Engineering

Research Center, Korea Advanced Institute of Science and Technology,
373-1 Kusong-dong, Yusong-gu, Taejon 305-701, Korea
ABSTRACT
In order to improve the production ofpoly(3-hydroxybutyrate) [P(3HB)], two different

recombinant bacteria, Escherichia coli and Alca/igenes eutrophus were investigated.
Firstly, recombinant E. coli harboring a stable high copy number plasmid pSYL107
containing the A. eutrophus polyhydroxyalkanoate (PHA) synthesis genes and E. coli.fisZ
gene was employed for the production of P(3HB) by fed-batch culture in a defined
medium. Suppression of filamentation by overexpressing the cell division protein FtsZ
allowed the production ofP(3HB) to a high concentration of 104 g/L, and P(3HB) content
of 70% with high productivity of 2 g P(3HB)/L-h in a defined medium, which was the
highest value reported to date by employing recombinant E. coli. Secondly, wild P(3HB)
producer A. eutrophus was metabolically engineered to amplify the activities of the three
enzymes, PHA synthase, beta-ketothiolase, and NADPH-dependent reductase, involved in
the synthesis of P(3HB). The A. eutrophus PHA synthesis genes were cloned into a broad-
host-range plasmid pVK101 and the constructed vector system was transferred into A.
eutrophus by electroporation. In flask culture, the final cell concentration of recombinant
A. eutrophus increased with decreasing carbon/nitrogen (C/N) molar ratio. On the other
hand, P(3HB) concentration was highest at the medium C/N molar ratio. For the fixed C/N
molar ratio, the concentrations of cell and P(3HB) were increased with increasing glucose
concentration. Comparison of cell growth and P(3HB) production by recombinant and
wild type A. eutrophus in batch cultures showed that the final P(3HB) concentration,
P(3HB) content, P(3HB) synthesis rate were all higher in the recombinant strain compared
with the wild type.
To whom all correspondence should be addressed.

INTRODUCTION
Poly(3-hydroxybutyrate) [P(3HB)] is an energy and carbon storage material

accumulated intracellularly by numerous microorganisms under unfavorable growth
conditions in the presence of excess carbon source (Anderson and Dawes, 1990; Byrom,
1994; Doi, 1990; Holmes, 1988; Lafferty et al., 1988). P(3HB) and other
polyhydroxyalkanoates (PHAs) have drawn much attention as candidates for
biodegradable plastics, because they possess material properties sirnilar to various
synthetic thermoplastics and elastomers currently in use and they are completely degraded
to water and carbon dioxide (water and methane under anaerobic conditions) by
microorganisms in various environments (Brandl et al., 1990; Byrom, 1987; 1991;
Holmes, 1985; Lee, 1996a; 1996b). The copolymer poly(3-hydroxybutyrate-co-3-
hydroxyvalerate), P(3HB-co-3HV), developed by ZENECA Bio Products was produced on
a fairly large-scale and soldunder trade name ofBIOPOLTM at US $ 16/Kg (Lee, 1996b).
These activities have currently been sold to Monsanto (St. Louis, MI, USA). This
copolymer can be used to make various products, including films, coated paper and board,
compost bags, disposable food service-ware, and molded products such as bott1es and
razors (Lee, 1996b). However, the much higher price of PHAs compared with
conventional plastic materials has limited their use. With an aim to lower the production
cost of PHAs, much research effort is currently devoted to improvement of strains,
increasing productivity and developing an economical purification process (Lee, 1996a;
1996b). Recombinant DNA techniques also can be used to modify or introduce new
metabolic pathways to broaden the utilizable substrate range, enhance P(3HB) synthetic
capacity, and develop novel polymers (Lee, 1996b). Recent advances in our understanding
of the biochemistry of PHA synthesis and cloning of PHA synthesis genes from many
different bacteria have allowed the development of various recombinant bacteria for the
production of PHAs.
Alcaligenes eutrophus is the most widely employed bacterium for the production of
P(3HB) since it accumulates a large amount of P(3HB) when an essential nutrient is
depleted in the presence of excess carbon source (Kim et al., 1994a; 1994b; Lee, 1996a;
Lee and Chang, 1995a). In A. eutrophus P(3HB) is synthesized from acetyl-CoA by three
sequential enzymatic reactions (Steinbuchel, 1991). Two acetyl-CoA moieties are
condensed to acetoacetyl-CoA by beta-ketothiolase. An NADPH-dependent reductase
converts acetoacetyl-CoA to D(-)-3-hydroxybutyryl-CoA, which is then added to growing
chain of P(3HB) by PHA synthase. The genes coding for these three enzymes were cloned
from A. eutrophus and expressed in Escherichia coli (People and Sinskey, 1989; Schubert
et al., 1988; Slater et al., 1988). Recombinant E. coli harboring the A. eutrophus PHA
synthesis genes is interesting, because it accumulates P(3HB) to a content as high as 95%
of dry cell weight and the cells of recombinant E. coli are easily disrupted for P(3HB)
recovery, and E. coli has been the best studied microorganism (Fidler and Dennis, 1992;
Lee and Chang, 1995s; 1995b, Lee et al., 1994a; 1994c). Wehave previously shown that
P(3HB) could be efficiently produced by recombinant E. coli harboring the A. eutrophus
PHA synthesis genes (Kim et al., 1992). High concentration of P(3HB) could be produced
with high productivity by fed-batch culture of recombinant E. coli harboring stable high
copy number plasmid in complex medium (Lee et al., 1994c). In semi-defmed medium,
which was a defined medium supplemented with small amount of complex nitrogen
source, up to 80 g/L ofP(3HB) could be obtained in 41 hr (Lee and Chang, 1994; 1995b).
However, this productivity could be obtained only in complex or semi-defined medium. In
a defined medium, less than 25 g/L ofP(3HB) could only be produced by similar fed-batch
culture (Lee and Chang, 1994). Cells of recombinant E. coli underwent considerable
filamentation during the synthesis of P(3HB), and the extent of filamentation was much
464
more severe in a defined medium compared with a complex or semi-defined medium (Lee,
1994; Lee et al., 1994b). Since cell filamentation caused reduction in growth rate (or no
further division of cells) and it was also responsible for less accumulation of P(3HB) in a
defined medium, filamentation suppressed recombinant E. coli was investigated. Cell
filamentation could be suppressed by the overexpression of essential cell division protein
FtsZ in E. coli (Lee, 1994). In this paper, we report high production of P(3HB) by
filamentation suppressed recombinant E. coli in defined medium.
Also, A. eutrophus has been used for the production of P(3HB) because the cells
accumulated P(3HB) to a high percentage of dry cell weight and the physiology of
bacterium was well understood. However, the use of A. eutrophus for the P(3HB)
production was impaired by its high cost of carbon substrate (Byrom, 1987). Since the
wild type A. eutrophus cannot utilize glucose as a carbon source, a mutant strain that could
utilize glucosewas developed and have been used for the production ofPHAs. To improve
the economics ofP(3HB) production by A. eutrophus, some works to enlarge the utilizable
substrate range have been carried out (Friehs and Lafferty, 1989; Pries et al., 1990).
However, these attempts have not been successful, because recombinant A. eutrophus
developed for utilizing cheap substrate grew poorly. In this study, recombinant A.
eutrophus is developed to increase the synthesis rate of P(3HB). In A. eutrophus, three
enzymes, beta-ketothiolase, NADPH-dependent reductase, and PHA synthase, are
involved in P(3HB) synthesis as an operon (Steinbuchel, 1991). In this study, these
enzyme activities were homologously amplified by introducing plasmid containing the A.
eutrophus PHA synthesis genes into A. eutrophus strain. To construct a recombinant A.
eutrophus strain, transformation protocol was also developed.
Baderial Strains and Plasmid DNA
The E. coli strain XLl-Blue (supE44 hsdRJ7 recAJ endAJ gyrA96 thf1 re!Al
lacFTproAB+laclqlacZdMJ5TnlO(te()]) (Stratagen, CA, USA) was used. A stable high
copy number plasmid pSYLl 07 (Fig. 1) containing the A. eutrophus PHA synthesis genes
and the E. coliftsZ genewas used (Lee, 1994).
A. eutrophus NCIMB 11599 was used as a bacterial host strain (Kim et al., 1994a;
1994b), and PHA synthesis genes cloned by Schubert et al. (1988) and a broad-host-range
plasmid pVK101 (Knauf and Nester, 1982) was used for the construction ofrecombinant
A. eutrophus.
Colture Conditions
Cells were maintained in 20% (v/v) glycerol at -80 C. The complex media used for
cell growth and DNA manipulation were Luria-Bertani (LB) medium (Sambrook et al.,
1989) for E. coli and NB medium (8 g/L Nutrient Broth, Difco Laboratories Detroit,
Mich.) for A. eutrophus. Chemically defined R medium supplemented with glucose, which
was original1y developed for fed-batch culture (Kim et al., 1994a), was used for the
production of P(3HB). The R medium contained (pH, 6.8, per Iiter): Glucose, 20 g;
(NH4)2S04, 4 g; KH2P04, 13.3 g; MgS047H20, 1.2 g; Citric acid, 1.7 g; Trace elements
solution, 10 mL (per Iiter FeS047H20, 10 g; ZnS047H20, 2.25 g; CuS045H20, 1 g;
MnS044-5H20, 0.5 g; CaCh2H20, 2 g; Na2B40710H20, 0.23 g; (N~)6Mo 7 024 , 0.1 g;
35% HCl, 10 mL).
465
SaN XbB Sm
p
K
Xh pSYL107
SI (10.9 kb) p
c PHA
biosynthcsis
operon
EP
P SI A Xb B
Figure I. Restrietion map of plasmid pSYLI07. Arrows indicate the direction of transcription.
Abbreviations: Ori, origin of replication: Ap, ampicillin; ftsZ, gene coding FtsZ protein; r, resistace, stb,
parB locus ofplasmid Rl; A, Accl; B, BamHl; C, C/al; E, EcoRI; H, Hindlll; K, Kpnl ; N, Notl; P, Pstl; Sa,
Sacl; SI, San; Sm, Smai; Xb, Xba!; Xh, Xhol. (redrawn from Lee, I 994)
Seed cultures were prepared in flasks and incubated in a rotary shaker ovemight at 30
C and 250 rpm. Fed-batch cultures of recombinant E. coli were carried out in a jar
fermenter (6.6 L Bioflo 3000, New Brunswick Scientific Co., Edison, NJ) containing 2 L
of initial medium with I 0 mg/L of thiamine. The dissolved oxygen level was maintained
above 20% of air Saturation by varying the agitation speed and pure oxygen percentage
automatically. The strategy of substrate feeding in fed-batch cultures was the pH-stat
method using a set point with a high limit, since it was observed that the pH rose rapidly
when carbon source became exhausted (Lee and Chang, 1994). When glucose was
depleted and pH rose rapidly to 6.91 , 55 mL ofthe feeding solutionwas added as a pulse
for a definite on-time. The feeding solution during the fed-batch cultures consisted of (per
Iiter): glucose, 700 g; MgS047H2 0 , 20 g; thiamine, 150mgor 250 mg.
The batch cultures ofrecombinant and wild type A. eutrophus were carried out at 30 C
and pH 6.8 in 2.5 L fermentor (Korea fermentor Co., Korea) containing 1.2 L of initial R
medium. The seed cultures were prepared in a 1,000 mL flask on a reciprocal shakerat 30
C. 200 mL of seed culture was used to inoculate the fermentor. The pH was controlled by
4 N NaOH solution during batch fermentation.
Antibiotics were added at the following concentration when required: ampicillin (Ap),
100 jlg/mL and tetracycline (Tc), 12.5 jlg/mL.
DNA Manipulation and Transfonnation _

Plasmid DNA was manipulated and analyzed as suggested by Sambrook et al. (1989).
E. coli cells were transformed with plasmid DNA by electroporation (Dower et al., 1988).
For the introduction of recombinant DNA into A. eutrophus, efficient transformation
method of electroporation was investigated in this study. A. eutrophus was grown in NB
medium at 30 C ovemight and 5 mL culture was inoculated to 250 mL of fresh prepared
NB medium. After optical cell density (OD60o) reached set value, the cells were harvested
by centrifugation at 3,000 xg for 10 min at 2 C and washed twice with 250 mL of ice-cold
de-ionized water. The cells were again washed with 10 mL 10% (v/v) sterile glycerol
466
solution and centrifuged. The cells collected were resuspended in 500 !J.L 10% (v/v) sterile
glycerol and immediately frozen at -80 C. The cells were concentrated to final OD6oo
above 100. For the electroporation, the frozen cells were thawed on ice and a aliquot of
cell suspension (40 f.!L) in 2 mm width of ice-cold cuvette was mixed with plasmid DNA.
By the use ofthe Bio-rad Gene Pulser (Bio-Rad, Richmond, CA, USA), A. eutrophus was
transformed. After electroporation, the cells were mixed with 1 mL ofNB medium and left
for 2 hr at 30 C before being plated. Appropriate dilution was plated on NB agar plate
containing Tc (12.5 f.!g/mL) and incubated for 48 hr at 30 C.
Plasmid stability was measured as described previously (Lee et al, 1994c).
Analytical Procedure
Cell growth was monitored by measuring the optical density at 600 nm. Cell
concentration, defined as dry cell weight per Iiter of culture broth was determined by
weighing dry cells. P(3HB) concentration was determined by gas chromatography
(HP5890, Hewlett Packard, Wilmington, DE) with n-butyric acid as an irrtemal standard
(Braunegg et al., 1978). Residual cell concentration was defined as cell concentration
minus P(3HB) concentration. P(3HB) content was defined as the percentage ofthe ratio of
P(3HB) concentration to cell concentration. The P(3HB) synthesis rate (qP(3HB)) is defined
as gram P(3HB) produced pergram residual cell per hour (Lee et al., 1996).
Enzyme Assay
Protein concentration was determined by Lowery method (Lowry et al., 1951). The
enzymes in P(3HB) synthesis, beta-ketothiolase and acetoacetyl-CoA reductase, were
assayed as follows (Lee et al., 1996): Cells harvested from the culture broth were washed
with distilled water, resuspended in 50 mM Tris-HCl (pH 8.1) containing 1 mM
phenylmethanesulfonyl fluoride as protease inhibitor and then were disrupted by
sonication (Sonic and Materials, Danbury, CT) at 4 C. Sonication consisted of four 15 s
bursts at the maximum setting. The lysate was centrifuged at 5,000 xg for 10 min at 4 C,
and the supematant was used for the determination ofthese enzyme activities. The activity
of beta-ketothiolase was measured by thiolysis reaction described by Nishimura et al
( 1978). The activity of acetoacetyl-CoA reductase was measured by the reduction reaction
described by Haywood et al. (1988).
Recombinant Escherichia coli Harboring the Alcaligenes eutrophus PHA Synthesis

Genes
We previously reported that 81 g/L of P(3HB) could be produced in 39 hr (

productivity of 2 g P(3HB)/L-h) by fed-batch culture of E. coli XLI-Blue harboring a
stable high copy number plasmid pSYLI 04 containing the A. eutrophus PHA synthesis
genes (Lee et al., 1994c). However, this productivity could be obtained only in a complex
medium. A !arge amount of expensive yeast extract and tryptone had to be fed along with
glucose during cultivation, which made this process economically unfeasible. In order to
reduce medium cost, a relatively irrexpensive semi-defined medium, which was a defined
medium supplemented with small amount of complex nitrogen source, has been
developed. Supplementation with tryptone, yeast extract, peptone, casamino acids, cotton
seed hydrolysate, beef extract, casein hydrolysate, collagen hydrolysate, com steep Iiquor,
467
or soy been hydrolysate promoted P(3HB) synthesis in flask cultures (Lee and Chang,
1995b). By fed-batch culture of recombinant E. coli XLl-Blue harboring another high
copy number plasmid pSYLlOS in the semi-defined medium, up to 80 g/L of P(3HB)
could be obtained with productivity of 2 g P(3HB)IL-h (Lee and Chang, 1994). In a
defined medium, however, less than 25 g/L of P(3HB) could only be produced by fed-
batch cultures of these two recombinant E. coli. In a defined medium, poor P(3HB)
synthesis was reasoned that the amount of acetyl-CoA and NADPH as a cofactor of
reductase available for P(3HB) synthesis would be less than semi-defined or complex
medium (Lee and Chang, 1995b). It was observed that cells of the recombinant E. coli
became considerably elongated when P(3HB) content began to increase in flask culture or
fed-batch culture, and the extent of filamentation was much more severe in a defined
medium (Lee, 1994; Lee et al., 1994b). Since cell filamentation resulted in growth
slowdown or stop and lower metabolic activity, P(3HB) production might be enhanced by
preventing filamentation. Among the various proteins involved in the cell division process,
the FtsZ protein is the most important one that acts as a cytoskeletal elements during
circumferential vagination of the septum and is found to be the target of several division
inhibitor. Plasmid pSYL107 was therefore constructed by cloning the 2.1 kb Hindiii-Clai
fragment containing the E. coli ftsZ gene into a stable high copy number plasmid pSYL 105
harboring the A. eutrophus PHA synthesis genes. The overexpression of FtsZ protein
prevented cells from filamentation as observed in flask culture of recombinant E. coli
XL1-Blue(pSYL107) in a defined medium. Also, P(3HB) accumulation by XLl-
Blue(pSYL107) was enhanced by more than two fold in a defined medium compared with
XLl-Blue(pSYLlOS) (Lee, 1994). On the basis ofthese results, fed-batch cultures ofXLl-
Blue(pSYLl 07) are carried out in a defined medium.
The final cell concentration, P(3HB) concentration, and P(3HB) content reached 107
g/L, 77 g/L, and 72.1% in 39 hr, respectively, resulting in the P(3HB) productivity of 2.0 g
P(3HB)/L-h, when the feeding solution contained 150 mg!L ofthiamine. During the entire
fed-batch culture, cell filamentation was not observed. Since P(3HB) is an intracellularly
accumulated polymer, high residual cell concentration with high P(3HB) content will
result in high production of P(3HB). This has been demonstrated experimentally with A.
eutrophus using the application of nutrient Iimitation (Kim et al., 1994a). Therefore, to
obtain high residual cell concentration nutrient requirement was examined. Because E. coli
XLl-Blue is a thiamine-deficient strain and thiamine should be fed during fed-batch
culture, appropriate feeding of thiamine seems to be important. When the concentration of
thiamine in the feeding solution was increased from I 50 mg to 250 mg/rnL, the time
profiles of the concentration of cell, P(3HB), and residual cell, and P(3HB) content are
shown in Fig. 2. Suppression of filamentation allowed production of P(3HB) to a high
concentration (104 g/L) with high productivity of 2.0 g/L-h in a defined medium. This is
the highest P(3HB) concentration obtained by employing recombinant E. coli and is
comparable tothat obtained withA. eutrophus (Wang and Lee, manuscript submitted).
Recombinant E. coli has several advantages sucli as easy PHA recovery and utilization
of various carbon sources over A. eutrophus. The success of efficient production of
P(3HB) by recombinant E. coli in cheap defined medium will finally realize its advantages
on reducing the cost ofP(3HB) production. In addition, the simplicity and reliability ofthe
cultivation process are noticeable. By pH-stat feeding strategy, the fed-batch culture shown
in Fig. 2 was fully automatically carried out without the assistance of on-line analyzer. Its
benefit for scaling up is obvious. During the entire culture, pH-stat feeding strategy was
reliable. It is well-known that simple feedback feeding strategy of pH-stat or DO-stat is
applicable for wild P(3HB) producers only during growth phase, or even not. When
P(3HB) accumulation phase under nutrient limitation started, pH or DO response upon
468
160
80
(A) (B)
140 70
::::J 120 60
r
0~
~ 100
t: c 50
c"0
0
__,.. .t
-~
,? ... ._ " ......

80 40
u
t:
"ut: o:l 30
,.
60
0
::c
u 40 14. "'
~ 20
:--
'II.
20 10
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Time (hr Time (hr)
Figure 2. Timeprofiles of (A) cell concentration, P(3HB) concentration, and residual cell concentration, and
(B) P(3HB) content during fed-batch culture of XLI-Blue (pSYL107) in R medium. The feeding solution
contained 250 mg!L of thiamine ( cell concentration, P(3HB) concentration, ~ residual cell
concentration, 0 P(3HB) content).
carbon depletion was not apparent. Therefore on-line analyzer or modeled feeding profile
must be applied, which makes process more complicating and more costing. P(3HB)
depolymerases may be partly responsible for such difference between the recombinant E.
coli and wild type P(3HB) producers. The depolymerases arenot present in recombinant E.
coli harboring the A. eutrophus PHA synthesis genes. Another nature of this recombinant
E. coli, which also contributes to the feasibility ofpH-stat, isthat it accumulates P(3HB) to
a high content without changing culture conditions. Thus nutrient Iimitation, which can
severely disturb cell growth and pH or DO rise upon carbon depletion, is unnecessary.
Some wild P(3HB) producers such as Alcaligenes Iatus and Azotobacter vinelandii also
accumulate P(3HB) in a growth-associated manner. However their growth-associated
manner is quite different from recombinant E. coli. It was reported that during fed-batch
culture of A. Iatus under balanced culture conditions, P(3HB) content was constantly kept
at 50% of dry cell weight (Yamane et al., 1996). In contrast, as shown in this study (Fig.
2), recombinant E. coli did not accumulate much P(3HB) (less than 20% of dry cell
weight) during initial cultivation stage (cell concentration less than 30 g/L); afterwards
P(3HB) concentration and content monotonously increased to high Ievel without changing
any culture conditions. This nature was also shown in our previous studies of fed-batch
cultures of recombinant E. coli XL1-Blue(pSYL104) in complex medium and XL1-
Blue(pSYL105) in semi-defined medium. It is not completely understood why the P(3HB)
accumulation was triggered when cell concentration reached a certain Ievel. Such nature is
also beneficial to using cheap agricultural waste or byproducts such as whey,
hemicellulose hydrolysate, or molasses as carbon substrate. These materials contain
various forms of nitrogen and phosphate sources, which can disable the application of
nitrogen or phosphate Iimitation currently applied for the production of PHA by fed-batch
culture of A. eutrophus.
The development of biodegradable plastics PHAs has been a long history. However,
their high production cost has been one of the major problems. To reduce the production
cost of PHAs, we show in this study that recombinant E. coli is a promising alternative for
the production ofP(3HB).
469
pVK101::PP1
(33.8 kb)
Sa/1
EcoR1
PHA synthesis genes
Figure 3. Restrietion map ofa broad-host-range plasmid pVKIOI containing the A. eutrophus PHA synthesis
genes (pVKIOI ::PPI). (redrawn from Schubert et al. 1988)
Recombinant Alcaligenes eutrophus with Amplified Enzyme Activities Related to

PHA Synthesis
In 1988, PHA synthesis genes in A. eutrophus have been cloned by three independent
groups (People and Sinskey, 1989; Schubert et al., 1988; Slater et al., 1988). Thereafter,
considerable efforts have been made to characterize the PHA synthesis genes of A.
eutrophus. In A. eutrophus, the genes for beta-ketothiolase (phaA), NADPH-dependent
acetoacetyl-CoA reductase (phaB}, and PHA synthase (phaC) were dustered in the order
ofphaC-phaA-phaB. They were organized in one single operon. The transcription start site
was identified 307 bp upstrearn of phaC and a potential transcription termination was
localized down strearn ofphaB (Steinbuchel, 1991). On the basis ofthese molecular data,
we investigate recombinant A. eutrophus with homologous arnplified enzyme activities to
increase P(3HB) synthesis rate.
Schubert et al. (1988) used a broad-host-range plasmid pVK101 for the cloning of
PHA synthesis genes in A. eutrophus H16 (shown below). Prieset al. (1990) have also
developed recombinant A. eutrophus for the utilization of lactose by use of vector system
including pVK101. pVK101 is a broad-host-range plasmid having tetracycline and
kanarnycin resistance and has been used for the transformation of several strains such as A.
eutrophus and Pseudomonads (Knaufand Nester, 1982).
There were transformation methods such as conjugation into A. eutrophus. However,
because this transformation had a problern of low transformation efficiency, in this study
we investigated transformation of A. eutrophus by electroporation, which is recently
developed. In the case of E. coli, the transformation efficiency as high as 109
transformation/j.lg DNA has been reported (Sarnbrook et al., 1989). Because there was no
report on the transformation of A. eutrophus until lately, several factors such as pulse
strength, extemal resistance, and the growth phase of competent cell have been optimized.
For the study of the transformation of A. eutrophus, pVK10l::PP1 constructed for this
study was used. By the use ofthe Bio-Rad Gene Pulser and 2 mm cuvettes, optimal results
were obtained with following settings: voltage, 2.5 KV; capacity, 25 !J.F; extemal
470
8
7
,.....,
....l 6
bb
'-'
c 5
0
-~
., 4
i
u
c
0
u 3
...
0
2
4 6 8 10 12 14 16
Mole of carbon/Mole of nitrogen
Figure 4. Effect of carbonlnitrogen molar ratio on the P(3HB) production and cell growth of recombinant A.
eutrophus in R medium containing 20 g/L ofglucose <dry cell concentration, 0 P(3HB) concentration).
resistance, 200 n. When the cells from different growth phases were tested to determine
the optimum electroporation condition, the maximum efficiency was obtained at early-
exponential phase (OD600 = 0.4). On the basis of these results, the efficiency of 103
transformants/~g DNA was obtained with pVK101 ::PP1 at optimal condition.
The stability of pVK1 01 ::PP1 in A. eutrophus was studied by repeated subculturing in
NB medium. After the subcultures were carried out for 80 generations, the fraction of cell
harboring plasmid was more than 75%. This result shows that plasmid pVK101:PP1 is
relatively stable in A. eutrophus.
Because A. eutrophus accumulates P(3HB) when the nutrient such as nitrogen or
phosphate is limited in the presence of excess carbon source, the carbon/nitrogen (C/N)
molar ratio has a significant effect on the cell growth and P(3HB) accumulation. In the
case of wild type A. eutrophus, when the C/N molar ratio was low, the nutrient Iimitation
necessary for P(3HB) accumulation was applied at high cell concentration, and low final
P(3HB) concentration and P(3HB) content were obtained. In contrast, when the C/N molar
ratio was high, the nutrient Iimitation was applied at early growth phase, and low final
concentrations of cells and P(3HB) were obtained. These effect of C/N molar ratio is
investigated for the recombinant A. eutrophus. The effect of C/N molar ratio on the
P(3HB) production and cell concentration of recombinant A. eutrophus is shown in Fig. 4.
When the C/N molarratiowas high as 14.7, low final concentrations of cell and P(3HB)
were obtained, but highest P(3HB) content of 66. 05% was obtained. When the C/N molar
ratio was low (ratio of 4.9), highest cell concentration of 6.95 g/L, low P(3HB)
concentration of 2.32 g/L, and low P(3HB) content of 33.37% were obtained. P(3HB)
concentration was highest at the medium C/N molar ratio (ratio of7.3). These results show
that recombinant A. eutrophus has similar trend to the wild type A. eutrophus on the effect
of C/N molar raio. Fig. 5 shows the effect of glucose concentration on cell growth and
P(3HB) accumulation. For the fixed C/N molar ratio (ratio of 7.3), the concentrations of
cell and P(3HB) were increased with increasing glucose concentration. When the
concentration of glucosewas increased above 30 g/L, poor cell growth was observed due
to inhibitory effect ofhigh concentration of substrate.
For the comparison of cell growth and P(3HB) accumulation, the batch cultures of
recombinant and wild type A. eutrophus have been investigated at the same condition. Fig.
6 compares the differences of cell concentration, P(3HB) concentration, and residual cell
471
6
3 4
bb
'-'
=
0 3
~
... ..... 0
c 2
"'
=
<.) 0 ....
0
u
0 ...
0
4 6 8 10 12 14 16 18 20 22
Concentration of g1ucose (g/L)
Figure 5. Effect of g1ucose concentration on the P(3HB) production and cell growth of recombinant A.
eutrophus in R medium at constant C/N molar ratio of 7.3 ( dry cell concentration, 0 P(3HB)
concentration).
concentration of recombinant and wild type strains during cultivation in R medium with 20
g/L glucose and C/N ratio of 7.3. The final cell concentration and P(3HB) concentration
were 9.5 g/L and 6.35 g/L in the recombinant A. eutrophus, respectively. Wild type A.
eutrophus accumulated 6 g/L of P(3HB) and final cell concentration was 9.5 g/L.
Recombinant and wild type A. eutrophus had the same final cell concentration, but,
recombinant had higher P(3HB) concentration and lower residual cell concentration than
wild type. Recombinant had P(3HB) content of 66%, which was 10% higher than wild
type in the same culture condition. In Fig. 7 P(3HB) synthesis rates are compared for these
strains. As shown, recombinant had higher P(3HB) synthesis rate than wild type during
12 12
(B)
(A)
10 _.-.,
10
3--. -l
--.
00
00
8 '-' 8
'-' s::
=
0
0
~ 6 ...
~
6
!: c
"'= "'s:: 4
(.)
(.)
s:: 4 0
u
0 u
2 2
0 0
0 10 20 30 40 50 60 0 I0 20 30 40 50 60
Time (h) Time (h)
Figure 6. Batch cultivation of (A) recombinant and (B) wild type A. eutrophus in R medium containing 20
g/L ofglucose and C/N molar ratio of7.3 (0 dry cell concentration, 0 P(3HB) concentration, il residual cell
concentration ).
472
0.12
0.12
0.10 0.10 (B)
(A)
0.08 0.08
=
;!; 0.06
?C
=
:I:
:;:: 0.06
C"-
C"
0.04 0.04
0.02 0.02
0.00
0.00
0 10 20 30 40 50 60
0 10 20 30 40 50 60
Time (h) Time (h)
Figure 7. Time profile of P(3HB) synthesis rate (A) recombinant and (B) wild type A. eutrophus during
cultivation described in Fig. 6.
cultivation. Also, the data of enzyme activities (beta-ketothiolase and NADPH-dependent

reductase) during cultivation showed that enzyme activities ofrecombinant were increased
to 2 times that of wild type.
Similar results have been obtained by repeated experiments comparing recombinant
and wild type strains. It was expected that when enzyme activities related to P(3HB)
synthesis (PHA synthase, beta-ketothiolase, and NADPH-dependent reductase) were
increased by homologous amplification, the P(3HB) synthesis rate in recombinant could be
increased. From the experimental results shown, final P(3HB) concentration and P(3HB)
content were increased by 6% and 10%, respectively in recombinant A. eutrophus. Also,
enzyme activities involved in P(3HB) synthesis showed 2 times increment and P(3HB)
synthesis rate was increased by 20% in recombinant. Although there is not significant
increase in recombinant strain, these results show that the production rate of recombinant
A. eutrophus is increased by the amplification of enzyme activities involved in P(3HB)
synthesis. Because ofthe low copy number ofbroad-host-range plasmid pVKlOl used for
this study, the enzyme involved in PHA synthesis may not be highly expressed enough to
show considerable increase in P(3HB) production and it makes small increase in P(3HB)
production. It is expected that ifvector system with high copy number could be developed,
distinguishable increase in P(3HB) production be obtained.
ACKNOWLEDGEMENTS
We thank Prof. A. Steinbuchel for kindly providing the A. eutrophus PHA synthesis
gene. This work was supported by the Ministry of Science and Technology and Ministry of
Education; and by the LG chemicals, Ltd.
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473
Braunegg, G., Sonnleitner, B., and Lafferty, R. M., 1978, A rapid gas Chromatographie method for the
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poly(3-hydroxybutyric acid) by recombinant Escherichia coli in flask and fed-batch cultures. J. Environ.
Polymer Degrad. 2: 169.
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Biotechnol. 52: 27.
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co/i strains: genetic and fermentation studied. Can. J. Microbiol. 41 (Suppl. I): 207.
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recombinant Escherichia co/i. Ann. NY Acad Sei. 721:43.
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synthesis and accumulation of poly-(3-hydroxybutyric acid), and morphological changes. Biotechnol.
Bioeng. 44: 1337.
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Escherichia co/i. J. Biotechnol. 32: 203.
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phenol reagent. J. Bio/. Chem. 193: 265.
Nishimura, T., Sato, T., and Tomita, K., 1978, Purification and properties of -ketothiolase from Zoogloea
ramigera. Arch. Microbio/. 116: 21.
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Peoples, 0. P., and Sinskey, A. J., 1989, Poly--hydroxybutyrate biosynthesis inA/caligenes eutrophus H16.
Identification and characterization ofthe PHB polymerase gene (phbC). J. Bio/. Chem. 264: 15298.
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poly(hydroxyalkanoic acid)- accurnulating Alcaligenes eutrophus and Pseudomonas saccharophi/a
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hydroxybutyrate synthetic pathway and synthesis ofPHB in Escherichia coli. J. Bacteriol. 170:5837.
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Alca/igenes eutrophus Hl6 poly--hydroxybutyrate biosynthetic pathway. J. Bacteriol. 170: 4431.
Steinbuchel, A., 1991, Polyhydroxyalkanoic acids, p. 124-213. in Biomateria1s: novel materials from
biological sources, D. Byrom, ed., Stockton, New York.
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culture of Alca/igenes Iatus, a growth-associated PHB producer. Biotechnol. Bioeng. 50: 197.
475
CHEMOENZYMATIC SYNTHESIS OF WATER-SOLUBLE SUGAR-BRANCHED
POLY (VINYL ALCOHOL)
Yutaka Tokiwa1 , and Masaru Kitagawa2
1 National Institute of Bioscience and Human-Technology (NIBH)

2 Research Institute of Innovative Technology for the Earth, NIBH branch
Tsukuba-shi, Higashi 1-1, lbaraki 305, Japan
INTRODUCTION
It is important to develop biodegradable plastics by utilizing natural substances. Natural

polysaccharides such as starch and cellulose are biomass existing abundantly on earth.
Saccharideis a good source of organic raw material (Lichtenthaler, 1991). But many problems
arise regarding thermolastic, moisture proof and compatibility properties when these
polysaccharides are used as materials of plastics. Hence the characteristics of polysaccharides
have tobe improved by physical, chemical or enzymatic modification as shown in Fig.l. Starch
[ Improvement by modification
with additives
I r-
[ Starch I Biending z
J (I)
[ Improvement by chemical J "'

;r.
0
Q.
modification (I)
(1<1
[ Modified starch J
R
g.
l

'[
Modification with enzyme ) '<
and chemical catalysts New synthetic polymer ..,3
(I)
[ Saccharides J containing saccharide "'

branch ....._
Figurel. Development of new biodegradable polymers by utilization of natural polymer materials
Sdence and Technology of Polymers and Advanced Materials

-+--------yHCH2, - - - - + -
C=O
I
CH20H 0
~~ OH OH
n
0 0
II II
~~~~~
OH OH
n
0
+---------------------------CHC~
CH,OH CH,OH
~ ~O/CONH-cH,
~o-1 ---r
OH OH ll
Figure 2. Sugar based polymers reported
is a renewab1e resource produced by p1ants distributed almost everywhere in the world, and we
are now examining the development of useful biodegradable plastics using tropica starch
(Tokiwa, 1997). In our previous report, we investigated physical modification of starch with
additives such as a biodegradable polymer, poly(e-caprolactone)(PCL) (Pranamuda et al.,
1996). Another approach to the improvement is chemical modification of starch. We
synthesized starch acetates having various degrees of Substitution and examined their
characteristics as plastics (Ueda and Tokiwa, 1995). A third approach is use of saccharides
derived from polysaccharides. Development of new materials derived from mono-, di-, and
oligo-saccharide, which are constituents of polysaccharide, Ieads to effective use of the earth's
resources.
Much attention has been paid to synthetic po1ymers containing sugar branch. These
polymers are very attractive as intelligent materials in many application fields, for example, in
478
~~'
~OH_ _._
OH
Enzymatic Chemical
synthesis polymerization
Figure 3. Strategy for producing sugar branched polymer
biofunctional materials, biochernical reagents and pharrnaceuticals (Dordick et al., 1994).

There is currently great interest in the role of sugar in vivo. Because sugars play an
irnportant part not only as an energy source but also in cell-cell recognition systerns, synthetic
polymers containing sugar branch have recently been the focus of intense research. There
have been rnany investigations on these polymers. For exarnple, Kobayashi et al. investigated
interaction between hepatocytes and oligosaccharide containing polystyrene as a material for an
artificial liver (Kobayashi et al., 1994), and Kitazawa et al. reported a polymerizable sugar
monomer, glucosyloxy- ethylmethacrylate (GEMA), as shown in Fig.2 (Kitazawaet al., 1990).
Nishimura et al. reported a synthetic carbohydrate polymer having pendant sugar residues from
the viewpoint of pseudoglycoproteins related to the asparagine linked type glycoprotein
(Nishirnura et al., 1991), and that water soluble glycopolymers having N-acetyl glucosarnine
branches can be used as a po1yrneric sugar acceptor substrate which is glycosylated with
glycosyl transferase, to develop an excellent rnethodology in oiligosaccharide synthesis
(Nishirnura et al., 1994). Kitano et al. investigated galactose residue containing polyrners as
devices for targeting to hepatocytes (Kitano et al., 1995). But these polyrners are not
biodegradable.
In the present study, we investigated the chracteristics of protease from S treptomyces on
enzyrnatic synthesis of polymerizable sugar, and further exarnined polymerization of the
resulting sugar ester.
STRATEGY FOR SUGAR BRANCHED POLYMER DEVELOPMENT
We are moving ahead with a strategy to develop the biodegradable sugar branched
polymer. The flfSt step is synthesis of polymerizable sugar ester catalyzed by enzyme. To
develop a new highly functional polymer, we exarnined chemoenzyrnatic synthesis of sugar
branched polymer. Highly selective enzyrnatic catalysis has been used to modify sugars
containing multiple hydroxyl groups in rnicroaqueous media (Therisod and Klibanov, 1986,
1987; Riva et al., 1988). Enzyme-catalyzed regioselective modification of sugars offers an
efficient process compared with conventional chernical synthesis. Recently,modification of
479
non-reducing sugars, such as a-methyl galactoside, with vinyl acrylate, was catalyzed by
enzyme, and the resultant acryloyl sugar was chernically polymerized to yield a sugar-based
polyacrylate (Blinkovsky et al., 1994; Chen et al., 1995; Martin et al., 1992). It has been
reported that enzymes undergo a catalytic reaction not only in an aqueous solution but also in
an organic solvent. In the case of regioselective modification of sugar by a chernical catalyst,
specific blocking and deblocking reactions are required because sugar has multiple hydroxy
groups. By enzyrne catalyst, regioselective transesterification of sugar is possible under milder
condition in one step. The second step of our strategy is polymerization reaction by chernical
catalyst. Some investigators have reported enzyme catalyzed polymerization of ester (Patil et
al.,l99lb; Linko et al., 1995; Matsumura et al., 1996). Polymerization by use of lipases or
proteases is useful for polyester synthesis. It was generally thought that high molecular weight
is not obtained by enzymatic polymerization. But recently Linko et al. reported that polymer
with high molecular weight was synthesized by Iipase.
Patil et al. reported that sucrose trifluorobutyrate was polymerized by protease in
pyridine (Patil et al., 199lb). The structure of sucrose polymer is shown in Fig.2. The
molecular weight is ca.l3,000. The polymer was degraded by protease easily in aqueous
solution. Patil et al. predicted that the sucrose containing polymer rnay have applications as a
water-absorbent, biodegradable plastic for use in diapers and hygenic products, water treatment
chernicals, and components of drug delivery systems.
Regarding the polymerizable sugar ester containing vinyl group, chernical catalysis is
convenient, since copolyrnerization and gelatination are possible. Hence we exarnined
synthesis of the polymer containing sugar branch catalyzed by enzyme and subsequent
chernical polymerization as shown in Fig.3.
ENZYMATIC SYNTHESIS OF POLYMERIZABLE SUGAR ESTER
Generallysugar is poorly soluble in organic solvents. One approach to overcorning the

disadvantage on the enzymatic synthesis of sugar ester, is to modify the sugars to increase the
solubility in organic solvents. Therisod reported that monosaccharides with blocked C-6
hydroxyl groups were transesterified in acetone, tetrahydrofuran (THF) and rnethylene chloride
by lipases (Therisod and Klibanov., 1987). Martin also reported that 6-position of non-
reducing sugars, methyl glycoside, was replaced with vinylacrylate by lipases (Martin et al.,
1992). lkeda reported that glucose complex with phenylboranie acid was increased in
solubility in organic solvents and was acylated with vinylacrylate enzymatically (lkeda and
Klibanov., 1993). Another approach to the enzyrnatic esterification of sugar is to use
hydrophilic organic solvents which are good solvents of sugar. Dirnethylforrnamide (DMF) is a
good solvent of sugars compared with other organic solvents such as pyridine, alcohol, THF
and so on. There are many reports regading sugar ester synthesis by use of Iipase and/or
protease in organic solvents such as pyridine (Therisod and Klibanov, 1986,1987; Klibanov,
480
Alkaline prolease Neutral prolease
Figure 4. Comparison of transesterification activity between alkali protease and neutral protease.
Protease (100mglml) from various origins was adEd to 5ml DMF solution containing 0.25M glucose and
IM trichloroethylbutyrate . The suspensionwas shaken at 35"C and 130rpm for 7days. The conversion rate
was calculated from decrease in the concentration of glucose by high performance liqlid chromatography
(HPLC). Glucose was OO!ermined by HPLC with refractive in!Ex measurements. A carbohyctate analysis
column, TSK gel Amide-SO (TOSOH), was used with a mobile phase of mixture of 75 % acetonitrile and
25 % waterat a flow rate of 1.0 ml/min. Alkaline proteases: proteasetype VU from Bacillus Iicheniformis
(Sigama) , protease type XXI from Streptomyces griseus (Sigma), subtilisin from Bacillus subtilis
(Boehringer Manheim), alkaline protease from Basillus licheniformis (Promega), alkalophilic proteinase
from Streptomyces sp. (ToyoboCo.), proteaseS fromBasilus sp.(Amano), proteaseN fromBacillus subtilis
(Amano), proleather from Bacillus sp.(Amano), esperase from Bacillus subtilis (Novo Nonisk), alcalase
from Bacillus licheniformis (NovoNonisk), bioprase from Bacillus subtilis (Nagase Biomedicals). Neutral
protease: proteae from porcine pancreas (Elastin product Co.Inc.), prolase from papaya (ICN), protease A
from Aspergillus oryzae (Amano), bromelain F frompineapple cannery (Amano), papain W-40 fromcarica
papaya (Amano), protease type U from Aspergillus oryzae (Sigama), protease type XV from Bacillus
polymyxa (Sigama).
1990; Oosterom et al., 1996). There is little inforrnation, however, on its synthesis in DMF,
which is superior in sugar solubility to other organic solvents. Only Bacillus subtilis
protease (subtilisin) has been found to be active in DMF as weH as in pyridine (Riva et al.,
1988 ; Carrea et al., 1989).
We screened commercially available lipases and proteases from various origins and for
synthesis of a sugar ester using glucose and activated fatty acid ester, 2,2,2-trichloro-
ethylbutyrate, in DMF (Shibatani et al., 1997). Although Iipase type II derived from porcine
pancreas and Alcaligenes Iipase showed conversion rates of glucose of 44.8% and 23.5%,
most lipases were inactive in rnicroaqueous DMF. On the other band, various proteases showed
high conversion activity. Fig.4 compares the transesterification activity between eleventh
alkaline proteases and seventh neutral proteases. Alkaline proteases showed higher glucose
conversion activity than neutral proteases. Several proteases from Bacillus species were found
to catalyze regioselective transesterification of sugars. Among alkaline proteases, the alkaline
protease from Streptomyces sp. was the most reactive in DMF (Conversion rate > 99% ). It is
481
known that in aqueous solutionthe proteolytic activity of this enzyme is higher at higher pH
range than the known alkaline protease (Nakanishi et al., 1974; Nakanishi and Yamamoto,
1974). Until now the enzyme has been used for proteolysis of insoluble protein and for
structure investigation of protein. From the above result, it is clear that this enzyme is useful
not only for protein chemistry but also for enzymatic synthesis of sugar ester.
1t is generally accepted that lipases and proteases can form acyl-enzyme intermediates.
Park et al. reported that proteases gave better results than lipases on the transesterification of
glucose and activated N-blocked phenylalanine in pyridine (Park et al., 1996). Furthermore,
Watanabe et al. reported that alkaline protease (Proleather) interacted with bulky acyl donors
more favorably than Iipase from Pseudomonas cepacia (Watanabe et al., 1995). In the present
study we also found that proteases are more effective on transesterification reaction using glucose
and trichloroethylbutyrate than lipases. Generally in aqueous solution Iipase catalyzes long chain
acyl donor, while Klibanov reported that porcine pancreas Iipase did not react with large
substrates in organic solvents (Klibanov, 1986). However there is little infomation on interaction
between enzyme and substrate in organic solvents. Zaks and Russen reported that substrate
specificity changed in peptide synthesis in organic solvent (Zaks and Russen, 1988). Possibly
the active site pocket of protease is moreflexible than that of Iipase in organic solvents.
Wang et al. reported that enolesters such as vinylacetate and isopropenyl acetate are
effective for transesterification reaction (Wang et al., 1988). Since enol group is a good leaving
group, which changes into aldehyde or ketone, reverse reaction does not proceed after
elimination. The reaction rate of vinylester is 20-100 times higher than ethylester. Hence
100
80
~ Enzyme
---
60
~ 0 mg/ml
c
0
...
;;;
0 40
~ 0.25 mg/ml
;>
c
0 -+- 1.25 mg/ml
u
20
-+- 2.5 mg/ml
-o- 5 mg/ml
0
-o- IOmg/ml
0 2 3 4 5 6 7
Reaction time (days)
Figure 5. Effect of enzyme concentration on the polymerizable sugar ester synthesis.
Protease (0-1 Omg/ml) from Streptornyces sp. was lrlledto 5 ml DMF solution containing 0.25M glucose aiXI
(IM) DV A. Thesuspension was shak.en at 35'C and 130 rpm for7 days. The conversion rate was calculated
from decrease in the concentration of glucose by HPLC. HPLC conditions were the same as in Fig.4.
482
vinylester of dicarboxylic acid is a good spacer arm for the sugar branched polymer synthesis.
It is possible to use a vinyl group of vinylester of dicarboxylic acids as a good leaving group in
trans-esterification reaction and another vinyl group for polyrnerization reaction.
The alk:aline protease from Streptomyces sp. was found to catalyze transesterification
of glucose with divinyl adipate, which is a Ionger spacer, to yield a novel polyrnerizable
glucose ester, 6-0-vinyladipoyl D-glucose. We frrst conducted a study regarding enzyme
concentration and other reaction conditions for effective polymerizable sugar ester synthesis
using glucose and DVA. Fig.S shows the effect of enzyrne concentration when using 0.2SM of
glucose and IM of DVA. The conversion from glucose into the ester increases with increasing
enzyme concentration. The conversion rate was about 70% at reaction time of7days when the
highest Ievel of enzyme (lmg/ml) was used.
We then exarnined the effect of the DVA concentration on the polymerizable sugar ester
synthesis using glucose and DVA. The enzyme concentration was Smg/ml. As shown in Fig. 6,
the conversion rate increased with increasing DVA concentration. In this experirnent, glucose
concentration was 0.2SM, which is almost the maximum solubility in DMF. Concentration of
DVA is a several times (3-8 times) that of the sugar. Since sugars have multiple OH groups,
many products occur by chemical catalysis. On the other hand, in this case by enzyme catalysis,
only 6-mono ester was observed under every reaction detected by thin layer chromatography
(1LC). In the presence of 2M DVA (4 times molar against glucose), high conversion rate was
obtained. The conversion rate saturated at the DVA concentration of 1. SM. In the presence of
more than 1. SM DVA (6 times molar against glucose), high conversion rates (more than 90%)
were obtained in a shorter reaction time (12 hours).
100
80
DVA(M)
~ -o- 2
E 60
"''"" -o- l.7S
-....
1:
0
....
"eil -+- l.S
> 40
CO
1:
0
.......... l.2S
u
20
0.7S
0
0 6 12 18 24
Time(hr)
Figure 6. Effect of DVA concentration on the polymerizable sugar ester synthesis.
Protease (5mg/ml) from Streptomyces sp. was adhl to 5 ml DMF solution containing 0.25M glucose aiXi
(0. 75-2M) DVA. The suspension was shaken at 35"C and 130 rpm for 24hrs. The conversion rate was
calculated from decrease in the concentration of glucose by HPLC. HPLC condition was the same as in Fig.4.
483
(a)
2
1.8
~
ca....
c 1.6
0
;;; DVA (M)
....

Q)
> 0.75
c

0
u
00 1.4
& 1.25
0:0
.s
1.2

0
1.5
1.75
0 2
0 2 4 6 8 10 12 14
Time(hr)
(b)
8
04-~~---r--~--~--
0 0.5 1.5 2
DVA(M)
Figure 7. Relationship between glucose elimination rate and DVA concentration.

(a): Logarithm of glucose concentration calculated as conversion rate subtracted from 100 is plotted against
reaction timein Fig.6. (b): The eliminationrate constant (k) was calculated from the slope in Fig.7(a).
484
First Glucose 36g(0.2mol) OCO(CH )4 COOCH=CH2
reaction
DVA 304ml(l.6mnl)
Enzyne 1.6g
DMF800ml
~a.----~ 0
OH
OH OH
Glucose 36g(0.2mol)
DYA 304ml0 6UMJ!l Second reaction
DMF800ml
44g (66%)
Glumse 36g(0.2mol)
Third
DV A 304m!< I 6moll
DMF800ml
reaction
38g (57%)
30g (45%)
Figure 8. Large scale synthesis of polyrnerizable glucose ester.
1.6 g of Streptomyces sp. alkaHne protease was adled to 800 ml DMF containing 36g (0.2 M) glucose an:!
304m! (1.6 M) DVA. Thesuspension wasstirredat 120to 150rpmfor4-10daysat35 'C. Thereactionswere
terminated after centrifugation by removing the supematant. The DMF was evaporated off. The product was
precipitated by leaving the reaction mixture to stand in a refrigirator and recrystallized by ad:ling acetone-
hexane. DMF solution containing the same reaction concentrations of glucose and DVA was adled to the
resulting pellet and the next reaction was initiated.
Glucoseelimination rate was evaluated from the data in Fig.6. The plot of logarithmic
glucose concentration against time was found to be linear as shown in Fig. 7(a.). Fig. 7(b)
shows tlie relationship between the rate (k) and DVA Ievel. The result was not a saturated curve
but a sigmoidal curve. These data mean that this enzymatic trans-esterification catalyzed by the
protease does not obey Michaelis-Menten kinetics. Klibanov et al., reported that
transesterification reactions catalyzed by porcine pancreatic Iipase in hexane obey Mikaelis-
Menten kinetics (Zaks and Klibanov, 1985). The different results between the two experirnents
may be caused by the different reaction conditions, such as kind of enzyrne.
The drawback of enzymatic synthesis is high synthesis cost owing to enzyrne expense.
This problern is overcorne by using an enzyme that is stable in DMF. We examined repeated
485
use of enzyme in large scale synthesis of polymerizable sugar ester. In this experiment,
protease was insoluble under the reaction condition. Hence we could easily remove enzyme
from the reaction mixture by centrifugation. The same enzymewas used 3 times in the reaction
conditions. The reaction procedure is shown in Fig. 8. Although reaction rate decreased with
increasing number of recyle times, high yield was obtained by Ionger reaction time. Time
course of conversion rate was shown in Fig. 9. This result implies that the enzyme is stable in
the reaction condition and repeated use of this enzyme is possible.
The structure of this esterwas determined by 13 C-NMR and IR. The results of infrared
(IR) spectroscopy of the sugar ester were as follows: C=O (1730 cm 1 ); C=C (1650 cm 1 ); OH
100
First
90
,..-._
80
QS2
'--"' 70 Second
<!)
~
C'::S 60
~
t: 50 T~
0
;n
,_ 40
<!)
>
t: JO
0
u 20
10
0
0 I 2 3 4 0 I 2 3 4 5 6 7 g 9 10
0 I 2 3 4
Reaction Time (days)
Figure 9. Timecourse of three cycles of polymerizable glucose ester synthesis.
Reaction condition was shown in Fig.8. The conversion rate was calculated from recrease in the
concentration of glucose by HPLC. HPLC condition was the same as in Fig.4.
(3400 cm 1 ). These results suggested that an ester containing a polymerizable vinyl group was
produced. The product was characterized by 13 C-NMR (DMSO-d6, 270Mhz): o 23.53,
23.83, 32.78, 33.52 (-CH2 - ), 64.01 (C-6a,C-6), 70.10 (C-5a), 70.35 (C-4a), 70.64 (C-4),
72.26 (C-2a), 72.98 (C-3a), 74.22 (C-5), 75.29 (C-2), 76.48 (C-3), 92.22 (C-la),
96.84 (C-1 ), 170.37, 172.81 (C=O), 98.15, 141.30 (C=C). According to the technique of
13C-NMR analysis of sugars (Yoshimoto et al., 1980), the result shows a downfield shift of
the peak at C6 and an upfield shift of the peak at C5. These shifts resulted from enzyme-
catalyzed transesterification of glucose with divinyl adipate at position 6 of glucose, yielding 6-
0-vinyladipoyl D-glucose.
486
920K 17K 7. 5K 0. 6K
l l l l
[mV]
200 A
100
0
0 20 40
Time (min)
[mV]
60 B
40.
20
0 _ __,___.
0 20 40
Time (min)
Figure 10. Gel permeation chromatograph pattems (GPC) ofpoly(glucose-adipate).
Polymer in molecular weight was ~remined by GPC with refractive incrx (TOSOH). An analysis
column, TSK 05000 PWXL + 04000 PWXL+G2500PWXL (TOSOH), was used with a mobile pha~e of
O.IM NaCI (A) or water (B) at a flow rate of l.Oml/min. Arrows indicate molecular weight markers for
polyetylene glycol (6,000 and 75,000) and polyethylene oxide ( 170,000 and 920,000).
CHEMICAL POLYMERIZA TION
Polyrnerization of vinylderivatives can be carried out using free radical initiators such as
azo initiator and redox initiator. Chen et al. reported that redox initiator is useful for
polyrnerization of sucrose acrylate in aqueous solution (Chen et al., 1994). They increased the
nurnber-average rnolecular weight to Mn 2,400,000 using Fe2+, arnrnoniurn sulfate and
hydrogenozide. But synthesis of copolyrners using hydrophobic copolyrnerization reagent
requires use of an organic solvent. Hence we exarnined polyrnerization using conventional azo
initiator, azobisisobutyroniyrile (AIBN), in organic solvent. The polyrnerization of 6-0-
vinyladipoyl-D-glucose was carried out as follows: in a 10 rnl sealed polyrnerization tube, a
rnixture containing 6-0-vinyladipoyl-D-glucose (0.5g), AIBN (2.5rng) and DMF (0.5g) was
heated at 60'C for 24 h. The resulting product was precipiated in acetone. The precipitated
487
material was dried under reduced pressure at 40C to give 0. 25 g of powder (Kitagawa and
Tokiwa, 1997).
Polymerizablility of the sugar ester monomer is restricted by the steric hindarance of
sugar moiety. Hence a long spacer between sugar moiety and terminal vinyl group is useful. 6-
0-vinyladipoyl-D-glucose was polymerized via conventional free radical methods (Fig.4) in
Dl\.1F with AIBN to give poly(glucose 6-adipate) of molecular weight (Mn ca. 7, 500). IR
spectrum revealed that vinyl group absorption (1650cm 1)disappeared, and 13 C-NMR data were
consistent with structure as follows: 13 C-NMR (DMSO-d6): o23.70, 23.90, 32.92, 33.30
(-CH 2 - ), 63.90 (C-6a,C-6), 69.00 (C-5a), 70.14 (C-4a), 70.48 (C-4), 72.04 (C-2a),
100
0
0
V")
t-" 80
i
u
~
~ 60
'+-<
0
..:.::
~
~
0..
40
'+-<
0
~
~ 20
'-'
~
~
<r:
0
0 0.1 10 100
Concentration of NaCI (mM)
Figure II. Effect of NaCI concentration on the GPC of poly(glucose-adipate).
Polymer in molecular weight was retremined by GPC with refractive inrex (TOSOH). An analysis
column, TSK G5000 PWXL + G4000 PWXL+G2500PWXL (TOSOH), was used with a mobile phase of
0-0.IM NaCI at a flow rate of 1.0 ml/min.
72.79 (C-3a), 73.39 (C-5), 74.57 (C-2), 76.28 (C-3), 92.15 (C-l a), 96.76 (C-l ),
171.92, 172.63 (C=O).
Fig.10 shows the pattem of gel permeation chrornatography (GPC) of glucosepolymer
eluted by distilled water or O.lM NaCI. When the polymer was eluted by O.lMNaCl, a single
peak appeared. But in case of distilled water, the GPC pattem indicated several peaks in the
higher molecular weight area.
We exarnined the effect of salt concentration on the GPC analysis of the polymer as
shown in Fig.1l. The area of main peak in Fig.lO(A) decreased drarnatically at less than lmM
NaCl. This polymer is linear, neutral and hightly water soluble. It seems probable that the
polymer was aggregated in the pure water and dissociated in NaCl solution.
488
... ( Spacer arm )
~
Fig.l2 Scheme of the sugar branched polymer
CONCLUSION
Highly selective enzymatic catalysis was used to modify sugars containing multiple
hydroxy groups in microaqueous media. We investigated the enzyme-catalyzed modification of
sugars expected to be used as materials for sugar-based biodegradable plastics.
Enzyme screening for sugar ester synthesis to catalyze regioselective modification of
sugars in DMF was performed , and we found that alkaline protease from Stretopmyces sp.
had high conversion activity (Shibatani et al., 1997).
In this experiment, protease-catalyzed transesterification of sugars such as glucose with
OVA by alkaline protease from Stretopmyces sp. in microaqueous DMF was exarnined. The
product was separated by crystalization and the 13C-NMR analysis of the products suggested
that 6-substituted sugar mono-ester containing polymerizable vinyl adipate group was
produced. Such sugar ester was polymerized in DMF with AIBN to yield glucose branched
poly(vinyl alcohol) (PV A).
Thesesugar branched-polymers consist of three parts, i.e. main chain, spacer arm and
sugar moiety. The sugar density, biodegradability and hydrophobicity can be changed by main
chain modification. Copolymerization reaction is useful for this purpose. 2-Methylene-1, 3, 6-
trioxocane (MTC) is a very useful monomer which can easily incorporate the ester-ether group
into the backbone of vinyl polymers by a copolymerization method. We are presently
attempting to synthesize the copolymer of MTC with this sugar ester monomer. We reported
the synthesis of copolymers of MTC with vinyl monomers such as styrene, methyl
methacrylate, and vinyl acetate (Hiraguri and Tokiwa, 1993). The distance between main chain
and sugar moiety is changeable by use of various divinylester of dicarboxylic acids as spacer
arm. Furthermore, mono-, di- and oligo-saccharides can be used as sugar moiety. By
modification of these three parts, we could design various types of polymers with only two
reaction step (enzymatic synthesis of sugarestermonomer and its chemical polymerization). In
sugar ester synthesis by enzyme, blocking and deblocking reaction arenot necessary (Wulff et
al., 1991). It is well known that PVA is degraded by some microorganisrns such as
Pseudomonas (Suzuki et al., 1973). But these microorganisms arenot widespread in the
489
natural environment. The new types of polymer we designed are expected to be easy to
degrade.
These polyrners may have application as a new type of water soluble biodegradable
material.
ACKNOWLEDGMENTS
This study was performed as a part of the development of Biodegradable Plastics

supported by the New Energy and Iudustrial Technology Development Organization (NEDO).
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Matsumura,S., Beppu,H., Tsukada,K., and Toshima,K., 1996, Enzymatic-catalyzed ring-
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490
Nishimura,S., Matsuoka,K., Furuike,T., Ishi,S., and Kurita,K., 1991, Synthetic
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sucrose-containing po1ymers, Macromolecules., 24: 3462
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491
PREPARATION AND POTENTIAL FOR APPLICATION OF
CATIONIC POLYSACCHARIDES IN COSMETIC FORMULATIONS
William H. Daly, Melissa Manuszak Guerrini, Doris Culberson,

and Javier Macossay
Macromolecular Sturlies Group,

Department of Chemistry,
Louisiana State University,
Baton Rouge, LA 70803
CATIONIC POLYMERS
Polymerie quatemary ammonium salts (polyquats) have a variety of uses in

cosmetic formulations due to their solubility in both aqueous and aqueous-alcoholic media.
Polyquats have been used as thickeners, emulsifiers, fixatives or film formers, and as
additives in formulations to improve combing of hair, manageability, body, curl retention
and substantivity of ingredients to keratin. 12 The particular application of a polymer
depends on the polymer's ability to absorb at an interface, stabilize dispersions, emulsify,
and confer the preferred rheology by means of a three dimensional network. 2 Cationic
ingredients are substantive to hair keratin due to the low isoelectric point of hair (pH =
3.67).3 However, the high affinity of some cationic polymers has limited their use due to
soiling (build up) and resistance to removal by anionic surfactants. 1
Cosmetic Applications of Chitosan Derivatives
Chitosan and its derivatives have been reportedly used as film formers in hair
products,45 setting agents,6 hair conditioners and shampoos. 7 However, the use of chitosan
and chitosan salts in personal care products has been limited. The insolubility of chitosan
derivatives in the solvent systems of these products, such as aqueous, neutral to alkaline
solutions, or anionic detergents, is the cause of limited use. Lang and coworkers have
investigated the synthesis ofwater soluble chitin and chitosan derivatives which might also be
compatible with anionic detergents. 5 Reactions of chitosan with epoxides such as ethylene
mcide, propylene oxide,8 butylene oxide and glycidol9 were found to yield water soluble
chitosan derivatives that were compatible with anionic detergents. 10 Mixtures of
glycidyltrimethylammonium chloride, 11 propylene oxide! 2 or glycidol 13 with ethylene oxide
Science and Techrwlogy ofPolymers and Advanced Materials

yielded cationic chitosans derivatives capable of use in all cosmetic formulations; while
substitution of short chain nonionic epoxides by long chain epoxides were found to yield
derivatives with detergent properties. 5 Finally, chitosan was sulfoalkylated with 1,3-propane
sultone to yield sulfopropyl substituted ampholytic or anionic derivatives. 14 These derivatives
are thought to be weil suited for use in hair products.
Recently, hydroxypropyl chitosan and hydroxypropyl trimethylammonium chitosan
chloride15 16 (Figure 1) were synthesized for evaluation in cosmetic applications. The initial
objective ofthis work was to characterize the solution properties and keratin affinities ofthese
materials. However, either the poor viscosity enhancing properties or poor compatibility with
anionic surfactants prompted an extension of the study to include cationic cellulose
derivatives.
NaOH
Isopropanel
(B)
CICH 2-CH-CH 2-N + (CH 3 h Cl .
bH Quat 188
Figure 1. Hydroxypropyl Chitosan and Hydroxypropyl Trimethylammonium Chitosan Chloride.
Cosmetic Applications of Cellulose Derivatives
Cellulose derivatives are used in cosmetics as film formers for nail lacquers, skin
and hair conditioners, and gelling agents in toothpaste, to name a few applications. Their
use is dependent upon the particular cellulose derivative and the modifications to the
grafred substituents. Quatemary ammonium cellulose derivatives are of particular interest
as conditioners in hair and skin products. Polyquaternium 10 (Figure 2) is a quatemized
[~~] OH CH20-(CH2CH20)x-CH2-CH-CH2-N (CH,), Cl.

I
OH
Figure 2. Structure of Polyquatemium 10.
494
hydroxyethyl cellulose polymer17 formed from the alkaline reaction of hydroxyethylcellulose
with epichlorohydrin followed by quatemization with trimethylamine. Incorporation of
approximately 1 cationic group per 2 anhydroglucose repeat units 18 Ieads to a derivative with
a relatively low average molecular weight per cationic charge (i.e. 670 glmol.) 19.2 and a high
density of polar groups. Polyquaternium 10 is used in shampoos, conditioners, gels, mousses,
and skin care products, such as Iotions, moisturizers and cleansers. 1.2 1 Due to the attributes
imparted to hair, such as manageability and ease of combing, Polyquaternium 10 has been
used frequently in shampoo formulations. 20
The binding interactions of polyquatemium polymers with hair keratin,2223
rheological and flow properties of polymer solutions, film forming and adhesion properties2"-
27 have been evaluated. In particular, the effects of molecular weight, pH, charge, electrolyte
interactions and surfactant interactions on behavior of Polyquaternium 10 has been studied in

great detail by Goddard and Faucher. 18' 2028.29 It is weil known that cationic polymer
deposition is decreased when surfactants are included in a formulation, especially anionic
surfactants. 30 All surfactants examined were determined to decrease the amount of polymer
adsorbed onto the hair fiber regardless of surfactant charge. 2028 Both anionic and cationic
surfactants were found to decrease the amount of polymer adsorbed greater than nonionic
surfactants. The anionic surfactants decrease sorption by formation of associative complexes
with the polymer. 1 Cationic surfactants tend to decrease sorption by competitive inhibition. 1
The major drawback to the use of Polyquaternium I 0 has been its limited desorption
from keratin. Faucher et a/. 18 determined that less than 15% of Polyquaternium IO was
desorbed from hair by distilled water in 30 minutes. In a similar study/9 a 0.1M solution of
sodium dodecyl sulfate (SDS) desorbed approximately 50% of the polymer in 1 minute and
70% in 30 minutes. However, a small amount of polymer still remained strongly bound to
the hair fibers after further treatment with SDS. 29 Salts were effective in the removal of
Polyquaternium I 0 from hair fibers. 18.29 Trivalent salts were more effective than either
divalent or monovalent salts. However, both dilute salt solutions and deionized water were
less effective than 0.1 M SDS in desorbing Polyquatemium 10 from hair fibers. 29 When
sodium chloride and SDS were combined, no synergistic effect was observed on amount of
polymer desorbed.
Aminoalkylcarbamoyl Cellulose Derivatives
Due to the high cost of chitosan derivatives, the production of aminoalkylcarbamoyl

cellulose derivatives directly from carboxymethyl cellulose (CMC)31 ' 33 has been explored.
These materials, (Figure 3) which are similar to Polyquatemium 10, have many potential
applications in the cosmetic industry. This paper will focus on the characterization of the
solution properties and keratin affmities of these materials. The aminoalkylcarbamoyl
cellulose derivatives are formed by conversion of carboxymethylcellulose using the following
reaction sequence (Figure 3). Sodium carboxymethylcellulose (NaCMC) is converted to a
water insoluble ester susceptible to nucleophilic attack by reaction with neat dimethyl sulfate
(Figure 3A). The methyl carboxymethylcellulose ester (MCMC) reacts under homogeneaus
conditions with neat diamines, such as N,N-dimethylethylenediamine (NNED), to yield water
soluble aminoalkylcarbamoyl methylcelluloses (CMCamide) (Figure 3B). Quatemary
arnmonium salts of the aminoamide derivatives may then be prepared by reaction with
iodomethane or 3-chloro-2-hydroxypropyl trimethylarnmonium chloride (Quat 188) to
produce monoquatemary (MQNNED) or diquatemary (DQNNED) derivatives respectively
(Figure 3C-D). The solution properties and antimicrobial activity of a family of these
compounds, namely those based upon the N,N-dimethylethylenediamine (NNED) moiety,
will be described and compared to the properties of Polyquaternium 10. The study will
include interactions with surfactants by solubility, pyrene fluorescence, and dynamic light
495
scattering, and bactericidal activity of the derivatives. The results of these studies will lend
insight to the applicability of these derivatives in cosmetic formulations as thickeners,
fixatives, conditioning agents, and preservatives.
(A)
(B)
CH 20-CH 2COOCH 3
[~oi'~~--~
MCMC CMCamide
[4:i(CH~ C~l [~:l'c"'

(C) 0 0
II II
CMCamide MQNNED
CH 2-CH-CH 2 N + (CH3h Cl.

\ I
0
l
CMCamide QUAT 188
l"'o NaOH
4Days
Room temperature
2CI
DQNNED
Figure 3. Aminoalkylcarbamoyl Cellulose Derivatives; (A) Reaction of NaCMC to form MCMC ester; (B)
Reaction of MCMC ester to form CMCamide; (C) Reaction of CMCamide to form MQNNED; (D) Reaction
ofCMCamide to form DQNNED.
496
EXPERIMENTAL
Materials
The surfactants, sodium dodecyl sulfate (99%) and reduced Triton X-100 {a-[4-
(1, 1,3,3,-tetramethylbutyl)cyclohexyl)-ro-hydroxypoly(oxy-1 ,2-ethanediyl)} (99%), were
obtained from Sigma Chemical Company (St. Louis, MO) and Aldrich Chemieals
(Milwaukee, WI), respectively. Polyquatemium 10, UCARE Polymer JR-400, was
obtained from Amerchol Corporation (Edison, NJ). The aminoalkylcarbamoyl cellulosic
derivatives, N-2-trimethylammoniumethyl carbamoyl cellulose chloride (MQNNED) and
N-(3-trimethylammonium-2-hydroxypropyl)-N,N-dimethylammoniumethyl
carbamoylmethyl cellulose dichloride (DQNNED), have been prepared in our
laboratories. 31 "34 Water was purified by reverse osmosis, deionization, and filtration
(Osmonics, Inc.). Ultra pure water used in light scattering experiments was obtained using
a NANOpure system from Bamstead.
Metbods
Precipitation Studies Pseudo phase diagrams were prepared for the following
system: SDS I Polymer I water. The solutions were prepared by addition of a concentrated
polymer solution (3%) to a solution ofSDS. The samples were shaken, placed in an oven at
60C for 8 hours, and allowed to cool slowly. The appearance of the liquid and precipitate
was judged visually following the method ofGoddard and Hannan. 19.J5
Phase diagrams were also prepared for systems of 1% Polymer I SDS I Triton X-I 00
varying the ratio of surfactants (I% total). The solutions were prepared in the same manner
as previously described varying the percentage of SDS from 0-1% (wlv) and maintaining a
constant polymer concentration of 1% (wlv).
Fluorescence Fluorescence spectra of the 1% Polymer I SDS I Triton X-100

complexes were recorded with a Fluorolog 2 Model F112X spectrofluorometer (Spex
Industries). Fluorescence emission spectra were taken at an excitation wavelength of335 nm.
The emission spectra between 360 through 450 nm was recorded for pyrene. All
measurements were performed in a I.O cm quartz cell at 25 1C. Sampies were prepared by
pipetting a volume of a pyrene stock solution into each via! and evaporating the solvent in
order to obtain a final pyrene concentration of I* I o' M. Concentrated solutions of polymer
and surfactants were added to obtain final concentrations of 1% polymer and 1% total
surfactant respectively. The samples were stirred and allowed to equilibrate for 24 hours
prior to measurement.
Dynamic Ligbt Scattering Dynamic light scattering (DLS) measurements were

made at scattering angles of 30-90 using a Lexel Model 95 Argonion Iaser at 514.5 nm.
During angle dependence studies, temperature was maintained at 25 0.05C. Polymer and
surfactant solutions were prepared as described in the fluorescence study and filtered through
0.2 f.1IIl Whatman PVDF filters to remove dust. Ionic strength ofthe solutions was adjusted to
0.10 M using a sodium chloride solution, which was filtered with a 0.02 mm filter. The
samples were placed in silanated cells and centrifuged to remove any remaining dust
particles. Measurements were made in an index matehing bath with toluene in order to
minimize stray light and reflections.
497
Dynamic light scattering defines a wave vector q = ( 4 1t n I A.. ) sin (8 I 2) where A.. is
the wave length of incident light in a vacuwn, e is the scattering angle and n is the refractive
index ofthe mediwn. The full homodyne intensity, autocorrelation function was measured at
30", 45, 60 and 90" with an ALV 5000 multiple-t digital correlator. The correlation
functions were recorded in real time "multiple-t" mode of the correlator in which 288
channels are logarithmically spaced over an interval from 0.2 J.lS to approximately one hour.
Dynamic Light-Scattering Data Analysis Asswning the scattered field to have

Gaussian statistics, the measured homodyne intensity autocorrelation function, g<2> (q,t), is
directly related to the theoretical first order electric field autocorrelation function, g< 1> (q,t),
through the Siegert relation:
g:z> (q,t) = 1 + B( 1 + f I glll (q,t) ll ) (1)
where f (S 1) is an instrwnental parameter and B is the baseline.

Since DLS measures the diffusion rate of particles in solution, the mutual diffusion
coefficient can be obtained from a plot of the decay rate of g<1> (q,t) versus time using the
following relationships:
glll (q,t) = (2~
r (3)
where r is the decay rate, q is the wave vector and Dm is the mutual diffusion coefficient.
The mutual diffusion coefficient is related to the hydrodynamic radius, Rn. by the
Stokes-Einstein equation:
kTI6pTJR.. (4)
where k is Boltzmann constant and TJ is the viscosity ofthe mediwn.
RESULTS and DISCUSSION
Precipitation Stndies with SDS
The complexation of Polyquatemiwn 10 and two aminoalkylcarbamoyl cellulosic

graft co-polymers with SDS was studied by precipitation above and below the CMC for
SDS (2.4 mglml). The pseudo phase diagrams of SDS I water I Polymer (Figures 4-6)
show the formation of clear solutions at low concentrations of SDS. An increase in
solution viscosity was observed along with formation of turbid or hazy solutions,
precipitates and gels as the percentage of SDS was increased. At high surfactant
concentrations, resolubilization of the polymers was observed. These results are in
agreement with previous studies of complexation of anionic surfactants and
Polyquaternium 10. 1935
The complexation of cationic polymers with anionic surfactants proceeds via charge
neutralization 35 (Eq. 5).
498
p+ + PD. (5)
where P is the cationic polymer containing n cationic charges per residue molecular weight
and n- is the anionic surfactant containing one anionic charge per residue molecular weight.
Theoretical charge neutralization occurs at a 1:I ratio of cationic and anionic charges
resulting in maximum precipitation ofthe polymer.
For Polyquaternium IO, the average residue molecular weight per cationic charge is
689 g/mol while the average residue molecular weight per anionic charge of SDS is 288
g/mol. Therefore, theoretical charge neutralization should occur at a weight ratio of 2.3: I.
Comparison of the observed maximum precipitation with the theoretical charge
neutralization for this system (Figure 4) indicates that this relationship holds true for
concentrations of polymer and surfactant ~ 0.200 and 0.100%, respectively. At polymer
concentrations < 0.200%, the concentration of SDS necessary to precipitate the
Polyquatemium I 0-SDS complex is independent of polymer concentration. This result
agrees with results observed previously for Polyquatemium 10 and SDS. 1935
ov 0
CMCofSDS
!
0.001 <>--<)--o,-.-,.O,.ft)--....T"'T-o...rn/lk---<r~:XX)r,.,Q---,.--r"T""T-rn-Q
0.001 0.01 0.1 10
Sodiwn dodecyl sulfate (%)
Figure 4. Pseudo phasediagram ofthe system Polyquaternium 10 I Sodium dodecyl sulfate I Water.
Symbols indicate: 0 clear solution; e precipitate; V slight precipitate; tJ. hazy solution; D gel; - - - - - -
Theoretical charge neutralization; and -------- Maximum precipitate observed.
The average residue molecular weight per cationic charge for MQNNED is 467
g/mol.; therefore, theoretical charge neutralization should occur at a weight ratio of 1.6:1.
The results for this system (Figure 5) indicate that this relationship holds true for
concentrations of polymer and surfactant ~ 0.020 and O.OI5%, respectively. At polymer
concentrations ~ O.OIO%, the concentration ofSDS necessary to precipitate the MQNNED-
SDS complex is independent of polymer concentration.
The average residue molecular weight per cationic charge for DQNNED is 569
g/mol.. Since the graft on DQNNED contains two cationic charges, two theoretical charge
neutralization weight ratios can be calculated. The first weight ratio, 2.0:I, is related to the
499
addition of one SDS molecule per two cationic charges. The second weight ratio, 1: 1, is
related to the addition of two SDS molecules per two cationic charges. The results (Figure
6) indicate that maximum precipitation of the DQNNED-SDS complex occurs between
these two theoretical charge neutralization lines. Therefore, for concentrations of polymer
-
~
0.1
I)1 0.01
0' 0 0 0 0 0
0.001
0.001 0.01 0.1 10

Figure 5. Pseudo phasediagram ofthe system MQNNEO I Sodium dodecyl sulfate I Water. Symbols
e
indicate: 0 clear solution; precipitate; V slight precipitate; hazy solution; 0 gel; - - - - - - Theoretical
charge neutralization; and ------ Maximum precipitate observed.
0
V
0
0
0
0 0
1::. 0
CMCofSDS

Figure 6. Pseudo phase diagram of the system OQNNEO I Sodium dodecyl sulfate I Water. Symbols
indicate: 0 clear solution; e
precipitate; V slight precipitate; A hazy solution; 0 gel; - - - - - - Theoretical
charge neutralization for 1 SOS; ......... Theoretical charge neutralization for 2 SOS; and -------- Maximum
precipitate observed.
500
and surfactant ;;::: 0.010%, the DQNNED-SDS complex precipitates tnaximally when
approximately 1.5 SDS molecules neutralize the charge of the 2 cationic sites. At low
polymer concentrations (< 0.010%), the concentration of SDS necessary to precipitate the
DQNNED-SDS complex is independent of polymer concentration.
Based upon the observed maximum precipitation patterns for the three systems, the
results indicate that the polymers precipitate at their respective theoretical charge
neutralization ratio when the concentrations ofpolymer are;;::: 0.010, 0.020 and 0.200% for
DQNNED, MQNNED and Polyquaternium 10, respectively. However, at polymer
concentrations :5 0.010%, the limiting SDS concentration necessary to precipitate increases
as the structure of the polymer is varied: DQNNED-SDS < MQNNED-SDS <
Polyquaternium 10-SDS. Therefore, when precipitation is independent of polymer
concentration, a polyelectrolyte containing two cationic charges per residue will precipitate
at lower percent SDS than its monoquaternary analog, and a monoquat closely associated
with the backhone will precipitate before a monoquat attached to a flexible spacer arm.
Precipitation Studies with SDS and Triton X-100
Factors affecting polymer-surfactant association are the micelle surface charge density
(cr), polymer linear charge density @, and the Debye-Hckel ion atmosphere thickness (K
1). 36 The corresponding experimental variables are the mole fraction of charged monomers in
the rnicelle (Ys0 s), structural polymer charge density (1/b) where b is the distance between
charges on the polymer backbone, and the ionic strength ofthe solution (1). 36 The flexibility
of the polyelectrolyte is believed to be another factor. 37 For a given polyelectrolyte at
constant I and b, a critical mole fraction, (Yc) corresponding to a critical micelle surface
charge density may be deterrnined. 36 Yc corresponds to the reversible forrnation of soluble
polyelectrolyte - mixed surfactant rnicelle complexes as deterrnined by initial increase in
solution turbidity. Beyond this phase transition, soluble complexes, liquid coacervate or
amorphaus precipitate may be forrned. 38 The complex phase is dependent upon polymer
concentration, surfactant concentration, molecular weight, micelle surface charge density,
polymer linear charge density and ionic strength. 3839
A polymer concentration of 1% (w/v) was chosen to be in the region between charge
neutralization and resolubilization. The purpose was to deterrnine the critical mole fraction of
SDS, Yc, for binding of the mixed surfactant micelies with the cationic polymers. The results
ofthis study (Figure 7) indicate that at concentrations of SDS;;::: 0.15%, precipitation occurs
for both Polyquaternium 10 and MQNNED mixed surfactant micelle complexes. The charge
density on the micelies causes them to bind strongly resulting in the onset of precipitation of
the complex due to charge neutralization. At concentrations of SDS :5 0.15% (Ysos :5 0.28) ,
single phase, clear solutions were observed. Therefore, Yc = 0.30 for the systems of
Po1yquaternium 10 and MQNNED - mixed surfactant micelle complexes.
For DQNNED, two phase systemsexist when the concentration of SDS is between
0.50% and 0.11 %. The charge density on the micelies is high enough to cause precipitation
of the complex but not sufficiently high to resolubilize the complex. There are two distinct
regions where one phase, clear solutions exist. The first region is at high micelle charge
density (1 ;;::: SDS;;::: 0.6%) and the second region at low charge density (SDS :5 0.10%); Yc =
0.22 for this system. The first region is attributed to the resolubilization of the complex by
full micelies (interpolymer - micelle complexation). The second region is attributed to the
binding of mixed surfactant micelies within the complex as the high percentage of Triton X-
100 will shield the polymer molecules from each other resulting in intramolecular polymer-
rnicelle complexation. At high concentrations of polymer and surfactant, Yc necessary to
cause precipitation is independent of the spacer group between the chain and the
501
DQNNED
DDDDDQQQ~~DD D
QQQQQQQQEJDDD O
MQNNED
Polyquat 10
~~~~~~~QQDDD O
1.0 0.8 0.6 0 .4 0.2 0.1 0.0 %SOS
0.0 0.2 0.4 0.6 0.8 0.9 1.0 % Triton X-1 00
Surfactant concentration ( 1% total)
Figure 7. Phase diagram for the systems I% Polymer I Sodium dodecyl sulfate I Triton X-100 varying the
precipitate and clear supematant; white precipitate and c1ear supematant; G

ratio of the two surfactants. Concentration of SOS varies between 0.0 and 1.0%. Symbols indicate: ~ clear
bJ hazy solution ; and Q
clear one phase solution.
monoquaternary substituent. However, Yc appears tobe influenced by the number of cationic
charges on the graft as DQNNED requires a lower micelle charge density to cause
precipitation than MQNNED.
Fluorescence
Pyrene is a strongly hydrophobic molecule with very low (2-3 mM) water solubility.
Changes in the vibronic fine structure intensities of the pyrene fluorescence spectra result
from changes in the microenvironment encountered by pyrene.40 The ratio ofthe I/1 3 bands is
high when pyrene is solubilized in a hydrophilic medium (l/1 3 = 1.8 for water); whereas, the
1/13 ratio is low for pyrene in hydrophobic medium (l/1 3 = 0.7 for hexane). Aqueous
solutions of the polymers were examined for the presence of hydrophobic domains in the
polymer molecules. The 1/1 3 ratio indicates that pyrene is solubilized in a hydrophilic
environment (Table 1). A ratio of 1.7 indicates that pyrene molecules reside in the solvation
shell ofthe polymer molecules.
Table 1. Fluorescence intensity ofpyrene in solutions ofpolymer, surfactant and polymer-

surfactant complexes.
System Ratio 11111

I% Polyquatemium I 0 1.7
1%MQNNED 1.7
l%0QNNED 1.7
1% Triton X-100 1.2
0.10% SOS & 0.90% Triton X-100 1.2
1% Polyquatemium 10 & 1% Triton X-100 1.3
I% MQNNED & I% Triton X-100 1.3
1% OQNNEO & 1% Triton X-100 1.3
1% Polyquatemium 10 & 0.10% SOS & 0.90% Triton X-100 1.3
1% MQNNEO & 0.10% SOS & 0.90% Triton X-100 1.3
1% OQNNEO & 0.10% SOS & 0.90% Triton X-100 1.3
502
In micellar and macromolecule systems, pyrene is preferentially solubilized in the
hydrophobic regions, and the intensity of the I/I 3 band ratio for pyrene in micelies should
decrease. 40 Pyrene fluorescence intensity in micelies of 0.10% SDS I 0.90% Triton X-100
and 1% Triton X-100 exhibit a ratio of 1.2 (Table 1). As the I/I 3 ratio is greater than 0.7 for
pyrene in hexane, the pyrene is solubilized in the hydrocarbon chain region of the micelles.
Therefore, if micelies are present in the polymer-surfactant complexes, the I/I3 ratio should
be approximately 1.2. The similarity in fluorescence intensity indicates that micelle
composition has no effect on the I/I3 ratio. This type of change in pyrene emission spectrum
has been well documented 4042 and has been connected to the formation of micelle clusters in
both the absence 40'42 and presence ofpolymer. 4345
Changes in pyrene fluorescence indicate that micelies are present in the polymer
surfactant complexes (Table 1). The I/I3 ratio of 1.3 is approximately the same as that of
pyrene solubilized in free micelles. The similar values ofl/13 for both surfactant and polymer
- surfactant complex solutions indicate that the polymer bound surfactant clusters and normal
micelies have almost equal polarity. 41 46 However, pyrene solubilized in the polymer -
surfactant complexes experiences a slightly more hydrophilic environment than in micelies
alone which is consistent with the concept of smaller micelies being bound along the polymer
strand. 43 For smaller micelles, one would expect the water penetration to be greater so that
the pyrene would encounter more of the polar palisade layer of the micelle and the water
associated with this layer.43
Dynamic Light Scattering
Cumulant Analysis For expenments at 25C, the correlation functions were clearly
monoexponential at all angles for the Polyquaternium 10 polymer; the MQNNED and
DQNNED polymers showing appreciable nonexponential character at low angles. The
polymer - mixed surfactant micelle complexes exhibited more complex correlation functions
with ''tails" and "plateaus". In all cases, a fourth order polynomial fit to the correlation
functions was applied to extract r, the decay rate which, for the purposes of this paper,
corresponds to the main diffusive mode. The decay rate increases linearly with q2 for purely
translational diffusion. Deviations from linearity usually signal the presence ofpolydispersity
andlor rotational motion. Figure 8 shows the dependence of r on q2 for each polymer and
polymer - mixed surfactant micelle complex. At a polymer concentration of 1 g/dL, r scaled
linearly with q2 at all angles for the Polyquat<?mium 10 polymer, but an upward curvature was
evident at high q for the MQNNED and DQNNED polymers. This effect was probably due
to polydispersity. At high angles, the scattering form factor drops off for !arge molecules
leaving the small molecules to dominate the scattering intensity and thus produce a positive
sloping effect in the plot. After addition of 0.10% SDS I 0.90% Triton X-100, the
Polyquaternium 10 - mixed surfactant micelle complex formed was uniform as judged from
the linearity of the plot. The data were replotted in Figure 9 to show the dependence of rlq2
on q2 Table 2 displays values of Dm, app the apparent mutual diffusion coefficient, obtained
from the intercepts of plots in Figure 8. The value of Dm. app increased after addition of the
surfactant for both the Polyquaternium 10 and DQNNED polymers, the effect being more
evident for the Polyquaternium 10 - mixed surfactant micelle complex. The behavior of the
MQNNED - mixed surfactant micelle complex was perplexing as the value of Dm, app
decreased by a factor of 2 after addition of surfactant implying an increase in the overall
dimensions ofthe polymer- mixed surfactant micelle complex.
503
24000
21000
18000
r 15000
(Hz) 12000
9000
6000
3000
0
0 1 2 3 4 5 6
q2 /1 o1o cm2
Figure 8. Plot ofr versus q2 for polymer and polymer- surfactant complexes. Symbols indicate: ( ) I%
Polyquatemium IO; ( D) 1% Polyquatemium IO I 0.10% SOS I 0.90% Triton X-100; ( e) I% MQNNEO;
( 0 ) I% MQNNEO I O.I 0% SOS I 0.90% Triton X-I 00; ( .& ) I% OQNNEO ; and ( t:;.) I% OQNNEO I
0.10% SOS I 0.90% Triton X-100.
4 0
u n
0
r 1q2 * 10 -7
. .
2
(cm I s) 3 -
2
A ~
...
~
-
,..,
0 V I
0 1 2 3 4 5 6
Figure 9. Plot of the apparent mutual diffusion coefficient versus q2 for polymer and polymer - surfactant
complexes. Symbols indicate: ( ) I% Polyquatemium I 0; ( D ) I% Polyquatemium I 0 I O.I 0% SOS I
0.90% Triton X-100; ( e) I% MQNNEO; ( 0) 1% MQNNEO I 0.10% SDS I 0.90% Triton X-100; ( .& )
I% OQNNEO; and ( t:;.) I% OQNNEOI 0.10% SOS 10.90% Triton X-100.
504
Table 2. Effect of surfactant addition on Dm.aw
Polymer o..,. Dm,app

!%Polymer 1% Polymer I 0.1% SDS I 0.9% Triton X-100
(cm21s) 107 (cm 21s) 107
Polyquatemium 10 2.97 3.98
MQNNED 0.26 0.11
DQNNED 0.31 0.39
Temperature dependence The effect of temperature on the relaxation time of the

polymers and the polymer-mixed surfactant micelle complexes was studied in the temperature
range 25 - 40C (Figures 10-12). The relaxation time of aqueous solutions of the polymers
was not greatly affected by temperature. However, the relaxation time of aqueous solutions
of Polyquaternium 10 - mixed surfactant micelle complexes was affected when the
temperature was increased to 40C. This phenomenon was indicated by both a bi-modal
decay curve in plots of normalized g<1l (t) versus log 10 t and a change in the solution from
clear to turbid. The relaxation times of aqueous solutions of both MQNNED and DQNNED -
mixed surfactant micelle complexes were not affected by increasing temperature to 40C as
indicated by unimodal decay curves for plots of g< 1> (t) versus log 10 t and a uniform increase
in relaxation times. The results of the temperature study indicate that aqueous solutions of
Polyquatemium 10 - mixed surfactant micelle complexes exhibit a different temperature
response than polymer - mixed surfactant micelle complexes formed with either MQNNED
or DQNNED. The slow mode in the Polyquaternium 10- mixed surfactant micelle complex
at 40C may originate from the formation of polyelectrolyte clusters resulting from either
attraction between the polyions or from entanglement ofthe polyelectrolyte chains. 46
Antimicrobial Activity of Quaternary Polymers
The antimicrobial activity of DQNNED versus methylparaben (methyl-p-

hydroxybenzoate) was studied using the Minimum Inhibitory Concentration (MIC) test.
Methylparaben was chosen as a comparison with the quatemary polysaccharide polymer as
it is the most frequently used cosmetic preservative. The MIC results for methylparaben
and DQNNED are shown (Table 3). The MIC for methylparaben was found to be 640, 800
and 1120 J.Lg I ml for E. coli, P. aeruginosa and S. aureus, respectively. S. aureus which is
a gram positive bacteria required twice as much methylparaben to inhibit growth as E. coli
or P. aeruginosa which are gram negative. The MIC of DQNNED, which contains two
quatemary nitrogens and carbamoyl group, was found to be 480, 480 and 1760 J.Lg I ml for
E. co/i, P. aeruginosa and S. aureus, respectively. This polymer inhibited growth as weil
as methylparaben. In the case of S. aureus, approximately 3.6 times more DQNNED was
required to inhibit growth as E. coli or P. aeruginosa.
The MIC ofthe combination ofDQNNED and methylparaben was found tobe 320,
160 and 800 J.Lg I ml of each of the compounds for the inhibition of E. co/i, P. aeruginosa
and S. aureus, respectively. This effect of the combination of DQNNED and
methylparaben on bacterial growth appears to be additive rather than synergistic. This
result shows that a quatemary polymer may be incorporated into a product and contribute
to the preservation of the product. Therefore, quatemary polymers may have dual roles in
formulation as rheology modifiers and preservatives.
The unquaternized aminoalkylcarbamoyl cellulose derivative did not exhibit
antimicrobial activity. This result indicates that the antimicrobial activity is a result of the
quatemary ammonium groups. However, polyquatemium 10 failed to exhibit any
505
(A)
1.2
1 .0
0.8
-::::- 0.6
~
a
-01) 0.4
0 .1 M NaCI
no surfactants
0 .2 0 =30
0.0
1E-6 1E-5 1E-4 0.001 0.01 0.1 1 10

Time/ms
(B)
1.0
0.8
-::::- 0.6
a
-
~
0.4 0.1 M NaCI

01)
SDS0.10%
0.2 0 =30
0.0
1E-6 1E-5 1E-4 0.001 0 .01 0.1 1 10
Time /ms
Figure 10. Effect oftemperature on the relaxationrate ofPolyquaternium 10 and Polyquaternium 10- Mixed
Micelle Complex: (A) aqueous solution of 1% Polyquaternium 10; (B) aqueous solution of 1%
Polyquaternium I 0 I 0.1 Oo/o SOS I 0.90% Triton X-1 00; The symbols indicate .& 25 c; C::: 30 c; and 0 40
c.
506
(A)
1.0
0.8
-=-
ci-
0.6
......,
-CO 0.4 0.1 M NaCI
no surfactants
0.2 e=30
0.0
1E-6 1E-5 1 E-4 0.001 0.01 0.1 1 10

Time/ms
(B)
1.0
0.8
0.6
-=-ci-
-
'-"'
0.4
CO
0.1 M NaCI
0.2 5050.10%
8=30
0.0
1 E-6 1 E-5 1 E-4 0.001 0.01 0.1 1 10
Time/ms
Figure 11. Effect oftemperature on the relaxationrate ofMQNNED and MQNNED - Mixed Micelle
Complex: (A) aqueous solution of I% MQNNED; (B) aqueous solution of I% MQNNED I 0.10% SOS I
0.90% Triton X- 100; The symbols indicate .& 25 c; : : : 30 c; and 0 40 c.
507
(A)
1.0
0.8
0.6
-=--
c:r
._..
-c.o 0.4
0.1 M NaCI
no surfactants
0.2 e=30
0.0
1 E-6 1 E-5 1 E-4 0.001 0.01 0.1 1 10

Time /ms
(B)
1.0
0.8
0.6
-=--
a
.........
-c.o 0.4
0.1 M NaCI
0.2 SDS0.10%
0=30
0.0
1E-6 1E-5 1E-4 0.001 0.01 0.1 1 10

Time/ms
Figure 12. Effect oftemperature on the relaxationrate ofDQNNED and DQNNED- Mixed Micelle
Complex: (A) aqueous solution of I% DQNNED; (B) aqueous solution of I% DQNNED I 0.10% SDS I
=
0.90% Triton X-1 00 The symbols indicate A 25 oc; 30 oc; and 0 40 C.
508
Table 3. MIC test results for methylparaben and DQNNED.
Compound Pathogen Concentration (llg/ml) uiJ
Methylparaben E. coli (25922) 800 2

640(b) 28
480 10
S. aureus (29213) 1280 I
1120(b) II
960 4
P. aeruginosa (27853) 800ibJ 12
640 11
480 8
DQNNED E. coli (25922) 640 5
480(b) 14
320
S. aureus (29213) 2080 4
1920 I
1760(b) 6
1600
P. aeruginosa (27853) 480(b) 12
320 4
Methylparaben and DQNNED E. coli (25922) 320(b) 16
S. aureus (29213) 960 3
800(b) 12
640
P. aeruginosa (27853) 160(b) 7
144 5
128 5
112 3
IJn = ttienumber of times the MIC test gave the particular concentration as the minimum inhibitory
concentration
(bJThe minimum inhibitory concentration for the compound(s) against a particular pathogen
significant antimicrobial activity .. More work in this area should be done in order to
investigate the effects of molecular weight, degree of quaternization, and inclusion of
electron releasing or attracting groups on the efficacy ofthese compounds.
CONCLUSIONS
1. All three polymers studied precipitate at the respective theoretical charge neutralization
ratio when the concentrations of polymer and anionic surfactant are greater than
0.010%. However, at polymer concentrations less than 0.010%, a fixed concentration
of SDS is necessary to precipitate the complexes. The magnitude of the fixed
concentration decreases as the charge density ofthe polymer increases.
2. For the polymer- mixed surfactant micelle complexes studied, the critical mole fraction
of anionic surfactant necessary to cause precipitation was determined to be independent of
spacer length for a monoquaternary derivative and dependent upon the number of cationic
charges on the graft.
509
3. Changes in the vibronic fine structure of the pyrene fluorescence intensity spectra
indicated that the miceBar regions formed in the polymer-mixed micelle complexes were
more hydrophilic than the micelies ofthe surfactant formed in the absence ofpolymer.
4. Temperature studies indicated that an aqueous solution of Polyquaternium 10 - mixed
surfactant micelle complex exhibits a different temperature response than the polymer -
mixed surfactant micelle complexes formed with polymers synthesized in our
laboratories.
5. The bacteristatic activity of DQNNED alone and in combination with methylparaben
indicates the dual role that quatemary polymers may have in cosmetic products. They
potentially may be used as thickeners or conditioners, and they may also exhibit
antimicrobial activity in the preservation ofthe cosmetic products
ACKNOWLEDGEMENTS
This work was supported by a Graduate Research Fellowship to M. Manuszak Guerrini

from the Society of Cosmetic Chemists.
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512
INTERACTION OF OLIGOPEPTIDES WITH HEPARIN
Ruifeng Zhao, Mamoru Haratake, and Raphael M. Ottenbrite
Virginia Commonwealth University
Richmond, Virginia 23284
INTRODUCTION
Macromolecular drugs, such as heparin and insulin, are easily degraded by acids and
enzymes in the GI tract and do not readily penetrate the lipophilic biomembranes, resulting in
low bioavailability by the oral raute. '-3 Currently, these drugs have tobe administered by in-
jections. Proteinoids,4-8 which can form microspheres with certain macromolecular drugs,
such as heparin and insulin, have been studiedas an oral drug delivery system.9- 16 These
spheres can protect drugs from acid and enzyme degradation in the GI tract. 10- 13 15 Recently, it
was found that these proteinoids can facilitate drug transport through the biomembranes, pos-
sibly, in the form ofa proteinoid-drug complex.9- 12 17 This non-covalent complex would alter
the conformation ofhydrophilic drug molecules into a more hydrophobic form for lipophilic
biomernbraue absorption. 917- 18 However, these proteinoid materials are mixtures of oli-
gopeptide dimers, trimers and tetramers with different structures and amino acid st>
quences. 1O-II Based on the proteinoid results, several series of structurally defined oligopep-
tides with specific amino acid sequences were synthesized as potential oral drug delivery car-
riers in order to study the mechanism oftbis novel oral drug delivery system. 18
To form microspheres, the oligopeptides require a balance ofhydrophilic and hydro-
phobic amino acids. Pyroglutamylglutamic acid (PyGluGlu) or pyroglutamylaspartic acid
(PyGluAsp) seem tobe important as the first two amino acid residues ofthe oligopeptides in
order to form microspheres. 19 Since these amino acids are hydrophilic, phenylalanine, tyro-
sine, alanine, valine and leueine were used as the hydrophobic moieties to balance the hydro-
phobicity of the oligopeptides. Three series of oligopeptides were synthesized with the
hydrophobic amino acids in a, y or both the a and y positions ofthe glutamic acid residue. A
benzyl ester (Bz) was used toblock the carboxyl functional group and a tert-butyloxycarbonyl
(Boc) group was used to protect the amino group ofthe amino acids. A stepwise condensation
process was used to synthesize these oligopeptides with diphenylphosphoryl azide (DPPA) as
a coupling agent and triethylamine (TEA) as a catalyst. Theseoligopeptides were purified and
characterized by 1H NMR, 1H- 1H NMR, 1H- 13 C NMR, IR, UV, ES/MS, reversed phase
HPLC. 18

The binding ofthe antithrombin III and positively charged oligopeptides to heparin
has been investigated by several different groups. 2 0-21 In this research, the interaction between
the synthesized oligopeptides and heparinwas evaluated by heparin affinity chromatography.
HYDROPHOBie CHARACTERISTICS OF OLIGOPEPTIDES
The hydrophobicity of a compound can be expressed by its partition coefficient Poet

between octanol and water. 22 This partition coefficient is one ofthe most widely used physical
parameters to predict the biological activities of new drugs. Currently, high-performance liq-
uid chromatography (HPLC) is being widely used for the determination of Poet since this
method is very simple, rapid and accurate. In many cases,23 a linear relation between log Poet
and the logarithm ofthe capacity factor k' (k' is the ratio ofthe real retention volume and the
void retention volume, the real retention volume is the difference between the measured reten-
tion volume and the void retention volume) in HPLC is observed. Based on this relationship,
log Poct values of the oligopeptides were calibrated from a standard curve developed from
compounds whose log Poet values are known. 23
In this research, the mobile phase was 50% methanol/water with 0.02% TFA (tri-
fluoroacetic acid) in order to maintain the pH at 2.30. Thus, the oligopeptide compounds were
in the molecular form rather than ionic form since the pK3 values ofthese Oligopeptidesare be-
tween 3.5--4.5 as determined by titration analysis. The log Poet values for the oligopeptides are
calibrated and depicted in Figure I.
Basedonthese log Poet values, there is no apparent difference [~(log Poet)< 0.1] be-
tween the two different trimer series, however, the hydrophobicity ofthe corresponding tet-
ramers is greater [il{log Poet)> 0.5] than that ofthe corresponding trimers. The hydrophobicity
ofthe oligopeptides with an aliphatic side chain increased as the side chain length increased
from alanine to valine, and to leucine. TetramerpED{a)F()F has a relatively smallerhydro-
phobicity than tetramer pEE( a)F(y)F since aspartic acid has a shorter side chain (-CH 2 -) than
2.5
g
,-...
1.5
e::,
Cl!
j 1
0.5
IOX 20X 30X 40X 50X 60X 70X

Oligopeptides
Figure I. Apparent hydrophobicity (log Poct) ofthe Oligopeptides. The l 0- series represents pEE with F, the 20-
series represents pED with F, the 30- series represents pEE with Y, the 40- series represents pEE with A, the 50-
series represents pEE with V, the 60- series represents pEE with L, the 70- series represents PE with F; X= I
represents the a-trimer (the end group in the a position ofE), X=2 represents the y-trimer (the end group in the y
position ofE), X=3 represents the a ,y-tetramer (the end groups in both a and y positions ofE).
514
glutamic acid (-CH 2CH 2-). However, pEE(a)Y(y)Y is less hydrophobic than pEE(a)F(y)F,
which may be due to the hydroxyl group on the tyrosine residues. PE(a)F(y)F and
pEE( a )F( y)F exhibited similar hydrophobic characteristics even though PE( a )F( y)F has a cy-
clic secondary amine.
HEPARIN AFFINITY CHROMATOGRAPHY
In this study, a SigmaChrom AF-Heparin affinity HPLC column (2.5 mL,

Sigma/Aidrich) was used with different mobile phases and at different pHs. The column was
prepared with highly porous 20 11m methacrylate gel particles, which have been functional-
ized with heparin.24 The heparin density for this column is 5 mg/g. Each heparin molecule is
covalently bonded to the polymer matrix through a bifunctional spacer such as amino or car-
boxyl groups by the cyanogen bromide method. 25 Multi-point coupling ensures stable attach-
ment. Immobilized heparin has two major interaction modes with ligands: as an affinity
matrix (e.g. , in its interaction with growth factors and antithrombin III) and as a cation ex-
changer due to its high anionic sulfate group content ( e.g., in its interaction with nucleic acid-
binding proteins where it mirnies the similarly polyanionic structure ofthe nucleic acid). 24 26
lt was found that, with the phosphate buffer mobile phase at neutral pH 7, the Oli-
gopeptides were not retained on the heparin affinity column. When the mobile phase was
changed to an acetate buffer with a pH of 4.1, several of the Oligopeptide tetramers,
pEE(a)F(y)F, pED(a)F(y)F, pEE(a)Y(y)Y and PE(a)F(y)F, showed short retention times.
However, when the mobilephasewas changed to an acetate buffer with a pH of2.27, some of
the oligopeptide tetramers showed significant retention (t > 4 min) on the heparin affinity col-
umn. The capacity factor (k') was calculated and depicted in Figure 2.
At pH 2.27, the Oligopeptidesare in their molecular form, which increase the possibil-
ity for H-bonding and hydrophobic interaction and decrease electrostatic repulsion. Basedon
the capacity factor data for the oligopeptides at pH- 2.3 shown in Figure 2, only four oligopep-
1.5
0.5
-O.S..L__ _ _ _ __ _ _ _ __ _ _ ____/
lOX 20X 30X 40X SOX 60X 70X
Oligopeptides
Figure 2. Retention behavior of the Oligopeptides on heparin affinity column at pH 2.3. The 10- series
represents pEE with F, the 20- series represents pED with F, the 30- series represents pEE with Y, the 40- series
represents pEE with A, the 50- series represents pEE with V, the 60- series represents pEE with L, the 70- series
represents PE with F; X= I represents the a-trimer (the end group in the a position ofE), X=2 represents the
y-trimer (the end group in the y position ofE), X=3 represents the a,y-tetramer (the end groups in both a and y
positions ofE).
515
tide tetramers, pEE(a)F(y)F, pED(a)F(y)F, pEE(a)Y(y)Y and PE(a)F(y)F, showed signifi-
cant retention (k' -1.0) on the heparin affinity column. The oligopeptide trimers, pEE(a)F,
pEE(y)F, pED(a)F, pED(a)F, pEE(a)Y and pEE(a)Y had very short and similar retention
(k' -0.25) on the heparin affinity column. The Oligopeptide tetramers pEE(a)A(y)A,
pEE(a)V(y)V and pEE(a)L(y)L were not retained (k'<0.2) on the heparin affinity column.
The four tetrapeptides that were retained on the heparin affinity column, pEE(a)F(y)F,
pED(a)F(y)F, pEE(a)Y(y)Y and PE(a)F(y)F, have aromatic groups on the terminal amino
acid residues; while the tetrapeptides that were not retained on the heparin affinity column,
pEE(a)A(y)A, pEE(a)V(y)V and pEE(a)L(y)L, have aliphatic groups on the terminal amino
acid residues. Consequently, the aromatic groups on the amino acid residues in the oligopep-
tides appear to have a major effect on the retention ofthese oligopeptides on the heparin affin-
ity column.
A correlation of the hydrophobicity log P values of the tetrapeptides with their capac-
ity factors (k') on the heparin affinity column was carried out. As shown in Figure 3, it is clear
that tetrapeptide pEE(a)L(y)L was not retained on the heparin affinity column even though
this tetrapeptide had almost a comparable log P value as pEE(a)F(y)F.It seems that hydropho-
bicity is not directly related with the retention ofthe oligopeptides on the heparin affinity col-
umn. However, the oligopeptide trimers containing an aromatic-ring, which have lower
hydrophobicity log P values than their corresponding tetrapeptides, also had much shorter re-
tention times on the heparin affinity column than their corresponding tetrapeptides. Further-
more, when the sodium chloride concentration in the mobilephasewas increased from 0.1 M
to 0.3 M, the retention (k') ofthe tetrapeptide pEE(a)F(y)F also increased from 1.72 to 1.86.
Since salts have been reported to increase hydrophobic interaction/027 it appears that hydro-
phobic interaction may be involved in the retention ofthe oligopeptides on the heparin affinity
column. Consequently, the aromatic amino acid residues have a significant effect (k' > 1.0) of
the oligopeptide retention on the heparin affinity column.
D Log(Poct)
0 k'
Tetrapeptides
Figure 3. Correlation of apparent hydrophobicity (log P) with heparin affinity column retention behavior (k') of
the tetrapeptides.
516
To further investigate interactions involved in the retention of oligopeptides on the
heparin affinity column, isopropanol was added to the above pH 2.27 mobile phase (I 0%,
v/v). Isopropanol is commonly used as an organic modifier to disrupt the hydrophobic interac-
tion between the solute and the matrix surface in the chromatography. 27 It was found that the
retention of the tetrapeptides on the heparin affinity column decreased -50% (Figure 4),
which implies that hydrophobic interactions are involved in the interaction forces ofthe reten-
tion of the oligopeptides on the heparin affinity column. In addition, when ethylene glycol
(9%, v/v), which is also a commonly used organic modifier in the chromatography to reduce
the H-bonding interaction between the solute and the matrix surface/0 27 was added to the pH
2.27 acetate buffer eluent, the retention ofthe tetrapeptides on the heparin affinity column de-
creased -25%. These data are depicted in Figure 4.
Basedon the data in Figure 4, it seems that hydrophobic interaction more than H-
bonding was involved in the interaction since the k' values with isopropanol were less than
those with ethylene glycol However, no quantitative relation was reported between the
amount of the organic modifier added and the value of hydrophobic interaction and/or H-
bonding or the capacity factor values. Consequently, one can only conclude that both hydro-
phobic interaction and H-bonding are involved in the retention of Oligopeptides on the heparin
affinity column in addition to the aromatic interaction which appears to be dominant.
One possible interaction mode of the immobilized heparin with the solute is that it
could act as a cation exchange agent due to the numerous sulfate groups. However, the oli-
gopeptides used did not contain any free amine group {except for PE(a)F(y)F}, which ex-
cludes the ionic bonding. In addition, the high concentration of sodium chloride (0.1 M NaCI)
should prevent ionic interaction.
It appears that the aromatic group has a specific effect on the retention of oligopeptides
on the heparin affinity column. To further study this phenomenon, the aromatic ring was deri-
vatized with different functional groups. Since the tetrapeptide pEE(a)Y(y)Y had two phenol
0 pH=2.3 buffe + 10% isopropanoD + 9% ethylene glycol

2
1.5
0.5
-0.5
Oligopeptides
Figure 4. Heparin affinity column retention behavior of the tetrapeptides in different eluents with organic
modifiers at pH 2.3.
517
4 lo Log (Poet) D k'
pEEYY 0-Me pEEYY 0-Ac pEEYY O-Pa pEEYY
Figure 5. Correlation of hydrophobicity (log P) with heparin affinity column retention. Behavior (k') for the
derivatives of the tetrapeptide pEE(a)Y(y)Y. 0-Me pEE(a)Y(y)Y is di(O-methyl) derivative , 0-Ac
pEE(a)Y(y)Y is di(O-acetyl) derivative and O-Pa pEE(a)Y(y)Y is di(O-phthalic acetyl) derivative.
groups, the hydroxy groups on the aromatic ring were derivatized with methyl, acetyl or
phthalic ester groups by reacting the -OH group on the tyrosine phenol of the tetrapeptide
pEE( a)Y(y)Y with methyl iodide, acetic anhydride or phthalic anhydride, respectively, under
alkaline conditions. The reversed phase HPLC log P data from 50% methanol/water at pH
2.27 and heparin affinity chromatography k' data from acetatebufferat pH 2.27 for these de-
rivatives are represented in Figure 5.
Based on these data, the hydrophobicity increased when the tetrapeptide was derivat-
ized with methyl, acetyl or phthalic ester group. The di(O-methyl) derivative had a higher re-
tention and the di(O-phthalic acetyl) derivative had a much higher retention on the heparin
affinity colurnn than the parent tetrapeptide pEE(a)Y(y)Y while the di-(0-acetyl) derivative
had a lower retentiontime than the parent tetrapeptide pEE(a)Y(y)Y on the heparin affinity
colurnn. lt is known that the methoxyl group is an electron-donating group while the acetyl
group is an electron-withdrawing group. Thus the electron density ofthe aromatic ring is in-
creased for the di-(0-methyl) derivative while the electron density ofthe aromatic ring is de-
creased for the di-(0-acetyl) derivative. Basedon the data, acharge transfer complex 28 may
be involved in the retention ofthese derivatives on the heparin affinity column since the de-
rivative with electron richer aromatic groups (0-Me) is retained on the heparin affinity col-
urnn Ionger than that with electron poorer aromatic groups (0-Ac).
In the case ofthe di(O-phthalic acetyl) derivative, two additional aromatic rings were
added to the compound so that the total number of aromatic groups was increased. This may
be the cause for the Iongerretention ofthisderivative on the heparin affinity colurnn. This ex-
planation was supported by the fact that oligopeptide hexamers pEE(a)FF(y)FF and
pEE( a)FY(y)FY both had a much Iongerretention on the heparin affinity colurnn than the tet-
rapeptides pEE(a)F(y)F and pEE(a)Y(y)Y (Figure 6).
In summary, the heparin affinity chromatography data indicate that the aromatic ring
is an essential component for the oligopeptides retention on the heparin affinity colurnn. The
interaction between the immobilized heparin and the oligopeptides is due to both H-bonding
and hydrophobic interaction, as weil as aromatic ring interaction probably through charge
transfer.
518
7
Log (Poet) D k'
6
0
pEE(a)F(r)F pEE(a)Y(r)Y pEE(a)FF(r)FF pEE(a)FY(r)FY
Figure 6. Correlation ofhydrophobicity (log P) with heparin affinity column retention behavior ofthe oligopep-
tide hexamers
CONCLUSION
As a conclusion, the interaction ofthe oligopeptides with heparinwas investigated by

heparin affinity chromatography. It was found that the aromatic ring containing tetrapeptides
are retained Ionger than the tripeptides and the aliphatic chain containing tetrapeptides on the
heparin affinity colurnn at a low pH. The aromatic ring appears tobe an essential component
in the retention of the oligopeptides on the heparin affinity colurnn. The association of these
oligopeptides with heparin is very weak (Kd - I 0-4) due to an interaction between the aromatic
rings and heparin, such as acharge transfer, in addition to hydrophobic interaction and H-
bonding. 18 This result is supported by the low heparin encapsulation efficiency (29 .I%) ob-
served in the tetrapeptide pEE( a )F( y)F aggregates.29- 30 The tetrapeptide pEE(a )F(y)F was
submitted to our collaborators for further in vivo tests with heparin.
ACKNOWLEDGMENT
The authors wish to thank Emisphere Technologies, Inc. for their financial support for
this project and Yoshitomi Pharmaceutical Industries, Ltd., Japan for their finance support to
M. Haratake during his stay in our laboratory.
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520
DENDRIMERIC ANTENNA SUPERMOLECULES WITH MUL TISTEP
DIRECTED ENERGY TRANSFER
Stephen F. Swallen, Michael R. Shortreed, Zhong-You Shi, Weihong Tant,

Zhifu Xu:J:, Chelladuri Devadoss#, Jeffrey S. Moore#, Raoul Kopelman*
Department of Chemistry, University of Michigan

Ann Arbor, MI 48109-1055
t Department ofChemistry, University ofFlorida, Gainseville FL 32611-7200

:j: PPG Industries, Pittsburgh, PA
# Department of Chemistry, University of lllinois, Urbana, IL 61801-3364
* Author to whom correspondence should be addressed. Department of
Chemistry, University of Michigan, Ann Arbor, MI 48109-1055
INTRODUCTION
Photoinduced energy transfer in large molecular systems is a vital process in many

biological systems. The primary step in these reactions, such as photosynthesis, is a multi-
step process of energy flow from a highly absorbing antenna molecule or moiety to a reaction
center.l-5 In general, however, this process is energetically disordered, and thus the energy
transfer is dependent upon mechanisms such as random walk, thermal activation, exciton
percolation, or a combination of these effects. 6-8 In contrast, a large, weil ordered molecule
with organized local electronic excitation states may provide an efficient means of directed
intramolecular energy transport. In this paper we examine a unique class of recently
synthesized dendrimeric molecules which exhibit such desirable properties.9,10 These
represent the largest purely hydrocarbon dendrimers which have been synthesized to date.
Following the frrst synthesis of a large dendrimeric system by Tomalia 11 in the early
1980's, the study of fractal-like supermolecules has increased steadily. The size and structure
of these self-similar species may Iead to a wide variety of informative experimental
investigations and potential applications. These include the study of micelle-like behavior in
weil structured systems, or electron transfer between widely spaced substituents via concerted
pathways along the molecular backbone.12 Of primary current interest is the prospect of
utilizing these molecules as antenna for efficient energy transfer reactions. 5,12-15
In designing these sets of molecules with an eye to their energy transfer
characteristics, several critical demands were considered. These included:

1) High molar absorptivity. Dendrimers in general are particularly weil suited to meet this
requirement, due to their large size. The congregation of a large number of absorbing sub-
units can give an extremely large extinction coefficient
2) Photostability. Due to the intense photoactivity ofthese supermolecules, it is necessary that
the chemical and structural organization allow rapid energy migration and efficient excitation
decay pathways. Weil designed dendrimers may thus be preferentially stable due to the ability
to rapidly distribute excitations over a very large molecular structure.
3) Energy bias. From a purely geometric standpoint, dendrimers would appear to provide
extremely inefficient energy transfer pathways. This is particularly true for molecular
structures in which excitons are to be directed from the dendrimer periphery toward the locus.
If intramolecular exciton migration between neighboring localized states is considered to occur
via random hopping, then strictly by probability analysis, the migration would be expected to
move preferentially outward toward the molecular periphery. This can be understood by
examining the branching structure of a given dendrimer. For example, given a coordination
number Z at each branching site, there are typically (Z-1) pathways leading out, away from
the center. This compares to a single pathway leading further inwards. The result is a (Z-1)-
fold greater chance of outward migration during each exciton hopping event. For this reason,
if efficient energy transfer toward the molecular locus is to be observed, a directed energy bias
must exist.
4) Large Stokes shift. In order to efficiently trap excitons which are ultimately funneled
toward the core of the dendrimer, a moiety with a lower localized excitation energy must exist
This can ultimately provide a practical means of obtaining the transferred energy via radiative
emission.
EXPERIMENT AL RESULTS AND DISCUSSION
Two unique series of these molecules have been synthesized, both composed of linear
chains of diphenyl acetylene (DPA) and constructed with three-fold symmetry: a "compact"
form which are perfectly self-similar and are ideal molecular representations of Cayley
treesl6,17, and an "extended" form which are nearly identical but contain linear DPA chains
of unequallength, thus making them only approximately self-similar. Due to the geometric
structure of both series, these molecules exhibit very interesting electronic characteristics.
Photoinduced 7t-electron excitations are observed to be tightly localized on individual
branches, rather than becoming delocalized over the molecular backbone. The bonding
arrangement at the branching nodes gives each DPA chain a weil defined vibrationless
electronic transition with an energy which is independent of the overall size of the molecule.
While this excitation localization is observed for both families of dendrimers, the slight
structural differences between the compact and extended series Iead to significant
photophysical characteristics. Due to the uniform nature of the compacts, energy transfer
between localized states is expected to occur via random exciton hopping. In contrast, the
localized chains of varying length in the extended series are found to have excitation energies
which vary inversely with the number of diphenyl acetylene units in each chain. By
structurally organizing the dendrimerssuchthat Ionger chains are found toward the center
(locus) of the molecule, a discrete energy funnel is created. Thus, a highly efficient, directed
pathway for exciton transfer in these supermolecules is observed.
In addition, an interesting set of derivatives of both farnilies of these large dendrimers
have also been synthesized and studied.9,13 By positioning a low energy trap moiety at the
locus, direct observations of intramolecular energy transfer can be obtained. Results are
522
compared for derivatives of both compact and extended series dendrimers, and dramatically
emphasize the energy funnel nature of the latter.
There are several characteristics of the diphenylacetylene molecule which makes it

ideal as the basic building element of dendrimers. As an isolated individual molecule in
solution, DPA has a fairly stiff planar structure, and is observed to have a well defined 11:-
electron excitation conjugation directed along the long axis. This gives rise to a strong
vibrationless electronic excitation in the near UV, along with a well defined vibronic structure.
Interestingly, this electronic character is preserved when many DPA units are joined to form
supermolecular structures. The absorption spectra 13 of both series of dendrimers very closely
reproduce that of diphenylacetylene, with a Stoke's shift on the order of 3000 cm-1. Such
large shifts are characteristic oflocalized excitations, which allow strong vibronic coupling.13
In addition to its energetic properties, the physical structure ofDPA contributes to the
unique aspects of the synthetic supennolecules. There are several characteristics of significant
note with respect to the structure of the compact dendrimers. As mentioned previously, and
as can be readily seen in the molecular drawings in Figure 1, the molecules are perfectly self
similar. The branches of each member of the series are each composed of precisely one OPA
unit. (fhe variations in bond length between branching points in the larger molecules are not
drawn to scale: all branches are, in fact, of identicallength. The molecules were drawn in this
manner for improved visual conveyance.) The name given to each member of the compact
series reflects the number of individual phenyl groups in the respective molecule. As with all
dendrimers, the number of basic elements grows exponentially with each successive
generation, and the number of periphery elements is on the order of the total number of
elements. (fhe compact dendrimers have just over 50% of all elements in the outermost shell:
the number of periphery elements is given by (n+2)/2, where n is the total number of elements
in the entire molecule.) Perhaps more significant, however, is the organization of the three-
fold coordination at each branching point. The fact that this bonding occurs at the meta
positions plays three crucial roles in the determination of the molecular characteristics:
1) This permits the maximum structural flexibility during design and synthesis. If
branching were to occur instead at the para positions, simple unbranched linear chains would
result. lf, instead, branching occurred at the ortho positions, large structural overlap would
rapidly take place, strictly limiting the maximum possible size of the dendrimeric system. The
meta positioning is thus the optimal balance between maximizing complexity while minimizing
structural overlap and possible resultant molecular defects.
2) Most importantly, the meta branching positions creates a resonative decoupling
between 11:-electron excitations on neighboring diphenylacetylene (DPA) units.l3,18 Thus any
electronic excitation is not conjugatively delocalized over the backhone of the molecule, but
instead is tightly localized on each individual DPA subunit. Spectroscopic evidence of this is
given Figure 2, which displays the electronic absorption spectra of all 5 compact dendrimer
molecules 13. Several important effects can be gleaned from this data which support the
postulation of excitation localization within individual diphenylacetylene chains. Qualitatively,
the absorption curves very closely match the functional shape of independent diphenyl
acetylene molecules in hexane. Of primary note is the existence of an energetic pinning of the
lowest energy peak for all molecules, regardless of size. The vibrationless excitation at 320
nm is held fixed, rather than shifting to lower energy. If excitations were delocalized within
the molecule, this peak would be expected to shift to the red as the dendrimer size is
increased. This is clearly not observed, suggesting that individual diphenyl acetylene chains
act as independent photoabsorbers. Every branch, being composed of an identical single,
isolated diphenyl acetylene unit, is seen to have the same excitation energy. This is coupled
523
with the fact that the absolute intensity of the absorption peaks increases monotonically with
nurober of DPA chains. The roolecular absorption of the coropact dendriroer series increases
nearly linearly with the nurober of localized absorbing diphenyl acetylene chains.
The existence of localized excited states in these dendriroer roolecules Ieads to an
interesting roechanisro of intramolecular energy transfer. Rather than being conjugatively
delocalized, excitonic migration roust occur via discrete hopping events. When coupled with
the fact that all absorbers have identical energy of excitation, energy transfer in the coropact
series roust be randoro. Exciton transfer between neighboring states can occur rapidly, but
with no energetic bias.
3) Upon examination of the structure of these dendriroers, it can be seen that the
branching pattern also plays a significant role in the observed efficiency of intramolecular
energy transfer. As exciton hopping is a randoro event, the probability is greater for rootion
out toward the periphery of the molecule than toward the core. Each branching point connects
directly to two identical sites that are further out, but only to one site that is closer to the locus.
This results in a roughly 2/3 chance that each hopping event will be in the outward direction.
Energy transfer froro the periphery to the locus is, therefore, decreasingly lik:ely as the size of
the dendrimers are increased. Thus, the coropact dendrimers are not expected to act as efficient
energy funnels.
The second class of roolecules under consideration, the extended dendrimer series, are
lik:ewise coroposed purely of diphenyl acetylene units. Unlik:e the coropacts, however, they
are not perfectly self-siroilar. Rather, they are coroposed of branching chains of unequal
length. Single unit DPA chains are found along the periphery, while increasing length linear
chains are found toward the roolecular core. While they retain 3-fold coordination at the
branching points, the perfect roolecular symroetry is broken. This can be seen in Figure 3,
depicting the structure of the extended series. These range in size froro 25 phenyl groups to
the largest purely hydrocarbon dendrimer currently synthesized, Dl27, with 127 phenyl
groups. (Ibis series is depicted as beginning with a 3-generation dendriroer, D25, rather than
M4
M10 ~
Figure 1. Compact series of dendrimer molecules. The filled circles represent phenyl groups, and the
connecting lines are acetylene moieties. The Iabels give the total number ofphenyl groups in each molecule.
524
2.00 10 8
1.50 10 1
1.00 10 8
5.00 10 5
0.00 t:;;;;;;=:==::::I:::::I:::~~~..........._.__jl...........L.....J..__._j
250 300 350 400 450
Wavelength (nm)
Figure 2. Absorption spectra for compact series of dendrimer molecules in hexane. In order of increasing
intensity, the curves are for the molecules M4, MlO, M22, M46, M94. The pinning'line at 320 nm identifies
the vibrationless electronic excitation due to alt single-unit diphenylacetylene moieties comprising the compact
dendrimers.
the smallest sizes given in the compact series. This is due to the fact that the outennost two
generations of each molecule are composed of single-unit OPA chains, identical with the
compact dendrimers. Thus the two srnallest, 04 and 010 are the same for the two series.)
The difference in chain lengths between the compact and extended dendrimers,
although subtle, produces important photophysical differences. The meta-branching positions
again result in well-localized excited states. The states, however, are no Ionger of equal
energy. The absorption curves for the extended series are given in Figure 4. The single-unit
OPA chains along the periphery give rise to the identical vibrationless peak at 320 nm that was
observed for the compacts. In addition, the Ionger chains, due to conjugation over a Ionger :n:-
electronic system, give rise to consecutively lower absorptions. The 025 molecule, with 2-
unit OPA chains, has an additional vibrationless peak at 353 nm. Likewise, the 058 and 0127
molecules, with 3 and 4 unit chains, respectively, show even further red-shifted peaks. In this
manner, a strong energy gradient is established within the molecular backbone. This results in
exciton hopping that is no Ionger a purely random process. Instead, the energy funnelleads to
weil directed, multi-step energy transfer toward the locus.
In order to examine this funneling mechanism, and to better utilize the energy transfer
characteristics, a set of molecular derivatives with a perylene pendant at the locus have been
synthesized. For both the compact and extended series, one of the three legs branched from
the core are replaced by an ethynyl perylene moiety. This was chosen for two reasons: frrst
because of the unit fluorescence quantum yield of perylene. Nearly all excitations which
transfer to this pendantwill be radiatively emitted. In addition, the ethynyl perylene exhibits a
weil localized excited state which is significantly red shifted relative to the states of the
dendrimer. Thus, it is expected to act as an efficient trap, readily accepting excitations from
neighboring states. Figure 5 gives the molecular structure of the perylene-substituted compact
series, W39 to W127, and the largest of the extended derivatives, which we tenn the
525
D25
Figure 3. The extended series of dendrimer molecules. The Iabels give the total number of
phenyl groups in each molecule.
1.00 10 11
5.00 105
0.00
250 300 350 400 450
Wavelength (nm)
Figure 4. Absorption spectta of extended series dendrimers in hexane. In order of increasing intensity, the
curves are for the molecules 04, 010, 025, 058, and 0127. The pinning line at 320 nm identifies the
vibrationless electronic excitation of the single-unit diphenylacetylene chains on the molecular periphery. The
redshifted peaks are due to linear OPA chains of2, 3, or4 units in the interior ofthe molecules.
526
nanostar. The absorption data for all these molecules are identical to the unsubstituted parents,
except for a decrease in intensity due to the existence of fewer absorbers, and an additional
absorption peak around 475 nm due to the perylene moiety. This suggests that the individual
diphenyl acetylene chains still act as welllocalized excited states, and that the perylene does
not perturb the electronic structure of the dendrimer backbone. These molecules can therefore
be used to study the ideal energy funneling characteristics of the extended dendrimers,
particularly in relation to the compact dendrimers, which are not expected to exhibit significant
well-directed transfer.
An energy Ievel diagram depicting the vibrationless electronic excitation energy for
each of the localized states in the nanostar is given in Figure 6. These values are determined
from the absorption spectrum in dichloromethane (not presented here, but discussed in detail
previously.)13 This provides a graphic representation of the impressive energy funneling
characteristics of this perylene-substituted dendrimer derivative. The single-unit
diphenylacetylene chains of the periphery of the molecule have an excitation energy of about
32,000 cm-1, while the interior DPA chains have energy values of 28,400 cm-1, and 26,500
cm-1 for chains of 2 and 3 DPA units, respectively. The perylene moiety is significantly red-
shifted, with a 0-0 peak at 21,000 cm-1.
In addition to the enhanced energy funnel characteristics of these dendrimers with the
addition of the perylenic pendant, this moiety may act to improve the photostability of the
dendrimers. Due to the high photoactivity of the dendrimer molecules, multiple photons may
be absorbed simultaneously, and rapidly funneled to the lower energy molecular center. While
the lowest-energy ethynylperylene state acts as a "supertrap" statel9,20, exciton annihilation
at this moiety may allow back transfer of energy to the top of the funnel. For instance, if a
second excitation arrives before a previous excitation has radiatively decayed, the two are
expected to "fuse"2-6,21 ,22, and the resulting higher energy excitation will transferbackward
into the dendrimeric antenna state. At that point, having many more non-radiative energy
~1-per W63-per
Figure 5. Perylene-substituted compact series (W7-per through Wl27-per) and the perylene-substituted
extended molecule referred to as the nanostar.
527
2~--------------------~~--------------------
Size (schematic)
Figure 6. Energy Ievel diagram of nanostar molecule, illustrating the energy funneling characteristics of
this perylene-substituted extended dendrimer. The single-unit diphenylacetylene chains on the periphery ofthe
molecule have a vibrationless excitation energy of about 32,000 cm-1, while the interior linear DPA chains
have energy values of 28,400 cm-1 and 26,500 cm-1 for chains of 2 and 3 DPA units, respectively. The
perylene moiety is signiflcantly red shifted, with a 0-0 peak at 21,000 cm-1.
decay channels, it will be reduced from an Sn to an St excitation. This resulting St excitation

will again flow into the pendant su~p. Alternatively, according to the Perlstein picture for
photosynthetic reaction centers23, 4, fusion inside the pendant is prevented, but back transfer
with accompanying fusion or non-radiative decay processes in the dendrimeric antenna is
allowed. Independent of the mechanism, such back transfer, and the concomitant prevention
of double or triple excitation of the perylenic pendant helps explain the increased photostability
of these dendrimersrelative to perylene or 1-ethynylperylene.
As a frrst qualitative examination of the transfer efficiency in the nanostar molecule,
the fluorescence spectrum is presented in Figure 7, along with the fluorescence of the two
parent molecules, 1-ethynyl perylene and the silane substituted dendrimer. All curves are
absolute intensity measurements, given identical excitation intensity at 312 nm (the excitation
energy of singe-unit DPA chains at the periphery of the dendrimer in dich1oromethane), and
sample concentrations of w-1M. The silane substituted dendrimer fluorescence exactly
matches the curve of 058, the unsubstituted parent, except for a decrease in intensity,
illustrating that the radiative emission is still from the excited states of the dendrimer
backbone. This contrasts with the emission curve of the nanostar, which is almost entirely
from the perylenic portion of the molecule. The dendrimeric peak at 380 nm has been
Unpublished comparison of Iaser photoexcitation studies of both crystalline and solvated samples of
various perylene-substituted dendrimer molecules, 1-ethynylperylene, and perylene. In addition, since energy
transfer is 1ess destructive to a molecule than direct excitation, excitation transfer provides a means to
increse the quantum efflciency and photostability of the perylenic Chromophore. This is analogaus to the
photosynthetic system23-25, where only one excitation at a time is transferred from the antenna to the
reaction center.
528
quenched by roughly 98%, with an ahnost unit efficiency shift of emitted photons to the
perylene. This suggests a nearly ideal energy funneling activity in the nanostar. (The total
ernitted energy, of course, is significantly decreased due to the large Stokes shift. The
remaining energy is rapidly dissipated as vibrational excitations, and ultimately lost as heat.)
The much smaller fluorescence intensity of the isolated ethynyl perylene emphasizes that the
nanostar's emission is the result of energy transfer rather than direct excitation into the
perylenic moiety.
A quantitative deterrnination of the efficiency of intramolecular energy transfer from
the dendrimer periphery to the .perylene trap can be deterrnined from Figure 8, which gives the
absorption and excitation curves of the nanostar molecule. The intensity of the vibrationless
perylene peaks at 475 for both spectra are nearly identical, emphasizing the unit quantum
fluorescence yield of this moiety. The transfer efficiency from each dendrimer generation to
the trap can be found by comparing the intensity of the absotption peak for that state relative to
the perylene absorption peak, and dividing this by the ratio of excitation intensities at those
same wavelengths. For the nanostar, this efficiency exceeds 98% from the widely spatially
separated periphery states (see Table 1.) For Ionger DPA chains in the interior of the molecule
(both energetically and spatially closer to the perylenic trap), this efficiency becomes
effectively unity. Thus, the energy bias in the nanostar is sufficient to overcome the inherent
geometric bias, and rapidly funnels all photoexcitations to the trap at the locus.
This efficiency, however, stands in marked contrast to a sirnilar exarnination of the
perylene substituted compact dendrimers (see Figure 5). The excitation and absotption curves
for the largest of these derivatives, W127-per, is given in Figure 9. In this case, while the
perylene peaks are again of equal intensity (by normalization), the excitation intensity of the
dendrimer peak is significantly reduced. Comparison of the pe!Uc magnitudes at 312 nm gives
a transfer efficiency in this molecule of only 56%. Given the perfectly symmetric, self-sirnilar
structure of the compact dendrimers, this vast decrease in energy transfer efficiency is
precisely the expected result. These species do not act as efficient energy funnels, but instead
experience energy migration out toward the periphery of the molecule. It should be noted,
however, that this efficiency is correlated with the size of the dendrimeric portion of the
molecule. As the molecular size is decreased, the closer proxirnity of the initial photoexcitation
site to the perylenic trap should Iead to increasingly efficient energy trapping, even in the
compact dendrimers which do not contain an energy funneling structure. This is observed by
comparison of absorption and excitation spectra for perylenic-substituted derivatives of the
compact series (see Table 1). As expected, the smallest of these, with a dendrimer portion
containing only 2 generations of single-unit DPA chains, has the largest transfer efficiency of
this series, at roughly 91%. Ofparticular interest in comparison to the nanostar is the W31-per
compact molecule. Both of these dendrimer derivatives have the same number of generations,
and thus the same number of absorbing units. (The nanostar contains slightly more phenyl
groups (39) than the compact W31-per, which is due to the longer, multi-unit DPA chains in
the former.) As can be seen in Table 1, the compact dendrimer has a notably
decreased energy transfer efficiency of 90%. In addition, this only occurs at a single
absorption peak, centered around 312 nm. This compares to the nanostar with several widely
spaced electronic absorption peaks, which makes it sensitive to a much more broad energy
spectrum. Thus it is clear that the highly absorbing nanostar, with its large molecular structure
and efficient energy funnel is the realization of a nearly ideal molecular energy transfer model.
CONCLUSIONS
The data presented here illustrate the excellent energy funneling characteristics of the nanostar
529
Figure 7. Fluorescence of silane-substituted extended dendrimer D39-SiH3 (left), 1-
ethynylperylene, (center), and nanostar (right). All samples were 3.0 x 10-7 M in
dichloromethane, with an excitation wavelength of 312 nm. Note the magnified scale of the
ethynylperylene.
150000
~-- AbsorJ:Xionl
~--=-- Exc~ct~
100000
300 350 400 450

Wavelength (nm)
Figure 8. Absorption and excitation spectra of the nanostar in dichloromethane. The arrows
indicate the vibrationless electronic excitations of one-, two-, and three-membered
diphenylacetylene chains, and the perylenic trap (left to right).
530
20
16
';?
~
'-" 12
-~
;g
8
~
4
250 300 350 400 450 500

wavelength (nm)
Figure 9. Absorption and excitation spectra of W127-per in dichloromethane. The

fluorescence was measured at 510 nm.
molecule peak wavelength transfer efficiency
W127-perylene 312nm 56%
W'T-perylene 312nm 91%
nanostar 312nm 98%
nanostar 353nm 99%

nanostar 372nm 100%
Table 1. Efficiency of energy transfer from localized dendrimer states to the perylenic trap for
perylene-substituted dendrimers.
531
molecule. This specially designed dendrimer exhibits rapid, well-directed, multistep
intramolecular exciton transfer. In addition, these species are very photostable, with an
extremely large absorption coefficients. Further experiments on these and other derivatives of
the extended dendrimers, including time resolved absorption-bleaching and detailed time-
rlependent fluorescence emission studies, will permit an accurate determination of the rates of
individual hopping events. This new class of "designer" molecules are tailormade as single
molecule light and exciton sources. The large size (125 Afor D127), excellent photostability,
and high photon efficiency will allow these supermolecules to the used as "supertips" for
optical nanoprobes and nanosensors, 12,26,27 as exciton sources for near-field and scanning
exciton microscopy,27,28 and possibly as material for organic light emitting diodes4 or
sensitization of photovoltaics. 29
ACKNOWLEDGMENTS
We acknowledge support from the National Science Foundation, Division of Material

Sciences, grant DMR-9410709. One of us (JSM) gratefully acknowledges the generous
support of the Office of N aval Research and the National Science Foundation.
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533
CELL BEHAVIOR ON POLYMER SURFACES
WITH DIFFERENT FUNCTIONAL GROUPS
Jin Ho Lee, I Jin Whan Lee,2 Gilson Khang,2 and Hai Bang Lee2
1Department of Macromolecular Science, Hannam University

133 Ojeong Dong, Daedeog Ku, Taejon 306-791, Korea
2iomaterials Labaratory, Korea Research Institute of Chemical Technology
P. 0. box 107, Yuseong, Taejon 305-606, Korea
INTRODUCTION
Recently a !arge number of research groups have studied the interaction of biomedical
materials with cultured cells because cell-compatible materials are thought to be very
important to many biomedical applications. Some of them have focused on the interaction of
cultured vascular endothelial cells and biomaterials to improve their blood compatibility
when vascular grafts are implanted in the body. Others have studied the interaction of tissue
cells with biomaterials to improve their tissue compatibility when the materials are implanted
as substitutes for organs, skin, bone, etc.
1t is recognized that the behavior of the adhesion and proliferation of different types of
cells on polymeric materials depend on the surface characteristics such as wettability
(hydrophilicitylhydrophobicity or surface free energy), chemistry, charge, roughness, and
rigidity. A !arge number of research groups have studied the interactions of different types of
cultured cells with various polymers with different wettabilities to correlate the relationship
between surface wettability and blood- or tissue-compatibility.l-4 One problern derived from
the study using different kinds of polymers is that the surfaces are heterogeneaus both
chemically and physically (different surface chemistry, roughness, rigidity, crystallinity,
etc.), which may result in considerable variation.
In a previous paper,5 we prepared a wettability gradient on polymer surfaces using
corona discharge treatment. The Wettability gradient was produced by treating the polymer
sheets with corona from a knife-type electrode whose power was changed gradually along

the sample length. The polymer surfaces oxidized gradually with the increasing power and
the Wettability gradient was created on the sample surfaces. The wettability gradient prepared
by the corona discharge treatment was used as a tool to investigate cell or protein interactions
continuously related to the surface wettability of polymeric materials.6
In this study, surfaces with differently chargeable functional groups but similar
wettabilities were prepared using low density polyethylene (PE) sheets treated by corona
discharge, followed by graft copolymerization and subsequent Substitution reactions.
Chargeahle functional group gradient surfaces where the surface density of grafted functional
groups changes gradually along the sample length were also prepared on PE sheets by
corona discharge treatment with gradually increasing power and graft copolymerization of
functional monomers. The effect of surface functional groups on cell adhesion and growth
was investigated.
SURF ACES WITH DIFFERENT FUNCTIONAL GROUPS BUT SIMILAR

WETTABILITIES
Surface Preparation and Characterization
PE sheet (250-300 11m thickness) was treated with a radio-frequency (RF) corona
discharge apparatus made by our laboratory in a manner similar to that used in a previous
work.s Briefly, a knife-type electrode was connected to the RF generator (Figure 1). The
cleaned PE sheet was placed on the sample bed and dry air was purged through the
apparatus at a flow rate of 20 liter/min. The electrode was 1.5 mm away from the sample
surface. At the same time as the sample bed was translated at a constant speed, 1.0 ern/sec,
the corona from the electrode was discharged onto the sample with the power of 50 watt at
100kHz.
Directly after the PE sheet was treated by the corona, it was immersed in 10 wt% acrylic
acid solution. The graft copolymerization of acrylic acid onto the corona-treated PE surface
was performed for I hr at 70 C in dry nitrogen gas atmosphere. The peroxides produced
onto the surface act as an initiator for graft copolymerization (Figure 2). The polyacrylic acid-
Connected to
....--~ RF generator
Knife.type
electrode
Dryair
inlet
Movable sample bed
Figure 1. Schematic diagram showing the corona discharge apparatus.
536
- - -
O }lH
. 02
cf
I H
0
I
(in air)
PE film
lcH,~H
COOH
~CH2NH2 ~CONH 2 ~COCI ~COOH
-
CH2NH 2 CONH2 COCI COOH
0
UAIH4 NH40H PCI 5 I
PE-CH 2N-i 2
1
PE-CONH 2
UAIH,
PE-COOH
~CH 2 0H
CH 0H 2
Figure 2. Schematic diagram showing the formation of functional group-grafted PE surfaces by corona
discharge treatment followed by graft copolymerization and subsequent substitution reactions.
grafted sheet was agitated in purified water at 70 C overnight in order to eliminate the
homopolymer probably formed on the surface. Some of polyacrylic acid-grafted sheets were
further treated with I 0 wt% PCis in dry ether for I hr at room temperature to convert
-COOH groups on the surface with -COCI groups. After the reaction, the sheets were
treated with saturated aqueous solution of NH40H for 1 hr at room temperature to produce
amide group (-CONH2)-grafted surface or treated with0.5 wt% LiAIH4 in dry ether for 24
hr at room temperature followed by soaking in concentrated HCI for I 0 min to produce
hydroxyl group (-CH20H)-grafted surface. Some of amide group-grafted sheets were also
treated with LiAIH4 solution to produce amine group ( -CH2NH2)-grafted surface.
The functional group-grafted surfaces were characterized by the measurement of water
contact angle using a contact angle goniometer (Model 100-0, Rame-Hart, Inc., U. S. A.)
The functional group-grafted PE surfaces were wetted more easily than the control (contact
angle (CA), about 96 degree) or corona-treated (CA, about 43 degree) ones as water was
dropped on the surfaces (Table 1). This may be due to the grafting of hydrophilic
functionalities. From the Table, we can see that the wettability of the different functional
group-grafted surfaces was not much changed by the kind of functional groups grafted. So,
we can investigate the effect of surface chemistry on cell behavior using the surfaces with
different functional groups but similar wettabilities.
The changes in chemical structure on the PE surfaces after the grafting of acrylic acid
and the substitution of carboxylic groups to hydroxyl, amide, or amine groups were
537
Table 1. Comparison of water contact angles of functional group-grafted PE surfaces.
Surface Contact angle I

PE-COOH 22.8 1.7
PE-CH20H 34.8 2.5
PE-CONH2 23.3 2.7
PE-CH2NH2 28.4 2.7
lsample numbers, n = 3.
Table 2. ESCA analysis of functional group-grafted PE surfaces.
AtQmi~ Z,
Surface -C-C- -{;;-0- O=C-N- 0={;;-0- 0/C ratio N/C ratio
PE-COOH 69 9 22 0.47
PE-CH20H 74 19 7 0.36
PE-CONH2 72 10 18 0.27 0.18
PE-CH2NH2 82 10 7 0.15 0.07
investigated by electron spectroscopy for chemical analysis (ESCA, ESCALAE MK II, V.

G. Scientific Co., U. K.). Table 2 lists the ESCA results of the functional group-grafted PE
surfaces, indicating the grafting of each functional groups on the surfaces.
Interaction with Cells
The functional group-grafted surfaces were mounted in similar test chambers (sample
surface area, 9.6 cm2) to those described by van Wachemet a!.2 The surfaces mounted in the
test chambers were equilibrated with Dulbecco's phosphate buffered saline (PES, pH 7.3-
7.4) free of Ca 2+ and Mg2+ overnight. After equilibrium with PES, the functional groups
grafted on the surfaces can be charged differently; the carboxylic acid groups are negatively
chargeable and the amine groups are positively chargeable, while the hydroxyl and amide
groups have neutral character.
After removing the PBS solution from the chamber, Chinesehamster ovary (CHO)
cells (CHO-KI-EH4, Oak: Ridge National Laboratory, U. S. A.) were seeded to the surfaces
(4 x 1Q4fcm2). The culture medium used was Ham's F-12 nutrient mixture containing 5%
newbom calf serum. After up to 4 hr incubation at 37 C under 5 % C02 atmosphere, the
surfaces were washed with PES and trypsinized. The cell adhesion to the surfaces was
determined by counting the number of detached cells with an electronic cell counter (Model
ZM, Coulter Counter, U. S. A.). The cells were more adherent on the functional group-
grafted surfaces than control PE surface due to the increased wettability by the grafting of
hydrophilic functional groups. As discussed earlier, the water contact angles of the functional
group-grafted surfaces decreased largely compared to that of control surface (about 96
degree) but were not much different by the kind of functional groups grafted. They were in
538
100
PE-COOH
PE-CONH 2
PE-CH 2 0H
--
80 PE-CH 2 NH 2
0~
c:: 60
0
"iii
Q)
~
"t:J
ctl 40
~
20
1 2 3 4
Culture time (hr)

Figure 3. CHO cell adhesion on functional group-grafted PE surface (Number of seeded cells, 4 x
J04/cm2). n = 3.
PE-COOH
Figure 4. SEM pictures of CHO cells grown on functional group-grafted PE surfaces after 4 day culture.
539
the range of 23 to 35 degree. As seen in Figure 3, the amine group-grafted PE surface
showed the best cell adhesion of the surfaces used, probably due to the positive charge
character in the culture medium; the !arge portion of cell or serum protein surface is
recognized as charged negatively, resulting in the electrostatic interaction ofthe surface of cell
or serum protein with the positively charged amine group-grafted PE surface. The
polyacrylic acid-grafted surface which is charged negatively showed poor cell adhesion. For
the surfaces with neutral functional groups, amide and hydroxyl groups, the hydroxyl group-
grafted surface showed better cell adhesion, probably due to the specific hydrogen bondings
between the surface hydroxyl groups of the polymer and the polar groups of the cell
surfaces, as reported earlierJ,S
Cell growth on the functional group-grafted surfaces was carried out for up to 4 days in
the same way as the cell adhesion experiment. The cells grown and spread on the surfaces
were examined by a scanning electron microscope (SEM, JSM-840A, Jeol Co., Japan).6
The growth behavior of the cells on the surfaces was similar to adhesion (not shown); the
positively charged amine group-grafted surface showed the best cell growth while the
negatively charged polyacrylic acid-grafted surface still showed poor growth. The surfaces
with neutral amide and hydroxyl groups showed a similar number of cell attachments;
however, the morphology of the cells attached to the surfaces was quite different as observed
by SEM (Figure 4). The cells were spread much more on the hydroxyl group-grafted
surface than the amide group-grafted one. The amine group-grafted surface showed best cell
spreading. Cells attached on surfaces are spread only when they are compatible on the
surfaces. It seems that the amine group-grafted surface is most compatible with the cells
among the functional group-grafted surfaces used.
FUNCTIONAL GROUP GRADIENT SURFACES
Surface Preparation and Characterization
The PE sheet was treated with the same corona discharge apparatus discussed earlier.
But, in this case a knife-type electrode was connected to the RF generator whose power was
gradually increased by a motorized drive (see Figure 1).5 At the sametime as the sample bed
was translated at a constant speed, 1.0 cm/sec, the corona from the electrode was discharged
onto the sample with gradually increasing power (from 10 to 50 watt). The sample sheet
(5.0 x 5.0 cm) was treated for 5 sec. By this treatment, the sample surface was continuously
exposed to the corona with increasing power and thus the water contact angles of the surface
gradually decreased (from 96 to 43 degree) along the sample length with increasing corona
power (not shown).9 The decrease in the contact angles (and thus the increase in wettability)
along the sample length may be due to the oxygen-based polar functionalities incorporated
on the surface by the corona discharge treatment. The oxygen-based functional groups
produced on the PE surface increased gradually with the increase in corona power, as
analyzed by Fourier transform infrared spectroscopy in the attenuated total reflectance mode
540
CH2=CH CH2=CH
I I
C=O c=o
I I
OH NH
I
Acrylic Acid (AA) SOaNa CH2
I
Sodiump-Styrene
CH2
I
Sulfonate (NaSS) CH2
I
/N,
H3C CH3
N,N-Dimethyl Aminopropyl
Acrylamide (DMAPAA)
Figure 5. Chemical structures of monomers used.
(FTIR-ATR) and ESCA in a previous paper.S From this result, it could be assumed that the
surface density of peroxides produced on the PE surface followed the same trend.
Functional group gradient surfaces were prepared by the corona discharge treatment
with gradually increasing power and graft copolymerization of AA, sodium p-styrene
sulfonate (NaSS), and N,N-dimethyl aminopropyl acrylamide (DMAPAA) (Figure 5).
Directly after the PE sheets were treated by the corona, they were immersed in the 10 wt%
monomer solutions. For NaSS and DMAPAA solutions, 0.1 wt% ferrous ammonium
sulfate as an initiator was added to the solutions. The graft copolymerization of the
monomers onto the corona-treated PE surfaces was performed for 1 hr at 70 C for AA and
4 hr at 80 C for NaSS and DMAPAA. During the polymerization, dry nitrogengaswas
continuously bubbled into the solutions. After the reaction, the monomer-grafted sheets were
agitated vigorously in purified water at 80 C overnight to remove the homopolymers
probably formed on the surfaces.
It was expected that the density of functional groups grafted on the PE surface increased
gradually (Figure 6) due to the peroxides produced on the surface by the corona treatment
with increasing power. Figure 7 shows water contact angles of the functional group-grafted
surfaces. The contact angles gradually decreased along the sample length with increasing
corona power due to the grafting of hydrophilic functional groups with the increasing density
on the surfaces. The changes in chemical structure of the functional group-grafted PE
surfaces along the sample length were investigated by FTIR-ATR. The FTIR-ATR spectra
were obtained using a Magna-IR Spectrophotometer 550 (Nicolet, U. S. A.) equipped with
KRS-5 internal reflection element. The characteristic absorption bands were compared for
the sections of the gradient. Figure 8 shows that the absorbance ratios increased gradually
along the sample length with the increasing corona power, indicating that the functional
group gradients were produced on the surfaces.
Interaction with Cells
The functional group gradient PE surfaces were used to study the effect of surface
functional groups and their density on cell adhesion and growth. After equilibrating the
541
Figure 6. Schematic diagram showing functional group gradient produced on polymer surfaces.
surfaces mounted in test chambers with PBS (pH 7.3-7.4) for 30 min, CHO cells (4 x
I04fcm2) were seeded to the surfaces. After equilibrium with PBS, the functional groups
grafted on the surfaces can be charged differently; carboxylic acid groups for AA-grafted
surface and sulfonate groups for NaSS-grafted surface are negatively chargeable, while
amine groups for DMAP AA-grafted surface are positively chargeable.
The CHO cells were cultured for up to 4 days on the functional group gradient surfaces.
Figure 9 shows the cell adhesion (after 1 day) and growth (after 2 and 4 days) behavior on
the DMAPAA-grafted surface. AA-grafted and NaSS-grafted surfaces showed a similar
trend. As the density of the functional groups increased, the cells attached on the surface
90
AA
NaSS
DMAPAA
4l
Cl
c 70
--
ca
( ,)
ca
c
0
-
(,)
...
4l
50
ca
3:
30+---~--~--r---~~~----~---.--~--~
0 2 3 4 5
Position from untreated end (cm)

Figure 7. Changes in water contact angle of functional group gradient PE surfaces along the sample
length. n = 3.
542
0.4
AA (C=O/C-H)
NaSS(S=O/C-H)
t. DMAPAA(C=O(Amide)/C-H)
-...
0.3
0
('(I
Cl)
0 0.2
c:
('(I
...
..c
0
1/1
..c
< 0.1
0 2 3 4 5

Figure 8. Absorbance ratios calculated from FTIR-A TR spectra of fu nctional group gradient PE
surfaces. n = 3.
3
1 DAY
-
U')
,...
0
~ 2 DAY
0 4 DAY
N
- )(
E
2
~
1/1
-
Q)
0
0
z
0
0.5 1 .5 2 .5 3.5 4.5
Figure. 9 CHO cell adhesion and growth on DMAPAA-grafted PE surfaces (Number of seeded cell s,
4 x 104/cm2). n = 3.
543
3
AA
II)-
0
.,...
~ NaSS
0 DMAPAA
~ 2
N
E
~
<II
-
Qj
CJ
c:i
z
0.5 1 .5 2.5 3.5 4.5

Figure 10. Comparison of CHO cell growth on functional group gradient PE surfaces after 4 day culture
(Number of seeded cells, 4 x J04/cm2). n = 3.
increased and then decreased. The cells were adhered and grown more onto the positions
with moderate density of the functional groups. This may be a hydrophilicity effect rather
than the effect of functional groups. The maximum adhesion and growth of the cells
appeared at around position 2.5 cm (contact angles, about 50 degree). In a previous paper,6 it
was observed that the CHO cells were adhered and grown more onto the positions with
moderate hydrophilicity of Wettability gradient surfaces. The fact that cells are more adhered,
spread, and grown on the moderately wettable surfaces was also observed by other research
groups2,3 as they cultured endothelial or fibroblast cells onto various polymer substrates
with different surface wettability. They explained that preferential adsorption of some serum
proteins Iike fibronectin and vitronectin from culture medium onto the moderately wettable
surfaces may be a reason for better cell adhesion, spreading, and growth. Proteins Iike
fibronectin and vitronectin are weil known to play an important rote for cell attachment onto
substrates.
The effect of different functional groups (i . e., charge effect) on the cell adhesion and
growth also appeared in Figure 10. The DMAPAA-grafted surface showed large amount of
cell attachment, probably due to the positive charge character of amine groups in the culture
medium. The AA-grafted surface which is charged negatively showed poor cell attachment,
as expected. The NaSS-grafted surface which is also charged negatively showed large
amount of cell attachment. This is an exceptional case since it was reported that the negative
zeta potential of NaSS-grafted surface was much higher than the AA-grafted surface.l 0
Kishida, et at.ll explained that this Iarge cell attachment to the NaSS-grafted surface is
closely associated with the extraordinary high protein adsorption to the surface. They
544
suggested that the existence of an aromatic ring close to the ionizable group might be
responsible for this.
The results of this study suggest that surface functional groups and their charge
character as well as wettability play important roles for cell adhesion, spreading, and growth,
even though cell-surface interaction is a very complicated phenomenon and thus it is not still
clear which property is really dominant for cell adhesion and growth on surfaces.
ACKNOWLEDGMENTS
This work was supported by grants from the Korea Ministry of Science and
Technology and the Korea Science and Engineering Foundation (Grant No. 941-1100-024-
2).
REFERENCES
1. J.M. Schakenraad, H.J. Busscher, C.H.R. Wildevuur, J. Arends, The influence of substratum surface
free energy on growth and spreading of human fibroblasts in the presence and absence of serum
proteins, J. Biomed. Mater. Res. 20:773 (1986).
2. P.B. van Wachem, T. Beugeling, J. Feijen, A. Bantjes, J.P. Detmers, W.G. van Aken, Interaction of
cultured human endothelial cells with polymeric surfaces of different wettabilities, Biomaterials
6:403 (1985).
3. Y. Tamada and Y. Ikada, Effect of preadsorbed proteins on cell adhesion to polymer surfaces,
J. Col/oid Interface Sei. 155:334 (1993).
4. H.B. Lee and J.H. Lee, Biocompatibility of solid substrates based on surface wettability, in:
Encyclopedic Handbook of Biomaterialsand Bioengineering, D.L. Wise, D.J. Trantolo, D.E.
Altobelli, M.J. Yaszemski, J.D. Gresser, and E.R. Schwartz, eds., Marcel Dekker, New York,
Vol. 1., P. 371 (1995).
5. J.H. Lee, K.G. Kim, G.S. Khang, H.B. Lee, and M.S. Jhon, Characterization of wettability gradient
surfaces prepared by corona discharge treatment, J. Col/oid Interface Sei. 151:563 (1992).
6. J.H. Lee and H.B. Lee, A wettability gradient as a tool to study protein adsorption and cell adhesion
on polymer surfaces, J. Biomater. Sei. Polymer Edn. 4:467 (1993).
7. J.H. Lee, J.W. Park, and H.B. Lee, Cell adhesion and growth on polymer surfaces with hydroxyl
groups prepared by water vapour plasma treatment, Biomaterials 1991, 12:443 (1991).
8. A.S.G. Curtis, J.V. Forrester, C. Mclnnes, and F. Lawrie, Adhesion of cells to polystyrene surfaces,
J. Ce// Bio/. 97:1500 (1983).
9. J.H. Lee, J.W. Lee, G. Khang, and H.B. Lee, Interaction of cells on chargeable functional group
gradient surfaces, Biomaterials 18:351 (1997).
10. T. Okada and Y. Ikada, Tissue reactions to subcutaneously implanted, surface-modified silicones,
J. Biomed. Mater. Res. 27:1509 (1993).
11. A. Kishida, H. Iwata, Y. Tarnada, and Y. Ikada, Cell behavior on polymer surfaces grafted with non-
ionic and ionic monomers, Biomaterials 12:786 (1991).
545
COMPOSITE HYDROGELS AS INTERVERTEBRAL DISC PROSTUESES
L. Ambrosio, R. De Santis, and L. Nicolais
Institute of Composite Material Technology, National Research Council,

and Interdisciplinary Research Centre on Biomaterials
University of Naples
P. le Techchio 80
80125 Naples, Italy
ABSTRACT
Different PHEMAIPCL serni-IPNs hydrogels composite systems, reinforced with PET

fibers, have been investigated for potential use as intervertebral disc prostheses.
The mechanical characteristics, such as the extent of the"toe region", the elastic modulus
in the linear region and the maximum stress can be controlled by varying the winding angle
of the fibers and matrix composition.
Uniaxial compression tests on the swollen samples showed an increase of the modulus
and maximum stress with increasing the content of PCL and PET fibers.
The composite PHEMAIPCL hydrogels showed compression properlies sirnilar to those
expressed by the canine intervertebral discs in different spinallocations.
Creep behaviour, hence dimensional stability of the artificial prostheses, have been
investigated.
Viscoelastic properties have been evaluated by dynamic-mechanical analysis, the tests
reflect the non linear behaviour of the composite structures.
Keywords: Hydrogels, composite, prostheses, mechanical properties, intervertebral disc.
INTRODUCTION
In this work PHEMA and different PHEMAIPCL serni-lnterpenetrating Polymer

Networks hydrogels and their relative composite systems reinforced with PET fibers have
been investigated for potential use as intervertebral disc prostheses.
The intervertebral disc is a fibrocartilaginous complex that forms -the articulation between
the bodies of the vertebrae. It consists of two components: the intemal semifluid mass, the
nucleus pulposes and the annulus fibrous. Both are anchored to the vertebral bodies by
cartilaginous end-plates.
The annulus is a concentric series of fibrous lamellae that encase the nucleus and strongly
unite the intervertebral bodies. Whereas the essential function of the nucleus is to resist and
restribuite compressive forces within the spine, one of the major functions of the annulus is
to withstand tension.
The intervertebral disc consists principally of collagen fibers embedded in a proteoglycan-
water gel. The latter component develops a large swelling pressure which enable the disc to
resist compressive properties I ,5.
The type and orientation of collagen in the disc have an irnportant influence on how Ioad
is distributed. In the disc there is a gradation of collagen type and orientation from nucleus to
annulus. The collagen fibers, contained in the concentric lamellae, are inclined with respect to
the vertical axis of the spine in a lay-up structure. From the edge of the disc inward to the
nucleus, the angle fiber orientation decreases from 62 to 45 degrees2,6. Water is the main
constituent of the disc, it occupies 65 to 85 per cent of the tissue volume depending on age
andregion.
The pathology of the intervertebral disc is mainly related to the aging and insufficient
nutrition state, in fact, with age the nucleus loses its gel-like character, compressive stress are
then no Ionger evenly distributed to the end-plates and annulus generating stresses in the
annulus leading to its degeneration. More critical Situations due to injuries such as complete
rupture of disc could be solved by using artificial disc. The current available intervertebral
disc prostheses are made by metals, metallic-polymer systems and polymers3-6.
Due to their biocompatible characteristics, high permeability and high hydrophilicity,
poly(2-hydroxyethylmethacrylate)(PHEMA) hydrogels7,8,12 were explored as potential use
for the matrix of the artificial disc.
However, the mechanical properties of these materials in the hydrated state are inadequate
for biomedical applications where mechanical strength is required.
The improvement of the mechanical performance of these hydrogels has been obtained by
the incorporation of hydrophobic component such as poly(caprolactone) (PCL) and
polymeric fibers9,10. Enhancing these properties will make hydrogels and related composites
more acceptable for many applications to come.
The incorporation of hydrophobic component such as poly(caprolactone) (PCL) into
PHEMA hydrogels results in materials exhibiting improved mechanical propertiesl0,13.
In this paper the compression, creep and dynamic-mechanical properties of PHEMA-PCL
s-lPNs reinforced with PET fibers are investigated and compared with those found on canine
intervertebral discll.
548
MATERIALS
Preparation of PHEMA/PCL Semi-IPN Composite Hydrogels
Polycaprolactone (MW=35.000), was dissolved in 2-hydroxyethylmethacrylate (HEMA)

monomer at 60C. After allowing the solution to cool, 0.5 wt% EDMA crosslinking agent
and 0.1 w% AIBN initiator were added. The percent initiator and crosslinking agent were
calculated with respect of HEMA. The reactive solutions covered the composition of 10%,
20%, 30% by weight of PCL in PHEMA.
Polyethylenetherephtalate (PET) continuos fibers (kindly supplied by Montefibre S.p.A.)
were wound helically by ftlament winding machine on polyethylene hoses with diameter of 6
mm. The fibers were preipregnated in the reactive solutions described previously and wound
on the hosemandrei until the fmal diameter of 10 mm was reached. The winding angle was
varied, from inside to outside, from 45 to 65 degree (samples 1, 2, 3) and from 45 to 90
degree (sample 4).The braided fibers were carefully removed from the mandrei and placed
into a cylinder mold having an inner diarneter of 10 mm. The reactive solution was then
poured in the mold and cured at 90C for one hour. After cooling the samples were placed in
distilled water for hydradation, then rods of 15 mm length were used for testing. This
technique permits to prepare samples with softer and more hydrophylic inner part (i.e.
nucleus) and a harder and less hydrophilic outer part (i.e. annulus).
METHODS
Compression Test
Five samples for each composition and composite structure were tested in compression in
the form of cylinders with length of 15 mm and diameter of approximate 12 mm according to
the water content. The compression tests were performed by screw-driven Instron 4204
mechanical testing rnachine. Specimens were placed between stainless steel plates, immersed
in distilled waterat T=37C, and compressed at a rate of 10 mm/rnin.
Creep Test
The creep tests were performed by MTS Bionix 858 on swollen composite hydrogel
PHEMA/PCL 80/20, reinforced with 40% by volume of PET fibers, in the form of cylinders
with length of 15 mm and diameter of 24 mm.
Specimens were placed between stainless steel plates and preloaded to a stress of 0.1 MPa
, immersed in distilled water at T=37C. A stress of 2 MPa was applied and the Strain was
recorded as function of time until4500 seconds.
549
Dynamic-mechanical Properlies
Viscoelastic parameters (E', E", E* and tan) have been measured by dynamic mechanical
tests using a MTS Bionix Test System. Tests have been performed in a force-control mode
using an MTS 662.200-ID loading cell of 2.5 KN full range.
Static Ioad was ranged from 1OON to 600N and all tests were performed with a 25N
dynamic load. The frequency was scanned from 0.4 to 10 Hz. An hold command of 30
rninutes, at each static load level, was adtempted before starting the dynamic frequency
sweep.
The tests were performed in physiological solution at 37C.
The stress-strain curves in compression of swollen composite systems are presented in

Figure 1. An initial toe region followed by a linear region can be observed, and this trend is
qualitatively sirnilar to that of the natural disc II.
The mechanical parameters are function of the concentration of the PCL in the s-IPN.
Infact, as reported in Table 1, an increase of the elastic modulus and the maximum stress
was observed, while a decrease of maximum strain was obtained. The value of the modulus
increases from 30 to 73 MPa and the maximum stress from 12 to 17 Mpa.
Considering the respective values of canine disc it can be observed that the composite
25r----------------------------r---------,
Max Stress Range of

20 Caoioe Discs in the
LUMBAR zooe
~ 15 - - - - - - - MaXStreRageof
Canine Discs in the
_ _ _ _ _ _ _ THORA.CIC_zone _
"'
~10
Cl)
Max Stress Range of
Canine Discs in the
CERVICAL zone
0 0.1 0.2 0.3 0.4 0.5 0.6

Strain (mm/mm)
Figure 1. Stress-strain behaviour of the composite disc prostheses

PHEMAIPCL 90/10; Winding angle 45-65
-<>-- (l) - (3) PHEMAIPCL 70/30; Winding angle 45-65
- - (2) PHEMAIPCL 80/20; Winding angle 45-65 - (4) PHEMA!PCL 70/30; Winding angle 45-90
550
semi-IPNs (sample 1, 2, 3) presented the optimum compressive properties for intervertebral
disc in cervical and thoracicll region as shown in Figures 1.
Since the values of the modulus and stress of canine intervertebral disc in the lumbar
region are still high 11, a different composite structure is proposed. PHEMNPCL 70/30 was
reinforced with 50% by volume of PET fibers with winding angle varying from 45 to 65
degrees, at the last end a 90 winding angle was used (sample 4). The stress-strain curve in
compression is represented by the curve (4) and related properties are reported in Tablel. As
expected, the increase of PET content and the presence of fibers at 90 at the last end of the
periphery resulted in an increase the modulus in the linear region, an increase of the
maximum stress and a reduction of the maximum strain. The value of the modulus and
maximum stress are respectively 129 and 20 MPa which are typical values of the canine
intervertebral disc in the lumbar region 11 as shown in Figure 1 and Table 1.
The behaviour of such artificial tissues can be therefore controlled by an appropriate
design of the soft composite prostheses realized by the filament winding technique.
Creep tests have shown time-dependent properties and dimensional stability of the
composite hydrogels to be function upon the composition of the matrix. The data from creep
experiments at the stress Ievel of 2 MPa are presented in figure 2. The higher content of PCL
in the PHEMA results in a reduced strain value at creep. In particular, the strain values after
4500 seconds varyied from 0.18 mm/mm to 0.22 mm/mm.
0.25
eE 0.2
6
g
gc 0.15 PHEMA/PCL 80/20
-o-
PHEMA/PCL 70/30
-+-
Cl)
=
Stress 2MPa
Winding Angle =
45- 65
40% by volume of PET fibers
0.1
0 2000 1000
3000 4000 5000
Time (sec)
Figure 2. Creep behaviour of the composite structures.
Table 1. Elastic modulus of the different composite structures compared to canine

discs in the different spine locations.
Phema!PCL 90/10 Phema/PCL 80/20 Phema/PCL 70/30 Phema!PCL 70/30
SAMPLE Winding Angle Winding Angle Winding Angle Winding Angle
45-65 45-65 450-650 45-9if
Elastic Modulus
E (MPa) 30.2 3.0 60.8 4.8 73.3 6.3 129.7 6.8
Natural Disc Zone CERVICAL THORACIC LUMB AR
Elastic Modulus
of Canine Natural Disc 25 + 50 50 + 80 80 + 140
Range(MPa)
551
Viscoelastic analysis is usually carried out by imposing a sinusoidal excitation function
and monitaring the response. If a sinusoidal force is imposed to the sample, the deformation
response of the material is composed by two components: the elastic (in-phase with
excitation) and viscous (out-of-phase), the total response willlag behind the excitation by a
phase angle cp. The phase lag results from the time necessary for molecular rearrangements
and is associated with the relaxation phenomena.
The dynamic behaviour can be characterised by just two parameters, typically the storage
and the loss modulus. The elastic part of the complex modulus (Eo*) is also called storage
modulus (E'), being correlated with the part of energy that is stored in the material, the
viscous part (E") is also called loss modulus being correlated to the dissipated energy. The
two parameters, the storage and the loss modulus, give indication on the viscoelasticity of the
material.
Due to the nonlinear characteristic of the stress-strain curves, the viscoelasticity of such
structures cannot be interpreted by the simple theory of linear viscoelasticity. For this reason,
the dynamic-mechanical properties were performed in a load control mode at an increasing
level ofthe static stress (ranging from 100 to 600 N). Acheck of "local" linearity was done at
any level of static stress and for this purpose, according to creep tests, a force hold command
of 30 minutes was adtempted before each frequancy sweep.
The amplitude ofthe dynamic stresswas of25 N.
Dynamic-mechanical analysis performed on composite prostheses are presented in Figure
3-4-5-6.
As for the natural tissues, the curves in Figure 3, 5 reflect the non-linear behaviour of the
composite structure. The storage modulus E' increases with the encreasing of static load and
frequency.
60
Dynamic Load= ZSN
-e-f= 10Hz
50 --o- f = 6.4 Hz
---t = 3.2 Hz
40 ~t= 1.6Hz
..-. -+-f= 0.8 Hz
eil
~ - f = 0 . 4 Hz
~ 30
'-'
~
20
10
0
0 100 200 300 400 500 600 700
Mean Level (N)
Figure 3. Storage modulus vs static load of PHEMA/PCL 80/20 reinforced
with 40% by volume with PET fibers.
552
5
Dynamic Load= 25N
----<>- f = 10 Hz
4 --o- f = 6.4 Hz
__"...._ f = 3.2 Hz
---o- f = 1.6 Hz
"-..._
:1 3 ~f=O.BHz
~ -fl!--f=0.4Hz
::E
'-'
ii.l 2
0 ~~~~~~~~~~~~~~~~~
0 100 200 300 400 500 600 700

Mean Level (N)
Figure 4. Loss modulus vs static Ioad of PHEMAIPCL 80/20 reinforced
50,---------------------------__,
Dynamic Load= 25N
----<>- f = 10 Hz
40 --o- f =6.4 Hz
- - f = 3.2 Hz
---o- f = 1.6 Hz
-f=O.BHz
30 -fl!--f=0.4Hz
10
0 ~~~~~~~~~~~~~~~~~~
0 100 200 300 400 500 600 700

Mean Level (N)
Figure 5. Storage modulus vs static Ioad of PHEMAIPCL 70/30 reinforced
lnfigure 4, 6 is reported the dependency of the loss modulus, E", versus static Ioad.
The loss modulus increases with frequency and static Ioad. The variation of the viscoelastic
response observed during the increase of the applied load results from a modification of the
contribution that matrix and fibers give to the overall dynamic-mechanical response. The
increase of the loss modulus with frequency is typical of rubbery materials and this.
behaviour can be related to the presence of the rubbery matrix. In this condition, the PET
fibers give poor contribution to the overall viscoleastic behaviour but this contribution
becomes more and more significant with the increase of the static load.
Natural intervertebral discs are viscoelastic materials. Hence, a proper design of artificial
prostheses should take into consideration time dependent contributions.
553
PHEMA/PCL 70/30 Reinforced with PET Fibers
5
Dynamic Load = 25N
4
~f= 0.4Hz
-----{r--- f = 0. 8 Hz
~t=1.6Hz
,.-._
~
3
~
-+-- f = 3.2 Hz
:E
'--'
--ffi--f= 6.4Hz
2 - t = 10Hz
~
0 ~~~~~~~~~~~~~~~~w
0 100 200 300 400 500 600 700

Mean Level (N)
Figure 6. Lass modulus vs static load of PHEMA/PCL 70/30 reinforced
The dynamic-mechanical analysis of the composite structure tissues suggested that the
effect of the state of strain on the dissipative characteristics can be reproduced by selecting
the right matrix and by an opportune geometrical design of the composite structure. The
rubbery behaviour can be mainly related to the rubbery behaviour of the matrix while the
glassy response, at higher Ievel of strain, is due to the progressive contribution of the glassy
fibers to the overall viscoelastic response. The use of composite structure permits to obtain
systems with compression properties close to that of the canine intervertebral discs of
different locations in the spinal column.
CONCLUSIONS
The composite prostheses can be rapresented by continuous fibers helically wound to

form a hollow composite cilinder.
The stress-strain behaviour of natural intervertebral disc can be reproduced by composite
structures. The tensile responses of such systems can be varied by modifying the matrix
composition and the winding angle of the fibers reinforcement.
The behaviour of such tissues can be therefore controlled by an appropriate design of the
soft composite prostheses realized by the ftlament winding technique. The control of the
matrix composition and geometrical configuration of the wo und fibers, allow a wide range of
mechanical properties. Low modulus region is related to the properties of the PHEMA and its
interaction with PET fibers, while the high modulus regions and fmal properties are mainly
due to the properties of the fibers.
Creep tests have shown time-dependent properties of the composite hydrogels to be
function upon the composition of the matrix.
Varying the composition of the hydrogel matrix, the winding angle and the quantity of
554
PET fibers, is possible to modulate the hydrophilicity and the mechanical properties of the
intervertebral disc prostheses.
Moreover, the PHEMA-PCL semi IPNs may allow natural tissue in-growth since PCL
degrades to leave voids in the network. In this way the implant can be anchored to the body.
These tests indicated that the use of composite hydrogels as disc prostheses is very
promising because it is possible to combine transport and mechanical properties which are
crucial for the performance of the intervertebral disc.
REFERENCES
1. R.H. ROTHMAN, F.A. SIMEONE, The Spine, 3rd edition, Vol. 1, W.B. Sauders
Company, Philadelphia, 1992, p. 182.
2. J.J. CASSIDY, A. HILTNER, E. BAER, Connective Tissue Research, Vol. 23,
1989, pp. 75-88.
3. W.G. HELLIER, T.P. HEDMAN, 17th Annual Meeting of the Society for
Biomaterials, Scottsdale, Arizona, USA, April5-9 1991, p. 224.
4. B. KADEN, R. SCHULTHEISS, G. LANG, H.J. SCMITZ, G. FUHRMANN, U.
GROSS, 4th World Biomaterials Congress, Berlin, Germany, April24-28 1992, p. 292.
5. C.R. MCMILLIN, A.D. STEFFEE, 20th Annual Meeting of the Society for
Biomaterials, Boston, MA, USA, April5-9 1994, p. 89.
6. M.V. HAWKINS, M.C. ZIMMERMAN, J.R. PARSONS, N.A. LANGRANA,
C.K. LEE, in Composite Materials for lmplant Applications in the Human Body:
Characterization and Testing, Jamison/Gilbertson Editors, ASTM Publications, STP 1178,
1993, pp. 17-26.
7. N. A. PEPPAS (Editor), Hydrogels in Medicine and Pharmacy, Vols I and TI, CRC
Press, Boca Raton, FL, 1987.
8. S. IANNACE, G. SABATINI, L. AMBROSIO, L. NICOLAIS, Biomaterials Vol.
16, 1995, N.3.
9. P.A. DAVIS, L. NICOLAIS, L. AMBROSIO, S.J. HUANG, Journal of Bioactive
and Compatible Polymers, Vol. 3, July 1988, pp. 205-218.
10. P.A. DAVIS, S.J. HUANG, L. NICOLAIS, L. AMBROSIO, in High Performance
Biomaterials: A Comprensive Guide to Medical/Pharmaceutical Applications, M. Szycher
(Editor), Technomic, 1991, pp.343-367.
11. J.J. CASSIDY, A. HILTNER, E. BAER, Journal of Materials Science: Materials in
Medicine, 1, 1990, pp. 69-80.
12. J. VINCENT, Structural Biomaterials, Princeton University Press, 1991, p. 60.
13. G.D. FRIENDS, J.F. KUNZLER, R.M. OZARK, Journal of Biomedical Materials
Research, Vol. 26, 1992, pp. 59-67.
555
APPLICATIONS OF TEMPERA TURE-RESPONSIVE POLYMERS
FOR OPTICAL RESOLUTION
Naoya Ogata
Department of Chemistry, Sophia University

7-1 Kioi-cho, Chiyoda-Ku, Tokyo 102, Japan
INTRODUCTION
Optical resolutions of racemic mixtures of optically active compounds are very imortant
especially in the areas of pharmaceutical and biomedical applications. Optical isomers
have normally almost the same chemical and physical properlies so that separations of
these optical, isomers are very difficult by conventional separation methods such as
distillation or recrystallization. Conventionally, optical isomers are separated by
Chromatographie method which utilizes adsorption and desorption behaviors through a
column of various matrices. However, this method is not suitable for a !arge scale
separation for industrial applications, although it is good enough for only analytical
purpose.
Stimuli-responsive polymers such as temperature-responsive polymers have been
extensively studied with a commmon name as "Intelligent Polymers". For a instance,
poly(N-isopropylacrylamide)(PIPAAm) is a water-soluble polymers having remarkable
hydration-dehydration changes in water medium in responce to temperature changes,
owing to a tranistion behaviors between hydrophilic and hydrophobic characters of
PIPAAm. The transition temperature is called as a lower critical solution temperature
(LCST). PIPAAm dissolves in water below 32'C (LCST), while it becomes insoluble
in water above 32'C to precipitate out of the aqueous solution and this dissolution-
precipitation behavior is reversible by temperature changes. In other word, the
precipitated PIPAAm can be redissolved in water by cooling temperatures below 32'C.
Since the dissolution-precipitation behavior is derived from a balance between hydrophilic
and hydrophobic characters of amide and iropropyl groups within the PIPAAm, the
LCST can be controlled from lower to higher temperaures by changing compositions of
IPAAm in use of other comonomers such as butyl methacrylate (BMA) or N,N-

dimethylacrylamide (DMA). The first paper to shift the LCST by copolymerization
was reported by S. W.Kim et al(I} and bio-related application was reported by
A.S.Hoffman(2).
When a chirat group is introduced into a copolymer of IPAAm. the chirat group would
have some interactions with optically active substrates in aqueous solution and one side of
optical isomers would be strongly adsorbed onto the copolymer of IPAAm, thus resulting
in phase separations from the aqueous solutions by simply rising temperatures above the
LCST. The expectation would Iead to a large scale optical resolution of optical isomers
for industrial applications, since the IPAAm copolymers can be recovered by separating
the adsorbed optical isomers with increasing tempemtures again above the LCST.
Thus, a novel optical resolution would be attained by the intelligent systems by using the
temperature-responsive polymeric adsorbent This papere describes novel optical
resolutions by using tempemture-responsive polymers.
EXPERIMENTALS
Monomer Syntheses
Following opticall active monomers were synthesized through chemical reactions as
shown below:
(1) N-isobutylacrylamide (IBAAm)
CHzClz CH2 =CH

"ct41lr"
t=O
I
NH
*ta
dJ:3'cHzCIJJ
(2) N-hydroxyisobutylacrylamide (HPMA)
CH3
I
+ CH;r-CH1-CH-CH1 -0H
1
Naoafi:.
"C,4 r" CHz=~
C=O
NHz I
(D )-2-Amino-1-butanol ?jiH
'CH
(L )-2-Amino-1-butanol Czlls
'cH20H
BPMA
2. Polymerization
Polymers or copolymers were obtained by a conventional radical polymerization by using

azobisisobutylonitrile (AIBN) as an initiator at 70'C in dimethylaformamide (DMF)/y-
butylolactone (BL)(l/1) as a solvent Polymers or copolymers were recovered by
pouring polymer solutions in excess acetone. Polymerization scheme is shown below:
DMF, AIBN , -fcHz-'fu-];-t-rnz-cH-t.;--

70"C, 24hr C=O t-o
r!m AR
6I 6I
~ 'cHzCill ~ 'tH3
558
CH3
I DMF I c;;l..,, AIBN .,
CHz=~ 7oc,24hr
C=O
I
r;a
*eH.....
."
Czlls CHzOH
3. Chamcterization of Polymers
Polymers or copolymers were chamcterized by Ff-IR, NMR or eiemental analyses.

Optical rotations of the polymers or copolymers were also determined by DIP-4 degital
rotameter in aqueous solutions.
4. LCST Measurements
LCSTs of aqueous solutions of polymers or copolymers were determined by measuring

optical transmittance of the aqueous solutions at 500nm with Shimazu UV1200
specrometer. Copolymers from IBAAm or the HPMA polymer were dissoved in water
in an amount of 0.1 wt%, in which equimolar amount of amino acids such as D- or L-
tryptophan (Try), glutanic acid (Giu) or phenylalanine (Phe) to the optically acive sites
(IBAAm or HPMA) were added to the solution in order to identify interactions between
the polymer or copolymers and these substrates in aqueous solutions.
Table I Copolymerization of IBAAm and IPAAm
sec-BAAm: IPAAm1) [a]:zo3)

sec-BAAm unit ~leid/% /mol% Mw2) 5119
30mol%
-,:"type 34.1 30:70 6000 +1.19
R-type 21.4 26:74 14000 -6.90
Racemic type 36.6 26:74 7600 0.00
~
S-type 37.1 50:50 8000 +5.98
R-type 35.5 48:52 8600 -7.47
Racemic type 40.6 50:50 7800 0.00
70mol%
S-type 32.8 64:36 11000 +10.49
R-type 21.8 70:30 12000 -14.93
Racemic type 29.8 68:32 12000 0.00
1) Determined by 1HNMR.
2) GPC in DMF.
3) Measured by polarimeter at 20"C (c = 1.18x1o5 mol 11 in water).
559
Results and Discussion
Homopolymer from IBAAm did not dissove in water. Therefore, IBAAm was
copolymerized with temperature-responsive IPAAm in various molar ratios. Maximum
molar ratio of optically active IBAAm for the copolymerization. was 70 mol% in order to
solubilize copolymers in water. Homopolymer from HPMA was soluble in water
below I O'C: and started to precipitae at 45'C:, showing a LCST behavior.
l. Copolymers Derived from IBAAm and IPAAm
Results of the copolymerization of optically active or inactive IBAAm and IPPam in

various molar ratios are summarized in Table I. The copolymers of below 70/30 molar
ratios of IBAAm and IPAAm were soluble in water. Copolymer compositions were
almost the same as feed ratios between IBAAm and IPAAm. Optical rotation values of
the copolymers in Table I indicated no racemization took place during the
copolymerization. Ff-IR and NMR spectra of the copolymers of optically active
IBAAM/IPAAm (50/50) are shown in Figs. 1 and 2, respectively. No significant
differences in Ff-IR and NMR spectra were observed for the copolymers derived from
optically active ( R-or S-types) or racemic IBAAms.
Fig. 3 indicates the LCST behaviors of the copolymers derived from racemic IBAAm and
IPAAm in various molar ratios in the absence and the presence of Try in aqueous
solutions. The LCSTs of these copolymers shifted toward lower temperatures from
25 to 10'C: (50% transmittance) with increasing molar ratios of IBAAm which is more
hydrophobic than IPAAm. With the addition of Try in the aqueous solution, the
LCSTs of the copolymers shifted toward higher temperatures and the shift temperatures
became greater with increasing content of IBAAm units in the copolymers. The LSCT
560
PPM
9 8 7 26 5 4 3 0
Fig. 2 NMR spectrum of eopolymer of IBAAm/OPAAm(S0/50)
..
Racemic sec-BAAm unit e in Water .A. D-Trp L-Trp
30mol% SOmol% 70mol%
100 100 100
lj.75
......
t t lj.75
......
tc )
lj.75
......
t
111

' ~\
jso :so jso
e ' '
~1s
E-<
"'
!15
~ .... ~lS
0 0 0
0 10 10 30 40 '0 60 0 10 10 30 40 60 0 10 20 30 40 so 60
Temperature I oc
,~
Temperature C Temperature C
Fig. 3 LCST behavior of eopolymers derived from meernie IBAAm and IPAAm
in the absenee or the presence of Trp.
(0.1 wt%, f...=500nm)
R-type sec-BAAm unit e

100
30mol%
."' ..,..
in Water .A. D-Trp
100
lj. 75
SOmol%
L-Trp
.-----.-:~~~~r------,

100 70mol%
lj.75
....
,...,._ _ _ _ ____,
"'
.. "...
...... ......
"'
-
t
"'
~
;so
"'
jso
~1s "'
0 L.-1....1....'-"L...I....-LI..i=:lll
]1s
E-< "'
0
0102030405060 0 10 10 30 40 50 60 10 10 30 40 ~~ 60
Temperature I oc Temperature I C Temperature I
Fig. 4 LCST behavior of eopolymers derived from R-type IBAAm and IPAAm
in the absence or the presence of Trp.
561
..........., -.
S-type sec-BAAm unit e in Water .t. D-Trp L-Trp
30mol% SOmol% 70mol%

100 100 100
~75
.._ ~75
.._
.,u
.... ~75
.._
.,u

~ c c
...
~50
e
!so ~50
~
...
~zs
E-<
!25 ezs ...
E-<
0 0
0 10 zo 30 40 50 60 0 10 zo 30 40 so 60 10 zo 30 40 50 60
Temperature I c Temperature I c Temperature I c
Fig. 5 LCST behavior of copolymers derived from S-type IBAAm and IPAAm
in the absence or the presence of Trp
shifts indicated that Try was adsorbed onto the copolymers, making the copolymers more
hydrophilic. However, the LCST shifts by the addition of Trp were the same for
either D- or L-Trp. In other words, no chiral recognition of the racemic copolymers
was observed although Trp was adsorbed onto the copolymers.
On the other hand, the chiral copolymers derived from either. R- or S-types of IBAAm
exhibited very interesting shifts of the LCST of the chiral copolymers. Fig. 4 indicates
the LCST behaviors oftheR-type IBAAm!IPAAm copolymers of various molar ratios ,
while Fig. 5 indicates the LCST behaviors of the S-type IBAAm/IPAAm copolymers of
various molar ratios, in both cases in the absence or the presence of Trp in aqueous
solutions.
Figs 4 and 5 indicate that the LCSTs of these optically active copolymers are almost the
same as those of the racemic copolymers. However, when Trp was added to the
aqueous solutions of these chiral copolymers, the shifts of the LCST were quite differect
in the presence of D- or L-Trp. As shown in Fig. 4, The LCST shifts of the R-type
copolymers in the presence of L-Trp became greater than those in the presence of D-Trp
and the difference of the LCST shifts also became greater with increasing contents of the
R-type IBAAm units. On the other hand, completely opposite behaviors of the LCST
shifts were observed for the S-type IBAAm copolymers, that is, the LCST shifts of the S-
type copolymers in the presence of D-Trp became greater than those of L-Trp and the
LCST shifts also increased with increasing contents of the S-type IBAAm units. No
such LCST shift defferences were observed for the homopolymer of IPAAm, although
the LCST of PIPAAm shifted toward higher temperatures by the adsorption of Trp onto
the PIP AAm. Therefore, it is celar that the LCST shifts of the copolymers were caused
by the chiral IBAAm units in the copolymers.
Fig. 6 summarizes results of the LCST shifts of the S-type copolymer (50/50) in the
presence of D- or L-Trp as functions of concenrations of the copolymer in aqueous
solution. The LCST shifts in the presence of D-Trp increased with increasing
concentrations of the copolymer in the aqueous solution, as shown in Fig. 6. These
562
36
AD-Trp
34 L-Trp
32 ePIPAAm
u
!.. 30
E-1
~28
26
24
22
0 0.5 1 1.5
Concentration /1o-4 moii-1
Fig. 6 LCST changes of the copolymers of S-type IBAAm/IPAAm(50/50)
as functions of the concentration of the copolymer
results strongly suggest that L-Trp was more strongly adsorbed onto the S-type
copolymers to make the copolymer more hydrophilic to shift the LCST toward higher
tempertaures, while reverse adsorption of D-Trp occured for the R-type copolymers.
The chiral copolymers derived from IBAAm and IPAAm recognize the chirality of optical
isomers of Trp so that the differect LCST shifts of the copolymers were observed.
These results suggest a novel optical resolution method by using the tempertaure-
responsive copolymer. It is expected that one side of isomers of Trp would be strongly
adsorbed onto the chiral copolymers when a racemic mixture of Trp is added into the
aqueous solution of the chiral copolymers and other side of isomer would ramain in the
aqueous solution with less interactions with the chiral copolymers. With increasing
temperatures above the LCST, the Trp adsorbed copolymers would precipitate out of
the aqueous solution, w hieb can be separated by a centrifuge and other side of isomers of
Trp would remain in the aqueous solution. Results of the optical resolution by using
this concept is summarized in Table li. It is seen in Table li that the optical resolution
of racemic Trp was attained by this novel method. However, complete optical
resolution of Trp was not attained, presurnably owing the chirality of the copolymers was
70mol%.
Another substrates except Trp were used for the LCST behaviors of the copolymers.
Fig. 7 indicates the LCST behaviors of S-type IBAArn!IPAAm copolymer (50/50) in the
presence of D- or L-glutamic acid (Glu) or phenylalanine (Phe). No shifts ofthe LCST
were observed in the presence of Glu, while the LCST of the copolymer shifted toward
higher temperatures in the presence of L-Phe, as in the case of Trp. Since Glu is
much hydrophilic and Phe is rather hydrophobic, the chiral interactions between the chiral
copolymers and optically acive substrates might be due to hydrophobic interactions
between optically active isobutyl group of the copolymers and indole group of Trp or
563
Table II Specific adsorption ofTrp to poly(IBAAm-co-IPAAm
(50/50) in aqeous solution
copolymer D-Trp L-Trp

(xl0-2 mmol/1) (xl0-2 inmol/1)
S-Type 2.3 (15.7%) 5.0(34.0%)

R-Type 6.7 (45.0) 4.0 (27.0)
Racemic 2.3 (18.0) 2.7 (15.7)
Intitial concentration ofTrp= 1.47x10-1 mmolll
phenyl group of Phe based on steric effects. Furhter investigations on the chiral
interactions between the copolymers and substrates will be carried out.
2. LCST Behavior of Poly(HPMA)
In order to obtain 100% chiral polymer which shows the LSCT behavior, hydroxyl group
was introduced onto the optically active butyl group. Optically active and inactive
HPMAs were synthesized as mentioned before and they were polymerized by a
conventional radical polymerization as in the case of the copolymers. Results of the
polymerization of HPMA are summarized in Table III and FT-IR and NMR stectra are
shown in Fig. 8.
Optical rotation values of the obtained polymers indicate that no racemization took place
during the polymerization. The LCST behaviors of the optically active or inactive
polly(HPMA) are shown in Fig. 9. The LCST of the racemic (DL) polymer was 45CC
and the LCST curve as functions of tempertaures was completely reversible. On the
other hand, the LCSTs of optically acive D- or L- poly(HPMA)s were much lower than
Duffersolution <Kli2POI =4.58xto-4 M, NII2HP04 =7.8Ssto-4 M, pH =7.4)
100 100 100
Trpfree e Pbefree e Glufree
,,
I
~
~ 75 L-Giu
~
~75 .L-Trp L-Phe -....75
...... A.DPhe A D-Giu
21
j:
A.D-Trp
...
41 41
l!l
' ..
Sso !so ~

I~
E-<
J~ \~
0 0 0
0 510152.0~303540 0 510152.0~303540 0 510152.0~303540
Temperature I C Temperature I C Temperature I OC
Fig. 7 LCST behaviors of copolymer derived from S-Type IBAAm/IPAAm

in phosphate buffer solution (0.1 wt%, A.=500nm)
564
Table III Characterization of HMPA and poly(HMPA)
[o:]20
689
Sample
Monomer Polymer ll,p/ c
D-HPMA -2.90 -2.88 0.15
L-HPMA +2.95 +2.55 0.14
DL-HPMA 0.00 0.00 0.27
~.0~------~~----~~------~------~--==~~~=
%T
80.0
75.0
70.0
65.0
60.0
55.0
50.0
45.0
40.0
35.0
30.0
25.0
~~nn~~~nn~~~~~~~~nn~~mm~~rrrrrrrrn
4000 3600 3200 2800 2400 2000 1600 1200 800 600 400
1/cm
8" 7
I
r
6" "5" 4 3""" 2 0 0

L1 ''''' PPM
11
,,,,,I
Fig. 8 Ff-IR and NMR spectra of poly(HPMA) (racemic)
those of the meernie poly(HPMA), that is, for D-poly(HPMA) at 28'C and for L-
poly(HPMA) at 35'C. Moreover, the LCST curves were not reversible, in other words,
the D-poly(HPMA) started to redissolve at 30'C and the L-poly(HPMA) at 20'C and a
565
--
- -
100 100
~75 ~~
~75 '
.)
Q,) Q,)
(,) (,)
c: c:
,
lil
..
..... 50
eil .....
~
..... 50 L L DL
a ..... D DL
e
-
')
tiJ
tiJ
c:
' -
c:
eil
s.. 25 eil
s.. 25
E-- ~
......
0 0
0 10 20 30 40 50 60 0 10 20 30 40 50 60
Temperature (C) Temperature (OC)
Fig. 9 LCST behaviors of poly(HPMA) in aqueous solutions
(0.4 wt%, A.=400nm)
strong hysterisis of the LCST behaviors was observed for the optically active
poly(HPMA). Normally, dissolution-precipitation behaviors of many LCST polymers
exhibit reversible changes at the same transition temperatures without showing any
hysterisis and this paper is the first case to report on the hysterisis of LCST polymers
1t is very interesting to find that the LCST shifted toward much lower temperatures than
racemic poly(HPMA) and that a strong hydterisis of the LCST behaviors was observed
for the optically active poly(HPMA). Presumably, the hydroxyl group in poly(HPMA)
might form a strong hydrogen- bonding in these optically active poly(PHMA), resulting
in crystalline forms when they precipitate out of the aqueous solutions. Further
research will be carried out in terms of the LCST behaviors and optical resolution by
using poly(HPMA).
CONCLUSION
A novel method of optical resolution was attained by using temperature-responsive
polymers having chiral groups. Optically active copolymers derived from IBAAm and
IPPAm could strongly adsorb one side of optical isomers of amino acids in aqueopus
solutions and they precipitated out of the aqueous solution, remaining other side of optical
isomers in the aqueous solution. Optically active poly(HPMA) exhibited an interesting
LCST behaviors in terms of hysterisis. The optical resolution by using the temperture-
responsive polymers Iead to a !arge scale industrial seperation of optical isomers.
References
1) Y.H.Bae, T.Okano, R.Hsu, and S.W.Kim, Makromol. C.fJem.,Rap. Comm.,

8,481(1989)
2) G.H.Chen and A.S.Hoffman, J. Biomater. Sei. , Polym. Ed., 6, 585(1994)
566
BIODEGRADATION AND MEDICAL APPLICATION OF CHITOSAN HARD
CAPSULE
Tsutomu Suzuki\ Takayuki Matsumoto 1, Yoshinori Hagino 1, Hideyuki

Tozaki2, Akira Yamamoto 2, and Shouzou Muranishi2
1Aicello Chemical Co., Ltd., Toyohashi, Aichi, JAPAN, 441-11

2Department of Biophamaceutics, Kyoto Pharmaceutical University , Kyoto,
607, JAPAN
INTRODUCTION
Chitin is a long chain polymer ofN-acetylglucosamine linked by -1, 4 bond, found in

exoskeletons of ernstaceans and in the cell wall of fungi and insects. Chitin is called the
second biggest biomass next to cellulose on the earth.
Chitosan, a deacetylation product of chitin, is a functional and basic polysaccaride
composed -1, 4 liked glucosamine and has very good solubility in acidic aqueous solution.
Chitosan also has some special properties like nontoxicity, biodegradability, biocompatibility
and anti-microbial activity. Therefore, it is expected that its application fields could be much
wider in near future.
In Japan, total consumption of Chitosan amounts 800 ton in 1994. The major use is
coagulating agent of waste water treatment. Now a day, uses for healthy foods and anti-
bacterial agent for foods preservation are more and more growing up. Another use for
medical application is a wound healing cloth developed by Unitica co., Ltd. in Japan.
Due to the low activity of protease in colon, interest in the targeting of peptide drags to
the colon has increased recently. Peptide hormones such as insulin and calcitonin are water
soluble high molecular compounds which are decomposed easily by low pH gastric juice and
proteases found in small intestine, Therefore these peptide drags are only currently
administered intravenously.
For this study, we prepared several size of Chitosan hard capsules and examined
effectiveness of Chitosan hard capsule to colon-specific delivery system.
Preparation of Chitos an Hard Capsule
Several size of Chitosan hard capsules for beagle dog, rat and human were prepared.

After encapsulating the contents, enteric coating were carried out. The chitosan being used
for this purpose is limited to the chitosan, its viscosity at 20"C of 0.5% solution in an
aqueous 1% acetic acid is 20-50 cps and its degree of deacetylation is 80-85 mole%
preferably. To promote a dissociation of chitosan hard capsules in the colon, starch and
cellulose powder are added to chitosan as a fillers.
In vivo Oral Administration Experiment to Beagle Dogs
Test capsules containing BaS04 granules and coated with a polymer soluble in the
small intestine were orally administered to six beagle dogs. Subsequently, the point of
capsules disintegration in the dogs' body was detected by means of X-ray photograph.
The oral administrations were carried out under feeding and fasting conditions.
In vivo Oral Administration Experiments to Male Wister Rats
The chitosan capsules contain insulin with or without sodium glycocholate (9.8 mg) as
absorption enhancers. These capsules were 3.5 X 1.6 mm and 1.2-1.5 mg, respectively. The
surface of these capsules was coated with hydroxypropyl mehtylcellulose phthalate-4 and
rosephthalate as enteric coating materials. Colon-specific delivery of insulin after oral
administration was investigated using chitosan capsules. Male Wistar rats, 200-270 g, were
fasted for 8 hours before experiments, and the capsules were orally administered with
polyethylene tubing under light ether anesthesia. The gastrointestinal transit of chitosan
capsules was examined by counting the number ofthese capsules afteroral administration to
rats. The colonic absorption of insulin was estimated by its hypoglycemic effect. Blood
samples were periodically collected and were centrifuged at 10,00 rpm for 5 min and plasma
were determined by glucose oxidase method.
In vivo Oral Administration Experiments to Adult Males
Test capsules containing salicylamide (addreviated as SA) and gelatin capsules

containing riboflavin ( addreviated as VB 2) as controls were prepared and coated with an
enteric coating agent. The two kinds of capsules were simultaneously administered orally
to thirty-one year old adult males. Urine samples were taken at regular time intervals.
Also, quantitative analysis of SA and VB 2 from the urine was carried out by means of
colorimetric method and lumiflavin fluorescence analysis, respectively.
RESULT AND CONCLUTION
In vivo Oral Administration Experiment to Beagle Dogs
Disintegration of the capsules were observed by X-ray photograph. All of the

capsules disintegrated only in the large intestine under both feeding and fasting
conditions (Table 1).
In vivo Oral Administration Experiments to Male Wister Rats
The effectiveness of the chitosan capsules to the colon specific delivery of insulin was
investigated by an in vivo absorption experiments. Figurel. shows the pharmacological
availability (P.A.. %) of 20 IU insulin with various additives after oral administration of
chitosan capsules. We found no hypoglycemic effect afteroral administration of20 IU insulin
568
Table I. Intestinal dissociation of the chitosan hard capsule on a oral administration to
beagle dogs.
No. f t 1 ~ 10 (hr)
1
small intestinal
--tr ---- -f
large intestinal
E-<
Cl)
< 2 --iii- dissolution
3
- iii
-.
4
-- --i - ---ii-
6
___ f ___ tf
No. t
1 -ifi
~ 1---2--1 -ih
3
------ ---
i
- ------
i
- - - ---i
4 fif
6 - -fif
569
Gclatin Cap ules
(Insulin 201U)
Chitosan Cap ule

(Insulin 201U)
Gclatin Capsules
(lnsuhn 201U. a-GC 9.8mg)
Chitosan Cap ule

(Insulin 201U, Na-Ge 9 .8mg)
0 2 3 4
P.A. %
Results arc express as mcan - S. E. of 5expcriments.
Figure l . Pharmacological availability (P. A. %) of insulin after oral administration of

various capsules.
solution. However, a significant hypoglycemic effect and plasma insulin Ievel were observed
after oral administration of chitosan capsules containing insulin, as compared with the gelatin
hard capsule. The P.A. % of insulin was further improved following oral administration of
this capsules containing 20 IU insulin with sodium glycocholate (9.8 mg).
In vivo Oral Administration Experiments to Adult Males
The maximum urinary rates (T max) of SA and VB 2 were 13 hours and 3 hours,
respectively (Figure 2). The time delay (more than 10 hours) ofTmax in the case of SA
was due to property of the test hard capsules themselves. The capsules used throughout
.-..
.... Chitosan capsule 20 '1:'
~
E10 ~
'-'
4) -3
s:: 4)
r:: s::
::1
15 '
.5
4) .5
"0 s::
' ;;::
CIS CIS
>-
tJ 10..8
I+:
~ 5 r::
......
"'
...... 0
!s::
0
~
...
CIS
5
- =
s:: 0
.2 e
~><
tJ
><
~
tLI
0
5 10 15 20
Time course after the administration (hr)
Figure 2. Urinary rates (Tmax) of SA and VB Phannacological availability (P. A. %) of insulin after oral
administration of various capsules.
570
this work did not dissolve in alkaline solution; the capsules were also not affected by
trypsin (a protease having high activity). Moreover, in the oral administration test on
beagle dogs, the capsules disintegrated only in the large intestine und er both feeding and
fasting conditions. From the results described above, the time delax of Tmax in the case of
SA administration to humankind strongly suggests a possibility that the chitosan oral
capsules disintegrated in the large intestine.
CONCLUSION
It was demonstrated that chitosan hard capsules with an enteric coating can be
transferred to the large intestine by oral administration and release their contents in
the large intestine. Thus, this capsule may be a useful carrier for colon-specific delivery
of peptide including insulin.
REFERENCES
1. M. J. Moore, et. al.; Int. J. Pharm. 34, 35-432 (1986).

2. S. Murray, et . al.; Science 233, 1081-1084.
3. T. Fujii and A. Terabe; Chem. Ind. 42, 811-819 (1991).
4. A. Yamamoto and S. Muranishi: Bio!. Pharm. Bull. 18, 929-931 (1995).
5. A. Terabe, and T. Suzuki: Proc. Int. Symp. Control. Rel. Bioact. Mater. 22,244-245
(1995).
6. A. Yamamoto and S. Muranishi: Proc. Int. Symp. Contro!. Re!. Bioact. Mater. 22,498-
299 (1995).
7. A. Yamamoto, S. Muranishi, A. Terabe, and T. Suzuki: Proc. Int. Symp. Contro!. Re!.
Bioact. Mater. 23,551-552 (1996).
571
DEGRADATION STUDIES OF ACTIVATED POLYEmYLENE
IN POLYETHYLENE-STARCH POLYBLENDS
N. M Surdia, E. Noorlaila, E. Rohaeti, Kushardianti, and M. Zaenuddin
Chemistry Department
Institute ofTechnology Bandung
n. Ganesha 10, Bandung 40132
Indonesia
ABSTRACT
Activation of the polyethylene prior to polyblending has been carried out by UV

irradiation, activation using strong acids, and by addition of a Ce4+ salt as
photosensitizer.
Ultraviolet irradiation was carried out at A, = 254 nm with variation of exposure
time. The blend was made with a composition of PE : starch = 2 : 1 with a cationic
surfactant as compatibilizer.
Characterization was done by FTIR analysis, tensile strength, intrinsic viscosity of
modified PE and PE after hydrolysis ofthe blend, swelling and SEM.
From the three methods examined, activation using Ce4+ salt as photosensitizer,
after 15 days of exposure towards UV light, seems to be the most effective one. So
activation of polyethylene seems to be able to promote photo- and bio-degradation of
polyethylene-starch polyblends.
Keywords: degradation, polyblend, polyethylene, starch.
INTRODUCTION
Polyethylene is very much used as packaging material. Since it is an inert polymer,

much effort has been made to modify polyethylene, e.g. by blending with starch and a
surfactant as additive to obtain a photo- and biodegradable blendl
Previous research2' 3 in this field revealed that by using a surfactant as additive and
applying a micro-organism, biodegraded primarily the starch and attacked only a small
part ofthe polyethylene.
It seems that degradation of PE-starch polyblends depends on the degradation
performance of polyethylene. So three individual methods of PE activation's prior to

Edited by P. N. Pfasad et al., Plenum Press, New York, 1998 573
polyblending have been carried out, i.e. (i) UV irradiation at A. = 254 nm; (ii) soaking in
an acid mixture of chromic- and sulphuric acid; (iii) addition of a Ce4+ complex as
photosensitizer and UV irradiation.
PE-starch polyblends were rnade: (i) with the UV irradiated polyethylene and (ii)
with the acid activated polyethylene.
Ultraviolet irradiation of polyethylene, either in pure PE or in polyblends, shows
first an increase in molecular weight and physical properties until a certain time, and a
decrease in properties afterwards. So photo- and biodegradation ofPE-starch polyblends
depends on the environmental influences, i. e. type of irradiation and additives used, on
polyethylene.
THEORETICAL BACKGROUND
Polyblend
A polyblend is a physical mixture of two polymers or more. The two polymers can
be of different structure, amorphous and semicrystalline, or it can be of different origin,
natural and synthetic. The interaction among the particles can be hydrogen bonding,
dipole-dipole interaction, or van der Waals forces. The roJe of additives in polyblends is
to induce the interaction among the particles or to strengthen the bonding through
covalent bonding or cross-linking.
Polymer Degradation
Degradation of polymers is a process which occurs with rupture of the main chain
backhone or the side group bonds. Two types of degradation are known, that is "random
degradation" which is characterized by rupture of the main-chain links, and
"depolymerization process" which is the reverse ofthe polymerisation process4 .
Both types of degradation may occur if the polymer is affected by heat (thermal
degradation), light (photodegradation), high energy radiation (radioactive degradation),
mechanical factors (mechanodegradation), chemical agents (chemical degradation),
enzymes, bacteria, fungi (biodegradationi. Random degradation has a tendency to
degrade randomly and/or cross-link.
As the temperature is increased, the scission probability for all kinds of bonds
increases. The presence of oxygen and impurities or ions can give rise to the initiation of
new chain reactions and thus to rapid deterioration of the polymer.
hv
(I)
R + 02 (2)
R02 +RH ROOH + R (3)
ROOH +hv RO + OH (4)
This peroxide group is considered as an impurity. It can be formed at elevated

temperatures in the presence of oxygen.
The addition of a photosensitizer will promote the formation of radicals by energy
transfer:
574
S* + p S + P* (5)
Or, it may cause hydrogen abstraction from a polymer:
S* + PH HS + P (6)
S* =additive; P = macro-molecule; P*, P = free radical
The radicals produced might attack the polymer6 .

Addition of a mixture of acids (Cr03 + H2S04) as oxidizing agent causes a
homolytic chain scission of the hydrocarbon. The radicals formed will be trapperl in the
solvent. A recombination of radical and Cr(VI) will occur in the cage forming a Cr(VI)
ester. This ester will then be hydrolysed forming an alcohol. Another possibility is the
formation of a carbocation which react with water to form an alcohol or elimination of
proton to form olefin7 .
EXPERIMENTS
Three main experiments were carried out, i.e. UV irradiation of polyethylene,

soaking ofpolyethylene film in a strong acid mixture, and polyethylene activation by Ce4+
as photosensitizer. These experiments were carried out prior to polyblending.
UV Irradiation. LLDPE was exposed to UV irradiation at A. = 254 nm and its

intrinsic viscosity was determined as function of time (10, 15 and 20 days). Exposed
LLDPE at its optimum condition was blended with com-starch and a cationic surfactant,
with a composition ofPE: starch = 2 : 1. This blend was characterized and compared to
a reference blend of unexposed polyethylene with the same composition. After that
biodegradation was carried out with variation of time (10, 20 and 30 days) using
Aspergillus Niger L-51, and then characterized again.
Soaking in Strong Acid Mixture. Three types of polyethylene films were made,
i.e. HDPE, LDPE and LLDPE. These films were made and soaked in a mixture of Cr03 :
H 20: H 2S04 = 29: 42: 29D/o with variation oftime (30, 60 and 90 minutes). Thesefilms
were then characterized.
Blends were made of HDPE, com-starch and a cationic surfactant with a
composition ofPE : starch = 2 : 1. One blend with pure HDPE and the other one of acid
activated HDPE. Both polyblends were then exposed to UV irradiation at A. = 254 nm
with variation of exposure time (1 0, 15 and 20 days), and after that characterized.
Activation by Ce4+ Salt as Photoseositizer. Films of LLDPE and Ce4+ salt with
variation of salt concentration (2, 4, 6, and 8 mmole/lOOg). Part of these films were
irradiated at A. = 254 nm with variation of exposure time (5, 10, 15 and 30 days).
Characterization ofthe irradiated and non-irradiated samples were done.
All the samples made in the above mentioned experiments were characterized by
FTIR analysis for structure, tensile strength, degree of swelling, intrinsic viscosities of
modified polyethylene and PE after hydrolysis of polyblend, and some SEM
photographs.
575
Tablel.lntrinsic viscosity ofLLDPE as function ofexposure time
Exposure time (days) lntrinsic viscosity (Poise)
0 I70
IO 280
I5 80
20 90
UV Irradiation Prior to Polybiending
The influence of photodegradation on pure LLDPE can be seen from Table I.

Crosslinking occur at the early stage of irradiation, but after I 5 days a sharp decrease in
intrinsic viscosity is obtained due to chain scission ofthe polymer.
The best composition of LLDPE-starch obtained from tensile strength
measurements was LLDPE : starch = 2 : 1. UV-irradiated LLDPE prior to blending used
in polyblend showed a higher tensile strength (1.039 kgf/mm2) in comparison to pure
LLDPE-starch polyblend (0.804 kgf7mm2) This phenomena is probably due to a higher
crosslinking possibility of the irradiated LLDPE towards starch, which is supported too
by the degree ofswelling ofpolyblends (LLDPE-pure = 25.4%, LLDPE-UV = 24.I%).
Polybiending did not change the FTIR spectra, also crosslinking could not be detected.
Biodegradation after 30 days using Aspergillus niger did not change the average
molecular weight of LLDPE after hydrolysis of the polyblend. So biodegradation
influences only the starch part ofthe polyblend and pulverises the LLDPE.
Soaking of Polyethylene in Acid Mixture
Infra-red spectra using the Reflection Absorption Spectroscopy (RAS) technique on

LLDPE revealed that additional peaks were formed due to the formation of C=O group
at I720 cm 1 and a conjugated C=C bond at I631,7 cm 1 Sodegradation ofPE occurred
due to acid oxidation.
Following the influence of oxidationtime on PE showed that tensile strength and
molecular weight decreased with time of oxidation (Table 2).
The optimum oxidation time was 60 minutes.
Table 2. Influence of oxidation time on LLDPE
No. of Oxidation Tensile strength lntrinsic

sample time (rnin.) (%) viscosity Mv
0 42.80 I3,5I7
2 4.22 42.34 I2,538
3 30 4.4I 40.82 I2,764
4 60 4.62 36.60 ll,I86
5 90 5.59 26.59 7,599
576
Table 3. Influence ofUV irradiationtime on IIDPE-starch blend
TimeofUV Melting point Degree of swelling

irradiation eq (%) Mv
da s
0 133.2 1.97 38,264

10 130.0 4.44 33,090
20 133.3 1.21 37,264
Acid soaked IIDPE - starch polyblend irradiated at '). . = 254 nm showed a decrease
in molecular weight and an increase in the degree of swelling after 10 days exposure
(Table 3).
This fact is due to chain scission, however after that crosslinking seems to take
place again.
FTIR analyses showed a shift of C=C stretch band and of C=O stretch band.
So acid oxidation of polyethylene prior to blending can promote degradation of the
polyblend. Some SEM photographs are shown as additional evidence of the degradation
process in Figure 1 and 2.
Addition of Ce4+ salt as Photosensitizer
FTIR spectra of samples containing Ce4+ salt did not change the position of peaks,
but on Iongerirradiation a C=O group band appeared at 1725 cmI From the Absorbance
Ratio (AR) of exposed to non-exposed sarnple, an optimum exposure time of 15 days
was obtained (Table 4). Supporting data were the tensile strength and the degree of
crystallinity.
The influence of Ce4 + complex concentration had been characterized by the Absorbance
Ratio, tensile strength and the degree of crystallinity (Table 5).
The optimum concentration of Ce4+ complex salt was 4 mmole/IOOg LLDPE. A strong
decrease in tensile strength and the degree of crystallinity shows that activation using a
photosensitizer promotes the degradation of polyblend.
(a) without oxidation (b) with acid oxidation
Figure 1. LLDPE film surfaces (lOOOx)
577
(a) Pure HDPE before UV (b) Pure HDPE after UV
(c) Activated HDPE before UV (d) Activated HDPE after UV
Figure 2. Polyblend ofHDPE- Starch (2 : I) (500x)
Table 4. Exposure time ofLLDPE with Ce4 salt
Length of Absorbance Ratio Tensile Strength Degree of

irradiation (AR) (rnPa) Crystallinity
(days) (%)
0 1.00 2.77 58.38

5 1.10 2.52 58.35
10 1.75 1.82 58.28
15 2.20 1.45 55.94
30 2.26 1.36 47.36
CONCLUSIONS
Polyethylene is a polymer very much used as packaging material, but is an inert

material. In order to obtain a photo- and biodegradable material, polyethylene has been
modified and blended with starch.
578
Table 5. Intluence ofCe4+ complex as photosensitizer
Ce4+ complex Absorbance Tensile Strength Degree of

concentration Ratio (AR) (mPa) crystallinity (%)
(mmole/1 OOg
LLDPE) (a) (b) (a) (b)
0 1.00 3.48 3.45 58.38 57.61

0.5 1.25 3.46 3.39 58.35 55.25
2 1.69 3.43 3.33 58.32 51.70
4 2.20 3.30 1.63 58.28 42.62
6 2.03 2.77 1.45 55.94 40.14
8 2.06 1.83 1.49 47.36 37.52
(a) = without irradiation

(b) = with irradiation for 15 days.
Three main experiments have been carried out, i.e. (i) UV irradiation ofPE prior to
blending; (ii) activation ofPE by using strong acids, and (iii) by addition of a Ce4+ salt as
photosensitizer.
The results showed that UV irradiation of PE increased the molecular weight, but
later on a decrease occurred after 15 days exposure time.
Activation of the polymer by acid oxidation (Cr03 + H20 + H2 S0 4) showed a
decrease in molecular weight, which means photodegradation is possible. The optimum
condition was soaking in acid for 60 minutes.
Activation using a Ce4 + salt as photosensitizer seems tobe more effective than the
other two methods. The optimum condition was 15 days exposures towards UV lights at
A. = 254-300 nm.
Characterization was done by FTIR, tensile strength, intrinsic viscosity, molecular
weight, degree swelling and SEM
So activation of PE seems to be able to promote photo- and biodegradation of PE-
starch polyblends.
REFERENCES
1. Goheen, S.M. and Wool, R.P., Degradation ofPolyethylene- Starch in Soil, J. of Appl. Polym. Sei.,
42:2691-2701 (1991).
2. Rachmayeni, The Injluence ofSurfactant as Additive in Polyethylene - Starch Blend, Thesis,
Chemistry Dept., ITB, Bandung, Indonesia (1993).
3. Cherernisinoff, N.P. (ed.), Handbook ofPolymer Science and Technology, Mareeil Dekker, lncs.,
N.Y. (1989).
4. Rabek, J.F., Experimental Methods in Polymers Chemistry, John Wiles & Sons, Chichester, N.Y.
(1980).
5. Schnabel, W., Polymer Degradation, Princip/es and Parfiele App/ications, Macmillan Publ. Co.,
Inc., N.Y. (1981).
6. Akio Negishi, Yoshitaka Ogiwara, Zenzijo Osawa, Photodegradation ofPP in the Presence ofFerric
Chloride, J. of Appl. Polym. Sei., 22:2953-2963 (1978).
7. Koichiro Kato, lnvestigation ofHDPE Film Surface Treated with Chromic Acid Mixture by Use of
2,4-Dinitropheny/hydrazine, J. of Appl.Polym.Sci.,20:2451(1976).
8. Cainelli, G. and Cardillo, G., Chromium Oxidations in Organic Chemistry, Springer-Verlag, Berlin
(1984).
579
WAVELENGTH SENSITIVITY IN TUE PHOTO-
DEGRADATION OF POLYMETHYL
METHACRYLATE:ACCELERATED
DEGRADATION AND GELFORMATION
Ayak:o Torikai
Department of Applied Chemistry

School ofEngineering, Nagoya University
Nagoya 464-01 Japan
INTRODUCTION
We have been investigating the wavelength effect on polymer degradation using

Okazak:i Large Spectrograph(OLS) which was built at the National Institute for Basic
Biology in Okazak:i Japan. Such studies contribute to identify the spectral region which
causes darnage on polymer materials. Polymethylmethacrylate(PMMA) is known to be
a degradation type polymer to photoirradiation. On irradiating PMMA at ambient
temperature in the presence of oxygen, the threshold wavelength of main-chain scission in
PMMA was found to be below 320 nm in our previous study 1. If we introduce some
chromophore having the absorption at Ionger wavelength than 320 nm, the threshold
wavelength of main-chain scission of PMMA would shift to the Ionger wavelength.
This means that photodegradation of PMMA is easily tak:e place in the wavelength region
of the terrestrial sunlight. Benzophenone(BP) and -carotene have one of their
absorption maxima at around 340 nm and 450 nm, respectively. So, in photoirradiation
of PMMA films containing BP or -carotene with radiation of Iongar wavelength than
320 nm, we can expect the accelerated degradation of PMMA under the terrestrial sunlight.
Under these considerations, we have investigated the wavelength sensitivity in the
photodegradation ofPMMA containing BP or -carotene.
EXPERIMENTAL
PMMA and PMMA containing BP or -carotene films were cast from acetone
solutions. Details of film peparation and purification of PMMA is already reported in
Science and Technology of Polymers and Advanced Materi/s

Edited by P. N. Prasad et al., Plenum Press, N ew Y ork, 1998 581
our previous papers 1 2. The film thickness were 0.01 to 0.05 mm. Irradiations of
monochromatic radiation were carried out in air at 23 c using Okazaki Large
Spectrograph(OLS). The details of equipmene and irradiation procedure4 have already
been described previously. The light intensity at each sample position was measured
by a Riken HK-I photon density meter. UV and FTIR spectra of photoirradiated
samples were taken on a Hitachi model 323 and a Jasco V-550 UV-Visible
spectrophotometer, and a Jasco 5300 FTIR spectrophotometer. Changes in average
molecular weight was followed by Gel Permeation Chromatography(GPC) measurement
using a Jasco PU-980 liquid chromatograph equipped with a 830 RI detector and a set of
Shodex STANDARDS P-82GPC columns. Polystyrene standards were used for
calibration. Tetrahydrofuran(THF) was used as a solvent and an eluent.
PMMA-BP System
On irradiation of PMMA containing BP with monochromatic radiation from OLS,
the optical density around 280 nm decreases with the increase of the exposure time.
3.0
(a)
2.4
J-'1 ,,"
II
Q)
u
c:
CU
.0
1.8
I..
0
II)
.0 1.2
c(
0.6
0
1800 1600 1400 1200 1000
Wavenumber(cm- 1 )
0.10,---------------------------.
Q)
u
c:
CU
.0
I..
0
II)
.0
c(
-o.so~~~~~~~~~~~~~~
1800 1600 1400 1200 1000
Wavenumber(cm-1)
Fig. l. FTIRspectra ofphotoirradiated PMMA containing 1.0 mol% ofBP. (a): (--------) Unirradiated;
(----) Irradiated to 3.7X 10 19photonslcm2 (b): Difference spectrwn showing disappeared fraction
by photoirradiatiion. Irradiation wavelength, 280 nm. (From Ref 6, with pennission)
582
Since such a decrease was not found in case of the photoirradiated PMMA with no
additive, the decrease in the optical density at 280 nm(- !::J. OD2so ) may be attributed to
the consumption of BP in PMMA. - !::J. OD2so plotted against the irradiation wavelength
and it was found the decreasing behavior in the intensity at 280 nm with respect to the
irradiation wavelength parallels the absorption spectrum of BP in the 320-400 nm region.
A typical FTIR spectra of photoirradiated BP-PMMA film and the difference FTIR
spectrum between unirradiated and irradiated BP-PMMA are given in Fig. I.
The decrease in intensities in l700cm- 1( v c=o) and 1100 cm- 1( v c-o-c) regions were found.
These decreases are responsible for the consumption ofPMMA. The band at 1660 cm- 1
disappeared by photoirradiation may be atributed to v c=o arising from BP.
The insoluble fraction in THF was produced in photoirradiated BP-PMMA with the
irradiation of 260-360 nm radiation. After fittering out the insoluble fraction, the
number average molecular weight(Mn) was measured by GPC. Number of main-chain
scission (Cs, Mn0/Mn - 1) were plotted against the irradiation wavelength in Fig. 2.
In PMMA with no additive, main-chain scission takes place with the irradiation of 260,
280 and 300 nm radiation. Cs is zero when the irradiations are carried out with the
radiation Ionger wavelength than 320nm. On addition of BP to PMMA, the degradation
of PMMA is accelerated and this acceleration is dependent on additive concentration as
shown in Fig. 2. The main-chain scission of PMMA containing BP takes place most
efficiently with the irradiation of 340 nm radiation. Cs versus irradiation wavelength
curve paralleles the absorption spectrum ofBP in the 320-400 nm region.
PMMA containing BP which had been photoirradiated at various wavelengths were
extracted with THF and the insoluble fraction in THF was dried in vacuum for 24hr.
Gel content{ (%) = W!Wo x 100} thus obtained is plotted against the irradiation
260 280 300 320 340 360 380

Irradiation Wavelength ( nm)
Fig. 2. Changes in the number of main-chain acission of photoirradiated BP-PMMA with irradiation
wavelength. Concentration ofBP: (e) 0 mol %; (0) 0.3 mol %; (LI.) 0.5 mol %; (A.) 1.0 mol%
(From Ref. 6, with permission)
583
100
80
...c:
riP
~
...c:
GI
60
0
u
Q)
40
l)
20
260 280 300 320 340 360 380

Irradiation Wavelength(nm)
Fig. 3. Changes in the gel content of BP-PMMA photoirradiated at various wavelengths. Concentration
ofBP: (O) 0.1 mol %; (e) 0.3 mol% (FromRef. 6, withpermission)
wavelength in Fig. 3. The fonnation of gel with respect to the irradiation wavelength
also paralleles the absorption spectrum of BP and gel content increases with the increase
of BP concentration in PMMA. No gel fonnation was observed when the samples were
irradiated with the radiation ofwavelength Ionger than 380nm.
BP is a weil known sensitizer in photochemical reactions. In BP-PMMA system,
BP absorbs photon energy to fonn a singlet excited state. The singlet excited state
transfonns to fonn triplet excited state of BP by internal conversion. Quantum yield of
this conversion was reported tobe 0.995 The triplet excited BP abstractshydrogen ftom
PMMA and leaves polymer on chain radical and ketyl radical. Oxygen attack to
polymer on chain radical produces peroxy radical. The produced peroxy radical
abstracts hydrogen ftom PMMA and leaves polymer on chain radical and hydroperoxide.
Hydroperoxide thus fonned Ieads to the main-chain scission of PMMA. While for the
crosslinking, recombination reaction between two polymer on chain radicals may play a
role to produce gel in photoirradiated BP-PMMA..
The details of the accelerated degradation and crosslinking reaction mechanism have
already been reported in our previous paper6
PMMA -Carotene System
The unirradiated -carotene-PMMA film has strong absorption bands at Ionger
wavelength than 320nm which is the threshold wavelength of main-chain scission of
PMMA. The intensities of these bands decrease with the irradiation of radiation Ionger
wavelength than 320nm. At the same time, intensity at around 260 nm also decreases
with the irradiation. The decrease in the intensity of this band(represented as the
relative intensity) was used as a measure of the degradation of PMMA. For PMMA
without additive the threshold wavelength was found to be 320nm. By adding -
584
carotene to PMMA the relative intensity at each wavelength decreased and the threshold
wavelength of PMMA degradation shifted to the Ionger wavelength. The decrease in
relative intensity is dependent on the concentration of -carotene in PMMA. It is clear
that accelerated photodegradation of PMMA by -carotene tak:es place in this case.
Main-ehain scission of PMMA is directly estimated by GPC measurement.
Changes in the weight average molecular weight which is shown by the molecular weight
ratio of the irradiated to the unirradiated(Mw/Mw0) was plotted against the irradiation
wavelength. By the addition of -carotene to PMMA, the threshold wavelength of
main-chain scission shifts to the Ionger wavelength than 320nm and found to be around
400nm. Gel formation was not found for the photoirradiated PMMA containing -
carotene. In any case, the accelerated degradation by -carotene at the irradiation
wavelength below 320 nm and at Ionger wavelengths than 320 nm is clearly observed in
the samples. Although the reaction mechanism of accelerated photodegradation of
PMMA by the addition of -carotene has not been fully elucidated, it is evident that -
carotene plays an important role in the accelerated photodegradation ofPMMA7.
CONCLUSIONS
1. Accelerated main-chain scission of PMMA by BP or -carotene was confirmed by

molecular weight changes in photoirradiated PMMA at various wavelengths. The
threshold wavelengths for main-chain scission in additive containing PMMA were found
to be 380 nm for BP-PMMA and 400 nm for -carotene-PMMA.
2. Photosensitized crosslinking of PMMA by BP was also observed. The threshold
wavelength oftbis reaction was also found tobe 380 nm.
3. The reaction mechanism of accelerated main-chain scission and crosslinking was
proposed for BP-PMMA system.
4. The experimental results show that the accelerated photodegradation of PMMA by BP
or -carotene is able to tak:e place under the terrestrial sunlight.
ACKNOWLEDGEMENT
The author would appreciate her co-workers whose names appear in the cited
references for their contribution to this work. The author also wishes to thank
Prof. Masak:atsu Watanabe and Mr. Mamoru Kubota of the National Institute for Basic
Biology for their advice and help in carrying out the exposure experiments.
REFERENCES
1. A.Torikai, M. Ohno and K. Fueki, Photodegradation ofpolymethylmethacrylate by

monochromatic light, J. Appl. Polym. Sei., 41:1023(1990).
2. T. Mitsuoka, A. Torikai and K. Fueki, Wavelength sensitivity ofthe photodegradation
ofpolymethylmethacrylate, J. Appl. Polym. Sei., 47:1027(1993).
585
3. M. Watanabe, M. Furuya, Y. Miyoshi, Y. Inoue, I. Iwahashi and K. Matsumoto,
Design and perfonnance ofthe Okazaki Large Spectrograph for photobiological
research, Photoehem. Photobiol., 36:491(1982).
4. A. Torikai, H. Kato, K. Fueki, Y. Suzuki, F. Okisaki and H. Nagata, Photodegradation
ofpolymer materials containing flame-cut agents. J. Appl. Polym. Sei.,
50:2185(1993).
5. W. Schnabel, Polymer Degradation, Hanser, Mnchen, (1981) p.343.
6. A. Torikai, T. Hattori and T. Eguchi, Wavelength effect on the photoinduced reaction
ofpolymethylmethacrylate, J. Polym. Sei. A: Polym. Chem., 33:1867(1995).
7. A. Torikai and H. Hasegawa, Wavelength etfect on the accelerated photodegradation
ofpolymethylmethacrylate, Polym. Degradn. Stab., submitted
586
PHOTOOXIDATION OF POLYPBASIC ETHYLENE-PROPYLENE POLYMERS
Jean-Luc Gardette and Patrick Delprat
Laboratoire de Photochimie Moleculaire et Macromoleculaire

UMR CNRS 6505, Universite Blaise Pascal (Clermont-Fd)
F-63177 Aubiere Cedex, France
ABSTRACT
The oxidation photoproducts resulting from the UV irradiation of a polyphasic polymer

P-EIEPR in conditions of artificial accelerated exposure have been identified by different
analytical methods. These methods included FTIR analysis of the polymeric matrix coupled
with derivatization reactions. The identification of the low molecular weight photoproducts
was carried out by chromatography and mass spectroscopy analysis. It was shown that the
oxidation photoproducts were those of the polypropylene phase, which is by far the most
oxidizable. Moreover our results showed unambiguously that the formation of the
photoproducts was resulting from the oxidation of the tertiary carbon atom, which is
consistent with the expected reactivities.
INTRODUCTION
Oxidation ofpolypropylene initiated photochemically, thermally or radiochemically, has

been studied for many years by several research groups, and the mechanisms by which
oxidation occurs can be considered as fairly weil understood 1 ~.
The present paper reports the photooxidative behaviour of a polyphasic ethylene-
propylene copolymer on the basis of identifications of the different products formed.
Polyphasic polypropylenes, consisting of blends of isotactic PP as major constituent and EPR
nodules, have been recently developed and become increasingly important in practical
applications.
Analysis of the oxidative evolution was based on FTIR analysis of the photooxidized
polymeric matrix. FTIR spectrometry permitted the identification of the photoproducts linked
to the macromolelcular chains or trapperl within the polymeric matrix. This analysis has been
completed by a mass spectroscopic analysis of the gaz phase in order to identify the low
molecular weight products that can migrate out of the polymeric matrix7 . The distribution of
the oxidation photoproducts within the matrix was characterized by microFTIR analysis of
the irradiated polymer8 .
Science and Technology of Polymers and Advanced MOlerials

EXPERIMENTAL
Polymer samples were obtained from the research center G. Natta of Himont (ltaly).
The polymer was a direct reaction polyphasic copolymer P-EIEPR containing 15% of
ethylene. The composition ofthe elastomer partwas 500/o propylene and 50% ethylene9 .
Irradiations were carried out in a SEPAP 12-24 (MPC-Paris) device that allows
medium-accelerated photoageing 10 . This device has been specially designed for studies of
photoageing in medium accelerated conditions. lt is equipped with four medium-pressure
mercury lamps emitting from 300 nm. The samples are irradiated on a rotating support
located at the centre ofthe chamber. The surface temperature ofthe samples is measured by a
platinum sensor in flat form applied to a reference sample. The chamber is designed to
operate with a test temperature between 50 and 80C.
Sampies were irradiated in the form of films prepared by pressing polymer (granules)
into films 100 Jlm thick at 200C for 1 min. Polymer plaques 3 mm thick prepared by
injection at 230C were also irradiated.
Fourier transform IR (FTIR) spectra were recorded with a Nicolet 800 spectrometer,
equipped with a TGS detector (64 scan summations at a minimal resolution of 2 cm-1).
Determination of the oxidation proflies was based on a method consisting in analysing a
microtomed shaving of a photooxidized sample in a plane perpendicular to the axis of
irradiationu. The spectra of narrow areas (around 10 microns in width) were successively
monitared by moving the sample along the axis of irradiation and the profile of concentration
of the photoproducts was then plotted by analyzing the different spectra obtained. The IR
microscope was a Nicolet Nicplan. A photoacoustic attachment (MTEC 200) was used with
the Nicolet 800 for recording photoacoustic (PAS) spectra ofthe thick plaque. Details on the
experimental procedure have been given previousll.
Analysis of the volatile photoproducts was carried out as follows : a polymer sample
with a surface of 30 cm2 and a thickness of 100 Jlm was irradiated. The gas phase produced in
the irradiation cell was then immersed into liquid nitrogen and after several tens of minutes
the top was opened in order to permit the gases to be pumped into the introduction chamber
of the mass spectrometer. In the following phase of analysis, the cell was progressively
warmed up in order to permit a differentiation between the volatile products following their
temperature of volatilisation. The mass spectra were successively recorded for analysis
carried out at different tempertures ofthe cell.
Photooxidized films were exposed to reactive gas at room temperature in a simple flow
system that could be sealed offto allow the reaction to proceed. SF4 treatmentwas carried
out in an all Teflonsystem because SF4attacks glass. The gases used included SF4 and NH3
FTIR Analysis of the Solid Matrix
The irradiation of a polymer film (thickness 100 Jlm) in the SEPAP 12-24 unit led to
noticeable changes of the IR spectra of the exposed sample. The main changes corresponded
to an increase of absorbance over a broad range. Figure 1 shows these changes in the 1900-
1500 cm- 1 and 3800-3200 cm- 1 regions, corresponding respectively to the domains of C=O
and OH Stretching vibration.
The carbonyl band shown on Figure Ia has a maximum at 1713 cm- 1 and a shoulder at
1780 cm- 1. The formation of hydroxylated photoproducts shown on Figure 1b corresponds to
the increase of a broad band with a maximum near 3400 cm- 1 due to hydrogen-bonded
hydroxylated functions.
588
0.8
0.6
J
...... 0.4
0.2
0.0~----~-----r----~----~~--~-----,----~r---~
1900 1800 1700 1600 1500
Wavenumber(cm-1)
0.6
1B
0.2
3800 3700 3600 3500 3400 3300 3200 3100 3000

Wavenmnber(cm-1)
Figure 1. Evolution of the spectrum of a photooxidized sample (thickness 100 microns) in the domains
1900-1500 cm1 (JA) and 3800-3000 cm1 (IB): (1) initial; (2) 28 hours; (3) 48 hours; (4) 70 hours;
(5) 88 hours; (6) 160 hours.
Application to the oxidized polymeric samples of the chemical derivatization reactions

previously proposed by Carlsson for the identification of oxidation products 12 permitted us to
determine the structure of the acids corresponding to the maximum at 1713 cm 1. The
reaction of SF4 with carboxylic acids Ieads to the formation of acid fluorides 13 . As shown on
Figure 2, SF 4 treatment carried out on photooxidized polypropylene induced the formation of
an absorption band with a maximum at 1841 cm- 1 and the decrease of the maximum at
589
1713 cm- 1. Former results 14 had shown that the band at 1841 cm" 1 indicated the formation ofa
fluorinated derivative from a carboxylic acid with the structure -CH(CH3)-C(O)OH. Residual
absorption after SF4 treatment showed maxima at 1722 cm" 1 (ketones), 1740 cm" 1 (esters) and
1770 cm" 1 (peresters, y-lactones). Exposure ofphotooxidized films to gaseous NH3 confirmed
these attributions.
1.0
0.8
0.4
0.2
0.0~~--.-~--.-~--.--.--.--.--r--r--r--.-,,-.-~
1900 1850 1800 1750 1700 1650 1600 1550 1500
Wavenumber(cm-1)
Figure 2. Effect ofSF4 treatment on a sample (thickness 100 microns) photooxidized for 120 hours:
(1) initial; (2) after irradiation; (3) after SF4 treatment.
Photooxidation of the Fractions
Extraction of the elastomeric ethylene-propylene phase was obtained by treating a

polymer powder prepared by pulverization in retlexing n-heptane. After hot filtration, the
EPR soluble phase was placed on a glass plate and films were obtained by evaporating the
solvent. Polypropylene films were obtained by pressing the insoluble part at 190C.
Comparison ofthe IR spectrum ofthe PP phase to the spectrum ofthe initial copolymer
perrnits us to verity that the main part of the EPR phase has been extracted. The analysis is
based on the comparison of the intensities ofthe band at 720 cm"\ attributed to the y(CH2)
vibrations of methylene groups. Films obtained from the two phases after extraction of the
EPR fraction in boiling n-heptane were irradiated in the SEPAP 12-24 unit. Irradiation of
films from the polypropylene phase led to the development of IR spectra that were similar to
those monitored in the case ofirradiation ofthe heterophasic copolymer.
Mass Spectroscopy Analysis ofthe Volatile Photoproducts
When the cell was maintained at the temperature of liquid nitrogen, three gases were
detected : methane, hydrogen and carbon monoxide. After complete elimination of these
gases by pumping, warming up the cell allowed detection of the appearance of carbon dioxide
590
at a cell temperature around -30C. After co2 had been completely pumped and the cell
warmed up to 0C, three volatile products were detected, identified as methanol, acetic acid
and acetone. Increasing the cell temperature to 20C permitted detection of acetic acid, water
and formic acid. At 60C, acetic and formic acid were still detected.
Table 1 gives the different photoproducts identified by analysis ofboth the solid matrix
and the gas phase.
Table 1. Products formed by photooxidation ofthe polyphasic ethylene-propylene

polymers.
Polymer filrns (IR analysis) Gas phase (MS)
c~ (liquid N2)
?13 ?13 (3400 crn1, reactive with
NOI2, SF4, h IS) H2 (liquid N2)
-cH2-y--rn2-y- CO (liquid N2)
OOH OOH
(3400 crn'1, reactive with c~ (-30C)

N012, SF4) CH3 OH (-30C)
~0
(1713/1755 crn', reactive CH3~ (0C)
r"3,0 OH
-y-c: with SF4)
H OH rn3 ff rn3 <ooq
0
(1760/1770 crn', reactive
withNH3)
HCOOH (20C)
(1780/1770 crn'1, reactive

withNH3)
-rn2-f(-rn3
0
-rn2-ff-rn2-
o
-c-o-
11
(1740 crn1, reactive with
0 NH3)
591
Deconvolution of the spectra
On the basis of the value given in table 1, one can plot a deconvoluted spectrum that
takes into account the different photoproducts identified by chemical analysis. Figure 3 shows
the results obtained in the carbonyl domain (1900-1500 cm" 1). lt is worthy to note the good
fit between the original spectrum and the spectrum rebuilt from the convolution of the bands
corresponding to the different photoproducts.
1.0
0.8
~
-e
0.6
0
rn
~ 0.4
0.2
0.0
1900 1800 1700 1600 1500
Wavenumber(cml)
Figure 3. Deconvoluted spectrum of a polymer film photooxidized for 110 hours(SEPAP 12.24/60C). The
absorption maxima are those determined from the chemical treatments on photooxidized samples.
(1) Spectrum before deconvolution; (2) spectrum rebuilt by convolution ofthe different absorption bands.
Determination of the Oxidation Profiles
The oxidation proflies were determined by measuring the depth dependency of the
absorbance at 1713 cm-1 that corresponds to the formation of carboxylic acids. Figure 4
represents the oxidation proflies monitored by micro-FTIR for both the film and the plaque.
Both the samples were microtomed following the usual method in order to obtain films with a
thickness of 50 j.lffi. This figure gives also the value determined by P AS-FTIR for the first 7
microns near the exposed surface of the plaque corrected to fit a thickness of 50 j.lm. This
thickness corresponds to the thermal diffusion length determined from j.l=(klpCooi12, where oo
is the modulation frequency of the IR beam, k the thermal conductivity of the sample, p the
density and C the specific heat. The results reported on Figure 4 permit the influence of the
thickness on the oxygen-diffusion effect to be evidenced. The thin films which is oxygenated
on both sides presents an homogeneous distribution of the oxidation products. At opposite,
the thick plaque which is oxygenated only on the exposed face, shows an important oxidation
profile, even in the first 50 microns that could be compared directly to the thin film.
Moreover, it has to be noted that the Ievels of oxidation in the first analysed layer, which are
7 microns in PAS-FTIR and approximately 12 microns in micro-FTIR, are in good
accordance.
592
0.6
0.5
-~ 0.4
--
M
! '-
"l;l 0.3
(1)
<.)
~
-0
<"' 0.2
0.1
0.0
0 50 100 150 200 250
Distance from the exposed surface (microns)
Figure 4. Oxidation proflies for samples irradiated for ISO hours (SEPAP 12.24/60C):(A) value determined
by PAS-FI'IR ; (B) profile determined by microFI'IR for a SOmicrons film ; (C) profile determined by
microFI'IR for a 3 mm plaque.
DISCUSSION
Our results indicate that the oxidation occurs mainly in the polypropylene phase. Only a
weak oxidation of the polyethylene cornponent is observed.
Most ofthe primary oxidation photoproducts (hydroperoxides) are tertiary. This result
indicates that initiation of the oxidation involves hydrogen abstraction on the tertiary carbon
atom, followed by addition of oxygen to form a peroxy radical that can abstract an hydrogen
atorn to the polyrneric backhone :
~ ~ <j>O <j>OH
r. + -rn2-y- -+ rH + -rn2-?- ---.. -rn2-y- -+ -rn2-y-
CH3 CH3 CH3 OI3
The hydroperoxides can decompose upon irradiation and Iead to an alkoxy radical
o. ?
- CH2- t (CH3)'- . This radical - CH2- C(CH3)'- can evolve by an hydrogen abstraction
.
pro ducmg .
terttary al co hl
os ?H 3)'-
-rn2-C(Oi or by -sctsston
. . . mvo
react10ns . I"
vmg t he
homolysis ofthe side bond (1) orthat ofthe chain bond (2).
The homolysis ofthe C-C bond (1) gives a methyl radical and a chain ketone:
593
Oxidation of the methyl radical would account for the formation of methane, formic
acid and methanol that are detected by analysis of the gaz phase.
The homolysis of the C-C bond (2) gives a chain-end ketone and a primary alkyl
radical:
9"
-rnz-y- -rnz. + H3c-rr--
rn3 o
The radical so formed can be oxidized to give a primary hydroperoxide that
decomposes to give an aldehyde. Oxidation of the aldehyde Ieads to the formation of an a.-
methylated carboxylic acid :
H
,0
-----. ---- __.
I
-y-~ -+
rn3 H
Another possible route is the induced decomposition of the primary hydroperoxides, as

shown in the case ofpolyethylene 16 :
ROz" } + l l
H-y-ooH ~. y-ooH
R
Oxidation of the primary radical competes with an isomerization by transfer of an
hydrogen atom that gives a more stable tertiary radical. Oxidation of the tertiary radicalleads
to the formation ofacetone, whose formation is detected by analysis ofthe volatile products:
This reaction regenerates the primary radical rn2rn (Qf3)"- that can be involved in a
further reaction producing acetone and acids. Carboxylic structures could be formed from the
acyl groups resulting from Norrish I processes of the intermediate ketone groups that are
obtained by oxidation of the tertiary carbon atom :
CjB3
- y crlz + rr -+ a-methylated acid
H 0
If one considers the kinetic curves corresponding to the formation of ketones and
acids in photooxidized polypropylene, it appears that this is not the main route for acid
formation. The photolysis of the chain-end ketones is, however, the source of production of
acetic acid.
Norrish type II reactions of ketonic groups that would Iead to vinylidenes are not Iikely
to occur significantly since no formation of an unsaturated group is observed.
Once formed, the chain-end a.-methylated acids can be oxidized. As a consequence
of inductive effects, the oxidation of the tertiary carbon adjacent to the carboxylic group is
not favoured. lt is the tertiary carbon in the y-position that reacts, which Ieads to a possible
scission of the backhone and the production of a.-methyl levulinic acid, that can be detected
by a Chromatographieanalysis ofthe solvent after extraction with chloroform5 .
594
f3-scission
These results permit the proposal of the following mechanism, that accounts for the
main routes ofphotooxidation ofpolypropylene (scheme 1).
Scheme 1. Main routes ofphotooxidation ofpolypropylene.
------.
hv, ~
?13
rn3-~-
00H
~ hv, Ll
?13 \
QI3-y+"OH
o \
595
REFERENCES
I. J.H. Adams, Analysis of the non volatile oxidation products of polypropylene. I. Thermal oxidation, J.
Polym. Sei. A-1 8:1077 (1970).
2. D.J. Carlsson, and D.M. Wiles, The photodegradation ofpolypropylene films, Macromolecules 2:597
(1969).
3. J.M. Ginhac, J.L. Gardette, R Arnaud, and J. Lemaire, Influence ofhydroperoxides on the photothermal
Oxidation of polyethylene, Makromol. Chem. 182: 1017 (1981 ).
4. J. Lacoste, D. Vaillant, and D. Carlsson, Gamma-photo and thermally initiated oxidation of isotactic
polypropylene,J. Polym. Sei.. Polym. Chem. Ed. 31:715 (1993).
5. P. Delprat, X. Duteurtre, and J.L. Gardette, Photooxidation ofunstabilized and HALS-stabilized
polyphasic ethylene-propylene polymers, Polym. Deg. Stab. 50:1 (1995).
6. RP. Singh, R Mani, S. Sivaram, J. Lacoste, and J. Lemaire, Thermooxidative degradation ofheterophasic
ethylene-propylene copolymers and their fractions, Polym. Int. 32:189 (1993).
7. J.L. Philippart, F. Posada, and J.L. Gardette, Mass spectroscopy analysis ofvolatile photoproducts in
photooxidation ofpolypropylene, Polym. Deg. Stab. 49:285 (1995).
8. P. Delprat, and J.L. Gardette, Analysis ofphotooxidation ofpolymer materials by photoacoustic Fourier
transform infrared spectroscopy, Polymer 34:933 (1993).
9. P. Galli, T. Simonazzi, and D. Dei Duca, New frontiers in polymer blends : the synthesis al1oys, Acta
Polym. 39:81 (1988).
10. J. Lemaire, R Arnaud, and J.L. Gardette, Le vieillissement des polymeres. 11. Principes d'etude du
photovieillissement, Rev. Gen. Caoutch. Plast. 613:87 (1981).
11. X. Jouan, and J.L. Gardette, Development of a micro(FTIR) spectrometric method for characterization of
heterogeneities in polymer films, Polymer 28:329 (1987).
12. D.J. Carlsson, R Brousseau, C. Zhang, and D.M. Wiles, Identification of products from polyolefin
oxidation by derivatization reactions, ACS Symp. Ser. 364:676 (1988).
13. W. Smith, The chemistry of sulfur tetrafluoride, Angew. Chem. /ntemation. Edit. 1:467 (1962).
14. C. Wilhelm, and J.L. Gardette, Infrared identification of carboxylic acids formed in polymer
photooxidation, J. Appl. Polym. Sei. 51:1411 (1994).
15. J.L. Gardette, and J. Lemaire, Advantagesand Iimits ofhydroperoxide titration methods in solid polymers,
J. Polymer. Photochem. 7:409 (1986).
16. J. Lacoste, and D.J. Carlsson, Gamma-, photo- and thermally-initiated Oxidation oflinear low density
polyethylene : a quantitative comparison of oxidation products, J. Polym. Sei., Polym. Chem. 30:493
(1992).
596
NYLON 66, NYLON 46 AND PET PHASE TRANSFER CATALYZED ALKALINE
DEPOLYMERIZATION AT ATMOSPHERIC PRESSURE
Maleolm B. Polk, Leighton L. Laboeuf, Munish Shah, Chee-Youb Won,

Xiaodong Hu, and Wen Ding
School ofTextile and Fiber Engineering

Georgia Institute of Technology
Atlanta, GA 30332-0295
INTRODUCTION
Plastic waste recycling is beneficial because it can Iead to a reduction in the amount of
waste generated, a decreased need for landfills, and a more rational utilization of resources.
An important source of polyethylene terephthalate (PET) for recycling is physically cleaned
post-consumer botdes which are ground to form flake, depolymerized, purified, and
repolymerized to form recycled resin bottles. Caustic treatment of polyester scrap involves
cleavage of the ester linkages. The reaction of aqueous sodium hydroxide (8-1 0% by
weight) with waste material in an autoclave at 210-250C and elevated pressure goes to
completion in about 3-5 hours 1. The rate ofhydrolysis may be enhanced by the presence of
accelerants2, 3 . Terephthalic acid and ethylene glycol may be recovered from the solution.
Haie used cetyl trimethylarnmonium bromide and lauryl dimethylbenzylarnmonium chloride
as accelerants for the caustic reduction ofPET.
The depolymerization of nylon 6,6 and nylon 46 involve hydrolysis of the arnide
linkages which are vulnerable to both acid- and base- catalyzed hydrolysis. In a duPont
patent4, waste nylon 66 was depolymerized at a temperature of at least 160C in the
presence of a propyl or butyl alcohol with an aqueous solution of sodium hydroxide in the
amount of at least 20% excess equivalents of the acid component to be recovered.
Thorburn5 depolymerized nylon 66 fibers in an inert atmosphere at what was reported to be
a super-atmospheric pressure of up to 15 atmospheres, at a temperature in the range of
160-220C, in an aqueous solution containing at least 20% excess equivalents of sodium
hydroxide.
PET Depolymerization
W e became interested in the application of phase transfer agents for depolymerization
ofpolymeric fibers while studying the alkaline depolymerization ofPET. A phase transfer
Science and Technology if Polymers and Advanced Materials

Ediled by P. N. Prasad et al., Plenum Press, New York, 1998 597
catalyst is used in catalytic amounts in a two-phase reaction system to cause the transfer of
one of the reactants into the normal phase of the other reactant in such a form that high re-
action rates are obtained. Our requirements were that the phase transfer agent be cationic
and have enough organic character such that it and the desired anion are partitioned into the
organic phase with high potential reactivity. Crown ethers, quatemary ammonium
compounds and N-alkyl phosphoramides have been used successfully as phase transfer
catalysts. Also, our plan was to develop an atmospheric pressure process. We discovered
that PET fibers could be hydrolyzed with 5% aqueous sodium hydroxide at 80C in the
presence of trioctylmethylammonium bromide in 60 minutes to obtain terephthalic acid in
93% yield. We were unable to isolate the small amount of ethylene glycol produced.
The results of catalytic depolymerization of PET are listed in Table l. Tetraethyl-
ammonium hydroxide was chosen because it was thought that the presence of the hydroxide
counter ion would aid in maintaining the hydroxide ion concentration in the reaction medium
during the course of the reaction. As the results indicate (Table 1), depolymerization was
somewhat inhibited. Conditions in the bath were favorable for a Hofinann elimination
reaction, and the integrity ofthe catalyst was probably affected.
Results (Table 1) for the quaternary salts with a halide counterion were promising.
Phenyltrimethylammonium chloride (PTMAC) was chosen to ascertain whether steric effects
bindered catalytic activity. Bulky alkyl groups of the quartemary ammonium compounds
were expected to hinder close approach of the catalyst to the somewhat hidden carbonyl
groups of the fiber structure. The results indicate that steric hindrance is not a problern for
PET hydrolysis under this set of conditions since the depolymerization results were
substantially lower for PTMAC than for the more sterically bindered quatemary salts.
Hexadecyltrimethylammonium bromide (HTMAB) was included in the investigation
because it had been employed previously. The past success ofHTMAC was attributed to its
long chain alkyl group. Mirnieking a long polymer chain, the hexadecyl group probably
aided in the solvation of PET. As expected, HTMAB made a respectable showing in these
experiments.
Trioctylmethylammonium chloride (TOMAC) and Trioctylmethylammonium bromide
(TOMAB) outperformed all other catalysts. It was postulated that the three octyl groups
were the proper length for solvation of the polymer, while at the same time small enough to
avoid sterically bindering the reaction.
In order to determine if TOMAB could be used to catalyze PET depolymerization for
more than one treatment cycle, the catalyst was recovered upon completion of one treatment
and added to a second bath for 60 minutes. The percent PET weight loss of the second
cycle was 85.7% compared to a weight loss of90.4% for the first treatment cycle.
Nylon 46 Depolymerization
Aqueous sodium hydroxide solutions containing benzyltrimethylammonium bromide

(BTEMB) were successfully used to depolymerize nylon 46 into low molecular weight
oligomer fractions. The depolymerization efficiency (% weight loss) and the molecular
weight of the reclaimed oligomers were dependent on the amount and concentration of the
aqueous sodium hydroxide and the reaction time. Table 2 exhibits the effects of
experimental conditions on the depolymerization efficiency and the average molecular
weight of the oligomers. The viscosity-average molecular weight was calculated from the
Mark-Houwink equation: [11] = Kmv, where Mv is the viscosity-average molecular weight,
K = 35.5 X 10-s dllg and a = 0.786. Nylon 46 fibers (Mv =41,400 g/mole) did not undergo
depolymerization on exposure to 100 ml of 25 wt% sodium hydroxide solution at 165C.
Out of 6 g of nylon fibers fed for depolymerization, 5.95 g were unaffected. When the
concentration of sodium hydroxidewas increased to 50 wt%, the depolymerization process
598
resulted in the formation of low molecular weight oligomers. Hence, even in the presence of
a phase transfer agent, a critical sodium hydroxide concentration exists between 25 and 50
wt% which is required to initiate depolymerization under the conditions used. Soluble amine
salts, were also obtained.
Table 1. Percentage ofweight loss ofPET at different temperatures
Temperature C Catalysts
--r:MAB-roMA.c:H~MABPiMAc
70 90.1% 70.0% 62.1% 17.2%

60 76.1% 62.8% 43.S% 9.7%
so 3S.8% 32.3% 23.2% 4.8%
40 18.4% 15.4% 10.S% 2.S%
30 S.8% S.1% S.S% 0.7%
20 0% 3.6% 0% 0.2%
10 0% 0% 0"/o 0%
0 0% 0% 0"/o 0%
Table 2. Properties of alkaline depolymerization products ofNylon 46
weight weight% volume weight% weightof intrinsic M.

BTEMB NaOH NaOH(ml) fibers oligomers viscosity (glmole)
(g) hydrolyzed fonned(g) (dUg)
0.2 2S 100 0
0.2 so 100 38.4 3.7 0.14 1846
0.2 so so 32.0 4.1 0.34 S946
0.2 so 100 39.3 3.6 0.13 1679
0.0 so 100 8.7 S.S 0.29 4704
In order to establish the feasibility of alkaline hydrolysis in respect to recycling of nylon

46, it was necessary to determine whether the recovered oligomers could be repolymerized
to form nylon 46. For this purpose, solid state polymerization was performed on nylon 46
oligomers formed via alkaline hydrolysis with 50 wt% NaOH at 165C for 24 hours. The
solid state polymerization process was carried out at 21 0C for 16 hours. Solid state poly-
merization ofthe nylon 46 oligomers resulted in an increase in intrinsic viscosity from 0.141
to 0.740 dVg. That corresponds to an increase in viscosity average molecular weight from
1846 g/mole to 16,343 g/mole.
Nylon 66 Depolymerization
A series of experiments were run in order to examine the applicability and efficiency of
benzyltrimethylammonium bromide as a phase transfer catalyst in the depolymerization of
Nylon 6,6. A known amount ofNylon 6,6 fiber ( MW= 30,944) was mixed with 200 ml of a
50% aqueous solution ofNaOH and 0.2 g ofBTEMB in 5 different runs. The mixturewas
heated at 143C for 24 hours under reflux. After 24 hours, on cooling, a white powder
mixed with short whiskers settled at the bottom of the flask. The solid was collected by
filtration. The reduced viscosity of the depolymerized Nylon 6,6 was determined in 88%
fonnie acid at 25C in a Ubbelhode viscometer.
Table 3 shows the effect ofthe feed ratio ofthe Nylon 6,6 to BTEMB on the viscosity-
average molecular weight ofthe depolymerized nylon.
599
Table 3. Effect offeed ratio on the depolymerization ofNylon 66
Experiment 1 2 3 4 5 6
Feed Ratio of 5 10.3 20.6 29.4 59.8 noPTA
Nylon/PTA (wt/wt)
Decrease in weight 40.3 49.5 55.5 42.5 40.8 -15.9
of Oligomers
Mv of Olisomers 1556 1912 1697 2396 1644
The product ofthe run with no phase transfer agent showed a 15.9% increase in weight
compared to the weight of the original nylon 6,6. The oligomer obtained had a viscosity
average molecular weight of 1644 (the original nylon 6,6 had a molecular weight of 30,944).
The runs with phase transfer agent produced oligomers with decreases in weight of 40-500/o.
These results suggested that in the absence of phase transfer agent only oligomers are
formed; however, soluble low molecular weight products are formed in the presence of
phase transfer agent. The oligomers obtained were repolymerized in the solid state by the
following procedure: The oligomers were heated in a tlask to 230C in a mineral bath (the
DSC melting temperature of the oligomers was 200C) while stirring and removing water
formed with a vacuum pump. The viscosity-average molecular weight of the nylon 6,6
obtained was ca. 23,000 (the molecular weight ofthe oligomeric mixturewas 1434).
Isolation of Adipic Acid
Nylon 66 fibers (6g) were depolymerized under reflux with 200 ml of 50% NaOH
solution in the presence of 0.2g BTEMB to form 0.55g of adipic acid (after acidification)
and 4.52 g ofoligomer. In a secend step, the oligomer obtained in step 1 was depolymerized
under the same conditions to form 0.72g of adipic acid and 1.62g of oligomer. In the third
step, the 1.62g of oligomer formed in step 2 were depolymerized with 50 ml of 500/o NaOH
solution and 0.54g of BTEMB to form 1.05g of adipic acid after initial exposure of the
oligomer to heat in an attempt to obtain hexamethylenediamine by distillation. The yields in
steps 1,2, and 3 were 57.8%, 38.7%, and 100+% theoretical. However we were unable to
isolate hexamethylenediamine. The overall yield ofadipic acidwas 59.6%.
CONCLUSIONS
Alkaline depolymerization ofPET in the presence of phase transfer agents resulted in the
isolation of terephthalic acid in yields as high as 93%. Hydrolysis of PET occurred at
temperatures as low as 20C; however, the best results were obtained at the highest
temperatures employed (80C). Phase transfer catalyzed alkaline depolymerization ofNylon
46 produced oligomers which could be repolymerized and soluble products believed to be
amine salts. Catalytic depolymerization of Nylon 66 produced oligomers and adipic acid in
reasonable yields. The isolation of adipic acid on depolymerization of Nylon 66 required a
stepwise approach involving the catalytic depolymerization of intermediate oligomeric frac-
tions.
ACKNOWLEDGEMENTS
The authors would like to acknowledge the National Textile Center and E.I. duPont de
Nemours & Company for financial support ofthe research.
600
REFERENCES
1. H. Ludewig. Polyester Fibres: Chemistry and Technology, Wiley, New York (1971).
2. AJ. Hall, Modjj}ring polyester fibers to get sheer, silky fabrics, Textile World.
113(9): 108 (1963).
3. S.M. Gawish, M. Gourgeois, and G. Ambroise, New quarternary surfactants for alkaline
hydrolysis ofpolyesters, Am. Dyest. Rep.73(12):37 (1984).
4. B.M. Miller, U.S. Patent 2,840,606 (1958).
5. J. Thorburn, U.S. Patent 3,223,731 (1965).
601
SOME TOPICS IN POLYMER RECYCLE IN JAPAN
Matsuo Hirami
Research and Development Center

Unitika Ltd.
23 Kozakura-Uji, Kyoto 611, Japan
INTRODUCTION
In this report, I would like to talk about the efforts of the polymer recycle in Japan
which has been made and is being performed by Japanese polymer industry (synthetic fiber
producers and plastics producers). After the War, Japan succeeded in the great economical
growth by rapid development of industry. However, it also brought about environmental
pollution of air and water. Around 1970, the regulation of air and water started, and due to
the efforts of municipal governments and industrial companies, the situation of air and water
pollution has been greatly improved. However, there still remains a big problem, that is,
the pollution of environment by waste disposals.
PRESENT STATUS OF JAPAN
Japan has to be very careful for the environmental protection, since the land is smalf.
Japan' s land encompasses an area of 378,000 km2 and the population is 126 million. Most
of Japan' s land is taken up by mountains and forest. The habitable area is 20% of the total
land and the population in the habitable area is 1,500 people per square km (one of the
highest in the world). During the past 50 years, Japan' s primary industry has shifted from
agriculture and fishing to manufacturing. According to such a change, the working
population has been concentrated to Tokyo (Metropolitan area), Nagoya (Chubu area) and
Osaka (Kinki area). Totalpopulation of three area is 26 million, which is 20% of Japan' s
total population.
This change in the population brought about the problems due to the massive waste
discharge including the waste from daily life and discarded durable consumer goods. The
effort of civic-minded organization to collect and process such a huge amount of waste
seems to be reaching the limit. Moreover, concentrated massive waste impairs the beauty of
natural environment.
The Fishery Agency of Japan found 37 thousands of drifting matters during the
investigation carried out along the total of 450 km around the coast and further area of Japan.
Science and Tech1Wiogy of Polymers and Advanced Materials

Foam polycstcr
FB Plastics
m Fishing implcmcnts
~ Fishing nct
0 Glass products
Meta!
l11ll Block
CJ Driftwood
ILI Drift scawood

D Othcrs
Figure 1. Classification of the floatage observed in the North Pacific. (Ibe Fisheries Agency in 1988)
Figure 1 shows the contents of the drifting matters 2 The drifting matters not only darnage
sailing ships (fisl!ing net and plastic-band clinging to the screws) but also are dangerous for
marine lives (fishing lines and nets often cling to wild birds, turtles and fur seals). Also the
accidents are reported that birds and turtles eat polymer pellets by mistake for foods.
TEXTILE-RELATED WASTES
In the total industrial waste of 400 million t/y in Japan, the amount of textile-related
industrial waste is 600 thousand t/y. On the other hand, the amount of total non-industrial
waste in Japan is 50 million t/y, and the textile-related waste amounts 2 million t/y (4.0%).
Some part of textile-related non-industrial waste is recycled (mainly reused), and the rest is
sent for incineration and landfill. Reuse is a primitive method of recycling; waste clothing is
collected and applied for lower quality products (downcycle) or reused as second-hand
clothing. It is to be noted that voluntary groups of local communities often cooperate to
collect waste clothing in addition to the activities of the civic-minded organizations.
Contrary to the case of single material products such as PET bottles, textile products
such as clothing are difficult in recycling because they usually contain several materials.
Fabrics are often complex by commingled or cowoven and applied for various fields.
Moreover, recycling of large products such as futon and carpet is troublesome and requirs
special care.
Japan Chemical Fiber Association founded by major Japanese fiber producers has been
performing the research on the recycle of synthetic fibers 3 ' 4 Recently in Sept. -Oct. 1996,
the association sent a delegation team to US and Europe conceming to the recycle4 The
information about the policy on recycle, the strategies of companies, the methods and their
application to recycle shall be utilized for developing the recycle system of synthetic fibers.
In February 1995, the Japan Chemical Fibers Association investigated a model recycling
system for synthetic fiber products, restricted in the products made of 100% polyester
(blouse, one-piece suits, etc. ), at the request from the Ministry of International Trade and
Industry at Chigasaki-city, Kanagawa Prefecture3 The results show that nearly 90% of
collected fabrics is re-usable as second-hand clothing. A questionnaire study performed at
604
Table 1. Problems and subjects to be studied in the recycle of 100% polyester-fiber
products as the conclusion of the investigation.
Process Possible Problems Subjects to be studied
Collection collection by local collecting cost establishment of the

community ammount collection system
PR
Separation Separation by consumer purity Iabeling

aud collecting company separation cost Separation method at
consumer side
Cutting separation of lining aud removal method -products with 100%

outer cutting cost polyester including
Removal of thread, sub-material
buttons, pads
Glinding glinding be processable by glinding cost devbelopment of a

extruder depolymerization in direct melting method
glindingprocess blending with high
Mw resin
Peletizing melting, extruding aud coloring effective filterization

peletizing depolumerization blending with high
removal of contaminants Mw resin
Molding molding process remited application new application

(value-adding)
the same time indicated rather high morality of people for the recycle. Various problems and
many subjects to be studied have arisen as a result of the investigation. The conclusion of
the investigation is summarized in Table 1.
PET BOTTLES
The commercial PET bottles were first applied to the COntainers of soi-sauce in 1977.
Later, the amount of the production has increased remarkably, and now the application
covers broad areas, namely food applications (beverage, liquor), living applications
(detergent, shampoo, cosmetics) and medical applications (eye drop, mouth-wash). The
production in the year of 1995 is 150 thousand tons, and will soon arrive at 180 thousand
tons. The recycled amount is 2,500 tons/year, and recyclingrate is 1.6 %. The collection
rate is increasing and will increase significantly after April of 1997, when the Container
Recycling Law comes into force. The law establishes the framework of the recycle system:
(1) Consumer must waste in separated manner such as PET bottles, (2) The local
government must collect them in separated manner, and (3) The manufacturer must reuse
them.
In 1993, With PET-Bottle Recycle Company Ud. was started supported by the
PET-Bottle Association, the members of which are 7 PET resin producers including , Teijin,
Nagase, Unitika and 12 processing makers including Toyo Seikan , Yamamura, Yoshino
and 5 supporting companies including Marubeni and Mitsui. With PET Bottle Recycle
605
Collection System
:eo~n~sum~~ers~J----1~
LI Local public bodies
Large retail stores
Scraps (bottle, cap, etc.)
Centrifugal dehydrator
Specic gravity separator

(Re-melting)
_________!_________ ,~------~
!_;;:_~:::__ ]I WT I
: PETband :
Specific gravity separation

Removal of PE,PP
Figure 2. A recycle system for beverage PET bottles.
Company constructed a commercial plant on March, 1996 at Tochigi Prefecture on the North
ofTokyo.
The schematic process image is shown in Figure 2, where we can realize the function of
each unit process from the figure.
The second plant is built in Mie Prefecture and scheduled to operate from 1997.
Products of PET resin reproduced by With PET-Bottle Recycle Company are supplied to the
members of PET-Bottle Association, and each member is applying it for various areas.
606
Table 2. The strategies of Japanese fiber manufacturers for the recycle of PET bottles.
Teijin shape: staple fibers

Usage: shirts (E/C mix.), etc.
Toray shape: staple fibers

Usage: uniform (PET 100%, E/C mix.)
Toyobo shape: staple fibers

Usage: uniform, shirts,
Kuraray shape: staple fibers

Usage: textile, food containers
Unitika shape: A-PET sheets, etc.

Usage: food containers, etc.
We present two exarnples. One is the case of Teijin which produces PET staple fiber by
utilizing the reproduced polymer and supplies the fabrics to the market as dress-shirts with
the brand-narne "Eco-PET" . Second exarnple is the case of Polytech Company, founded in
1991 as a joint company of Unitika, Marubeni and Osaka Kasei. The cornrnercial plant is
located in Wakayarna prefecture on the South of Osaka. This plant produces sheets of
amorphaus polyester (A-PET) with a uniform thickness by melt-extrusion of the mixture of
reproduced polymer and virgin resin. The ability of the plant is 10,000 t/y. Recycled PET
by Polytech is used for various applications, that take advantage of its transparency,
deep-drawing processability and chemical-proof characteristic, food Containers, vessels for
liqueur, various packages, bottles, etc.
Table 2 summarizes the strategies of Japanese fiber makers for the recycle of PET bottles
and waste filrns 4
CHEMICAL RECYCLE
The chernical recycle systems are employed on the line of production in big chernical and
polymer chemistry companies. Table 3 shows the exarnples for three major synthetic fibers
(PET, Nylon, AN) 3
Table 3. Current Status of Recycling of a Synthetic Textile Mill. (An exarnple

of the rnill advanced in recycling)
In-mill recycling
Outside processing
Original ratio ratio
Type of Waste Volume r a t e - - - - - - - - - - - - - - - - -
materials material Chemical Thermal Disposal Scrapping
by sale
Polyester Polymer Block. 20% 2% 11% 2% 2% 3%

Waste thread and tlue 80% 20% 45% 10% 5%
Nylon 6 Polymer block. 20% 20%

Waste thread and tlue 80% 75% 5%
Acrylic Polymer Block. 20% 20%

Waste thread and tlue 80% 65% 5% 7%
607
Chcmical decomposition
0 Recycle
(Chemical)
Environmcntal life
culture Organization
.
rcpOrt of
collection fmish
I
Figure 3. Nylon 6 uniform recycle network.
The system of collecting and chemical recycl has been attempted to apply to the fishing
net market. ~ discussed above, recycling textile fabrics is difficult because of its variety of
products and applications. However, if the material of the concemed textile is specified and
the distnbution route is well-established, the recycle system could be systematically designed
relatively in a easy way. Recently, Toray demonstrated an excellent example of this type of
recycling system, that is "nylon 6 uniform recycle network5 ", as shown schematically in
Figure 3.
Finally, I will show a research work of "Alkali decomposition of PET' with NaOH in
non aqueous EG" developed by Prof. Oku, Kyoto Institute ofTechnologl. The procedure
is as follows. The schematic diagram of the procedure is shown in Figure 4. The collected
PET' waste are not necessarily clean. They are pulverized and thrown in non aqueous EG in
the reactor, and sodium hydroxide is added. Decomposition is made under a mild condition
and accelerated by adding of an ether-type solvent such as dioxane and tetrahydrofuran to
EG. The laboratory-scale experiment has just been finished. Prof. Oku said that this
system is simple and useful for the application in the future.
THERMAL RECYCLE
A novel type of energy recovery technology for waste plastics has been developed by
Ube Chemical Company supported by the govemment (the so-called NEDO of MITI, New
Energy and Industrial Technology Development Organization Japant Its purpose is
developing the economical solidized-fuel system which utilizes industrial wastes including
plastics as a high quality energy resource. The process flow of the waste plastics in Japan is
shown in Table 4. In the total amount of 4, 950 thousand tons of the waste plastics is sent
for land-filling and incineration without being recycled. The system is designated to collect
608
2-equivs of
reactor
14_ _ _ _.....~ NaOH
I pulve~zed I
PET bottle-----1~~ plastiCS --t~~~'----!-____./
r:
150'C, 80min
'
acid HX
TPA
Figure 4. Chemical recycle system of PET wastes with NaOH in nonagueous EG.
waste plastics with a great variety of waste materials, different types of polymers, and
out-put product of a small graintype of solidized-fuel. The schematic flow of the process is
shown in Figure 5. The collected wastes are packed in a container with ID card of bar-code
system, in which information such as type of material, weight, shape and size of waste
particles are descnbed. When a container comes at the gate, information in the bar-cord is
read and stored in the computer. The product of this system, the solidized-fuel is supplied to
power generation. In order to keep the efficiency of power generation, the temperature is
maintained constant during time. Therefore, the quality of solid fuel must be uniform. The
waste plastics in the COntainers are mixed so as to satisfy the required condition, by the
indication of computer. The period of this project is three years (1994 - 1997). The test
operation has been made successfully in Ube plant.
BIODEGRADABLE FIBER: CELLULOSE
Although the biodegradable fiber is beyond the scope of this study, I would like to put a
short comment on the biodegradable fiber, "cellulose", relating polymer recycle system. In
Table 4. Recycle flow ofwaste plastics.
Incineration; electric generation; 1,200 kt

3,600t kt (52%) others; 2,400 kt (35%)
Totalwasted plastics; Land-filling; 2,550 thousand tons (37%)

6,900 kt
recycled material; 550 kt
effective recycle; 750 thousand
recycled prodncts 170 kt
tons (11%)
others; 30 kt
609
0\
0 Seperation
Plastic Waste
(block)
Pulverization a=I)
Plastic Waste 1 1 I
(powder)
Paper
'eJ
Elending of Wastes
I SludgelI - - - -
Collection Area [-ASf]

~ ' ' ..------L-- . - - - - - - - - - - . .....------- --,
information of control of
waste materials supply volum
( c::::
Conputer for
Quarity Control
calorific value
of solid fuels
Apparatus for
guaritvcontrol
sample
Figure 5. A Energy recovery system for waste plastics.

the previous symposium in Kuala Lumpur, we presented the biodegradable fibers of
synthetic polymers8 Unitika has been developing a biodegradable fiber of poly-caprolactone
(PCL). Note that PCL and cellulose fibers have the same level of good biodegradability. A
huge amount of cellulose exists in the earth, and the global scale of recycle between air and
land works well. We believe that cellulose will come back as a major fiber material in the
next century. There are two kinds of resources of cellulose, one is cotton and the other is
wood for chemical cellulose fiber such as rayon and acetate. If the food crisis occurs, much
more agricultural land will be required, and then the land for cotton cultivation will be
necessarily decreased. From this point of view, the chemical cellulose fiberwill have an
advantage.
CONCLUSION
I will summarize the content of my presentation. As an attempt of PET-bottle recycle,

With PET Bottle Recycle was constructed and has been successfully operated. Several
similar plants will start in other locations. PET resin reproduced by With PET Bottle
Recycle are utilized to provide PET products, e.g., amorphaus PET sheets and PET staple
fabrics. The Japan Chemical Fibers Association examined a model recycling system for PET
fabrics. Several useful recycling systems are presented: chemical recycling of PET at KIT,
complete recycling system of nylon fabrics at Toray, and a novel thermal recycle system for
mixed plastics at Ube. The significance of cellulose as a biodegradable polymer is indicated.
Finally, I wish to emphasize that Japan should contribute to the eco-problem on the
world-wide basis by supplying the technology of environmental protection which have been
investigated and established in Japan so far. Then, "Key Words "are as follows.
1. Sustainable development of industry and economy in harmony of environment
2. Challenging efforts of science and technology, associated with social science
3. Internationalinformationexchange and technical collaboration
ACKNOWLEDGEMENT
I would like to thank many parties and organizations who supported and helperl me for
preparing this report. Especially, I acknowledge the members; Japan Chemical Fibers
Association, New Energy and Industrial Technology Development Organization (NEDO),
Polytech Co., Ud., Prof. A Oku at Kyoto Institute of Technology, Toray Industries, Inc.,
Ube Industries, Inc. and With PET Bottle Recycle Ud. I also acknowledge Mr. M.
Nakamichi of Unitika Ltd. for his assistance.
REFERENCES
(1) "Plastic Waste", Plastic Waste Management Institute (1992).

(2) H. Moroboshi, Kougyouzairyou, 38, 26(1990).
(3) Research Report on the "Model Recycle System of Synthetic Fibers", Japan Chemical
Fibers Association (1996).
(4) Research Report on the "General Survey on the Recycle of Synthetic Fibers", Japan
Chemical Fibers Association (1997).
(5) Brocher of Toray Co.: "Nylon 6 Fabrics, Chemical Recycle Uniform".
(6) A. Oku, L. C. Hu and E. Yamada, tobe published in J. Appl. Polym. Sei.
(7) Qean Japan, 73, 49(1995).
(8) M Mochizuki and M Hiram~ in "Polymers and Advanced Materials", P. N. Prasad, E.
Mark and T. J. Fai, Eds., Plenum Press, New York (1995).
611
CORPORATE MANAGEMENT IN TUE AGE OF GLOBAL
ENVIRONMENT AWARENESS - A CASE STUDY OF PET BOTTLE
RECYCLING ISSUES IN JAPAN
Naoya Yoda
Kansai Research Institute (KRI)

3 Rokuban-cho, Chiyoda-ku, Tokyo, 102 Japan
Keio University, Faculty ofScience and Technology
3-14-1 Hiyoshi, Yokohama, 223 Japan
INTRODUCTION
The global environmental issues are key factors for the business development
toward the year 2000. From the industrial ecology perspectives, the management strategy
of industrial ecology should be implementedas an essential tool in the decision-making
process oftop management policy in chemical industry in order to respond to the global
environmental challenges. The focus of effort of recovery and recycling of both
industrial material of pre-consumer solid waste and post-consumer solid waste become
more important in recent years. As a case study, the current problern of recycling of PET
bottle business in Japan is reviewed and analyzed in this article. 1
To cope with the global issues of alliances for environmental sustainability, the
social systems of ecology in our local communities such as recycling post-consumer
solid wastes should be established. In order to maximize productivity of global
environment, the closed system of recycling materials should be re-evaluated and
established as new social and industrial systems. Global environmental productivity is
defined as the ratio oftotal output to total consumption ofmaterials and energy. concepts
such as "Seahorg 's Closed System" and "Inverse Factories" should be considered if
environmental productivity is tobe maximized. 2
The R&D expenditure of both environment and energy saving in Japan reached to
200-350 billion yen for each project in 1995. lt is needless to say that the global
environment must be investigated under collaboration of geographically distributed
nations, and it should be stressed more that this subject must be dealt with people of
different cultural and/or societal background. To encourage large market for recovered
material, a growing "buy recycled" movement has emerged. Govemment and industry
have announced purchasing preference for products which contain post-consumer
recycled materials where they are available at required price, performance and quality.
The environmental soundness of products can be enhanced through "Total Quality
Management" (TQM). 3

VISION OF RECYCLED SOCIETY AND GLOBAL ENVIRONMENTAL ISSUES
From the industrial llCology perspectives, the management strategy of industrial

ecology should be implementedas an essential tool in the decision-making process oftop
management policy in chemical industry in order to respond to the global environmental
challenges. The focus of effort ofrecovery and recycling of both industrial material of
pre-consumer solid waste and post-consumer solid waste become more important in
recent years. To encourage large market for recovered material, a growing "buy
recycled" movement has emerged. Govemment and industry have announced
purchasing preference for products which contain post-consumer recycled materials
where they are available at required price, performance and quality. The current
issues of technology management of industrial ecology and life cycle assessment in
manufacturing industry are discussed. To cope with the global issues of alliances for
environmental sustainability, the social systems of ecology in our local communities
such as recycling post-consumer solid wastes should be established. In order to
maximize productivity of global environment, the closed system of recycling materia~s
should be re-evaluated and established as new social and in~ustrial systems. 45
In early stage of production systemssuch as basic design of electronic devices,
the structural design of atmnic and molecular Ievel shoL1ld be introduced to minimize
enviromnental impact. In addition to the pollution control and the environmental
response in the manufacturing plant sites, implementin~ an environmental business
strategy is requires in the business planning. Re-engin~ring of business involves a
combination of product and organizational changes. 678
It is our urgent task for academia and industry to review the system and reconstruct
it together with creating plenty ofnew type ofknowledge. New type ofknowledge may
be inter-disciplinary that may bridge many domains independent in the past. knowledge
systems may be reconstructed on a base of new domain-construction principles. For
example, it is established by shifting from object-theoretical principle to process-
theoretical principle. For manufacturing industries, the revision of definitions oftheir
activities is essential. The definition of manufacturiqg industry is that it puts raw
material into factory that outputs the relevant products., although the raw material is
useless but the products are useful. The ditierence of usefulness between them is ~
value added in the products. 9 10
The raw material is not an existing entity but circulating one as apart ofthe natur~l
belong to the earth that is nothing but a circulating system. Therefore, the definition of
the manufacturing industry should be given as a part of the earth. Academia and
industry have respective mission to fight against a newly ernerging evil, that is the
Table 1. Comparison ofR&D Expenditure of Japanese National Research Projects

for Enviromnental Projection (billion yen)
Item 1985 87 88 89 90 91 92 93 94
Environment 150 156 170 200 238 256 261 264 291
265 313 318 353 353 371 375 411
Energy Savings
__, 353
NewEnergy 38 34 29 28
.45 50 49 57 51
... 24 "
14 16 18
52 59 65 75
Biotechnology*
Aerospace 150 170 178 195 218 218 204 248 231
( reterence)
*For Resources and Environment

(Source: Statistics Bureau, the Japanese Government)
614
destruction of global environment. Jn order to expect the victory in this fighting, highly
integrated collaboration between them is of necessity. Therefore, international
cooperation isanother important factor. 11 12
The trends of R&O expenditure of the Japanese govermnent for global
environmental protection in the period of ten years in 1985-94 are summarized in
Table I. lt shows the R&D expenditure of national projer;:ts of environment and energy
saving in Japan reached to 300-400 billion yen for each project in 1994.
lt is needless to say that the global enviromnent must be investigated under
collaboration of geographically distributed nations. It should be stressed that this subject
must be dealt with people of different cultural and/or societal background in order to
visual ize important points that might be overlooked when single-cultural people discuss
with easy mutual understanding or sometimes collusively. 131415
ALLIANCE FOR GLOBAL SUSTAINABILITY
The Alliancefor Global Sustainability (AGS PROJEC7J has a structure that

will undoubtedly perform these tasks, where ditTerent nations; researchers from variolls
academic domains; academia and industrialists come together for the collaboration.
In every product and process engineering, the total cost should be reduced by minimizing
resources and energy consumption as weil as the envirortmental impact. ln terms of
management strategy and the organizational restructuring, green accounting practices
will allow business to intemalize environmental costs as apart of corporate strateb'Y 16
"The environmental Charter" was endorsed at the First International Symposium
of Environment and Polymers held in October 1995, organized by the author as
Program Committee Chairman and the Executive Director of the Society of Polymer
Science Japan, held at the United Nations University in Tokyo. The guidelines were
endorsed on tlve items at th!! Symposium outlined below; namely, industry will consult
with, and seek the understanding and cooperation of coqsumers, and will conduct its
business in confonnity with these guidelines. 21
1
,' ~ - - - - - - - - - - -- - - - - -
Upstream Mldslream
- - -- - - - -
Downstteam
CONSUMPTION
Ae
R81118
___.. a
Recovery I
INPUT
[........----~] +
ClUTPUT
I t :
>---.---------------------_. '
I .,__. c I
I
I Recycte I
System Boundary
(Source: KRf data)

Figure 1. BasicModel for the "Recycle Society"
615
From an industrial ecology perspective, recent Japanese trends in changing
environmental policy of manufacturing industry were overviewed. Highlighted as the
basic frrunework for the new policy direction is the latest legislation, the ba..Yic
Envirunmental Law in 1993 in Japan. The goal of improving the overall
environmental efficiency was identified as a global sustainable society in the context of
the "Seaborg 's recycle society. " A simple model of the recycle society is illustrated
in Figure I.
There are two types of approaches currently in use id to improve the environmental
attributes of products; one called Design for Environment (DFE) or Product
Assessment (PA) in Japan. It requires environmental and recycling considerations at
the stage of molecular design, product design and engim:ering design. As shown ip
Figure 2, in 1990, Japan has a variety of environmental problerns and only 14 percent of
total arnount of raw material and finished products have been recycled.
As we approach the 21st Century, the chemical and material process industry face
many challenges. The task before us is not merely one of the rethinking the problems
caused by the pursuit of aftluence in a culture that encourages mass consumption, we
must also deal with global problems caused by the pursuit of aftluence in a culture that
encourages mass consumption, and we must also deal with the global problern of
poverty and population growth, and aim to band over tQ future generations a healthy
environment that allows suitable economic and industrial development.
Human civilization's present pattern of economic growth and development in
future will become more difficult to sustain. Clearly, important globalgoalssuch as
energy conservation and environmental protection must be pursued with more
determination. Global environmental productivity is defined as the ratio oftotal output
to total consumption of lUflterials and energy. concepts such as "Seaborg's Closed
System" and "Inverse factories" should be considered if environmental productivity is
tobe maximized. Polymersare essential to achieve this goal. They arenot part of tbe
problern but part ofthe solution. They help to save resources in numerous application$.
They help to save resources in numerous applications. The problern we face is to make
the public aware of it. 171819
IMPORT EXPORT
V 0
- -=- lt~-----,r---~-0_1_ Jl/-.2 "="
"i
---__.;:::- : TOial Re1101111:11 Toll! Reeourca
_/7950 380
l
: Exttaclfon UM
DO~~WSTIC
lCJJ .
=> 2,100 2,350 Food80Consum=>od
"" 1,440
MATERtALS -----~: 770 1

FuaiConlumod 400
lnduslrlol Wutel 21
WASTES
7
t~--
N.B. Alliglns ln mllllan -
Data Soun:el : Ollldal Slalllllc:s
Figure 2. Japan's Annual Material Balance oflndustry in 1990
616
Responsihle activity will help them is understand and convey the message that
material recovery and product life cycle analysis are important goals. They are the
important new technologies tobe established. Furthermore, the development of a more
sustainable system for polymer technology and use should contribute to introducing a
more dynamic social and economic system Pursuit pf environmental protection,
product life cycle assessment (LCA) and the sound management of natural resources by
academia and industry should be added to company goals like profit, sales and cash flow,
and it eventually enhances the basic mission and daily practices of corporations. As we
approach the 21st century, advanced nations should establish a vision for contributing to
the international community through the development of an improved, environmentally
sounder, polymer technology. 20
By demonstrating that it takes environmental problems seriously, the business
world can gain the trust and corporation of the public. This will foster a beneficial
relationship between producers and consumers, and Iead to a healthier and more
sustainable development ofthe world's economies.
With this in mind, the Federation of Management in Polymer lndustry, Japan
(KOBUNSHI DOYUKAI) , where the author organized the Symposium adopted the
Tokyo Declaration in October, 1995 by the approval ofparticipants. The management
of Japanese manufacturing industries will consult with, and seek the understanding and
cooperation of consumers, government officials, and other, and will conduct its
business in conformity with these guidelines. 21
CASE STUDY OF PET BOTTLE RECYCLING IN JAPAN
The case study of current Japanese plastic bottle recycling business is reviewed and
the environmental issues of polyethylene terephthalate (PET) bottle is presented in this
section.
Environmental A wareness and Plastic Recycle Business in Japan. In the
case steady ofPET bottle business in Japan, the following five environmental issues are
discussed.
1) Aspect of ecology and industrial ecology, 2) Global environmental awarenes!l,
3) Trends of PET polymer consumption, 4) Recycling process in action, and S)
Unsolved problems for environmental soundness.
From the industrial manasement viewpoint, there are several current management
issues in terms ofthe global environmental awareness as tbllows;
I) alliances for environmental perspectives.
2) the global environmental productivity is defined as ratio of total output divided
by/total consumption of material and energy in the so called, "Seaborg's closed system".
3) new concept of inverse factory of closed loop is important with respect to the
conventional process ofproduction factory.
Regulations. In Japan, the future re-resourcing enforcement law is enacted as
recycling law in 1991. The PEr bottles are designated as "the second-class
designated product" in 1993. By the recycling law of packaging enacted in 1995 in
Japan, and bottle producers should observe the law, and commercial PEr bottles in the
market should be either re-used or recycled under new regulation enacted in June, 1997.
Guideline for collection is as follows; including PET bottle, should be recycled
( 1) In the category of second designated products and the beverages, of Iiquors and
soy-sauce bottles are included. (2) The products are spbject to remove closures. C
In the recycle plant, the products should be kept clean by tl:\e following tive processes;
Process 1: rinse, Process 2: no other polymers, especially PVC,
Process 3: no hazardous products, Process 4: no contaminants,
Process 5: classitied collections.
617
Aspect of ecology is described in Table 2 by three categories in tenns oftime frame.
Table 2. Aspects of Ecology

1. Remettiation : Paying for past mistakes
2. Treatment, storage and disposal : Present, End-pipe treatment
3. Iod ustrial ecology : Paradigm shift tor the future.
In Table 3, industrial ecology is divided into three stages of life cycle ofthe product,
namely , (1) rnanufacturing process, (2) safety by products in use and 3) recyclability
of products in waste.
Table 3. Irrdustrial Ecology

1. Processes; which are environmentally benign during manufacturing
2. Products; which are environrnentally benign and safe during their use
manufacturing
3. Products; which at the end of their usefullives can be economicaUy recycled
without adverse impacts on the environment and without increasing
net cost
There are a variety of new environmentally sound packaging materials besides

PET bottles, recently developed in Japan. Example of functional packaging materials
and containers are summarized in Table 4.
Table 4. Example ofFunctional Packaging Materialsand Containers
(1) Ministry of Agr./ Microporous films for fresh vegetables.

Toppan Printing Evaluation of packages.
(2} Ministry of Agr./ Jointresearch on ecological packagings (1991-95).

food makers/ Research on biodegradable packages (9 groups).
packaging makers (K. Murauchi, PlasticsAges, 155 (Jun.1996))
(3} Toyo Seikan High barrier retort container, Oxyguard.

Containing oxygen absorber.
(4) Kaito Chem. Anti-biotic Iaminate film, containing zeolfte based

(Sumitomo Chem. group) antibiotic material.
Outline of the first and second specified products of resourcing enforcement law ip
1993 is summarized in Table 5.
As it is shown, PET bottle tilled with soft drinks or soy sauce is designated as thj:!
second specitied products in 1993. As described in Table 6, the Ministry of
International Trade and lndustry in Japan set the packaging recycling target in 2000 as
summarized in Table 6. Recycling percentage ofPET bottle was attained up to only
1.8% in 1995, and the recycle target is set up to 10% by the year 2000.
The conventional containerssuch as alumirrum cans and steel can show recycling target
up to 70 - 75% as shown in Table 6.
Data ofPET Bottles consumption in Japan in 1990- 1995 are surnmarized in
Table 7. In 1994, only 9.4% (1,366 tons) were recycled from total production of 176
thousand tons. Projections of plastic recycling in 1997 -98 are up to 30% per year.
Recycling System and Technology. The recyclin~ system of PET bottles art::
designed as shown in Figure 3. The support of municiiJill govemment is essential t()r
the customers whose used bottle are collected in local areas, The collected bottles are
618
Table 5. Outline ofthe First and Second Specified Products
The first specified products

11 Simple wireless
1 Automobiles communication instrument
2 Unit type air conditioner 1 2 Citizen band radio
3 TV set 13 Word processor
4 Electric refrigerator 14 Video camera
5 Electric washer 1 5 Headphone stereo
6 Electric implement 16 Electric cieaner
7 Personal computer 17 Electric razor
8 Cordless telephone 1 8 Electric tooth brusher
9 Car phone 19 Horne electric medical treater
10 MCA system 20 Electric toy automobiies
communication instrument
The second
specified products
1 . PET bottle filled 2. Containers filled

with drinks or soy with alcoholic drinks
sauce
Table 6. Packaging Recycling Target in 2000 by the Ministry of International

Trade and lndustry
.
(The Chemlcal Dally: June 12 1996)
2000 1995
(Recent target) (Oid target) (Result)
Paper 56(%) 55*(%) 53.4*(%)
Steel cans 75 60 73.8
Al cans 70 60 65.7
Glass bottles ss- 55* 55.6*
EPS lish box, 35 25 27.3

appliance package
1994
PET botlies (17,500 t) -2001 1.8
(Source: KRI data)
transported to the recycled process factory, and returned to the PET manufacturers in the
form of flakes or pellet for reuse.
For the management and safety study of industrial structure of PET bottle recycling
business, Japan PETBottle Association has been established in Tokyo since 1972. The
infrastructure is shown in Figure 4.
A pilotplant of 3,000 T/Y capacity in 1996 are opeqtted in Tochigi Pretecture ip
Japan as shown in Figure 5.
The reclamation process flow sheet of PET bottles is described in Figure 5. The
plant has several process such as rernoving foreign materi~s, 2) cleaning and separation
of colored bottles, followed by 3) erosher to obtain flakes after 4) fine pa.rticle separatioq.
In Table 8, the Japanese PET Bottle Trade Association and its rnember cornpanies df
Association are listed. As shown in Table 8, therl! are twelve bottle rnolding
companies, who are rnembers of Japan PET Bottle Association (PBA) founded in 1972.
In addition, there are seven polyethylene terephthalate resin producers in the PBA.
There are also five supporting mernber companies, who are distributors of a variety of
619
~
Distribution of
Beverages Local
Beverage
Manufacturer Governments
Transportel I Reclaimed
Supplying
:V.:......---, Collected
Bonles r- I Bottles Product
I 0 Collector Ql Processing
I . Factory
Supplying Resins
Resin Q~
Manufacturer
Reclaimed
Products
.--------'{7'------,
(Note: Reclaimed products cannot be used as
containers for beverages for the time being) Usage of Reclaimed Products
FigureJ. Recycling System ofPET Bottle

recycled PET tlakes and a variety of products such as fabri.;;s and molded parts.
Recycled products of PET Bottles include the following items, and a variety of
appl ications are in the markj!t development stages recycled articles; (l)Textiles,(2)Non-
woven tabrics, (3)Sheets, (4) Bottles, and (5)Packaging and construction materials. The
Table 7. Trends of Japanese PET Bottle Consumption in 1990-95

(Source: KRI data)
USAGE 1990 1991 1992 1993 1994 1995
Soy sauce 12,000 12,500 13,200 13,300 13,468

}22,900
Other satlCP.!'> 1,526 1,722 3,746 5,221 7,348
Edible oils 1,849 1,642 1,899 2,195 1,689 1,700
FOOD 6,223 5,739 5,766 7,734 10,133 10,600
PACKAGING Alcohlic drinks
Soft drinks * .80,786 89,383 97,025 102,764 126,681 129,200
FOOD PACKAGING TOTAL 102,384 110,986 121,636 131,214 159,319 164,400
Detergents and shampoos 11,166 11,358 11,515 11,830 11,801 11,800

Cosmetics 1,504 1,451 2,294 2,495 2,740 2,800
NON-FOOD 1,629 1,960 1,662 1,205 1,963 2,000
PACKAGING Pharmaceutical products
NON-FOOD PACKAGING TOTAL 14,299 14,769 15,471 15,530 16,504 16,600
GRANDTOTAL 116,683 125,755 137,107 146,744 175,823 181,000
SECOND DESIGNATED PRODUCTS () 99,009 107,622 1!5,991 123,798 150,282
Units : M. Tons.
Japan PET Bottle The Council For

Association PET Bottle Recycling
Japan Recycling Business

Partnership for PET Bottle
National Soft Drink
With PET Bettle lndustry Association
r-
Recycling Co., Ltd_
With Waste Japan

Co., Ltd.
Figure 4. Business Structure of PET Bottle Recycling Industry
Japan Recycling Law of packaging was enacted in April 1997. In the PET bottle
recycling business, the following items are problems to be solved bv the
manutacturers.(l) Cost analysis including life cycle assessment, (2) Inn~vative
technologies, and (3) Product development of new applications.
In concluding plastics recycling issues, the following etlort should be devoted to
full-t1edged recycling business ofPET bottles.
621
0\
~
Separation work:
Spar.tion ot colot.-d Only crushing is
botlitt and colortut boonle-t. procened.
II Crusher
I(\/'Iot Typ)
HotAir Drying Fugment.J compo~d of PE (thesecond Bonles are crushed

Removing the
remaining tnd PP''' lt h: Houonthc cleaning process) into flak~ cond itions .
aluminum waur.and 'ETbottlts and
mttab: hntltttltd down.
:~
/
'
The resin becomes .a matetia.l
for reclaimed products.
~~~
Hot Air Drying
(the final cleaning process)
Processing Capacity: 5,000 tons I year
Figure 5. Flow Sheet of Reclamation Process of PET Boules

105
Swi:tzerland (102)
100 Sweden (1 02)
Australia (92)
95 France (86)
Canada (84}
><
-8 90 W. Germany (80)
.s ltaly (80)
1 85
U.K. (75)
U.S.A. (75)
80 Japan (67)
75
70
65
60
1973 1975 1977 1979 1981 1983 1985 1987
-year
Figure 6. Trends of Energy- Consumption Index of Major OECD Countries
in Terms of Unit GNP (Energy Consumption per GNP)
2~~--------------------------------------------------~
.c
~ 220
l
0
i
200 199.5199.5
180
160
140
12oL--L-J--~~--L-~~--L--L-J--L--L-J--~-L-J~~~~~
1973 74 75 76 n 78 79 so 81 82 83 84 as 86 87 aa 89 so 91
- year
(Source) Based an prlce of 19851n GNP
Figure 7. Trends ofEnergy Consumption Versus Unit GNP in 1973-1991
623
(1) Total quality management (TQM),
(2) Cost reduction,
(3) Technology innovation tor recycling,
(4) New sewage system in municipal government,
(5) l'v1aterial and energy recycling in a clean system, and
(6) Development ofnew applications
Table 8. Member Companies of Japan PET Bottle Association (as of October, 1995)
.Bottle Molding Companies (12 comtlanies)

1) Dainippon Ink and Chemicals, Inc. 7) Mitsubishi Plastics Inc.
2) Dainippon Printing Co., Ltd. 8) Tomikawa Chemical Industry Co., Ltd.
3) Denki Kagaku Kogyo K. K. 9) Toppan Prinitng Co.
4) Hokkai Can Co., Ltd. 10) Toyo Seikan Kaisha, Ltd.
5) lnoac Corporation Ltd II) Yamamura Glass Co., Ltd.
6) Mitsubishi Gas Chemica1 Co., lnc. 12) Yoshino Kogyosho Co., Ltd.
Resin Producers (i companies) Suppotting Members (5 companies)

I) Japan Unipet Co., Ltd. I ) Marubeni Corporation
2) Kanagafuchi Chemicallndustry Co., 2)Mitsubishi Shoji Plastics Corporation
Ltd. - Kanebo Ltd. 3) Mitsui & Co., Ltd.
3) Kuraray Co., Ltd. 4 )Nichimen Co., Ltd.
4) Mitsui Petrochemica1 lndustries Co., 5)Nagase & Co., Ltd.
Ltd.
5) Nissei ASB Machine Co., Ltd.
6) Teijin Limited
7) Unitika Ltd.
GUIDELJNES FOR CORPORA TE STRA TE:GIES FOR GLOBAL

ENVIIWNMENT
As described in the previous section, both industry and academia must focus on
business activities and research aimed at ultimately leading to the establishment of new
economic and social systems which are more protecti ve of the environment and
sustainable over the long run.
Historically, the environmental costs such as the cost of managing, tracking and
controlling hazardous waste, have been incorporated into overhead expenses.
lncidentally, however, environmental costs, issues and opportunities, are being addressed
as a component of corporate strategy. Traditionally only environmental, safety and
health staffhave been concemed with environmental risks and cost.
However, as environmental issues are internalized, other employees such as design
and manufacturing engineers will begin to sec that they too must play a rote in
minimizing the environmental impact of cooperation's product and process. In the
same way, the "total quality management" (TQM) emphasizes the importance of every
employee in determining product quality, so does industrial ecology stress the role qf
each person in actively minimizing environmental impact. 12"14
Implementing an environmental business strategy requires a combination of product
and organizational changes. At the product Ievel, environmental concems must g~t
addressed starting with the design stages. Environmental design check lists and
CAD/CAM tools can help to incorporate environmental concems early in the product
realization process. In tellJIS of organizational changes, green accounting practices will
allow business to internalize environmental costs as a part of corpomte strategy.
Furthermore, managers should become accountable for the environrnental performan(;f!
of their companies. 15- 19
624
Annu11 Volume
10
!i
1.5
~
.:.:
"',...
0
1.0
0.5
0
Packaging Cellular Bottlu Adhesive' EJectrlcal Automobile; Houslng
Plastics Container Coaling Appllancu Construcllon
Life Span Day Week Month 1 Year 5 Years 10 Years 10- 30Years
(Source: KRI data)
Figure 8. Plastics Resin Consumption and Projected Life
ENERGY CONSERVATION AND GLOBAL SUSTAJNABILITY
The comparison of trends of energy consumption index (1975=100) of majqr

OECD countries, Canada, U.S. and Japan in 1975-1987 as shown in Figure 6.
The energy consun1ption index (1975=100) of major OECD countries, Canada, U.S. and
Japan is among the best, whereas index of U.K. and U.S. decreased to 75 (25%
reduction) within 13 years.
When the ratio of energy consumption per GDP is traced in 1973 -1992 in Figure 7, it
dropped from 199.6 kl of fuel oil/ 0. I billion yen in 191?3 to 125.3 kl of fuel oil/0.1
billion yen in 1991.
CHALLENGE OF GLOBALSUSTAINABILITY
Responding to the challenge of global sustainability, tl1e plastics resin consumption in

several applications are compared in Figure 8 in terms of projected life span of different
appl ications. F or example, such cases of plastics are compared with packaging, cellular
plastics, bottle container, electronic appliances, automotive and constructions in the
period of a day, a week a month, up to ten to thirty years.
The trends of unit energy requirement of major industries such as steel, paper and pulp,
cement and petrochemieals in Japan in 1973-91 are shown in Figure 9. Comparing with
the energy consumption between 1973 and 1991, it shows reduction of energy
consumption of major Japanese industries was 15% in steel up to 40% in petrochemical
industry in the period of eighteen years in 1973-91. The integrated energy statistics of
the Japanese manufacturing industries in 1973-91 are reviewed in these items. The
index of annual energy consumption of chemical industry (1973=100) decreased to
70 in 1987, and dropped from 41.3 to 28.9 trillion kcal, by introducing a variety of
modification of energy conservation process and irreremental manufacturing technologies
in every step ofthe production system.
The analysis of risk assessment and risk management shows research of risk
characterization is necessary in terms of hazard identification and assessment. In Table
625
>< 115
"E
r
- 110
1os
/

o-o,,
, '
'o..
o 1 1
- steel
o - paper/pulp
,4.... cement
/ ',_......-paper pu P tr- petrochemical
.....
1oor-~~~--~~--~------------------------~----------~
\
"
~ \
95
...........
90 ......... ~
"., \ '1:\
85 ~-)", ',
~:::.dt"' ~ .,
80 ..... '-~')\.
75

.....,..,~,
C1~
70
\~~i.~.....
\ ~.... 6-
cement
J.
perrochemical ----+''llr-4...~ - .:-::-.,...,~"'~t":"'_..l......
65 "'"t>--o.._ --'Q
"" ,_,.4--.. . ._
60~~~--~~--L-~~--~_.--~~~--~~--~~-~--~~~
1973 74 75 76 77 78 79 80 81 82 83 84 85 as a7 aa a9 so 91
(Source) Mm - yaar
1) Index 1977 = 100 for petrochemicallndustry
2) Steel industry, adJusted for production conditlon of 1973
3) Others nominal unlt energy requirement
(Source: KRI data)
Figure 9. Trends of unit energy requirement of major industries in Japan in 1973-91
2, in terms of the environmentally sound design, impact ofmaterial save, waste save and
cost save are summarized in sie items such as material substitution, process modification
and life cycle assessment. We must solve these global environmental issues through
international cooperation based on the basic concept of economic symbiosis. 21
One goal of the new chemistry is the creation of new materials with a variety of
functions for environmentally sound technology. This will be materialized by studying
specialty polymers with fine structure and the assembling ofmolecular aggregates on the
molecular design combined with sophisticated devices of material recycling.
Material science is capable of creating new material of an environmentally sound
technology that can meet demands for expanding human activities while conserving
energy and recycling resources. 22' 26
ACKNOWLEDGMENTS The author is indebted to Mr. H. Okada and Mr. T.

Kobayashi, Chief Consultants ofKansai Research Institute for valuable discussions.
REFERENCES
1. N. Yoda, Invited Ieeiure presented at "the 4th International Conference in Frontier of in
polymers and Advanced Materials" at Cairo, Egypt, (J anuary 4-1 0, 1997).
2. N. Yoda, Invited Leelure Presented a "the International Symposium oflndustrial Ecology," Sponsored
by the National Academy ofEngineering at Newporteach, CA, U.S/.A. (May 9-12, 1994).
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Manufac1uring," Sponsored by U.S.-Japan Center in NewYorkJETRO, and Vanderbilt University on
(March 25-26, 1994) in Washington, D.C. U.S.A.
4. N. Yoda, JCIP (Japanese Commission on Industrial Performance) ,"Made in Japan" H. Yoshikawa ed.
Diamond Publishers, Tokyo (April, 1994).
5. N.Yoda, Environmental1ssues and Plastics Industry, TBR lntelligence (Toray Corporate Business
Research, lnc.) Vol.4, No. 2, p. 15 (1992).
626
6. N.Yoda, Industrial Management and Globalization in the New Chemical Age, ibid.,
Vol. 5, No. I, p. 28 (1992).
7. N.Yoda, Public and Private and Setting Research Agenda for the Japanese Chemical Industry, ibid,
Vol. 1, No. 2, p.48 ( 1989).
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p. 81 (1989).
9. N. Yoda, International Competitiveness, Presented at the Am. Chem. Soc. Symposium, Washington,
D.C.U.S.A. (1990).
10. N Yoda,. Introduction ofNew Materials in Industry: Management Analysis, Invited Lecture
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Introduction ofNew Materials, Stockholm, Sweden (1990).
11 N.Yoda, Techno-globalism and Technological Management Strategy: the Issue for the Globalization
of Japan, TBR Intelligence, Vol.2, No.2, p.56 (1990).
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ibid, Vol.3, No.l p.23 (1990).
13. N.Yoda, R&D Globalization: Challenge for Japan in the Paradigm Shift from Wealth to
Brainpower,ibid. vol.3, No.2, p.38 (1991).
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Delivered at the 28th US -Japan Business Conference, Pittsburgh, PA, U.S.A.(July, 1991).
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Delivered at the 29thJapan-US Business Conference, Tokyo, Japan (July, 1992).
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Presented at the Memorial Symposium for Herman P. Mark at Polytechnic University of New
York (1992); J. Polymer Sei. Polymer Symposium, Vo1.75, pp. 125-136 (1993).
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on Technology Management, Pepperdine University, Santa Monica, CA, (1992).
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Pittsburgh, Carnegie Mellon Univ.) Yokohama, Japan (1994).
20. N.Yoda, lnvited Lecture, "Technology ManagementandInnovation ofPolymer Science and
Technology," Delivered at the Symposium on Polymer Science and Technology for the 21st
Century in Honor of Otto Vogl in New York (1992); Progress in Polymer Science, Vol. 19,
pp. 975-994 (1994).
21. N.Yod!!-> Organizer and Chairman of Program Committee, Proceeding of the First International
Symposium on Environment and Polymers (ISEP95) held at the United Nations University" Tokyo,
Japan sponsored by the Soc. Polymer Sei. Japan and KOBUNSHI DOYUKAI, October 18-
19, (1995).
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Heidelberg, Germany (1996).
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.U. S.A. ( 1997).
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Encapsulants of Integrated Circuit Chips and High Temperature Photoresist for Electronic
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pp.18-21 (May, 1997).
627
RECYCLING OF POLYAMIDE 66 AND 6
H. Peter Kasserra
Dupont Canada, Inc.

Research and Development Center
P.O. Box 5000, Kingston, Ontario, Canada
Thank you for inviting me to participate in this conference. I am pleased tobe able to de-
scribe to you our program at DuPont directed towards developing a closed-loop recycling tech-
nology for nylon. This presentation is based on work completed at the Experimental Station in
Wilmington, Delaware and at our Research and Development Centre in Kingston, Ontario.
It will be obvious from the scope ofwork done that our corporation has a strong set of
environmental values and that we are taking the necessary steps to ensure that nylon, a mate-
rial that has been so important to the success of our company, will continue tobe an environ-
mentally friendly product weil into the future.
In early 1996 the Environmental Leadership Council of DuPont took a further initia-
tive by developing this policy statement specifically for polymer recycling. It provides the
business units with guidance as they address the principles ofResponsible Care to which the
DuPont Corporation has committed itself.
It also provides a structure as we seek opportunities for source reduction, reuse andre-
cycle and emphasizes the value ofintegrating these options into our business plans early in the
development process. We will have to find the balance between meeting the needs of society
and those of our shareholders as we develop our recycling strategies for the next century.
This overhead provides a composite view of the pile of carpet on which we are cur-
rently building our program. The proportion ofpolyamide carpets, i.e. nylon 66 and nylon 6,
in that pile varies somewhat with location but is well over 50% in North America.
+ DUPONT BELIEVES THA T POLYMER RECYCLE IS AN

IMPORTANT ELEMENT OF AN OVERALL BUSINESS
STRATEGY TO CONSERVE THE USE OF RAW
MATERIALS.
+ HOWEVER, RECYCLE IS ONL Y ONE OF SEVERAL
OPTIONS THAT INCLUDE SOURCE REDUCTION, REUSE
AND APPROPRIA TE WAS TE DISPOSAL.
+ WE BELIEVE THA T SOUND ECONOMICS AND
ASSESSMENT OF TRUE RISK, COMiNED WITH AN
INFORMED CONSUMER BASE, WILL EFFECTIVELY
DRIVE APPROPRIATE BUSINESS STRATEGIES.
Figure I. Dupont's recycling policy.

Edited by P. N. Prasad et al., Plenum Press, N ew York, 1998 629
DIRT
22%
LATEX/
FILLER
30% FACE
FIBER
40%
BACKING
8%
1500 kt/yr USED CARPET TO LANDFILLIN N.A.

Figure 2. New nylon from old carpet. (1500 kt/yr ofused carpet is sent to landfills in North America.)
POST-CONSUMER PRODUCT COLLECnON
FEEDSTOCK RECLAMA nON
MELT RECYCLING
CHEMICAL RECYCLING
Figure 3. Integrated Dupont recycling business.
The carpet industry realizes that it needs to find ways to keep this stream out ofland-
fills and hopes to do this in a manner that avoids legislative action.
I would also like to emphasize that our focus is not solely on carpets. There are many
other sources ofnylon that will need tobe recycled in the future and some ofthese might be
easier to handle than used carpet.
lt will require the integration of several major undertakings to make the recycling of
nylon a viable business proposition. I am part of a team that has been formed within DuPont
called the Nylon Recycle Solutions Business Segment to ensure that we have all ofthe pieces
connected for a successful program.
I will briefly review for you these four activities beginning with the carpet collection
operation that is the source ofthe majority of our recycle material today. Both our carpet recla-
mation and melt recycling processes are commercial while chemical recycling is still in the
development stage.
This overhead addresses the integration within our company. Many of us wonder,
however, whether an industry-wide approach will not be required to make large-scale recy-
cling commercially viable?
PARTNERSHIP FOR CARPET RECLAMAnON (PCR)
50+ COLLECnON CENTERS IN N.A. TODAY
COLLECnON, CONSOLIDA nON AND

TRANSPORTAnON TO CHATTANOOGA, TN
CURRENTLY PROCESSING >500 tlmo CARPET
EXPAND 20-30x IN N.A. BY YEAR 2000
Figure 4. Post-consumer carpet collection.
630
NYLON CARPET ,....---....,
66&6 CUT
SHRED SEP- SEP- GRIND
CHIP ARATE ARATE 1.5mm
NYLON
Figure 5. Carpet reclamation process.
In 1991 DuPont formed a partnership that brings together carpet mills, carpet dea1ers,
waste management and transportation companies as well as customers with a common envi-
ronmental goal.
The PCR program takesback all types of carpeting beginning with the removal of car-
pet from the user. The carpet is stored and consolidated locally until enough is collected to fill
a tractor-trailer ( 15-20 tonnes ). The carpet is then transported by road or sometimes by rail to
Chattanooga, Tennessee where our first carpet reclamation facility has been located. I will de-
scribe that process shortly.
This program is presently focused on the commercial market where we can hope to get
!arge quantities ofsimilar carpet back in a relatively clean way. Studies are underway to evalu-
ate the best method of collecting residential carpets.
After transportation to Chattanooga, the used carpet is sorted into essentially two !arge
piles
polypropylene backed nylon carpets, and
other carpets.
The nylon carpet, whether PA66 or PA6, is first passed through the dry process which
is basically a series of size reduction and separation steps. This provides a dry mix of 50-70%
nylon, 15-25% polypropylene and 15-20% Iatex, fillers and grit. Water is added in the second
step to form a slurry for the wet process where the shredded fiber is washed, screened and fur-
ther purified in a proprietary density separation process. A 98% pure nylon fiber is produced
along with a by-product of98% pure polypropylene.
Our Chattanooga facility started operation at a commercial scale in 1995 and will be
expanded over the next year.
The carpets in the non-nylon pile are shipped off-site, fiberized and converted to
wood-like products or felt-like materials by another company. The important consequence of
this isthat none ofthe carpet collected under our PCR program goes to landfill for disposal.
631
BLEND
P-C
RES IN
BLEND INSPECT PELLETIZE EXTRUDE
c;ONTROL
CERTIFY
Figure 6. Carpet fiber nylon compounding process.
The recovered carpet fiber nylon (CFN) is shipped to DuPont's compounding facility
in Ravenswood, West Virginia where it is densified and melt-filtered to achieve some addi-
tional cleaning. This post-consumer nylon is then co-extruded with virgin polymer (ratio 1:3)
and other ingredients such as glass and minerals into a moldinggrade engineering resin. Fol-
lowing normal pelletizing, inspection and blending, the product is sold as one of our MIN-
LON line of black engineering resins (PCRFE22C or PCRFE6202) with post-consumer
nylon content.
This form ofmelt-recycling is the "today" component ofDuPont's commitment to re-
cycle. The "tomorrow" component is shown on the next overhead.
Our chemical recycle process converts post-consumer (p-c) nylon, PA66 or PA6 or
mixtures thereof, into virgin-like hexamethylenediamine (HMD) which is one ofthe mono-
mer building blocks ofnylon 66.
The proprietary step ofthe recycle process is also called ammonolysis in which am-
monra is used to depolymerize the nylon and convert some ofthe break-down products into
US PATENT 6,302,766 (APRIL 12,1994)
AQUEOUSWASTE
CRUDE
MONOMERS
FRACTIONAL
DISTILLATION
CATALYST-----~
AMMONIA----41~
HIGH BOILERS
1 - - - - - - - - - - - - - - - - R E C Y C L E ...............!
Flgure 7. Nylon chemical recycle process.
632
6
... +EXPERIMENTAL DATA

~ 6
z
0
i= 4 ~~~--~~.--.--~--------~CN
0 ~~~----~. .-.--~~------~L
:::>
0
3 ~-----.----~~----~------~MD
~
Q.
Ir:
w 2
:!E '---~------------~-------ADN
0
z 1
0
:!E
0
0 600 1000 1600 2000 2600
TIME
Figure 8. Ammonolysis reaction computer simulation.
species that can subsequently be hydrogenated to make HMD. Ammonolysis is carried out
under a pressure ofabout 70 atm and at temperatures in the range of300 C. Caprolactam, if
nylon 6 is present in the p-c feedstock, can be recycled to the reactor or recovered as a refined
caprolactam product.
This is a true example of closed-loop recycling that permits new nylontobe generated
from old thus minimizing consumption of our non-renewable resources.
The ammonolysis process ofpolyamides involves very complex chemistry incorpo-
rating both the breakdown reactions ofthe polymer as well as the dehydration reactions ofthe
amide functions to produce nitrile groups. The presence of potentially two different nylons in
the feedstock, feedstock impurities and high temperature further complicate this process by
introducing numerous side-reactions.
Wehave developed a computer simulation model ofthe ammonolysis process incor-
porating close to 80 differential rate equations in order to approximate the possible reaction
mechanisms involved.
This overhead demonstrates experimental verification of our model for the steady
state production rate of the four major monomers generated by ammonolysis of nylon 66
(ADN/HMD) and ofnylon 6 (CL/ACN). Similar agreement between experiment and predic-
tion has been obtained for the major intermediates and the more important by-products.
+ COLLECTION LOGISTICS AND COST
+ P-C MINLON COMPARABLE TO VIRGIN RESIN
+ RECYCLE HMD QUALITY EQUAL TO VIRGIN
+ 25% RECYCLE CONTENT CARPET PRODUCED
+ EQUILIBRIUM CONTROLLED AMMONOLYSIS

OF PA66 AND PA6
+ LIFE CYCLE INVENTORY RESULTS POSITIVE
Figure 9. Key leamings.
633
INTEGRATION AND SCALE OF OPERATIONS
CHEMICAL PROCESS YIELD
BEGINS AND ENDS WITH THE CONSUMER
ENVIRONMENTAL HIERARCHY OF RECLAMATION
IMPACT OF LEGISLATION AND SOCIETAL NEEDS
Figure 10. The economic challenge.
Our carpet collection operation has demonstrated that a partnership of committed in-
dustries and individuals is the only cost-effective way of dealing with the collection of post-
consumer goods at a meaningful scale.
Molded parts made from our post-consumer MINLON products have successfully
passed on-vehicle tests and have found commercial application as air cleaner housings.
Our carpet samples with 25% recycle content have received favourable reaction in the
market place.
Wehave been able to demoostrate through our pilotplant work that chemical recycle is
a technically and operationally viable process. We now know where improvements are needed
and hope to accomplish these with our second generation pilot plant.
We will continue our life cycle assessment studies based on early results from a life cy-
cle inventory comparison which suggests that chemical recycle is a good environmental
choice.
While the technological problems of recycling are not minor, the economic viability
of even the simplest recycling scheme poses a significant challenge. Integration and scale of
operations require careful consideration in an environment where feedstock production is to-
tally unlike that normally found in chemical industry. Compare e.g .. HMD from p-c carpet
with HMD from crude oil. Although the chemical recycle process is the most desirable one
from the standpoint of creating a closed-loop system, it is also the most complex one and thus
mostsensitive to the economic impact ofprocess yield.
Recycling begins with the enduser, the consumer, who must be made aware that in the
hierarchy of reclamation, source reduction, reuse and appropriate waste disposal are all op-
tions that deserve economic consideration. When society as a whole decides that we are con-
suming non-renewable resources at an unacceptable rate, then closed-loop recycling will
become mandatory and chemical recycle the process of choice.
1 .......-- .- .... - ......... -

- ..... - ......................... - ................ .
..... 0.8
cn TOTAL
0
(J ------- - - - - .. ------
Q
0.6
w = : : ................................. - .... - .................. - .......... ..
N
::::; 0.4 INGREDIENTS
-- . - .... -
~
a::
0 0.2 OTHERVAR.
z
FIXED
0
MONOMER CAPACITY
Figure 11. Cost/capacity relationship.
634
1995 CARPET RECLAMATION
P-C MINLON RESIN
CHEMICAL RECYCLE PILOT PLANT
1996 GEN II AMMONOLYSIS PILOT PLANT
OTHER RECYCLE TECHNOLOGY OPTIONS
1997 ENHANCED COMPUTER MODEL
ECONOMIC REVIEWS
1998/99 DEMONSTRATION UNIT
INCREASED CARPET COLLECTION AND
RECLAMATION CAPACITY
200? COMMERCIAL FACILITY
Figure 12. Program and schedule.
SO MUCH DONE -
SO MUCH LEFT TO DO
WINSTON CHURCHILL
Figure 13. Recycling.
This overhead shows the effect ofscale on the normalized cost ofmanufacture (COM)
of refined recycled HMD by the chemical recycle process.
The two important features to note are
the ingredients cost, in particular the feedstock cost, represents a significant por-
tion of the total COM, and
cost is a non-linear function of capacity.
We do not expect to meet the cost ofvirgin HMD at low recycle HMD production rates
and are exploring the scale required to make this process competitive.
Part of that study is further development of our ammonolysis technology using a
second-generation pilot plant at Kingston, which is just about to be started up.
DuPont has been collecting carpets since 1991 and with the recent acquisition ofMSA
industries which is one ofthe largest commercial carpet installers in the United States, will be
significantly expanding this program over the next year. We are also assessing the need for
more facilities like our Chattanooga reclamation operation.
We believe we will be able to show major process improvements with our second-
generation chemical recycle pilot plant. The experimental results will be used to verify our en-
hanced process simulationmodeland will also allow us to generate basic engineering data for
!arger scale facilities.
With this information we will review the economics ofthe entire nylon recycle busi-
ness from collection through to chemical recycle or whatever recycle process the end-product
justifies in order to help us focus our resources where they are most needed. Currently we see
the need for a commercial scale chemical recycle facility early in the next century.
I hope that I have left you with the impression that a truly holistic approach to recy-
cling represents a significant challenge to industry which is after all only part of our greater
society.
Wehave come a long way, if only in recognizing the magnitude ofthe challenges fac-
ing us. We at DuPont have leamed that to make a good nylon is not easy, and to breakdown a
good nylon in a controlled and economically viable process is even harder.
We Iook forward to that opportunity.
635
SOL-GEL TECHNOLOGY FOR FRENCH INERTIAL
CONFINEMENT FUSION PROGRAM
Philippe Belleville
CEA- Centre d'Etudes de Limeil-Valenton

94195 Villeneuve Saint Georges Cedex, FRANCE
INTRODUCTION
It is well established by manufacturers and users that optical coatings are

generally prepared by the well known Physical Vapor Deposition (PVD) technology.
Sol-gel technology is an effective and competitive alternative. This paper will first
emphasize on the sol-gel thin film history and link the historical development in this
field with the works concerning the technology for high power Iasers. Next, the
chemistry of the sol-gel process will be discussed, as well as the production of optical
coatings and the related deposition techniques. Finally, the paper will describe the
preparation and performance of different types of sol-gel optical coatings we have
developed to fulfill the requirements of a future 1.8-MJ/500-TW (351-nm) pulsed
Nd:glass Iaser. This powerfullaser is to be used for our national Inertial Confinement
Fusion (ICF) program, to demonstrate at the laboratory scale, ignition of deuterium-
tritium fusion fuel. This paper will provide a convincing argument that optical coatings,
are some ofthe useful products available from sol-gel technology.
SOL-GEL OPTICAL COATING HISTORY
Today, through a collaborative program, both CEAIL-V and LLNL are

addressing, the critical physics and technology issues for demonstrating and exploiting
high gain Inertial Confinement Fusion (ICF). Both believe that a compelling strategy for
respective national ICF programs is to demonstrate ignition and moderate gain at the
very beginning ofthe next century with an upgrade to the existing Phebus (France) and
Nova (USA) Iasers to provide 1.8 to 2-MJ of 0.351-~-tm light in a nanosecond pulse
regime.
The proposed MJ-range Iaser system in France will consist of 240 "beamlets"
each having a final optical aperture of 40-cm. The beamlets would likely be grouped
into compact and efficient 4 x 2 arrays to form 30 main beamlines. While Phebus used a
multistage, single-pass amplifier design, the MJ-laser will use a single-stage multipass
Science and Techno/ogy of Polymers and Advanced Malerials

amplifier design shown in Fig. 1. In the CEAIL-V multipass architecture, called "L-
turn" a Iaser pulse enters the resonator cavity near the focal plane of the spatial filter and
then passes to the rear of the cavity through a multisegmented amplifier (MSA) and
reflects off the cavity-end mirror. The pulse then makes three additional passes through
the resonator cavity (Ml-M2) before being directed-out of the cavity. In our "L-Turn"
multipass concept each pass is following a different optical pathway. In this design, the
amplified pulse is then transported through a series of mirrors to the frequency-
conversion array and finally focused onto the target.
Compared to Phebus which uses 109-cm diameter turning mirrors, in our
proposed MJ-laser concept the aperture of the turning mirrors has been decreased
largely because of improvements in Iaser damage thresholds. The aperture of these
mirrors will be 60-cm x 40-cm for a 45 incidence positioning. The final optics in the
CEA/L-V system include a target-chamber vacuum focusing Jens and a debris-shield. It
is clear that the cost of such a !arge Iaser system is a strong function of the Iaser damage
resistance ofthe bulk optics and coatings. That is why, for the last eight years, CEA/L-
V has maintained a substantial research and development effort on the preparation of
suitable, cost-effective optical coatings by a solutionroutesuch as the sol-gel process1' 2
MIRROR M2 OUTPUT
PICK-OFF MIRROR
AMPLIFIER
MIRRORM1
Figure I. Schematic diagram of the "L-Turn" configuration for a typical "beamtet" of the proposed 240
to 288 beamtet MJ-range Iaser design. The Ml-M2 cavity-end mirrors, lenses and some optical
components in the amplifier would be soI-gel coated.
SOL-GEL CHEMISTRY AND PRINCIPLES
A "sol" is a colloidal suspension of solid particles in a liquid. In such a system

the colloidal particle is sosmall (- 1 to 1000-nm) that gravitational forces are negligible
and interactions are dominated by short-range forces, such as van der Waals attraction
and surface charges. Colloidal or particulate gel formation is the result of a decrease in
the surface charge ofthe suspended particles, consequently the solloses its mobility and
becomes able to maintain its shape without the mold. Gels can also be obtained by
controling the polymerization of an hydrolyzed starting compound. In such a system, a
3D-network crosslinking develops until a high-molecular weight polymeric gel results.
The gel point is the time (or degree of reaction) at which the last bond is formed that
completes the network.
638
In the sol-gel process, the starting compounds also called precursors, for
preparation of a colloidal particle consist of a metal or metalloid element surrounded by
various ligands (appendages not including another metal or metalloid atom). Comrnon
precursors include inorganic materials (salts containing no carbon) and organic
compounds (alkoxides). Metal alkoxides are generally very reactive species which may
be due to the presence of electronegative alkoxy groups. These precursors are, therefore,
extremely susceptible to hydrolysis by atmospheric moisture and require careful
handling. Moreover, hybrid organic-inorganic materials can be obtained when non-
hydrolyzable organic ligands are bonded to the precursor. Such hybrids3, known as
ORMOSILs (ORganically Mdified SILicates) and ORMOCERs (ORganically
Mdified CERamics) revealed very unique properties and are now extensively used for
sol-gel optics.
Depending on the amount of water, hydrolysis of meta! alkoxides may go to
completion or stop while the metal is only partially hydrolyzed. Two partially
hydrolyzed molecules can link together in a condensation reaction. Once the wet gel is
produced, a drying step is required to get what it is called a xerogel. To convert this
xerogel into a useful product, a firing and sirrtering step is then necessary. Final
products vary from films, to fibers, to fine homogeneous powders, to porous matrices
and to monolithic bodies. The advantages of the sol-gel approach over the traditional
melting technique of solid raw materials include chemical purity and homogeneity,
flexibility in the selection of compositions, processing at relatively low temperatures
and producing monolithic articles close to their desired final shape, thereby minimizing
the finishing cost.
SOL-GEL OPTICAL COATING PRODUCTION
Coatings are most likely the best opportunity for the promotion of the sol-gel
technology in modern industry. By far, oxide coatings have been the most widely
investigated and there are two different kinds of sol-gelliquid systems which have been
used for their preparation : the polymeric and the colloidal systems. Each system may
require quite different handling depending on the properties of the liquid and the nature
of the product which is desired.
For the preparation of Iaser darnage resistant optical coatings such as
antireflective, highly reflective and polarizing coatings, the use of the standard
polymeric approach has abandoned in favor of coatings elaborated from colloidal sols4 .
The main reason for this choice is the fact that most multilayered coatings deposited
from polymeric solutions craze and peel when heated due to stresses formed by
shrinkage. On another hand, the colloid-based thin films consist of layers of nanosized
amorphous or crystalline oxide particles of high purity grade and having a high surface
area. Depending the final coating use, these colloids may be also combined with
binders, fillers, water-repellent compounds, lubricants and coupling agents. Because
colloidal coatings are stress-free, they can be deposited without crazing or flaking effect
to build up thick films.
DEPOSITION TECHNIQUES
Of the many liquid coating methods available, so far, only three have the
capability of laying down very thin layers of precise and uniform thickness. The most
639
widely used are dip5 and spin6 coating. Laminar-flow coating which has been developed
conjointly with Convac-Fairchild (Vaihingen, Germany) is a comparatively new
technique 7 In the laminar-flow coating technique, also called meniscus-coating,
substrates are coated in an upside-down position using vacuum-chuck for substrate
carriage. A substrate is placed in contact with the liquid film such that a narrow
meniscus is created between it and the applicator tube and this latter is then smoothly
moved horizontally relative to the substrate. A liquid film is transferred to the substrate
as the applicator tube translates and the coating is formed after solvent evaporation. This
coating principle is schematically represented in Fig. 2.
deposited film
slot tube
translation movement
. Distance (slot tube/substrate) is critical : -200~m

. Translationspeedsare in the range 5 to 15 mrn/s
Figure 2. Meniscus region ofthe laminar flow coating technique.
Investigations8' 9 have shown that the coating thickness is proportional to

deposition rate va. with 0.65<a<0.73 depending the nature of the coating solution. A
problern unique to the laminar flow coating method and critical for multilayer coating
preparation only, is particle contamination due to the thick film or dripe line that can
build up at the point where the meniscus cuts and detaches from the substrate. This
problern can be minimized by cleaning the substrate edge at intervals during the coating
runs. Today, using the coater prototype developed with Convac, this coating method has
revealed particular promise for the deposition of so I-gel high reflective coatings on !arge
square or reetangular flat substrates.
ANTIREFLECTIVE (AR) COATINGS
Antireflective coatings are basically of three types. The first and siruplest type is
a single-layer coating in which the coating index is ideally equal to the square root of
the index of the substrate assuming air is the extemal medium. The other two types are
multilayer systems of two or more layers of different indices and, lastly, graded-index
systems where the index is uniformly and continuously graded from the substrate, to the
extemal medium. At CEA/L-V, we have developed four kinds of sol-gel antireflective
coatings, all based on single-layer or multilayer designs. These AR coatings consist
mainly of amorphous silica in the polymeric and/or colloidal state combined in certain
cases with other metallic oxides, binders, fillers, hydrophobic and lubricating agents and
adhesion promoters.
640
Standard Single-Layer Antireflective Coating
This coating is a single-layer system made of nanosized spherical particles ( 10-

nm average diameter) of amorphaus silica and deposited from a colloidal suspension.
The single-layer AR coating we are routine1y using is prepared from a Stber silica
sol 10 . This silica sol synthesis is based on the base-cata1yzed (arnmonium hydroxide
catalyst) hydro1ysis of tetraethoxysi1ane in ethanol with a Si/H2 0 molar ratio of 1/2.2
and at room temperature. In basic conditions, hydrolysis in silicic acid followed by
formation of insoluble silica colloidal particles is favoured over condensation to soluble
polymers.
Since, when deposited, the silica spheres do not pack perfectly together, the
resulting coating is a porous film (~ 57% porosity). That is the air present within the
space between particles which allows lowering the refractive index to a value of 1.22.
The silica coating is of high purity and this contributes to a UV cut-off as low as 200-
nm. This antireflective coating is easily abraded since no chemical bond exists between
independent silica particles and with the substrate. It is of no concern in our current laser
applications and in fact is an advantage as it allows easy removal of the coating by a soft
scrubbing without damaging the optical form of the surface beneath. The ability to drag
wipe for vigoraus cleaning, for example, might be useful and beneficial. To accomplish
this, a method in which the particle to particle adhesion could be increased with no
change in optical properties would be desirable.
Thomas 11 found that it was possible to incorporate a siloxane hinder into the
suspending medium of a Stber silica sol. In this case, the soluble siloxane was
converted to silica after solvent evaporation and acted both as a binder and as a filler for
the colloidal particles. In this work, quantitative results were presented for the
preparation of AR coatings varying in refractive index from 1.22 to 1.44. More recently,
at CEA/L-V, we discovered that treatment of a porous silica coating with ammonia
vapor resulted in a consistent strengtherring of the coating with no loss in optical
performance 12 A suitable explanation of this observation consists of a base-catalyzed
condensation as proposed by Iler13 . First, particle surface silanals are deprotonated by
the NH 3 catalyst giving Sio- species. The latter nucleophilic entity attacks an adjacent
neutral silicate specy to generate a siloxane bond (495-cm 1 band assigned to Si-0-Si
bending mode) through a condensation mechanism. Moreover, this particle-to-particle
linking favorates the H-bonding of neighbour particle via vicinal silanols (3660-cm 1
band assigned to mutually hydrogen-bonded surface hydroxyls). These chemical
changes have been evidenced by FT-IR analysis as shown in Fig. 3.
100
80
T(%)
,,
~
- Sial AR-ooalirg
- - - 111-13-treate:l Sial AR-alalirg vertical pol.
ro:J 450
2800 1800 1200
arr1
Figure 3. FT-IR spectra of a porous silica coating with and without NH 3-treatment (framed spectra
correspond to polarized beam measurements).
641
After treating the coating with ammonia vapors for roughly 5 hours, the increase
in strength accompanied by a shrinkage of the coating thickness (~ 20% of the original
thickness) is completed. The antireflective function is retained. This indicates that the
porosity and hence the refractive index remain unchanged.
The ammonia hardening post-treatment enables us to alcohol drag-wipe and
physically touch AR-coated glass substrates. However, the resulting coating can not be
as far considered as a scratch-resistant product. This improvement is now routinely use
for AR sol-gel coatings since it allows more convenient handling of coated parts and
still if required an easy removal of the coating by a suitable chemical process.
Two-Layer Antireflective and Environmentally Protective Coating
This optical coating is especially recommended for Potassium Dihydrogen

Phosphate (KDP) crystals used as harmonic converters on high power Nd:glass lasers
and also for phosphate Jaser-glass amplifier rods.
The Phebus laser uses KDP arrays as harmonic converters. The crystals in these
arrays were originally coated with the standard single-layer porous sol-gel AR coating
which has been described before. While optically very good, this coating did not
provide environmental protection for the KDP surface. Use of transparent organic-
inorganic materials (ORMOSILs) is investigated as a protective coating on KDP
crystals and phosphate laser-glass rods.
The methyl silicone used is (CH3 Si0 15 )m, with a refractive index of 1.41. This
hybrid material is a high purity product prepared by the hydrolysis of
methyltrimethoxysilane and is supplied as a soluble prepolymer in ethanolic solution. It
is applied by dipping and, after 16 hours curing at 150C, gives a dense and insoluble
coating of optical quality. When applied on KDP (index 1.49-1.51), this coating is
sufficient to reduce reflection from 4% to 2% per surface. For coating phosphate Jaser-
glass surfaces, we selected a methyl phenyl silicone such as (CH 3 C6H 5Si0),m with a
refractive index of 1.49. This material is obtained by the hydrolysis of
methylphenyldiethoxysilane and is supplied as a soluble prepolymer in flake form. The
flakes are subsequently dissolved in ethanol. The dense, insoluble glass-like silicone is
obtained after dipping in the prepolymeric solution and curing for 12 hours at 180C.
When applied on Hoya LHG-8 Jaser-glass (index 1.51-1.52), this coating is sufficient to
reduce the reflection from 4.5% to 3.5% per surface.
When KDP and phosphate Jaser-glass surfaces are coated with the suitable
silicone, residual reflections remain. The transmission of these silicone-coated surfaces
can be improved by simply overcoating with the standard porous silica quarterwave AR
coating from an ammonia-free coating sol. Theoretical calculations indicated that this
two-layer system would give a broad transmission increase which could be arranged to
cover two harmonics by a suitable choice of coating thickness. The Phebus laser now
uses silicone-so! AR coated SHG-crystals (for use at 526.5 and 1053-nm) and THG-
crystals (for use at 351-nm). Typically, the gain in transmission is ranging 6.5-7.5% at
the wavelengths of interest
"Flucosil-11" : An Abrasion Resistant and Hydrophobie Broadband AR-Coating
To improve the pumping efficiency of the numerous laser disk amplifiers to be

used in such a facility, we have developed at CEA/L-V, a two-layer coating specifically
for use on the blast-shield component. This blast-shield optical component is placed
between the flashlamps and the Iaser disk amplifiers to prevent darnage of the costly
amplifiers by possible explosion of a flashlamp.
642
100
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,,........... .,\.
r\~.
,
I
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I ' '
r- 96
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__._____~
',
c -
L
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I
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!
I
I
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'rr ii'
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GI' '
I
vl\fl
Cl I
I
t- 82
::z:: I
..J 0 f\. I J.,;.... \. /\ ao
300 400 500 600 700 800 900 1000
Wavelength (nm)
Figure 4. Transmission spectra of a bare and both side coated soda-lime (Schott B-270) sample and
related Iransmission gain at the LHG-8 glass absorption bands.
Flucosil-II coating has been successfully prepared on both glass and plastic
substrates 14 . The Flucosil-II coating is a composite system made of colloidal zirconia
embedded in a nonionic amide polyvinylic filler, colloidal silica bound with a
polysiloxane hinder and an alkylsilane or preferentially a fluorosilane agent as a
lubricating and water-repellent material to smooth the coated surface. The preparation of
Flucosil-II consists first of applying a nearly dense zirconia-polyvinylpyrrolidone
(Zr0 2-PVP) layer having a refractive index close to 1.72 and which is halfwave-thick at
a centered wavelength of 600-nm. Then, this material is UV -cured (I. = 195-nm) to
avoid partial wash off by further application of coating solutions. Then, a Sirsiloxane
low-index material is dip-coated onto ZrOrPVP. An ethanolic suspension is used for
the Sirsiloxane coating material and this gives excellent uniform coatings. This
coating has a refractive index of 1.26 and is quarterwave-thick at a centered wavelength
of 600-nm. For excess solvent removal, coating is air-dried over 15-min or to shorten
the process exposed to an infrared-lamp light during 5-min. Finally, to improve the
abrasion resistance and confer some hydrophobicity properties to the resulting two-layer
antireflective coating, the porous low-index outer layer is overcoated with a thin layer of
a fluoropolymeric solution. After deposition onto the silica porous layer, few of the
hydrophobic material permeates the porous matrix and consequently changes a bit the
layer refractive index value by raising it from 1.26 up to 1.30.
The substrates which have been coated on botlt sides with the two-layer Flucosil-
II coating have demonstrated a 6.5 to 7.2% transmission gain over the whole visible
spectrum, as shown in Fig.4, with a transmission exceeding 98% from 0 to 40 angle of
incidence. The associated p-polarization reflection measurements, gives values below
0.5% from 10 to 40 and about 1.0% at 47 over 500 to 800-nm spectral range.
HIGHLY REFLECTIVE (HR) COATINGS
At CEA/L-V, the colloidal route has also been used to prepare simple HR
coatings consisting of alternating layers of quarterwave-thick high and low refractive
index components.
643
Colloid-Based Highly Reflective Coatings
Today, our investigations are based on the incorporation of a second phase

binder and/or filler to starting colloidal suspensions. Such a material has to be soluble in
the suspending medium of interest and must not flocculate the colloidal suspended
solid. Also, it must not dissolve or wash off on subsequent applications of coating
solution (in the preparation of multilayer systems for instance). Finally, this binder has
to be transparent at the wavelength of interest and also to have a !arge bandgap. If binder
concentration is progressively increased to enhance the coating strength, the porosity
will decrease until the pores are full and consequently the refractive index will increase.
A further addition results in increasing interparticle distance and the packing density
will decrease as the refractive index does.
We have preferred the use of a nonionic amide polyvinylic binder compatible
with both water and alcohol solvents. Polyvinylpyrrolidone (PVP) has the best
combination of properties for binder use. Considering the structure of the monomer unit,
it is seen to have an amphiphilic character. When added to a colloidal suspension, the
amphiphilic character of PVP helps maintain colloidal stability and reduce flocculation
through a steric stabilization mechanism.
Methanolic and acidic stable suspensions of Zr0 2 , Hf0 2 , AIOOH and Ti0 2
containing 10 to 20% water and PVP K-90 (MW = 360,000) were readily prepared and
could be used as such for coating. The fact that our coating media were essentially
alcoholic, was found to be beneficial for lowering surface tension and giving easier flow
characteristics and coating thickness uniformity. As all these Suspensions were to be
used to prepare multilayer HR coatings, we were interested in obtaining the maximum
refractive index. This index is directly dependent on the PVP/oxide ratio and the
optimum ratio was determined in a separate experiment in which the porosity of an
oxide coating prepared from a suspension containing no PVP was first determined and
the amount of PVP required to fill the air space in the coating then calculated. Ratios
varied for the different oxides and ranged from 10% by weight binder for Ti0 2, 15% for
Hfb 17.5% for Zr02 and 30% for AIOOH. The experimental index values were about
5% lower than the theoretical predictions, this may be explained by a Iack in particle
encapsulation conducting to a residual porosity in coating. To prepare multilayered HR
coatings we have selected ZrOrPVP as the high index material (n 1053 = 1.72) and
colloidal Si2 as the low index material (n1053 = 1.22). In such a system, for a
reflectance of 99%, generally up to 20 total quarterwave layers of alternating high and
low optical indexes are necessary.
The refractive index of Zr0 2 coating made of colloidal particles was increased
from 1.57 to 1.72 by addition of 17.5% to 20% by weight of PVP relative to zirconia.
Using Zr02 particles prepared by the hydrothermal treatment of a
ZrOClzfH2 0/(NH2 ) 2 CO precursor mixture, the maximum refractive index value we have
achieved is 1.72 with roughly 20%-by-weight binder content.
TEM analysis revealed that Zr0 2 particles were crystalline (mainly monoclinic
with few % tetragonal) and appeared as monodispersed parallelepipeds with the Iongest
dimension averaging 30-nm. Coatings were produced by spin coating, laminar-flow
coating and also dip coating. Moreover, after each PVP-containing layer deposition, a
UV -curing (A = 195-nm) was necessary for complete reticulation of the polymer and to
make it insoluble. In our work, during UV-curing, the coating is subjected to a 6-nm
shrinkage of the original coating thickness. It has been shown the fact that if the UV-
curing operation was too hard and/or too long, the PVP could be degraded until
complete removal therefore restoring the porous zirconia coating material with a
refractive index of 1.57.
644
~---------------------------------------------------r100
(SI02/AIOOH)16
(Si02/Zr02-PVP)9
Wavelength (nm)
Figure 5. Camparisan of sol-gel HR coatings prepared with different high index materials. Si0/ Zr0 2-
PYP multilayer mirrored coatings achieve slightly better optical performance than Si02/AlOOH for
about 40% the number of fewer layers and have a broader retlection peak which gives a better tolerance
in layer thickness.
Typical transmission spectra for both SiO/AlOOH and SiO/ZrOrPVP mirrored

coatings for normal incidence use are shown in Fig. 5. Of note for the SiOiZrOrPVP
30
1Phebus e-beam HRs I IMJ-Iaser sol-gel HRsl
25
0 Tuming~mirror requlrement
uncondltioned (!} Cavltymirror requirement
condltloned
20
VI
c:: ~
M
.... 15
E
u
::; 10
0
Ti02/Si02 Zr02/Si02 5102/AIOOH Si02/Zr02-PVP
1w Triehroie 1w 10>
Figure 6. Camparisan of average unconditioned laser-damage thresholds for the original Phebus HR
coatings and the current unconditioned and conditioned thresholds for sol-gel HR coatings designed for
use on the MJ-class Iaser concept.
645
system is the much lower nurober of layer pairs (about half) demanded for over 99%
reflection and the !arger width (twice) ofthe reflection peak.
Laser Darnage Thresholds of the Sol-Gel-Based HR Coatings
Our investigations have revealed that the darnage threshold of some colloidal
oxide coatings was dramatically increased when PVP-binder was incorporated into the
coating composition. For ZrOrPVP single-layer coatings we have measured a
considerable enhancement in Iaser strength by a factor of 8.5, i.e., from 2,5-J/cm2
without PVP to 20-21-J/cm2 with PVP addition@ 1064-nm wavelength and 3-ns pulse
duration.
As for AR coatings, most if not all of the sol-gel HR coatings we have prepared
have experimentally shown a conservative ,o.s scaling from 1 to 10-ns pulse duration.
Fig. 6 shows the unconditioned and conditioned darnage thresholds of sol-ge1
Si02/AlOOH and Si02/Zr02-PVP HR coatings compared with the thresholds of the
Phebus e-bearn HR coatings.
CONCLUSION
A major factor determining and dimensioning the Iaser architecture and aperture
size in the 1.8 to 2-MJ/500-TW (351-nm) CEA/L-V Iaser project is the darnage
threshold of the optics and coatings.
Room temperature and atmospheric pressure deposited coatings such as sol-gel
for AR applications and silicone for environmental protective coatings have high optical
and Iaser darnage performance and can be applied at a low cost compared to
conventional vacuum deposition processes. Today, we are considering using such a
technology to AR coat the lenses, windows, blast-shields, debris-shields, flashlarnps and
harmonic converters required by our proposed 240-beam MJ-class Iaser. This
technology is under further development to demonstrate the preparation of multilayer
highly reflective coatings for use as cavity-end mirrors in the MJ-class Iaser design.
Such work for the development of Iaser darnage resistant optical thin films by
the sol-gel process has opened new and promising prospects in other area. For instance,
based on CEA/L-V sol-gel development, a product with the trade narne KELAR is
now commercially available from Dimensions & Lavis Group in France.
ACKNOWLEDGEMENTS
Author is very indebted to Herve Floch for earlier work and guidance, to J-J
Priotton for technical support, and to Ph. Pegon from Reosc company for large-area
coating preparation.
REFERENCES
1. H. G. Floch & P. F. Belleville, "Soft Coatings Simplify Repairs to Laser Optics", Opto & Laser
Europe, 9, 30, February (1994).
2. H. G. Floch & P. F. Belleville, "Damage-Resistant Sol-Gel Optical Coatings for Advanced Lasers at
CEL-V", J. ofSol-Gel Sei. & Techno!., 2, 695 (1994).
3. C. Sanchez & F. Ribot, "First European Workshop on Hybrid Organic-lnorganic Materials",
Bierville, France, Universite Pierreet Marie Curie Proc. (1993).
646
4. H. G. Floch & J-J Priotton, "Colloidal Sol-Gel Opticai Coatings", American Ceramic Society
Bulletin, 69, (7), 1141 (1990).
5. C. J. Brinker et al, "Sol-gel Thin Film Formation", J. Ceram. Soc. Japan, Intern. Edition, 99, 843
(1991).
6. L. E. Scriven, "Physics and Applications of Dip Coating and Spin Coating", Mat. Res. Soc. Symp.
Proc. 121, 717 (1988).
7. H. G. Floch & P. Belleville, "Procede de Fabrication de Couches Minces Presentant des Proprietes
Optiques", French Patent n 92 08524, assigned to CEA.
8. H. F. Bok et al., "Method ofMeniscus Coating", US. Patent 4,370,356 (1981).
9. P. F. Belleville & H. G. Floch, Sol-gel optical coatings processed by the laminar flow coating
technique Sol-gel Optics I! Conf., SPIE's Proc. 1758, 40 (1992).
I 0. W. Stberet al, "Controlled Growth of Monodisperse Silica Spheres in the Micron Size Range", J.
Colloid Interface Sei., 26, 62 (1968).
II. I. M. Thomas, "Method for the Preparation of Porous Silica Antireflection Coatings Varying in
Refractive Index from 1.22 to 1.44", Appl. Opt., 31,6145 (1992).
12. P. F. Belleville & H. G. Floch, "Procede de Fabrication de Couches Minces Presentant des
Proprietes Optiques et de Resistance a !'Abrasion", French Patent no 93 03987, assigned to CEA.
13. R. K. ller, "The Chemistry of Silica", John Wiley & Sons Inc., New York (1979).
14. H. G. Floch, P. F. Belleville & P. Pegon, "Sol-Gel Broadband Antireflective Coating for Advanced
Laser-Giass Amplifiers", Sol-Gel Optics III Conf., SPIE's Proc. 2288, 14 (1994).
647
SMART THIN FILMS VIA THE SOL-GEL ROUTE
Jacques Livage
Chimie de la Matiere Condensee

Universite Pierreet Marie Curie
4 place Jussieu- 75252 Paris- France
INTRODUCTION
The sol-gel route appears tobe very convenient for the depositionofthin films by
such techniques as spin-coating or dip-coating.l The sol-gel process is based on the
hydrolysis and condensation of molecular precursors.2 The molecular engineering of
these precursors provides a chemical control of condensation reactions giving
nanostructured the oxide materials. In sol-gel chemistry two chemical routes are
currently followed depending on the nature of the molecular precursors ; the inorganic
route with meta! salts in aqueous solutions and the metal-organic route with meta!
alkoxides in organic solvents. In both cases the reaction is initiated via hydrolysis in
order to get reactive M-OH groups. This reaction can be simply performed by adding
water to an alkoxide or by changing the pH of an aqueous solution. 3 Condensation then
occurs leading to the formation of metal-oxygen-metal bonds. More and more condensed
species are formed from the solution leading to oligomers, oxopolymers, colloids, gels
or precipitates. Oxopolymers and colloidal particles give rise to sols which can be
shaped, gelled, dried and densified in order to get powders, films, fibres or monolithic
glasses.l ,2
This paper addresses the structure and physical properties of vanadium oxide thin
films deposited via the sol-gel reute. It shows how different materials can be obtained
depending on the choice of the molecular precursor solution. Vanadium oxide gels can be
made from vanadate aqueous solutions or from vanadium alkoxides.4 The condensation
of vanadic acid gives long ribbon-like oxide particles which behave as lyotropic nematic
Science and Technology of Polymers and Adyanced Materials

Edited by P. N. Prasad et al., Plenum Press,"New York, 1998 649
liquid crystals. Thick films in which ribbons align along the same direction can be
deposited. These oriented coatings exhibit improved electrochemical properties as
reversible cathodes for Iithium batteries. Amorphous oxo-polymers are formed via the
controlled hydrolysis of vanadium alkoxides. They allow the deposition of optically
transparent thin films that exhibit interesting electrochromic properties and switch
reversibly from yellow to green upon electrochemical reduction. Moreover, alkoxide
derived films can be easily reduced into vanadium dioxide. These V02 thin films exhibit
thermochromic properties and could be used as optical switches in the infrared. The
transition temperature of V02 films can be modified by doping the vanadium oxide with
other cations.
LA YERED OXIDE GELS FROM AQUEOUS SOLUTIONS
Polycondensation of Vanadic Acid
Vanadium pentoxide sols are prepared via the acidification of aqueous solutions of
sodium metavanadate NaV03 through a proton exchange resin. A yellow solution of
decavanadic acid H6V IO28 is first obtained that polymerizes slowly giving rise to a red
gel. Depending on vanadium concentration, viscous gels or colloidal solutions can be
obtained. The formation of vanadium pentoxide gels occurs around the point of zero
charge (pH",2) from the neutral precursor H3 V04 in which vv is fourfold coordinated. It
can be described as follows. 5
- Coordination expansion first occurs via the nucleophilic addition of two water
molecules. This gives hexacoordinated species [VO(OH)3(0H2)2]0 in which one water
molecule lies along the z axis opposite to the short V=O double bond while the second
one is in the equatorial plane opposite to an OH group. One V-OH2 and three V-OH
bonds are formed in this plane so that x and y directions are not equivalent (Fig.la).
-Fast olation reactions, along the HO-V-OH2 direction (y axis) give rise to olated comer
sharing chain polymers whereas slower oxolation reactions, along the HO-V-OH
direction (x axis) link these chains together leading to the formation of edge sharing
double chains (Fig.l b).
The condensation of vanadic acid then Ieads to the formation of ribbon-like oxide
species. Such ribbons can be clearly seen by electron microscopy.6 They are about
0.5!lm long, lOnm wide and lnm in thickness (Fig.2a). When deposited onto a flat
substrate, V20s,nH20 gels or sols give rise to ordered coatings in which the ribbons are
stacked one upon the others along a direction perpendicular to the substrate. This can be
clearly evidenced by X-ray diffraction showing the 001 harmonics typical of a 1-D order
(Fig.2b). The basal spacing between V20s ribbons increases when the amount of water
increases, d= 8.8A for n=0.5 and d=ll.5 for n=l.8. The shift d",2.8 corresponds
to the intercalation of one water layer between the ribbons. 7
650
z
(a)
~
-----
(b)
Figur!! I. Suggestcd mechanism for the formation of vanadium pcntoxide gels from aqueous solutions
of vanadic acid at pH~2, (a) coordination expansion, (b) condcnsation
651
!countsl
40000
001
35000
30000
25000
20000
15000
10000 003
5000 004
0.0
Figure 2. Schematic drawing of V205 ribbons (a) and X-ray diffraction pattem of ordcrcd coatings (b)
Electrochemical Properties of Vanadium Oxide Gels
Acid dissociation of water molecules occurs at the V20s!H20 interface leading to

the formation of H30+ species. The hydrated vanadium oxide then behaves as a
polyvanadic acid Hx V20 .nH20 (x=0.3). It exhibitsfast proton conduction and the a.c.
conductivity ofthin films increases with the water content, i.e. with the water pressure
(0"300 = 3.1Q-2Q 1cm 1 for n = 1.6, 0"300 = 5.1Q-5Q- 1cm 1 for n = 0.5)8 Humidity
sensors have been developped taking advantage of th is property. They are made of V20s
based inorganic gels mi xed with an organic polymer (hydroxy propyl methyl cellulose).
The impedance of thesehybrid films decreases by about two orders of magnitude when
the relative humidity increases from 80% to 97%.9
V20s,nH20 xerogels are also mixed valence compounds in which some
vanadium ions are in the y4+ state (V 4+fV5+", 1%). They exhibit electronic conduction
arising from the hopping of unpaired electrons between V4+ and y5+ ions. Their
electrical conductivity increases with the amount of v 4 + (0300"' 4.1Q-5Q- 1cm 1 for
y4+=1%, a3oo= 2.J0-3Q-lcml for y4+=IO%). Antistatic coatings based on vanadium
pentoxide gels have then been patenred by Kodak.IO
652
Vanadium pentoxide V205 is a promising candidate as reversible cathode for
Iithium batteries. Its redox potential is higher than 3 Volts with reference to Iithium and
specific capacities as high as 125 Ah/kg could be obtained. The discharge curve of
crystalline V20s exhibit several steps corresponding to the formation of different
LixY205 phases (Fig.3a). However, despite its layered structure, this crystalline oxide
behaves as a 3-D framework rather than a Van der Waals host and Iithium insertion
remains no Ionger reversible beyend the first two steps (x:o;1).
Interactions between V20s ribbons in vanadium oxide gels are much weaker than
in the crystalline oxide. Water molecules are intercalated in the interlamellar space and
ionic species can diffuse easily through .the oxide network. The electrochemical behavior
of vanadium pentoxide gels V20s,nH20 as a reversible cathode for Iithium batteries is
therefore quite different from that of the crystalline oxide. I I The discharge curve exhibits
a single p1ateau araund 3.1 V (Fig.3b). A faradaic yield close to 1.8 eN20s and a
capacity close to 250 Ah.kg-I are obtained at 2V corresponding to the reduction of all V5+
ions into V4+. Cycling experiments show a good reversibility and almost 70% of the
initia1 capacity is recovered after 30 cycles for a current density j=0.05 mA.cm-2. I2 This
improved behavior of gels should be due to the weak interactions between V20s layers
allowing the insertion of Li+ ions between the ribbons rather than in the channels as for
crystalline V20s. It has tobe poimed out that the discharge curve becomes almostlinear
when water is removed from the xerogel, the layered structure is lost and the material
becomes amorphous.13
50 100 150 200 0/Ah/kg-1

0
4.5
4.0
+' I
~ 3.5
....J
g~ 3.0 (a)
2.5
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Figure 3. Discharge curve of Y205. (a) crystalline oxidc, (b) vanadium pcntoxide xerogcl.
653
Sol-Gel Synthesis of Vanadium Bronzes
Because of their Iayered structure, vanadium pentoxide gels are able to intercalate
a wide variety of inorganic and organic guest species.l4 Intercalation in V 20s gels is
much easier than with usual crystalline layered compounds. It occurs readily at room
temperature within a few minutes when the gel is dipped into an aqueous solution of ionic
salts. The internal structure of the oxide network and the 1-D stacking of the V20s
ribbons are not destroyed. The basal distance increases and intercalation can be easily
followed by X-ray diffraction. lntercalation mainly involves cation exchange reactions
with the acidic protons of the gel. Chemical titrations show that the exchange capacity of
vanadium pentoxide gels for monovalent meta! cations M+ is close to 0.3 eqNzs. This
value corresponds to the number of acid protons measured by protometric titration.lS
Sodium intercalation for example Ieads to Nao.33V20s,1.5H20 compounds. The layered
structure is preserved with a basal distance d=ll. This ordered stacking is not only
preserved upon intercalation of meta! cations but also during a thermal treatment.
Anisotropie coatings of vanadium bronzes -Nao.33Y2S in which about 16% of the
vanadium ions are in the reduced y4+ valence state were made upon heating
Nao.33 V20s,l.6H20 gels. Thesesol-gel bronzes crystallize around 350C and exhibit the
same monoclinic structure as the usual vanadium bronzes obtained via conventional solid
state reactions at 700C. However X-ray diffraction suggests that (a,c) planes are
preferentially oriented parallel to the substrate while the tunnels of the bronze structure
remain perpendicular to the substrate. The electrical conductivity of such layers is highly
anisotropic (0;; = 2Q-lcm-l, G_L= 2xJQ-3Q-lcm-1)_16
(b)
(a)\
x (Li!V 20s)
Figure 4. Discharge curves of -Nao.33Y20S (a) prepared via solid state reactions (b) prepared from
vanadium pentoxide gcls.
654
Vanadium bronzes are known to be potentially attractive positive electrodes for
Iithium barreries. The preferred orientation of sol-gel Iayers could even enhance the
diffusion of Li+ ions into the host lattice. The electrochemical insertion of Li+, using
LiCI04 (1~1) in PC as an electrolyte, takes place in the potential range 3.5-2.4 V (vs.
Li/Li+). Three well defined steps are observed corresponding to the filling of the different
crystallographic sites of the bronze structure.
The influence of current density on the discharge curve clearly points out the better
electrochemical performance of the sol-gel materials compared to the corresponding
bronze prepared via solid-state reactions at 700C (Fig.4). Whatever the current density,
the faradaic yield is about twice !arger, about 0.8 instead of 0.5 Li+ per mole of bronze
can be reversibly inserted into the sol-gel materials.This is probably due to the faster
lithium diffusion through the oriented sol-gel film. The chemical diffusion coefficient of
Iithium (Du ".lQ-10 cm2s-1 for 0<x<0.3) is almost two orders ofmagnitude !arger than
in the solid state derived bronze. The reversibility remains good in the potential range
3.8-1.8 V. A capacity of about 120 Ahkg-1 is still recovered after 50 cycles, twice the
capacity obtained for solid state bronzes.17,18
As shown by N. Baffier and coworkers, the sol-gel process offers a versatile
route for the synthesis of cathode materials.18,19,20 Many meta! cations can be
intercalated in the layered structure of vanadium oxide gels leading to a !arge variety of
sol-gel bronzes exhibiting improved electrochemical propenies. Even new crystalline
phases such as Feo.12 Vz05.16 have been synthesized via the intercalation of Fe3+ ions
into the Iayered structure of vanadium pentoxide gels.21 Three reversible reduction steps
are observed between 3.8 and 2V, at 20C, using LiCI04 (IM) in PC as an electrolyte.
They correspond to a faradaic yield as high as 2.5F per mole. The presence of Fe3+ ions
in the vanadium pentoxide matrix provides improved cycling propenies at high discharge-
charge rates (C/4). A specific capacity of 200 Ah.kg-1 is recovered after 40 cycles in the
3.8-2V window.
AMORPHOUS OXOPOLYMERS FROM VANADIUM ALKOXIDES
Hydrolysis and Condensation of Vanadium Alkoxides
Vanadiumoxidegels can also be madevia the hydrolysis and condensation

of alkoxide pecursors. Vanadiumalkoxides VO(OR)3 were prepared upon heating under
reflux a mixture of ammonium vanadate and alcohol.
NIL! V03 + 3 ROH ~ VO(OR)3 + 2Hz0 + NH3 (OR = OPri, OAmt)
The reaction is carried out in cyclohexane and water is eliminated via azeotropic
distillation. The resulting alkoxide is purified by distillation under reduced pressure and
dissolved in its parent alcohol (c""0.5 mole/1).
Vanadiumoxidegels are then formed via the hydrolysis and condensation of these
655
alkoxides as follows :
VO(OR)3 + 3 HzO ::::::> VO(OH)3 + 3 ROH (hydrolysis)
2 VO(OH)3 ~ Vzs + 3 H20 (condensation)
These reactions Iead to different products depending on the hydrolysis ratio
h=(H20)/(V20s).22
For !arge hydrolysis ratio (h> 10), all alkoxy groups are removed giving fully
hydrolyzed VO(OH)3 precursors. As for aqueous solutions, this Ieads to the formation
of V20s,nH20 oxide gels made of ribbon-like particles. Because of the !arge amount of
organics, these gels are usually more reduced and slightly less organized. The acid
dissociation of V -OH groups at the oxide/water interface also occurs and the electronic,
ionic and electrochemical propenies are similar to those of the gels obtained from
aqueous solutions.
More interesting results are observed when a small hydrolysis ratio is used (h",l). All
alkoxy groups are not hydrolyzed preventing the formation of an oxide network.
Amorphaus oxo-polymers [Vz0s-x(OR)x] 0 rather than polyvanadic acids are formed.
Alkoxy Iigands remain bonded to the oxide network and can only be removed upon
heating above 300C.
Thin films can be easily made via the deposition of an alcoholic solution of
vanadium alkoxide by spin-coating or dip-coating. The alkoxide film is left in air so that
partial hydrolysis occurs spontaneously due to ambient humidity. The coating is then
dried around 80C with an infrared heater. The adhesion to the substrate seems to be
much better than when aqueous precursors are used. This is due to the remaining alkoxy
groups that can react with Si-OH groups at the surface of the silica substrate giving
covalent Si-0-V bonds. These thin films are optically transparent and appear to be
amorphaus by X-ray diffraction. They still contain non hydrolyzed organic groups that
can only be removed by calcination and should be considered as vanadium oxopolymers
rather than vanadium oxides or polyvanadic acids. Because of the organic components,
vanadium is more reduced than for aqueous polyvanadic acids and as deposited films
usually exhibit a pale green color (V 4 +", 109c ). Their electronic conductivity is therefore
quite high (cr3oo"' 1Q-3Q-lcm-1)_23
Electrochomic Properites
Electrochromic materials are characterized by their ability to change in color upon

charging/discharging in an electrochromic ce!J.24 Transition meta! oxides such as W03,
have been widely studied for display devices or smart windows. These oxides usually
turn blue upon reduction. We have shown that thin films deposited from vanadium
alkoxides also exhibit nice electrochromic properties. They turn from pale yellow to pale
green within about ls upon applying a voltage of 2 V and could be used either as a
colored electrode or a counter electrode.25
656
Therefore the electrochemical insertion of Li+ was studied by cyclic voltammetry
using a three-electrode electrochemical cell. The working electrode was made of a
vanadium alkoxide thin film deposited onto a Sn02:F electrode. The electrolyte was a
solution of LiCl04 (1M) in propylene carbonate (PC). A platinum grid was used as the
counter electrode and Ag/AgCI04 as a reference (VAg/Ag+= 3.55V vs LifLi+). Cyclic
voltammetric experiments were carried out in the potential range -1.5,+1 V (vs. Ag/Ag+)
at a scanning rate of 50mV.s-l. The voltammograms recorded with a thin film deposited
from vanadic acid exhibit two peaks (Fig.5a) for both reduction and oxidation. Li+ ions
are reversibly intercalated during the cathodic potential sweep and deintercalated by the
subsequent anodic sweep. Such a behavior is close tothat observed for crystalline VzOs
showing that these gels cannot be considered as amorphous as shown previously. The
-1
-1.5 '-'--'-'-'-'-'--'-'--'-.L.......L......._.__._...._.__.__,........._..J..-L__._....._._...J
-1.500 -1000 -500 0 500 1000
V (mV)
Figure 5. Cyclic voltammograms ofvanadium oxide thin films (a) deposited from aqueous solutions (b)
deposired from vanadium alkoxides
651
same experiments performed with vanadium alkoxides give very different
voltammograms (Fig.5c) exhibiting featureless reduction and oxidation curves. They are
typical of amorphous materials. This shows that as hydrolysis proceeds, vanadium
alkoxides progressively transform into amorphous oxopolymers. No preferred
orientation can be seen by X-ray diffraction.
Thermochromie V02 Thin Films
Vanadiumdioxideis known to undergo a reversible metal-insulator transition

around 68C. Above this temperature the free-electron carrier conductivity increases
abruptly and vanadium dioxide becomes infrared reflecting while below 68C it is
transmitting and relatively non-absorbing. The transition temperature can be easily
decreased by doping with high-valent cations (Nb5+, Mo6+, W6+) or increased with low-
valent dopents (Al3+).26,27 Most basic studies have been performed on single crystals. A
large resistivity drop with a small hysteresis of about 2C is observed around the
transition temperature. However the structural distortion associated with the
crystallographic transition prevents the use of bulk V02 for practical applications. Single
crystals break upon cycling whereas thin films appear to be able to survive stresses
during repetitive cyclings. They would therefore be much more convenient for optical
applications.
Optically transparent VOz thin films can be easily prepared from vanadium oxo-
alkoxides VO(OR)3.23 The alkoxide is deposited by spin-coating onto pure silica
_.....
0
10
E
..c:
0
..._.,
u
()
c::
B
<ll
c;;
u
~
0,1
20 30 40 50 60 70 80 90 100
Temperature eC)
Figure 6. Metal-insulator transition in V()z thin films deposited from vanadium alkoxides
658
substrates. The reduction of the vanadium oxide and the crystallization of Y02 occur
when a thermal treatment is performed under a reducing atmosphere (Ar-H2 5%). The
pure Y02 phase is obtained upon heating two hours at 500C. Each coating is about 0.05
!J.m thick and four coatings for instance have been deposited in order to have vo2 films
0.2 !J.m in thickness. Dense optically transparent thin films, made of Y02 crystals about
0. 1 !J.m in diameter are fom1ed. Doped Mx Y02 (M = W6+, Al3+) thin films are prepared
under the same conditions. The vanadium alkoxide solution is just mixed with a given
amount of molecular precursor such as WOCl4 or Al(OBu 5 )2(etac) (etac=C6H903)
dissolved in the parent alcohol (PriOH or Am 10H). The mixed solution is then deposited
by spin-coating and heated as previously.28
Electrical measurements were perforrned on crystalline YD2 films with the conventional
four-probes method . The switching properties are observed around 70C and the
resistance of the sample drops by almost three order of magnitude during the
semiconductor-metal transition (Fig.6a). A heating-cooling hysteresis effect of about
l0C is observed. It is of the same order of magnitude as those usually observed on V02
thin films.
YD2 thin films can be used for making electrical switches.29 The switching device
is simply madevia the deposition of gold electrodes, 0.4 mm apart, at the surface of the
V02 film (thickness"' 0.2 !J.m). These electrodes are evaporated through a mask so that
the geometry of the inter-electrodes space can be accurately controlled. An a.c. voltage is
applied to the device and the current-voltage (!-V) curve is recorded onto an oscilloscope.
A typical curve is shown in figure 7. Along the OA line, the device follows an Ohm's
Jaw, Y=RI. The film is in the insulating state and its resistance is quite high, "OFF" state.
However as the current increases, the film is heated via the Joule effect. At a given
Ihreshold voltage (V lh"'50V) the temperature of the film becomes !arger than its transition
10 B
;--..
6
<E '~............ \.,
'-" .,,
......... 4 .,.
2 A
~
-- 1 V (Volt)
0
0 10 30 40 50
Figure 7. Electrical switching devicc bascd on the mctal-insu lating transition in V02 films depositcd
from alkoxides
659
temperature and the vanadium dioxide becomes metallic. Its resistance drops by a factor
of about 1Q3 , "ON" state. The voltage decreases while the current increases (line AB).
The device remains in the "ON" state as long as its temperature is higher than the
transition temperature i.e. as long as the current is !arger than the holding current lh""0.6
mA (point C). Beyond this point, the film switches back to the "OFF' state (Iine CO).
The optical transmission of Mx V l-x02 thin films was measured in the infra-red at
a wavelength A.=2.5J.1.m in the temperature range l5C-100C. IR transmittance exhibits a
typical hysteresis loop around the transition temperature (Fig.8). For pure V02 films,
optical switching occurs around 80C upon heating and below 60C upon cooling. In the
metallic state, optical transmittance drops by almost two orders of magnitude and
becomes smaller than I% suggesting that the reflectivity of Y02 films is quite high
(Fig.8a). The temperature at which the optical switching occurs is significantly smaller,
around 40C upon heating, when the film is doped with 2% of Nb V (Fig.8b). Transition
close to ambient temperature can even be obtained with about 5% of wvr. The reverse is
observed with AIIII doped Y02 films for which the optical switching occurs around 90C
upon heating (Fig.Sc).
CONCLUSION
This paper shows that vanadium oxide films deposited from gels may exhibit
different properlies depending on the way they are made. The chemical composition and
structure of the condensed phases formed upon hydrolysis and condensation strongly
depends on the chemical route followed during the formation of the oxide network.
Vanadic acid precursors in aqueous solutions give ribbon-like oxide particles. Upon
drying, aqueous nematic sols and gels give rise to anisotropic coatings that exhibit some
preferred orientation.30 Water adsorption and dissociation at the oxide-water interface
Iead to the acid dissociation of V-OH groups and improved electrochemical properties.
Vanadiumalkoxides give similar products when hydrolysis is performed with a !arge
excess of water. However amorphous oxopolymers [V 25-x(OR)x]n rather than hydrated
oxide ribbons Y20s,nH20 are formed in the presence of a small amount of water. Such
precursors are specially convenient for making optically transparent Y02 thin films. This
may be due to the reducing power of the non-hydrolyzed alkoxy groups. With alkoxides,
V02 films are formed upon heating 2h at 500C, whereas with polyvanadic acid, they
have tobe heated 12h in the same conditions.
ACKNOWLEDGMENTS
The author would like to thank his coworkers who have been involved in this work, Noel
Baffier, Fabien Beteille, Guillermo Guzman and Roger Morineau.
REFERENCES.
1. Sol-Gel Technology, Ed. L. Klein, Noyes Pub., Park Ridge (USA) 1988
2. C.J. Brinker, G.W. Scherer, Sol-Gel Science, Academic Press, San Diego (1990)
3. J. Livage, M. Henry, C. Sanchez, Progress in Solid State Chemistry, 18:259 (1988)
4. J. Livage, Chem. Mater., 3:578 (1991)
5. M. Henry, J.P. Jolivet, J. Livage, Structure and Bonding, 77:153 (1992)
6. J.J. Legendre, J. Livage, .!. Colloid and Interface Sei., 94:75 (1983)
7. P. Aldebert, N. Baffier, N. Gharbi, J. Livage, Mater. Res. Bull., 16:669 (1981)
8. J. Livage, Solid Stare lonics, 50:307 (1992)
661
9. A. Inubushi, S. Masuda, M. Okubo, A. Matsumoto, H. Sadamura, K. Suzuki, High
Tech Ceramics, Ed. P. Vicenzini, Elsevier Pub., 2165 (1987)
10. C. Guestaux, J. Leaute, C. Virey, J. Via!, US Patent 3,658,573 (april 1972)
11. R. Baddour, J.P. Pereira-Ramos, R. Messina, J. Perichon, J. Electroanal. Chem.,
277:359 (1990)
12. R. Baddour, J.P. Pereira-Ramos, R. Messina, J. Perichon, J. Electroanal. Chem.,
314 (1991) 81
13. K. West, B. Zachau-Christiansen, M.J.L. Ostergard, T. Jacobsen, J. Power
Sources, 20:165 (1987)
14. P. Aldebert, N. Baffier, J.J. Legendre, J.Livage, Rev. Chimie Minerale, 19:485
(1982)
15. Gharbi, N., Sanchez, C., Livage, J., Lemerle, J., Nejem, L., Lefebvre, J., Inorg.
Chem., 21: 2758 (1982)
16. L. Znaidi, N. Baffier, M. Huber, Mat. Res. Bull., 24:1501 (1989)
17. J.P. Pereira-Ramos, L. Znaidi, N. Baffier, R. Messina, Solid State Ionics, 28-
30:886 (1988)
18. S. Bach, J.P. Pereira-Ramos, N. Baffier, R. Messina, J. Electrochem. Soc.,
137:1042 (1990)
19. J.P. Pereira-Ramos, S. Bach, J. Farcy, N. Baffier, Mat. Res. Soc. Symp. Proc.,
369:191 (1995)
20. S. Maingot, R. Baddour, J.P. Pereira-Ramos, N. Baffier, P. Wilmann, J.
Electrochem. Soc. ll:L158 (1993)
21. B. Pecquenard, J.C. Badot, D. Gourier, N. Baffier, R. Morineau, J. Solid State
Chem., 118:10 (1995)
22. M. Nabavi, C. Sanchez, J. Livage, Eur. J. Solid Stare fnorg. Chem., 28:1173
(1991)
23. G. Guzman, R. Morineau, J. Livage, Mat. Res. Bull., 29:509 (1994)
24. C.G. Granqvist, in Handbook of lnorganic Electrochromic Materials, Elsevier Ed.,
Amsterdam (1995)
25. J. Livage, Solid Stare Ionics, 86-88:935 (1996)
26. F.J. Morin, Phys. Rev. Lett., 3:34 (1959)
27. J.B. Goodenough, J. Solid Stare Chem., 3:490 (1971)
28. J. Livage, G. Guzman, F. Beteille, P. Davidson, J. Sol-Gel Sei. Techn. (in press)
29. G. Guzman, F. Beteille, R. Morineau, J. Livage, J. Mater. Chem., 6:505 (1996)
30. P. Davidson, A. Garreau, J. Livage, Liquid Crystals, 16:905 (1994)
662
SYNTHESIS AND PROCESSING OF NANO-SCALE
MATERIALS THROUGH CHEMISTRY
Helmut K. Schmidt
Institut fr Neue Materialien gern. GmbH

Im Stadtwald, Geh. 43 A
D-66 123 Saarbrcken, Germany
INTRODUCTION
The so I-gel process can be considered as a method for the preparation of non-metallic
inorganic materials by a chemical route. This general definition, however, does not match
completely the specifics of this process since the so! phase is considered to be indis-
pensable. The preparation of precursors for inorganic materials, for example, ceramies by
precipitation processes or chemical vapor reaction to synthesize powders has been known
for long times and industrially used widely as, for example, the Bayer process for the
production of alumina powders. In order to make this type of processes efficient, the
precipitation takes place under thermodynamic conditions, under which no disturbance of
nucleation and growth takes place in order to obtain well-defined precipitates easy to be
filtered or processed. Another example is the hydrothermal process, for example, developed
by Degussa, or the fabrication of zirconia 1, where the transport mechanisms for crystal
growth under elevated pressure and temperature conditions and the formation of thermody-
namically stable and well crystallized phases is easier than under low-pressure, low-
temperature conditions. If nucleation and growth take place under conditions where the
nuclei absorb surface charges, each nucleus grows independently and no aggregation takes
place if the surface charges (related to the so-called Zeta-potential) are in the range where
the resulting repulsing forces are strong enough to avoid agglomeration. Moreover, if the
concentration is off the feet and the resulting concentration of particles in the liquid system
is low enough to keep the distances in a range where the Stern's potentiae does not switch
into attraction, colloidal solution can be kept stable. These thermodynamical conditions, in
general, are chosen for sol-gel processing in order to produce sols. The structure of these
sols may consist of macromolecules, more or less polymer type, or small particles which
are mainly spherical. It was found that these sols may be used for the development of
coatings, and this was one of the driving forces for scientists to investigate the reaction
mechanisms of the production of sols and the gelation3 Gelation, in general, takes place if
sols get destabilized either by removal of the surface charges or by overcoming the critical
Science and Techlwlogy of Polymers and Advanced Materials

Edited by P. N. Prasad et al., Plenum Preas, New York, 1998 663
:(;::(:).: :i:.): :('):
collo1dal :~=.=0: =6.:
ol
.xu :Q:
:():~
' poinl uf
/ero dmrgc:
polymer -~'t_-- gcl limnation
1) pc so I
-~--0~-
duster
t)pc so I
Figure I. Scheme of the gel Formation from sols by different mechanisms. a: destabilization by removal of
electric charges, e.g. pH value change; b: overcoming the critical distance in Stern's model.
distance, as shown in fig . I. The removal of surface charges is easy to be obtained by

moving the system into the range of the point of zero charge, for example, by adapting the
appropriate pH values. By upconcentration of the so!, for example, through removal of the
solvent, the critical distance between the particles is overcome, and the repulsion changes to
attraction. This, for example, can easily be observed by dip coating processes, as investi-
gated in detail by Brinker4 8oth mechanisms, however, Iead to a more or less rather spon-
taneaus gel formation with an irregulary shaped network with a rather high pore volume.
This consideration described above reveals also the weak points of sol-gel processing.
lt is very difficult to obtain high solid contents in the sol, and that Ieads, in general, to low
density gels. The pores are, in general, filled with liquids, producing strong capillary forces
and subsequent problems during drying since the mechanical strengh of gels is low5. So
films and green bodies made from gels, in general, are fragile and of low density. In the
second step, if one wants to produce dense materials from gels, high shrinkage rates have to
be taken into consideration. For this reason, the sol-gel process is not considered as a
reasonable method for the fabrication of ceramic parts, for example, even if sintering tem-
peratures can be kept rather low.
One of the consequences is that sol-gel processing, in general, only is used for the
fabrication ofthin films or particles like ceramic powders, if purely inorganic systems are
envisaged, and another consequence is, that large-scale industrial applications still are the
rare exception. However, one of the interesting aspects of sol-gel processing is the fact that
nanoscale dimensions are "available".
664
The question arises, how far these phases can be stabilized and utilized for the
fabrication of materials. In this paper, some basic considerations how to achieve this target
and material developments based on Si0 2 nanoparticles as examples for utilization are
given.
THE SOL-GEL PROCESS AS A BASIS FOR NANOTECHNOLOGIES
Based on nucleation and growth processes, in a growing system starting from a

nucleus size of a few angstrms, a nano-scale phase is "automatically" obtained as an inter-
mediate. Nano-scale particles have recently gained increasing interest as intermediates for
the fabrication of various new materials. In fig. 2, some of the interesting properties of
-32.
1!' . c I n2
n',.-n'.l . tRj
.
"transparcncy" y ~ ncw optical matcrials
c:,, \
'
n~ /1.~
(passive and activc)
c"- vol. fract. ~ '
~ Raylcigh scattering ncglcctablc, ifd < irr),!

quantum size effects ~ activc materials.
Iasers, LO, scnsors
surface area ~ c::llalrsts. adsorbents.

sen ors, binders, lo\\
sintcring ccramics.
\ n d mcmbrancs
\ = _F_ _ 100 ~ polymer matrix nano-
interface
v"(I-F)( v"'_, ,) composites, hard coatings ,
F filtcr \olumc fraction fi.mctional coatings.
for d 2 nm. r 7.5 nm smart nanocomposites
F 0.15
~ v = 30 %
"disordered"
intcrfacc intcrfacc
Figure 2. Some interesting properties of nanoparticles and materialspotential based on this.
nanoparticles are summarized. As a result of various basic properties of nanoparticles, there

is a !arge potential for the fabrication of new materials. For this reason, it is worthwhile to
investigate the usefulness of the sol-gel process for the fabrication of nanoparticle or
nanoparticle-containing systems, such as composites. The simplest step in this connection is
the fabrication of sols, as already described above. There is extensive Iiterature about sol-
gel processing which cannot be discussed here. An overview can be obtained from the
eonferenee books of Better Ceramies Through Chemistrl- 8, Sol-Gel Opties9 - 11 and the
Workshop on Glasses and Ceramies from Gels 12 - 14 and the Iiterature eited therein. But only
a few artieles are related to the fabrieation of nanoparticles 15 16 . One of the most diffieult
steps is to make use of the nano-seale particles from eolloidal sols for the fabrieation of
materials Iike eeramies, eomposites or thiek films. To aehieve this, two basie problems have
to be overcome: first, to inerease the solid content of sols if a wet processing step directly
from the solutions is desirable, ani second, to avoid agglomeration in a sense that no weak
brittle gels with low solid content~ are produced. In addition to this, if the particles should
be used for eomposite materials, for example, optical transparent systems, it is necessary to
665
generate surface reactivities on the particles to make them compatible to the corresponding
matrix system. If this can be achieved, interesting prospects exist for making many useful
materials, as already indicated in fig. 1.
For these reasons, the "simple" sol-gel process by using electrostatic forces to keep the
particles apart, has to be changed, and other methods have to be introduced to fabricate
processable nano-scale particles. One of the concepts described in detail in 17 - 18 is related to
the fact that surfaces of very small particles react very similarly to ions in solution, as
shown in different examples, e.g. in 19. It could be shown that IR spectra of complex formers
Iike -diketones with aluminum alkoxides do not differ from IR spectra of these complex
formers absorbed to nanoparticle surfaces. This was shown with ethyl acetoacetate com-
plexed with aluminum alkoxides or absorbed to nano-scale boehmite particles, with pro-
pionic acid in form of aluminum propionates or absorbed to boehmite particles, or meth-
acrylic acid complexed to zirconia alkoxide 20 or to adsorbed nanoparticles of zirconia 21 .
This Ieads to the concept that it is possible to modify oxidic nanoparticles with various
surface modifiers to form sol-like bonds, complex-formed bonds, and, of course, if hydro-
lyseable silanes are used, the formation of surface oxygen silicon bonds also is possible.
Moreover, it has been found that carrying out hydrolysis and condensation in the
presence of this type of surface modifier, nucleation and growth can be influenced to obtain
appropriate particle sizes, as shown in fig. 3. The particle size distribution obtained by these
processes depends on the total concentration of the system and gets narrower with decreas-
ing solid content.
20
16
E
""
<:
..::. ..::.
~
"
;:; "
.~ 8
~ 12 mclhacr} lic ncid
::::
;; E'"'
' 10 "
-,:; "
'5
;:;
u"
"
... "" u"
e,., :::
" "0 " "t:
c..
....
~
V
~
V
~ "'a.
]
:JJ
r: "' "
OJ
e
Oll
"
~
"'
;:;"
.
()
>urlitce modi Ii er o!4 0 16 o1s 110 112 1.14
molar nuio x :Zr
Figure 3. Examples for the tailoring of particle size by varying the surface modifier concentration during
hydrolysis and concentration; a: comparison of different types of modifiers; b: intluence of the modifier
concentration shown with acac and methacrylic acid.
In the figure, it is shown timt there is a strong influence of the type of surface modifier
on the particle size, obtained with identical ratios of surface modifiers and the dependence
of the particle size as a function of the surface modifier concentration with acetyl acetone
(acac) and methacrylic acid as examples. As one can see from fig. 3, there are similarities
between the type of surface modifiers, and this can be related to the bond strength; for
example, acetyl acetone and ethyl acetoacetate bond much stronger and more completely to
the surface and Iead to smaller particle sizes. This rises the hypothesis that the surface free
666
energy to be expressed by the coverage of the surface with the modifiers governs the par-
ticle size. The higher the modifier concentration, the more surface area has to be produced
to reduce the surface free energy, and this Ieads to smaller particles. In fig. 3b, this is
confirmed by the influence of the surface modifier concentration on the particle size. The
higher the concentration is, the more surface to bind the surface modifier has to be pro-
duced, which also Ieads to decreasing particle size with increasing surface modifier concen-
tration.
This surface modification not only can be used to produce size-controlled species, but,
fcir example, the methacrylic acid bonded to the particle surface can be used for polyme-
rizing the particles into polymer networks22 - 24 . It could be shown that many new nano-
composites can be prepared by using this approach. Due to the small particle sizes, which
cim be obtained by choosing the appropriate parameter, as shown in fig. 2, the particle size
of the zirconia can be kept in the range between 2 and 5 nm, and optical composites can be
obtained.
If photopolymerization is used, it can be carried out with common photo catalysts23
and this has been investi'gated by photodifferential scanning calorimetry. It could be shown
that the reactivity in these complex systems with nanoparticles is surprisingly high, and that
conversion rates at elevated temperatures ( 120 C) above 90 % are obtained, as determined
by infrared spectroscopy. Films produced from these composites can be used for photo-
lithographic patterning, such as Iaser writing or mask aligner techniques 25 . If masks are
used, and if the film is irradiated through masks, inhomogeneities are introduced into the
materials, leading to the so-called Colburn-Haines effect. Through the chemical potential
produced by the consumption of double bonds in the irradiated areas, a mass transport
occurs to compensate the loss. It was of interest, how far methacrylic acid-covered zirconia
nanoparticles are involved in these diffusion processes. Forthis reason, cxperiments have
been carried out the details of which are described elsewhere26 to find out whether the
coated nanoparticles are mobile or not. Zirconia nanoparticles seemed to be of special
interest because they exhibit a relatively high refractive index compared to the polymeric
matrix. In order to separate the diffusion of the unpolymerized matrix monomers from the
unpolymerized methacrylic bond to the particle surfacc, methacryloxysilanes have been
chosen as monomers since these double bonds fixed to the silicon can be immobilized by
the formation of an inorganic backbone by hydrolysis and condcnsation, which is a reaction
not affecting the organic polymerization. In fig. 4, the schematics of this process is shown,
as weil as the refractive index differences tobe obtained by this method. As one can see, the
diffusion of nanoparticles with a refractive index highcr than that of the matrix should Iead
to an index gradient after full area polymerization.
Refractive index measurements before and after polymerization in the different areas
and as a function of the Zr0 2 content revealed that in Zr0 2 containing films, a LI.", which
was built up to 2.10- 2 , is found, whereas in Zr0 2 free films, after full area polymerization,
the L'l. 11 , which was built up between unpolymerized and polymerized zones, disappears. In
fig. 5 the results are shown. There is a clear connection between the Si methacryloxy : Zr
ratio and the maximum L'l. 11 If no Zr0 2 is present, Ll.n becomes zero after full area poly-
merization. Before full area polymerization, the appearant L'l. 11 results from the higher density
ofthe polymerized zones. With r equal to 0.1, the maximum L'l. 11 is obtained, which is attri-
buted to a high diffusion coefficient as a consequence of a relatively low Zr0 2 nanoparticle
concentration (Zr0 2 R; 2 nm26 ). With increasing Zr0 2 concentrations, the L'l. 11 gets lower and
the time period to reach the maximum decreases, indicating a decreasing ofthe diffusability
of Zr0 2 particles. The diffusion comes to a stop with the propagation of the polymerization.
In fig. 6 the Zr EDX line scan of a resulting optical grating is shown. The line scan shows
667
-
hV hV
~ ~: organo alkoxysilanc L'l.." 2 10'

: double bond
01 : mcthacryloxy coated ZrO, nano particles
Figure 4. Draft of the principles of the diffusion process initiated by the consumption of the Zr0 2 bonded
methacryloxy grouping by polymerization.
0.025
20
(a)
0.020
(c)
---
_.--=-----+-
.. .
15
0.015 ,?---J(':. __
I , ------------ (b) 10
--------------------
0.010
5
0.005 + - - - - - < l t - - - - t - - - - - + - - - + - - - - t - +
0 0.1 0.2 0.3 0.4
Zr: methacryloxy silane
Figure 5. Development of "'" values in photopolymerized films prepared from methacryloxy silane, Zr(0Bu)4
and methacrylic acid'ft" 23 Curve (a) shows the "'" values after 15 min UV exposure through a 5 ttm mask and
curve (b) after an additional full area polymerization as a function ofthe Zr: Si methacryloxy ratio r; curve
(c) shows the time required to obtain the maximum value ofthe diffraction efficiency as a function ofthe Zr:
Si ratio, too.
668
........"
"'
" 0.9
.e

~
: . l
~

~i
. 1:
--~ I
)
1
distancc from origin [pm]
Figure 6. Zr EDX line scan over a Zr0 2 nanocomposite film after mask aligner and subsequent full area
photopol ymerization'ft" 27.
that the Zr concentration follows very weil the mask width of 5 j.liTI and proves that Zr really
diffuses into the preliminary irradiated zones. This process can be used for holographic
grating or fresnel lens fabrication as weil as for data storage. By leaving residual charges on
the particles and employing electrodes, the particles can be moved in direction to the anode,
and gradients over !arger areas are obtained. As shown in 26 , a gradient index step of 0.07 in
lenses of about 1.5 cm in diameter was obtained. This method opens the possibility of
tailoring gradients in !arger components according to the employed electric field .
MATERIAL DEVELOPMENTS
Ceramic Powders
As described elsewhere 18, by using the surface modifier approach, a !arge number of
non-agglomerated particles have been synthesized and used for materials fabrication. An
overview is given in table 1. Moreover, by combination of the CGP with solvothermal
techniques 29 , weil crystallized particles (5Y-Zr0 2) are produced by continuous flow
methods. An example for the crystallinity and uniformity is shown in fig. 7.
Binder materials
As shown in 18 , a !arge variety of surface modifiers can be employed. Especially
colloidal silica as available from various industrial companies is a very interesting sol-gel
precursor because it is a commercial product and cheap. Moreover, the particle size
commercially available ranges between 5 and 30 nm. These products, in general, are charge
stabilized, and from all these problems known from conventional sol-gel processing occur.
So, surface modification of these particles seems to be an interesting raute for novel
materials from Si0 2. One ofthe interesting principles ofsubstituting charge stabilization by
chemical stabilization is to control the particle-to-particle interaction. From the application
point of view, the addition of Si02 nanoparticles to sol-gel processed materials has led to
interesting hard coating materials 35 36. Based on these considerations, a surface modi-
fication method has been developed by Jonschker37 , which showed that colloidal silica
processed by this route Ieads to the possibility of increased solid contents without gelation.
The scheme of the reaction is shown in fig . 8. As a consequence of th~ reduced particle-to-
669
Figure 7. Electron m icroscopic image of 5Y-Zr02,n., :"'-
particle interaction and increased solid content, it was possible to produce thick films by
simple dip coating steps from these sols35 38, and wet coating thicknesses of 10 to 20 J..lm
and densified coating thicknesses of up to 10 J..lm became possible in a one-step dip-coating
process. After the formation of an emulsion, the system becomes one-phasic by the forma-
tion of alcohol by hydrolysis which acts as agent to provide sufficient solubility for the
water phase. By variation of R' and the concentration of TEOS, R'Si(OR)3, H20 and H+,
the binding properties and the reaction rate could be adapted to various applications.
One of the most interesting properties for the application of nanoparticulate systems is
the strong particle-to-particle interaction, which sums up to considerable binding forces per
volume unit. But after "gelation", this does not Iead to strong gels because the overall
density of gels is very low. In fully densified inorganic materials, the overall binding force
is high, leading to brittle materials with low fracture touglmess. With respect to sealants,
which require properties like good stress dissipation, inorganic materials with their low
R'Si(OR)~
Si(OR)

colloidal
4
silica sol
, . .
emuls1fytng
HCI
11
o
o
o
o
0
o
o
o
o
0
---+
tJ -
I'
HO-~i~GHO
0
1_
RO-~l-0
6R
o_s,_cH,
H
"'9 nm
OHOH I.
(SiO)
,, OH
'
OH
H
'I
2-p aS IC 1-phaSIC H l
HO-:sLCH,
6R .
Figure 8. Reaction principle ofthe formation ofpartially surface-modified Si02 sols. R' = methyl, phenyl 37
670
Table 1. Overview over nanoparticles fabricated by the surface modifier approach (controlled growth
process, CGP) (details are published elsewhere) 18 19 28 ' 34
System Primary Crystal Doping Synthesis

Partide Size Structure (mol%) Technique
(nm)
Zr0 2 5-10 monoclinic Y,, Pr, , Sc'" controlled growth
tetragonal 0-8 microemulsion
cubic
Sn02 3-5 Cassiterite Sb'" controlled growth
0-10
PZT 10-20 Perowskite controlled growth
Yz03 10-20 cubic Eu, controlled growth
0-3
Y(OH) 3 20 amorphous Eu,. controlled growth
0-3
Ti0 2 5-50 Anatase Al' controlled growth
Rutile 0,5
In20 3 10-30 hexagonal controlled growth
ITO 10-30 hexagonal Sn controlled growth
1-10
a-Al 20 3 60 Corundum controlled growth
HAP 5-30 hexagonal controlled growth
(hydroxy
apatite)
Fe20iFe3 5-10 Magnetite microemulsion
04 Maghemite controlled growth
BaTi03 50-100 Perowskite controlled growth
fracture toughness are not the best choice. If inorganic sols, for example, are used for glass
fiber binding, brittle products are obtained which are not elastic and easily can be crumbled
to dust If organic groupings are introduced by Si02 nanoparticle surface modification,
clearly depicts that the uncovered stainless steel is covered with a dark oxidation layer. The
coating thickness is kept between 3 and 5 llm, and this is sufficient to obtain oxidation pro-
tection, but also protection from attacks from acids. Due to its low thickness, the coatings
are flexible, and shaping after coating is possible. The abrasion resistance of this glass-like
coating is comparable to float glass and 1000 cycles taber abrader with an alumina-filled
ruhher wheel (500 g) show that a scratching of the surface is hardly detectable. For deco-
ration purposes, the coatings can be outfitted with metal colloids42 and transparent coloured
coatings on any stainless steel surface (e.g. brushed, sanded) for architectural and other
applications have been fabricated. In fig 9b (I) optical waveguides fabricated by rapid
annealing (RA) and in 9b (2) the formation of micropattems by embossing are shown38 .
By an appropriate time/temperature profile, fully densified Si02 layers without residual
stress at room temperature are obtained by RA. In fig. lOb (2) it is remarkable that densifi-
cation takes place without loosing the preciseness ofthe pattems.
In fig. 9c composites made from natural fibers like straw or cotton are shown. Due to
the specific coatings of the nanoparticles, which have polar as well as unpolar groupings,
even straw, which is difficult to bind with most of the commercial sealants, can be bonded
to high-strength composites in a fast process. Composites with straw, for example (only
polyurethane is suitable), show a density of about 0.2 g/cm' and a pressure strength of 4
671
c
Figure 9. Products made by Si02 nanotechnologies. a: Corrosion, staining and abrasion resistant coating on
stainless steel; samples heated to 900 oc for I hr; (I) coated, (2) uncoated sample; b: (I) optical Si02 wave-
guides on Si; (2): Si02 parts made by embossing of Si02 gels before and after densification; c: composite
materials made from Si02 binders and natural products, (I) plywood/cotton; (2) straw with and (3) without
plywood; d: core sand for casting water taps from R brass.
MPa, which is extraordinately high forthistype of low-density materials41 ' 43 and, in addi-
tion to this, are inflammable.
Similar to the fiber bonding process, it is also possible to bind core sands, as shown in
fig. 9d. Core sands are used for meta] casting with complex shapes and have to be
removed easily after the casting process is finished. For core sands, the phenolic resins in
use cause serious environmental problems. With a new SiOrbased hinding system, these
prohlems can be reduced almost to zero since only a very small concentration of organics
are present in the system, which hurn out very easily to form carbon dioxide and water.
In casting technology for parts where cores are needed, ahout 30 % of the cost at
present result from environmental issues (e.g. washing of flue gases from phenolic resin
decomposition, recycling of used core sands covered with pyrolysis products of phenolic
resins). In these cases, the use ofthe new inorganic hinder will have an interesting potential
in faundry industry. The technological advantage of the hinder compared to water glass
based binder in core sand technology is its tailorable curing rate, which already has heen
adapted to technical requirements in the process using heated moulds (hot box technology).
672
CONCLUSIONS
As a conclusion, it is to say that chemistry provides very interesting tools for the deve-
lopment of new materials through nanotechnologies. Compared to other techniques, the
fabrication of nanoparticles can be designed through chemical engineering which, in
general, allows the production of low-cost, high-volume materials.
As one of the most important topics, the surface modification of nanoparticles has
been identified. Through these surface modification, the interfacial free energy between the
nanoparticles' surface and the surrounding matrix can be reduced to a Ievel that the particles
are well-dispersed in the matrix. This Ieads to the concept of new optical materials,
introducing the physical properties of materials which, in general, cannot be used for
opticals in this type of composites.
Aside from optics, nanoparticles open up interesting industrial applications, e.g. in the
form of binders, for polymers, for hard coatings, and even for ceramics. Chemical nano-
technologies seem to be at their infancy, but first products on the market already have
shown their usefulness.
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673
19. R. Na and H. Schmidt, Formation and properlies of chelated alumiumalkoxides, in: Ceramic Powder
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21. H. Schmidt, Application ofOrmocers, in: Ceramic Transactions Val. 55: Sol-Ge/ Science and Techno-
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22. H. Schmidt, R. Kasemann, T. Burkhart, G. Wagner, E. Arpac and E. Geiter, lnorganic-organic hybrid
coatings for meta! and glass surfaces, in: ACS Symposium Series No. 585: Hybrid Organic-lnorganic
Composites, J. E. Mark, C. Y.-C. Lee and P. A. Bianconi, eds., American Chemical Society, Washington
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23. C. Becker, M. Zahnhausen, H. Krug and H. Schmidt, Characterization of the photopolymerization -
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inorganic sol-gel nanocomposites", New Journal of Chemistry, Vol. 18, N. 10, 1117- 1123, 1994.
25. F. Tiefensee, Ph. D. Thesis, University ofSaarland, Saarbrcken (1994).
26. H. Schmidt, Entwicklung, Mikrostrukturierung und Anwendung von Keramik-polymer-Nanokompo-
siten, in Proc. Werkstoffwoche 1996, Symp. 9, DGM-Informationsgesellschaft mbH (in print).
27. F. Tiefensee, P. W. Oliveira and H. Schmidt, Organic-inorganic composite materials: optical properties
of laser-atterned and protective-coated waveguides, in SPIE Proc. Sol-Ge/ Optics 1758:448 (1992).
28. R. Na, D. Burgard, private communication.
29. D. Burgard, R. Na and H. Schmidt, German Offen No. OE 195 15 820 AI, 04-29-95.
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Patent No. EP 0 587 672 BI, 02-14-96.
31. D. Burgard, Master's Thesis, University of Saarland, Saarbrcken, Gennany (1992).
32. D. Burgard, C. Kropf, R. Na and H. Schmidt, Routes to deagglomerated nanopowder by chemical
synthesis, in Better Ceramies Through Chemistry VI, Mat. Res. Soc. Symp. Proc. Vol. 346, A. K. Cheet-
ham, C. J. Brinker, M. L. Mecartney and C. Sanchez (eds.), Materials Research Society, Pittsburgh/PA
346:101 (1994).
33. D. Burgard, R. Na and H. Schmidt, Synthesis and colloidal processing of nanocrystalline (Yz0 3 stabi-
lized) Zr0 2 powders by a surface free energy controlled process, in Mat. Res. Soc., Symp. Proc.,
Pittsburgh/PA, 432: 113 ( 1997).
34. D. Burgard, R. Drumm, R. Na and H. Schmidt, Herstellung und Verarbeitung von nanoskaligem
(stabilisie1tem) Zr0 2 ber einen kolloid-chemischen Proze, in Proc. Werkstoffwoche /996, Symp. 6, G.
Ziegler, H. Cherdron, W. Herme!, J. Hirsch and H. Kolaska (eds.), DGM-lnformationsgesellschaft mbH,
Frankfurt/M. (1997).
35. R. Kasemann, H. Schmidt, E. Arpac and V. Gerhard, German Offen No. DE 43 38 361 AI, 11-10-93.
36. G. A. Pate!, C. Park, S. J. Kubisen, United States Patent No. 5,411,807, 05-02-95.
37. G. Jonschker, Master's Thesis, University of Saarland, Saarbrcken (1992).
38. M. Mennig, G. Jonschker and H. Schmidt, Sol-gel derived thick Si02 coatings and their thennomecha-
nical and optical properties, in SPIE Proc. Sol-Gel Optics 1758:125 (1992).
39. M. Mennig, G. Jonschker and H. Schmidt, Verfahren zur Herstellung von Glas mit verbesserter Lang-
zeitstandfahigkeit bei erhhten Temperaturen, European Patent No. EP 0 642 475 BI, 06- I 9-96.
40. M. Mennig, G. Jonschker, H. Schmidt and P. Kahanek, Flame retardent coatings on glass, Glas-Inge-
nieur 3:54 (1994).
41. G. Jonschker, Ph. D. Thesis, University of Saarland, Saarbrcken (in print).
42. !NM brochure "Edelstahl in neuem Gewand", Saarbrcken (1997).
43. G. Jonschker, private communication.
674
ENVIRONMENTALLV FRIENDLY ADHESIVE SYSTEMS
P. 0. Oiesen and Peter Folting
Plant Fibre Laboratory, Royal Veterinary and Agricultural University,

Agrovej 10, 2630 Taastrup, Denmark
INTRODUCTION
Much have been written and said about the global ecological crisis we are facing, a
crisis which is caused by an exponential increase in the consumption of energy and raw
materials, and use of substances harmful to the environment. Furthermore, the mountains of
waste - some of which are poluting the ecosystem - are growing to unacceptable heights.
These problems mainly apply to the developed countries. Thus, we cannot go on with the
present methods of production even if we wish to maintain the present Ievel of production.
However, we arenot going to maintain this level but to increase it considerably. Politically
there is an intemationally growing understanding that the less developed countfies must have
a higher living standard. Furthermore, the world population is estimated to double within the
next 35 years. As a result , the world production may treble or quadruple within the next 35
years. As the ecosystem is already threatened, new ways have to be found for future
consumption. It is obvious that the energy expenditure has to be cut or kept at an acceptable
Ievel. Politically this is weil understood and as a result there is a growing interest in the use
of biomass for energy and a lot of resources have been put in to research and development of
bio energy projects. What is less politically understood or even known is the potential for
industrial use of biomass for new materials and products. If we are going to multiply the
world production in the future where shall the raw material then come from ? Obviously
more and more products have to be made from renewable resources, which means biomass.
But how much money has been put into this kind of research ? As I far as we know, it is
relatively little.
If we are going to promote the understanding of biomass as a great potential for new
products, we have to show that products based on biomass may be produced with less
environmental impact than products based on non-renewable raw materials. In the past,
biomass has been used on a large industrial scale for the production of pulp and paper, fibre
and particle boards, textiles, as solid wood for the building industry, etc. However, little
attention was paid to the ecosystem earlier as the problems were not identified, and thus little
attention was paid to energy expenditure or pollution. As a result the present production of
bio-based products is not developed with the aim of causing as little environmental impact as
possible. However, the future consumers will demand "ecological" products, which again
willlead to more strict legislation the beginning of which we have already seen, for example
C02 tax, restrictions as to the use of various substances, etc. Each time the legislation is
tightened up, the biobased products are favoured. Thus, the development in society favours
the industrial use of bio-based products if we at the same time are able to prove that these
products are less environmentally harmful than products based on non-renewable raw
materials. But are we able to prove this ?
If we wish more political attention (and resources) for industrial use of biomass for
new materials and products we also have to provide the politicians and the consumers with
facts documenting the benifits of of such a utilization.

In this paper we shall only discuss the industrial use of plant fibres, which are by far
are the largest part of the biomass.
No industrial products are by definition environmentally friendly as no products can be
produced without the use of energy. Thus, weshall not talk about environmentally friendly
products as this would give the consumer the impression of a better product than we can
produce. Instead we shall talk about products with as little environmental impact as possible.
The production is composed of a number of processes, some of which are less
environmentally friendly than we could wish. Presumably the defibration process and some
of the adhesives used are key problems seen with the eyes of the future marked. Future life
cycle assessments will teil us more about this.
The aim of this paper is to discuss the possibilities of using less environmentally
harmful adhesive systerns in making plant fibre based composites.
BINDING SYSTEMS
The present fibre composite production may be divided into two groups: One in which
the fibres are bonded together by rnixing the fibres with an adhesive and one in which the
fibres are bonded without adding an adhesive (auto-adhesion).
In the first case the binding mechanism is between the fibre surface and an adhesive.
The technique is weil established within the MDF-board industry and for making automobile
indoor panels.
In the second case the binding mechanism is due to non-covalent bonds between fibres
as weil as entanglement. The technique is weil established within the paper and Masonite
board production. The technique is very attractive both from an environmental and econornic
point of view as the cost for a binder can be saved.
Since the physical and chernical properties of plant fibre surfaces are poorly
understood and sice these properties are of greatet importance for the bonding mechanism
this area ofresearch has been given high priority at the Plant Fibre Laboratory. This research
will hopefully lead to a better understanding of the underlying mechanisms making an
optirnization of the production possible.
Two auto-adhesive systerns have been studied: An enzyme treatrnent and the so called
"closed system". In relation to the enzyme treatment it is investigated what impact the
treatrnent has on the fibre properties and how changes in these affects the auto-adhesion.
Changes in the surface properties is exarnined by wetting analysis. The work with the
enzyme treatrnent will be presented at this conference by Claus Felby in a special paper.
The main results o~ the work with the closed system will be presented in the following.
THE CLOSED SYSTEM
Background
The closed system concept is to press fibre mats in a steam tight press thereby
increasing the self bonding effect. By pressing the fibre mat in a closed system the method
utilizes the moisture inside the fibres to create a steam pressure softening and activating the
lignin. By plasticizing or softening the lignin, the glass transition temperature is decreased
(Goring 1963) and the lignin starts to flow creating a higher bonding area between the fibres
(Back 1987).
The closed system principally consistes of a metal frame with a silicone-rubber seal
located inside the frame, hereby preventing moisture from evaporating. Mats are placed
inside the frame and compressed in the hot press between two stainless steel plates. The
thickness of the final board is controlled by the frame, which function as a distance bar
between steel plates (Felby and Folting 1995).
Materials and Methods

Beech fibres from Junckers MDF factory in Denmark have been used. The beech chips
are fiberized in a pressurized discrefmer at 8 bars at a temperature of about 170 C. From
mats formed in the laboratory composites of 200x200x4mm were produced at two density
levels (750 and 1000 kgtm3), at three press temperatures (150, 175 and 2000 C) and at six
676
press times (1, 2.5, 5, 7.5, 10 and 15 minutes). The average moisture content of the fibres
was 10%.
During hot pressing the mat/composite was surrounded by a meta! frame with a sealing
moulding so that the steam created in the composite during hot pressing was trap within the
system. As moisture lowers the glass transition temperature of the Iignin, the trapped steam
enhances the flow of the Iignin during hot pressing. As a result more and better bonds are
created between fibres and less intemal Stresses are formed.
Results
A detailed paper about the whole experiment will be published elsewhere when the
experiments are finished. Here some main results are presented.
The international standard for intemal bond of strength (IB), prEN-622-5:1994
demands a strength of 0.60 and 0.80 N/mm2 for dry and wet conditions respectively. The
Standards for swelling prEN 622-2 and prEN 622-5 demand that hardboards does not swell
more than 30 and 20 % under dry and wet conditions respecktively and MDF-boards do not
swell more than 35 and 20% respectively. Compared with these standards the following
prelirninary conclusions may be drawn:
1. Press temperature of 1500 C does not meet the demands, only at press times of 15
rninutes, acceptable results are achieved, but such long press time is not acceptable
from an industriel point of view. Thus in the following only press temperatures of 17 5
and 2000 C are discussed.
2. The high density boards (1,000 kg/m3) easily fulfil the demands, reaching IB
strengths up to 3.0 N/mm2 for relatively high press temperatures: at five rninutes for a
press temperature of 2000 C and at 15 rninutes for 1750 C. However the IB demands
are met already at 2.5 and 5 minutes respectively, whereas the swelling demands first
are met at 5 and 10 rninutes respectively.
3. The medium density boards (750 kg/m3) reach IB strengths of up to 1.0 N/mm2
and meet the demand for press times of 7.5 rninutes. The swelling demands are met at
press times 5 and 10 minutes respectively.
The above mentioned conclusions are only preliminary. They are a result of our first
experiments with the closed system. However, the results are encouraging having obtained
good strength properties, some times very good strength properties. On the other hand
swelling seems to create bigger problems requiring Ionger press times to meet the standards.
Another encouraging fact is the great variation found between replicates, which means
that much better results than the average are obtained for some test specimens for reasons we
do not know yet. Apparently some factors which are not part of the experiment play an
important role. Thus, if these factors can be identified and put under our control, the closed
system seems to be a very prornising adhesive system both from an econornic point of view
(saving the relatively expensive glue) and from an environmental point of view.
LITERATURE
Back, E.L., 1987: The bonding mechanism in hardboard manufacture. Holzforschung
41:247-58.
Felby, C. And P. Folting, 1995: Environemtally safe adhesive systems. In: Forskning i
industriel anvendelse af non-food-afgr~>Sder, ATV, p. 71-8.
Goring, D.A.I., 1963: Thermal softening of Iignin, hemicellulose and cellulose. Pulp and
Paper Magazine of Canada 64:517-27.
677
LIGNOCELLULOSIC POLYMER COMPOSITES
Ryszard Kozlowski and Malgorzata Helwig

Institute of Natural Fibres, Poznan, POLAND
INTRODUCTION
Most of the plants growing all over the world are typical biotechnology works of
lignocellulosic natural polymer. They can be divided into three groups: annual, biannual and
perennial plants. The lignocellulosic materials of perennial origin are e.g. wood and bamboo.
Wood as lignocellulosic material has been used for centuries for different applications: as a
fuel, construction material, and later as a chemical raw material, mainly for pulp and fiber as
well as particleboards and some fine chemical products.
Annual consumption of wood in the world is very high. In 1990 it amounted to 3.5 billion
m3 and the world population at that time was 5.2 billion, while the estimates for the year of
2010 are 4.66 billion m3 and about 8.7 billion, respectively. Figure 1 shows the forecast
conceming world wood consumption and forest area against the population background
(Strykowski, 1996; Schmincke, 1996). The data point not only to the deficiency of forestry
resources but also to the great impact of increasing wood consumption and decreasing forest
area on the globe environment. lt has been established that the annual increase in world
population is 1.4%, while the rise in total wood consumption is 1.3% and the forest area
decreases at the same time by 0.4-0.5%. The situation described above varies in different
parts of the world. The highest deforestation takes place in poorly developed countries of
Africa, South America and Asia, whereas the wood output in Europe and North America is
considerable lower than annual increase in the forest biomass.
At present, over a half of wood consumed in the world is still used as a fuel and the
remainder makes industrial timher the demand for which will increase by over 50% within
the next 20 years. According to the forecast (Strykowski, 1996; Schmincke, 1996) the
highest average wood consumption in the world will occur in the first decade of the 21-st
century and will amount to over 1.5 m3 per person.
Considering this fact during the last decades many countries attached importance to
development of lignocellulosic source of annual and biannual plant origin.
For many years these raw materials, especially cotton and bast family of plants, were mainly
used for textiles production. The next figure show the statistic data of cellulosic fibres
production compared with man-made fibres (Johnson, 1996; Kozlowski, 1993).
Man-made fibres appeared in a real scale after 1960. Then their great development occurred.
Changes in the consumption of raw materials consumption between 1984 and 1994
depended mainly on geographical regions. High level of their development and consumption
was observed in Europe, Japan and North America. At present a stabilization in the world
consumption of man-made and natural fibres is observed. lt should be called rather
coexistence than competition.
World production of natural cellulosic fibres is presented in Figure 3.
lt should be mentioned that production offlax and hemp fibres is considerably growing after
1993.

12
I(}
II
PopuJation (1.4% annual rowth)

Total wood conswnption
(1.3% annual growth) m3
Forest rea (0.5% annuaJ lo ), ha
2050
Figure I. World population, forest area and wood consumption, years 1980-2050*.
1411
Ul
10()
c
2 KU
c
~ (,()
s
-tfl
:w
I) 0
("cllul c (c I cotlon) otton Wool Man-made

0 O.hcr Populallon clfcct Econonuc grO\\th
Figure 2. World fibre consumption, million t, years 1890-2050*.
Now these lignocellulosic raw materials are not only a source of excellent fiber for textile
production, but also make a new prornising raw materials for very useful and different
composites.
We should leam more about the basic functions of natural fibres in developing synthetic
fibres for their new functions and for human clothing.
For example, the details of how a silkworm undertakes its spinning with perfect energy
conservation still remains a mystery. We know only that silkworm swings its head in the
shape of figure "8" and spins silk fiber at room temperature. Although natural fibres such as
silk, wool, cotton, hast fibres have been extensively investigated scientifically, the
mechanism oftheir formation is not yet fully understood (Hongu and Philips, 1990).
680
20
..=
15
~
= 10
()
1971-81 nwm~c
Collon llcmp .Rmmc
Figure 3. World production ofnaturallignocellulosic fibres, years 1971-1987, million tons*.
lt is now becoming clear that the studies of natural polymers can Iead us to new high-
functionality polymers. For example, the knowledge of natural polymers is now leading to
the development of new biocompatible polymers (Hongu and Philips, 1990).
LIGNOCELLULOSIC RA W MATERIALS
Since early days of mankind history, man was using different plants, besides wood, in order
to prepare products indispensable to life. Houses were constructed not only from wood.
Until now they are built also of bamboo and palm stems and roofed with reed, straw, palm
leaves, etc. In the past, the most popular insulating materials were reed and straw of various
grain plants. Fumishings were (and still are) made of available plant materials, e.g. barnboo,
osier; grass and straw are used to manufacture mattresses, cotton, flax and other
lignocellulosic materials to make textiles for upholstery. Early technologies based upon non-
wood plant raw materials. In this place we should mention textiles madeofflax (approx.
8000 B.C.) and paper which was manufactured from papyrus in ancient Egypt and from
hemp and rarnie in ancient China.
From environmental point of view the most important advantages of lignocellulosic materials
are their renewability and recyclability. Now only about 2% ofPET is recyclable, however,
at the sametime 15-30% of waste paper, approx. 55% of glass and approx. 80% of meta!
scrap recycle in industry.
Natural fibres are obtained from different sources. The following diagram presents a
classification of natural fibres . Most of them are of vegetable, that is to say, of
lignocellulosic origin.
Lignocellulosic raw materials for composites are obtained from different parts of plants.
Table I includes the most important plants of commercial value as a lignocellulosic source
and presents their basic chernical composition.
In addition to cellulose, the main components of lignocellulosics are Iignin, hemicelluloses,

pentosans. The roJe of isolated Iignin in the chemical industry grows incessantly. This by-product
obtained during the manufacture of cellulose found its application, among others, as:
a Substitute for phenol-formaldehyde resins in composites,
a natural polymer which can be modified to higher reactivity, and applied as follows:
- agrochemicals,
- for packaging, Iaminates, moisture barrier coatings, stiffening agent (boxboard),
681
- friction materials (brakes, pads ),
- wood adhesives (plywood, waferboards, particleboards, fiberboards),
- plastic moulding (autornative)
- foundry mould binders
- antioxidants.
A bright future in the cellulose industry opens before the new technology of pulping - the Alcell
process developed by Repap Enterprises Inc., Montreal, Canada. Experimentation using organic
solvents to dissolve and separate wood components was first documented in the early 1990's. It
was not until the early 1970's that the commercial use of organic solvents for wood pulping was
seriously considered. The new method consisting in the treatment with ethanol at 195C under the
pressure of 29 bars appeared in 1990. In 1994 the production started in the first commercial
Alcell Mill in Mirarnichi, New Brunswick, Canada, of capacity of 144 thousand tons of pulp.
The most important advantages of the Alcell process are its high yield of high-purity products
and the absence ofwater (ethanol is recovered) (Pye and Lora, 1991; Winner et al., 1991). Table
3 shows yields of different products depending on lignocellulosic raw material used.
In the cellulose industry the interest is growing in production of pulp and paper from agro-
based lignocellulosic raw materials such as bagassa, bamboo, reeds, esparto, hemp, flax,
abaca, sisal, grass, etc. (Young, 1997). The amount of pulp made of non-wood resources is
still growing. In 1995 the capacity of non-wood pulp production was 6.8% in total, and the
forecast for 1998 is about 11%. Figure 4 shows the world production of pulp and paper and
the growing contribution of cellulose of agro-plant origin to the above production. Cellulose
of the latter origin is of very high quality due to the fiber length and it is used mainly for
manufacturing high quality paper (cigarette paper, securities, etc.). Further increase in the
contribution of agro-plant cellulose is foreseen and it should reach about 15% in 2010 (the
total production in the mentioned year is estimated to be about 480 million tons) (Kozlowski,
Grabowska et al., 1997).
At present, the widest application of non-wood lignocellulosic raw materials, besides textile
industry, is in the panels industry. It concerns structural boards as weil as insulating boards.
One of the first materials used for this purpose were flax and hemp shives. Generally, the
raw materials for particleboards production can be classified into the following groups:
residues of the bast fibre plants: flax and hemp shives, jute, sisal, roselle fibers (karkadeh);
bagasse, reed stalks, cotton stalks, grass-like Miscantus; residues of the oil plants: rape,
sunflower, oil flax, vetiver roots; residues of food plants: grape-vine stalks, palm leaves and
Diagram 1. Type of natural fibres.
NATURAL FIBRES
ANIMAL VEGETABLE MINERAL

(asbestos)
Silk Wool (sheep) Wood Bast

(conWerous, decduous) (flax, hemp, jute,
kenaf, ramie, reed,
roselle [karkadeh], etc.)
Hair Leaf Seed

(alpaca, camel, CCIN, (abaca [manila], hennequin, (cotton, ka~ ooir)
goat - mohair, cashmere, sisal, date-palm, pin..,ple, etc.)
horse, rabbit, etc.)
Cane Straw
(bagasse, bamboo) (rice, wheat, oat, rye,
oom, oil flax rape)
Grass
(esparto, elephant grass)
682
Table L . Is.
Basic chemical composition of lilmoce11uIose raw matena
Material Approximate c:ontents of main c:hemic:al compounds [%I
Cellulose Lignin Pentosans
Coniferous wood* 40-45 26-34 7-14
Deciduous wood* 38-49 23-30 19-26
Cotton 90-95 - -
Kapok 65-70 5-15 2-10
Flax fibres 64-71 2-15 2-5
Flax shives 36-47 24-30 21-30
Hemp fibres 60-67 3-14 5-10
Hemp shives 40-52 22-30 17-25
Kenaf* 31-39 15-19 22-23
Roselle fibres**** 70-72 12-13 1-3
Jute 55-65 10-15 15-20
Ramie 60-70 1-10 5-12
Abaca (Manila) 55-65 7-10 16-19
Sisal** 63 7.5 22
Date-palm** 58 15.3 20
Pineapple** 69.5 7.5 21.8
Bagasse* 32-44 19-24 27-32
Esparto* 33-38 17-19 27-32
Elephant grass 35-40 10-15 10-20
(!vfiscantus)
Bamboo*** 33-45 20-25 30
Reed* 44.75 22.8 20
Phragmites communis
Grain Straws 27-37 12-21 20-34
* SOURCE: Rowell, /996 *** SOURCE. L1ese, 1992
** SOURCE: Pandey and Ghosh, 1995 **** SOURCE: Eweida et al., 19i4
Table 2. Yield of oroducts per unit of lilmocellulosic raw material used in Aleeil "process*.
Produc:t Lignoc:ellulosic: Raw Materials
Hardwood Straw Bagasse
Pulp 47% 47% 72%
Acetic acid 2% 3% 2%
Furfural 1% 2% -
Alcell Iignin 19% 14% 17%
Xylose I Xylitol 5% 5% -
Total: 74% 71% 91%
stalks, small grains, peanut and rice husks, small grain straw. Some non-wood
lignocellulosic raw materials of major importance are discussed below.
BAST FIBRES RESIDUES
Bast fibre plants such as flax, kenaf, jute, ramie, reed were cultivated by man for many
thousand years. They are also described in many publications (e.g. Kozlowski, 1993;
683
'()()
.J)() -.:m-1.\'ood Pulp_

.1()() C\\'ood Pulp
c 1\()
~
...
;:: 1CKl
<:;
e ~~()
c 21 410
.!CKl 15
~
e I ~U 93
240
l<Kl 176
160
u 127
II
19'18 2U )(I
Figure 4. World papennaking pulp production capacity, years 1975-1998, million metric tons!year.
Pandey and Ghosh, 1995; Manokaran, 1990, Sanadi et aL, 1997; Rowell, 1997;
Laufenberg, 1997; English, 1997).
One of interesting annual plants is roselle (karkadeh) belonging to Hibiscus farnily, just as
kenaf. This plant is cultivated in the same way as kenaf and can be grown in fairly wide
range of climatic conditions (Eweida et al., 1974).
At the end of 1980's and in the beginning of 1990's a considerable Stimulation occurred in
the bast fibre industry in many countfies of the world. It could be called a renaissance of bast
fibre plants. This situation can be explained by the general trend toward natural products
including health food and health clothing based, among others, on oil flax and fiber flax. In
flax cultivation and processing, a great progress is observed and new technologies of
breeding and harvesting were applied. Decortication process is now provided in the field and
crop of fiber rises significantly.
The other reason was the marvelous discovery that fibrous plants cultivated in the polluted
areas can decontaminate soil from heavy metals in the natural way. For example, 1 ha of
hemp can extract from the polluted land about 500 g Cu, 160 g Pb and 30 g Cd (Kozlowski
et al., 1997).
Such plants can be used for fibre and pulp production as well as lignocellulose boards, with
no negative effect on the environment. These plants are a good example of 100% utilization
and a full recycling of annual plant residue.
When used for the manufacture of textiles, bast fibres have a number of desirable qualities
qualities (Shannon, 1993; Kozlowski and Manys, 1994; Kozlowski and Helwig, 1996): as
natural cellulosic fibres have an attractive lustre distinct from that of other fibres; they are
capable of being colored with dyes, affording an extensive palette of shades which possess
hieb fastness when exoosed to lieht and to other aeencies encountered durine their useful
life; hey have high tensile strength and resistance to tearing, becoming approximately 20%
stronger when wet; they are comfortable to wear, able to transmit heat and to absorb moisture
readily, they has good draping properties, do not generate static electricity and are not prone
to pilling; they have excellent soil-release properties since the fibres shed a microscopic layer
to expose a fresh surface each time the material is laundered; they possesses high hygienic
properties even in blends with other natural or man-made fibres in content above 30%. Bast
fibres, however, suffer from certain less desirable features which limit their wider use
(Shannon, 1993): they have a natural rigidity because of the high degree of cellulose chain
orientation which comprise its structure; the 'dry-back' effect - a phenomenon which
manifests itself after wetting and drying, as the material takes a firm 'set' in the precise
configuration in which it was dried. This is probably caused by a re-distribution of hydrogen
bonds during the wetting/drying cycle; bast fiber yams Iack extensibility (the extension of the
fibre is only 1.8% at break). Consequently, close-fitting garments made from woven fabrics
do not stretch and recover in response to body movements; they tend to discolor if dried at
684
temperature above 700C; for some end uses, resistance to abrasion is not satisfactory. Bast
plant residue - shives are used as a raw material for particleboards, as sorbents (kenaf)
(Rowell, 1997), in chemical (furfural manufacture) and pulp industries. Hemp, kenaf, jute
and flax shives have the following advantages comparing to wood: lower energy required for
the chopping and drying which has a considerable effect on the reduction in costs of
manufacture, low bulk density and usefulness for the production of boards in a wide range
of density and thickness, high hardness, resilience, slenderness, and smoothness of
particles. These advantages allow for a good gluing of the surface with a low use of
adhesives as weil as the production of boards of good mechanical properties with lower bulk
densities.
While considering economic, technological and exploitation aspects of these raw materials
we have to mention the following problems: presence of a considerable percentage of
impurities (waste fibre, sand, dust, roots) and that is why a special technology is required for
the raw material purification, unpleasant odor of shives caused by the volatile fatty acids
adsorbed by the shives, pH of raw materials varies to a wide extent, depending on the
method of fibre extraction, therefore the process has to be conducted under carefully
controlled conditions.
Hemp shives, unlike the flax shives and jute residues, require: crumbling of the raw
material, greater amount of adhesives, stronger binding of particles due to a considerable
content of a soft core in the inner part of stalks. The shive properties can be altered in a fairly
small range, depending on geographicallocation, local conditions of cultivation, fertilization,
variety, etc.
BAGASSE AND REED STALKS
Sugar cane is cultivated in many parts of the vvorld and bagasse is the residue material
obtained every year during sugar production. First of all, it is used as a fuel in sugar plants,
the remainder is employed for lignocellulose board production.
Reed is available from natural reed habitats, which are not a result of cultivation of any kind.
Hence both the yield and efficiency are a result of naturallocal conditions. The most valuable
part of the plant - the stalks - is 1.5-5 m long with walls of thickness ranging from 0.6-2
mm. The stalks are used for particleboard production. The properties of reed straw are
sirnilar to those of sugar cane. The moisture content is the lowest during winter (14-21% ).
The reed straw is used for the production of reed boards which can be used in the building
industry and for plaiting of different products for home use. The reed resources in Poland are
estimated for 70-75 thousand ton/year. The reed residue is estimated for 4-5 thousand tons
and is tobe considered also a raw material for particleboard production.
Reed has the following advantages: low density (60-70 kgtm3) in unpressed state at the
moisture content of 15%, the lowest known water adsorption among all organic building
materials (most probably due to a high silica content), low expansibility,
good performance under the flame conditions probably due to a considerable silica content.
Its disadvantages are: high ash content (approximately 2.5-2.8%) which includes calcium,
silicon, magnesium and potassium oxides. The high ash content is the reason for quick
blunting of cutting equipment, necessity of suitable crumbling of raw material because of the
presence ofwaxes covering the stalks which influence board quality.
The economic problems regarding reed a.nd reed residues consist in: raw material stock
localized in remote areas of the country which increases transportation costs, size and the
quality of raw material and the need of material storage associated with this fact.
From the technological point of view the reed residue is a very good raw material for the
production of light boards to be used in building industry, manufactured as special products,
namely water-, fire-, and fungi resistant boards (Kozlowski, Mieleniak and Przepiera,
1994).
BAMBOO
Another interesting lignocellulose resource is bamboo which grows in tropical countries of
Asia and it is the fastest growing plant. lt reaches its full height of 15-35 m within a period of
685
2 to 4 months. lt should be also mentioned that bamboo is one of the most efficient sources
of biomass. lt is very important lignocellulosic raw material because at least 2.5 billion
people depend on the use bamboo (Manokaran, 1990) and the value of bamboo products
worldwide is estimated at about 7 billion $ US per annum (Liese, 1992).
Studies of bamboo, carried out especially in India and in the Philippines, have proved
suitability of bamboo as a concrete reinforcement. Laminated bamboo, glulam or bamboo has
been also developed as a structural and decorative material in variety of styles. lt is also
peeled and processed into ply with various adhesives. The manufacture of hardboards and
particleboards will be explored in the near future (Liese, 1989).
Building panels from woven bamboo mats with saw dust or coconut coir pith as fillers
reduce the shortage of wood for such purposes (Liese, 1989).
GRASS AND LEAVES AS A LIGNOCELLULOSIC SOURCE
A valuable raw material for the particleboard, pu1p and composite production is elephant
grass Miscantus giganteus. 1t belongs to perennial grasses. This grass is characterized by a
very high efficiency of biomass per area unit, 17-25 tondry mass per ha in temperate
climate, and contains relatively high amount of cellulose. The discussed grass, due to its
ability to accumulate heavy metals, can be also cultivated on polluted areas. The research on
the possibility of this plant cultivation and its possible applications is carried out in many
countries (Hasse 1990).
Another interesting lignocellulosic raw material is pineapple leaf fibre which was a subject of
some research performed at the INF in the cooperation with the South India Textile Research
Association in the field of linen and pineapple fibre-containing yarns (Manys and Mazur,
1996). The new pineapple yarns, obtained by using Parafil 1000 or Parafil 2000 spinning
systems, in blends with different natural or man-made fibres appeared to be a promising
material for the textile industry.
OlL PLANT RESIDUES AND STRAW
Vetiver is native to tropical and subtropical countries. This is a perennial grass which is about
2 m in height. Each bush consists of approximately 25 stalks. The length of roots is about 45
cm. A fresh root weights about 65 g. This species is used for the extraction of oil which can
be used in pharmaceutical and cosmetics industries (Kozlowski, Mieleniak and Przepiera,
1994).
Rape straw is still the residue material which due to its properties cannot be fully utilized in
the agriculture. In most cases the straw is chopped and distributed in the field. Taking into
account the climatic and soil conditions, rape can be cultivated on the acreage of 8 -10
thousand ha in Poland (Kozlowski. Mieleniak and Przeoiera. 1994).
Great resources of oil flax can be found in Canada, USA, Argentina and China. The waste
straw of rape, oil flax and small grain plants can be excellent raw materials for the
manufacture of insulating boards and composites.
COTTON AND OTHER VEGETABLE STALKS
Cotton grows in the countries of moderate temperature, e.g. 17-270C throughout the year.
The bushes are 0.5-1.5 m tall depending on the variety of cotton and cultivation conditions.
After harvesting of fibre balls, stalks are the residue left in the fields, which is used as a raw
material for lignocellulose board production, especially in the countries poor in forests. The
efficiency of the material is low in the proportion to the content of the Cortex, fibre, husks
and leaves. The boards are light brown.
Another Ugnocellulosic raw material used for particleboard industry are grape-wine stalks
(Kozlowski, Mieleniak and Przepiera, 1994).
686
FOOD PLANT RESIDUES
Valuable raw materials for lignocellulose board production are also many other residues such
as: stalks, rice husks, peanut husks, hop, wicker residues, etc. Successful attempts at using
these materials for lignocellulose board production were made many times, e.g. by
Siempelkamp Company, the INF and others.
COMPOSITES OF LIGNOCELLULOSICS WITH MAN-MADE AND

NATURAL POLYMERS
Lignocellulosic polymer composites included a wide range of products of different

applications, from construction or insulation panels made of wood pieces, particles and
fibres, through specialtextiles (geotextiles and non-woven textiles) to plastic products based
on polymers fllled with lignocellulosic particles.
Lignocellulosic polymer composites are made mainly for the following purposes:
to bond lignocellulosic particles with polymer glue (lignocellulosic boards based on the
organic and inorganic binding materials); to reinforce polymeric material with lignocellulosic
particles or fibers; to modify polymeric material, e.g. make it biodegradable; to modify
lignocellulosic materials with polymers which results in the material improvement, e.g.
lirnited permeability and better dimensional stability (wood, textiles), and higher resistance to
biodegradation.
In Table 3 the most important lignocellulose-polymer composites are listed. In many areas of
application lignocellulosic raw materials should be modified to improve properties of a
composite (e.g. adhesion, bio-resistance) and to enable successful production. Major
lignocellulose - polymer composites were described below with a special emphasis on
composites based on non-wood lignocellulosic materials.
PARTICLEBOARDS
The composition boards, including particleboards (extruded and platen pressed) and
fiberboards, especially medium-density fiberboards (MDF) belong to the most abundant
materials for construction, furniture, and interior decoration (wall and ceiling paneling). They
are, however, very young materials produced and used by man. No one has been able to
coin a good, descriptive term acceptable to everyone for this relatively new branch of forest
product industry (Maloney, 1977).
The main lignocellulosic raw material used for particle and fiberboard industry is wood, but
in many countries other agro-based residues, mentione:d in above chapte-r, are successfully
utilized. Table 4 presents data on particleboard production in different countries. Annual
plant wastes: flax and hemp shives, jute stalks, bagasse, reed stalks, cotton stalks, grass-like
Miscantus, vetiver roots, rape straw, oil flax straw, small grain straw, peanut husks, rice
husks, grape-vine stalks and palm stalks are cheap and valuable raw materials for
lignocellulose board production. lt is worth to add an important fact that production
technology is sirnilar to the lignocellulose board production from wood particles.
The specificity of board production from annual plant waste consists in raw material
preparation, including purification and sorting of the material. Lignocellulose boards from
annual plant wastes are characterized by a wide range of densities 300-750 kgfm3. Main
fields of the application of annual plant waste boards are building and fumiture-making
industries and transportation.
Table 5 shows physical and mechanical properties of boards made of jute stalks, cotton
stalks, bagasse, bamboo and peanut husks, tested by Siempelkamp and manufactured
according to Siempelkamp technology. The results shown in Table 5 refer to the three-layer
boards, 19 mm thick, manufactured under laboratory conditions by Siempelkamp Company.
687
~ Table 3. Composites based on lignocellulosic raw materials and polymers.
it I
Composite Raw Materials

Lignocellulosic and other Polymer
Structural composites:
Glulam beams wood boards, bamboo, bast fibres as tensile and urea, melamine, phenol, isocyanate, resorcinol, vinyl
compressive members polyacetate
Laminated veneer lumber (LVL) wood veneer as above
Parallel strand lumber (PSL) as above as above
Oriented strand lumber (OSL) as above as above
Panels:
Plywood wood veneer, bamboo urea, melamine, phenol, isocyanate, resorcinol, vinyl
polyacetate
COM-PLY wood veneer and lignocellulosic particles as above
Partideboards wood particles, flakes, saw dust; shives offlax, hemp, as above and protein: casein, soybeans based; Iignin
kenaf, jute, roselle fibers (karkadeh); bagassa, reed,
straw, vetiver roots, etc.
Medium density fiberboards (MDF) lignocellulosic fibres urea, melamine, phenol, isocyanate, resorcinol, vinyl
polyacetate
Oriented strand boards (OSB) lignocellulosic strands as above
Lignocellulosic-mineral wood wool, paper, lignocellulosic particles including cement, gypsum, lime, magnesium silicate,
waste paper pulp, mineral particles, e.g. vermiculite, polycondensated product ofurea borate and phosphate
microspheres, mineral wool, asbestos, glass fibers with silicate*, organic resins
Special functional (water-, fire-, bio- as above, fire retardants, fungicides as above
resistant)
lnsulating (thermal, acoustic, radiation) vegetable stalks, lignocellulosic particles, wood veneer, urea, melamine, phenol, isocyanate, resorcinol, vinyl
paper polyacetate
Polymers filled or reinforced with
Iignocellulosics:
Thermosetting polymers lignocellulosic fibres including waste paper, saw dust, urea, phenol, resorcine, isocyanate, epoxy resins, pure
flour melamine,
Thermoplastic polymers wood saw dust, flour; short fibres, waste paper PP,PE,PVC,PS,PA,LDPE
Natural polymer lignocellulosic fibres including waste paper, saw dust, natural rubber, casein, modified starch,
flour
Textiles:
Lignocellulosic and man-made fibers cotton, flax, hemp, kenaf, rosella, ramie, jute, kapok, wool, silk, polyesters, polyamides, polyaramide, acrylic,
blends coir, pineapple, abaca, sisal, henequen modacrylic, olefm, Iycra, man-made cellulosic fibres:
viscose, rayon
textiles improved with polymers as above starch, gelatin, urea, melamine resins (sizing), urea,
melamine resins (wrinkling), condensation products of
formaldehyde with urea, thiourea, guanidine, melamine,
e.g. DMU, DMEU, DMDHEU (abrasion), reactive
dyestuffs: triazine or pyramidine or vinyl sulfonate
derivatives (dyeing), meta! (metallization),
textiles coated with polymers as above PVC, polyurethane
Non-woven textiles** including geotextiles as above and wood wool, straw, bentonite, active carbon, soy oil, rape oil,
vermiculite, silica
absorption chemotextiles including filters as above urea, phenol, resorcine, isocyanate, epoxy resins, pure
and sorbents melamine
Packaging wood, wood wool, bamboo, paper including wastes starch, silicates, urea resins, polyvinyl alcohol, Iignin
* SOURCE: Kozlowski, Helwig and Przepiera, 1994.
** SOURCE: Brunschweiler, 1995.
0\
&3
Physical and mechanical properties of particleboards from annual plant residues,
manufactured according to the INF technology, are shown in Table 6. The table contains
results obtained for 19 mm boards.
MEDIUM DENSITY FIBERBOARDS
Among modern materials are medium density fiberboards (MDF). They consist of wood
fibers or annual plant fibers (82% ), gluing amino resin (9% ), paraffin ( 1%) and water (8% ).
The production of MDF from fibers of annual plants started in 1985, when the Sunds
Defibrator company in Thailand developed the process of MDF manufacture from bagasse.
Next factories based on bagasse were built in Pakistan, China and India. The production of
straw-derived board materials is intended or has already begun in Great Britain and Canada.
This fact points to a growing interest in the utilization of annual plants to mak:e board
materials for a variety of purposes. Annual renewability of plant raw materials and
considerable annual cellulose increment, which is three times as high as annual ring of trees,
give the reasons for this growing interest (Kozlowski, Mieleniak: and Przepiera, 1997).
Crumbled hemp, flax and kenaf straw and shives also belong to excellent raw materials for
the MDF production. The manufacture of MDF requires appropriate defibering of raw
materials and preparation of fibrous mass of stable quality parameters. Modem
thermodefibrators offered by leading companies in this field (particularly by Sunds
Defibrator) enable to produce fibrous mass from any sort of wood and many annual plants.
Quality of these fibers allows to mak:e excellent MDF without a necessity of additional
crumbling and classification of fibrous mass (Kozlowski, Mieleniak: and Przepiera, 1997).
Medium density fiberboards compared to particleboards offer the following advantages
(Kozlowski, Mieleniak: and Przepiera, 1997): higher structural homogeneity, small
roughness and closed surface, dimensional stability which is considerably higher than that of
solid (uniform) wood and currently known wood-derived materials, capability of easy and
uniform dyeing, bending strength and tensile strength which are higher than those of
particleboards ofthe same density. MDF can be also compared with solid wood. In the latter
case, the advantages of MDF are seen in the following facts (Kozlowski, Mieleniak: and
Przepiera, 1997): drying and seasoning are unnecessary, fiber orientation is of no importance
Table 4. Approximate production data on lignocellulose boards made of annual plant residues in different
countries*
Production
Number of Plants Capacity, Kind ofRaw Kind of Board
Country
thousand m3 per Material Produced
year
Franceand 3 20 tlax, saw dust shives/wood
Belgium particle boards
Bulgaria I 10 flax and hemp flax and hemp
shives shive boards
Czech Republic 4 IOO flax shives, saw shive-saw dust
and Slovakia dust boards
Poland 4 I40 flax shives, wood wood particles/
chips, saw dust shive boards, non-
flammable boards
Hungary I 20 hemp shives hemp shive boards
Romania 2 30 hemp shives hemp shive boards
FormerUSSR 5 75 flax shives boards from
1 20 cotton waste waste cotton
China I 7.5 tlax shives flax shive boards
Cuba 2 I5 bagasse bagasse boards
*SOURCE: Kozlowski, Mlelemak and Przepzera. 1994.
690
to frontal processing, varnishing of MDF can be done with equally good effe~t as in the case
of wood, yield related to raw material is incomparably higher.
The above advantages have established MDF' s prominent position in the furniture making
industry, where the application of medium density fiberboards is regularly growing. They
are used particularly for purposes, where particleboards cannot be employed, e.g. for
moulding of edges, varnishing of surfaces and edges, veneering of surfaces and edges with
thin foil, etc. In Europe, the high rate of MDF production increase occurred in the late
eighties and since then it regularly goes up. Properties of MDF based on flax, hemp and
kenaf are shown in Table 7.
Properties of these experimental boards generally meet and often exceed the ASTM and other
standards for MDF. With pressurized refining, surface quality was acceptable as well
(Lloyd, 1996).
The use of whole stalks of bast materials can be necessary to provide sufficiently high
performance characteristics for bast materials. The advantage of using the whole stalks is
further strengthened by the fact that many countries have minimized the use of only flax
shives as a furnish material. The whole stalks make a more promising option for furnish in
the light of their improved performance characteristics. Such an approach must be
competitive in terms of raw material cost, however, some cost may well be saved by
removing the decortication step from the processing of the whole stalks (Lloyd, 1996).
Table 5. Physical and mechanical properties of particleboards made of armual plant waste, produced
accordinU?;tO th e s1empeIkamptechnoogy'.
1 *
Properties Unit Bagasse Cotton Jute Reed Bamboo Peanut
Stalks Husks
Density kg/m 3 600 600 580 730 625 750
Modulusof MPa 20-21 16- 17 15- 16 22-23 18- 19 17- 18
Rupture
Interna! Bond MPa 0.4- 0.5 0.4-0.5 0.5-0.7 0.4 - 0.5 0.6- 0. 7 0.5- 0.6
Swelling % 6-7 5-6 12- 15 6-7 6-8 -
Thickness after 24
h
*SOURCE: Niedermmer Information Matenals ojS1empelkamp Company
Table 6. Physical and mechanical properties of particleboards made of annual plant waste, produced
*
accord.mg to the INF techno logy.
Hemp Shives Flax Shives+ Saw Dust
Property Unit Flax Yetiver
Shives Particle- Three- Layer Particle- Three-Layer Roots
board Particle- board Partideboard
board
Density kg/m 3 600 600 600 650 650 650
Modulusof MPa 16-18 15-16 17-18 17-18 17-18 16-17
Rupture
Interna! MPa 0.3-0.4 0.4-0.5 0.5-0.6 0.5-0.6 0.5-0.6 0.5-0.6
Bond
Swelling % 15-20 16-18 20-25 8-10 12-13 10-12
Thickness
after 24 h
*SOURCE: Kozlowski and Pwtrowski 198i. -
691
INSULATING BOARDS
Annual plants residues such as rape straw, oil flax straw, small grain straw, reed and reed
wastes are useful for the insulating board production, for instance according to the "Strarnit"
method (Kozlowski, Mieleniak and Przepiera, 1994).
The production makes a continuous process proceeding in the device which includes six
machines. The production is a programmed, multifunctional cycle with an automatic
temperature control (Kozlowski, Mieleniak and Przepiera, 1994). The press is uniformly fed
with raw materials, firmly compacted and pressed. At the same time the compacting
mechanism moves gradually pressed material which is subsequently blended in a continuous
way. The cardboard is fed from rolled bales which are placed over and under a board formed
. Then the board is placed in a tunnel where it is dried and the glue bond is hardened
(Kozlowski, Mieleniak and Przepiera, 1994).
An improvement in these type of boards from the point of view of water sorption as weil as
fire resistance can be performed by introducing silicates or the INF-developed fire retardant
Fobos M-2L, which is a product of polycondensation of urea polyborate and polyphosphate
with silicate (Kozlowski, Helwig and Przepiera, 1994).
LIGNOCELLULOSIC- MINERAL COMPOSITES
Composites of this type can be divided as follows: cement bonded composites, gypsum
bonded composites, other mineral adhesive bonded composites, organic resin bonded
composites based on lignocellulosic and mineral particles, paper and another lignocellulosic
material covered gypsum boards.
Cement bonded lignocellulosic composites are building materials suitable for exterior and
inierior use. They are resistant to fire, posses very good sound attenuation properties and can
be made resistant to rotting after a special treatment of lignocellulosic material with
Table 7. Phvsical and mechanical orooerties ofMDF based on bast fibres and UF resin*.
Property Unit Flax Hemp Kenaf
Density kg/m 3 785 880 817
Interna! Bond MPa 0.55 0.21-0.59 0.75
Modulus of Rupture MPa 29.0-35.4 7.8-20.8 19.3
*SOURCE: Lloyd. 1996.
Table 8. Phvsical and mechanical prnperties of insulating boards depending on raw material used*
Raw Material
Property Unit Rape Straw Oil Flax Straw Small Grains Unclassified Reed and
Straw Straw Reed Waste
Thickness mm 50 1.5 50 1.5 50 1.5 50 1.5 50 1.5
Density kg/m 3 270 490 420 490 270
Moisture content % 18 18 18 18 18
Water absorption % 220 190 210 195 200
Compression strength MPa 0.80 l.l5 1.00 1.15 0.08

Bending strength MPa 1.20 1.60 1.35 1.60 1.20
Thermal conductivity W/mK 0.071 0.069 0.073 0.069 0.071
Acoustic insulation at
frequencies:
50-3200Hz - 20 19 20 -
3200 - 12800 Hz - 22 21 22 -
*SOURCE: Kozlows/a. Mzelemak and Przepzera. 199-1.
692
Ta ble 9 . boards.m companson withthose of shiveboards*.
P ropertles ofth ree- ayer compos1te
Parameter Unit Type of board
shives VERCOM
Density kglm3 600 640
Thickness swelling after 24h, not less than % 20 6.4
Water absorption after 24h, not less than % 90 32.7
Bending strength, not less than MPa 15.0 14.8
Resistance to stretching in perpendicular direction, MPa 0.34 0.33
not less than
Screw holding strength perpendicularly, not less Nimm 55 56.
than
Ability to hold screws parallel, not less than Nimm 40 49
Thermal conductivity WlmK 0.100-0.106 0.124
Formaldehyde content mgllOOg :;; 10 4.3
SOURCE: Kozlowski et al.. 1996
Table 9 presents mechanical and physical properties of VERCOM composite boards in

comparison with those of shiveboards.
fungicides. Lignocellulosic fibres are frequently employed as a substitute for asbestos. One
of areas of their use are asbetos-cement boards, which in the past were commonly used
roofing. Experiments carried out at the INF have proved that paper waste and short fibres
can be used as substitutes for asbestos (Mankowski et al., 1994).
The process of manufacturing gypsum bonded composites could utilize wood waste and
other lignocellulosic wastes as weil as "chemical" gypsum obtained as a result of chemical
reaction proceeding during desulfurization of combustion gas (Lawniczak et al., 1994).
Gypsum bonded composites are widely used in building industry, however, they arenot
resistant to water (Lempfer, 1994; Englert et al., 1994).
An example of lignocellulosic-mineral composite bonded with a polymer (typical of
particleboard adhesives) is a three-layer incombustible particleboard VERCOM(, which was
recently developed at the INF (Kozlowski et al., 1995; Kozlowski et al., 1996). These
particleboards are characterized by the presence of lignocellulosic particles in the core,
whereas their faces are made of verrniculite.
POLYMERS FILLED WITH LIGNOCELLULOSIC MATERIALS
1t is a growing interest in composites prepared on the basis hast fibres and other agro-fibres
as a filler and/or reinforeerneut of thermoplastic matrix. This problern was paid a lot of
attention (Mieck et al., 1995; Hermann and Hanselka, 1995; Liese, 1989; Paukszta et al.,
1995; Sanadi et al., 1997).
One of the limitations of lignocellulosic particles as board material is the necessity of
processing at a relatively low temperature (up to about 200(C) in order to avoid
lignocellulosic material decomposition and prevent from the evolution of volatile matter,
because the latter results in a deterioration of composite properties kompozytu (Paukszta et
al., 1996; Sanadi et al., 1997).
In some cases there is a possibility of a short-time heating at elevated temperatures.lt results
from the above that polymers which can be employed to manufacture such composites are
limited to thermoplastics such as polyethylene (PE), polypropylene (PP), polyvinyl chlortde
(PVC), and polystyrene (PS) (Sanadi et al., 1997).
Lignocellulosic materials are added to polymers in the form of small particles, short fibres or
flour. The main problern is to obtain good adhesion between the polar lignocellulosic
particles or fibres and thermoplastic matrix. As it was in the case of reinforced fibres based
69-3
on glass, carbon, aramid, etc., which are widely used nowadays, the commercial scale
success was achieved when problems with interface layer were solved. In the case of bast
fibres we took into consideration their high higroscopicity and very low adhesion to
polymer, i.e. the fact that there is no good adhesion between hydrophobic matrix and
hydrophilic cellulose fiber (e.g. adhesion between PP matrix and flax fiber). This difficulty
was overcome by special finishing of bast fibers. Examples of such finishing (Mieck et al.,
1995) are given below:
silane treatment, use of polymers containing functional groups, treatment with substances
showing hydrophobic properties.
Among silanes which can be employed for the studies of the fiber-PP system only two
groups can be considered: silanes containing functional alkyl groups of different length,
silanes which can react with matrix according to radical mechanism, i.e. those with vinyl,
methacrylic or azide groups.
The reaction between silane-treated surface and PP requires using of so-called radical-
forming compounds, which become active at temperature of polymer processing by releasing
radicals that initiate the reaction. Dicumyl peroxide and dibenzoyl peroxide are examples of
such substances.
The other method of increasing the adhesion between lignocellulosic fibers and PP matrix
consists in the use of polymer containing functional groups. This method leads to covering
of fibres with a thin layer of polymer-like substance and results in a compatibility between
fiber surface and matrix, which increases adhesion. In the case of PP, such substance is
usually maleic anhydride grafted PP (MAPP). There are many commercial MAPP products
available of different molecular weight and different maleic anhydride (MA) concentrations.
The MA groups, in esterification reactions with cellulose hydroxyl groups, are able to form
PP film strongly bound to fibers. There is also a great potential in fiber composites
chemically modified with other anhydrides.
TEXTILE BLENDS
Naturallignocellulosic fibres comparing to man-made ones posses many advantages when

used in textiles. However, they also have some limitations. These limitations are often
eliminated by blending with man-made fibres. Biendingis done for several reasons (Hollen,
et al., 1988):
to produce fabrics with a better performance than that of pure lignocellulosic fabrics, i.e. to
combine advantages of both components in the product, to improve spinning, weaving and
finishing efficiency for product uniformity, to obtain better texture, hand and fabric
appearance, e.g. a small amount of rayon may give luster and softness to cotton, linen and
other lignocellulosic fabrics. for economic reasons, to obtain cross-dyed effect or create new
color effects according to different dyeability of fibres, to improve hygienic properties of
product.
Extensive research has been done by the fiber manufacturers to determine just how much of
each fiber is necessary in various fiber constructions. lt is very difficult to generalize about
percentage, because the percentage varies with the kind of fiber, fiber construction, and
expected performance (Hollen et al., 1988).
It was proved that the addition offlax or another bast fibres significantly improved hygienic
properties of blends with man-made fibres (Kozlowski and Manys, 1995, Kozlowski and
Manys, 1997).
Du Pont's unique concept (used commercially since 1970) produced a soft supple fabric of
fairly light weight (50 g/m2). The process is suitable for use with cotton and other cellulose
fibres and is prepared for absorbent medical purposes where a soft, non-irritating material is
required to contact the skin.
694
TEXTILE COMPOSITES
Textile composites combine various layers of different desired properties in a fabric. The use
of renewable cellulosic natural fibres as reinforcing fillers in fibre composites or adding a
fibre blend in technical textile products is appealing because of the properties of the resultant
composites and because of the environment viewpoint. The advantages of bio-fibres are low
cost and a possibility of using renewable biodegradable raw materials in some technical
textile products to a much greater extent than it is being done today (Sishoo, 1995).
For textile composites comprise many products of different type (Hollen et al., 1988):
fabrics coated with rubber, PVC, polyurethane, flocked - fibers are forced into a fabric
substrate and held by an adhesive or electric bonding to make a pile figure or overall pile on
fabric, used in apparel, upholstery and automotive fabrics, bonded fabric - two or more
fabrics are made to adhere together by an adhesive or flame-foam process, Iaminated fabric
off grain, and many come apart (used in apparel, shoes and industrial products), quilted-
one or two fabrics and wadding, batting or foam are stitched together by sonic vibration
(used in ski jackets, rohes, comforters, quilts and upholstery), foam and fiber- fibres and
polyurethane solutions are mixed together, cast on a drum, or forced through a slit to make
fabric.
All above mentioned products could be produced on the base of lignocellulosic fibres.
Bonded fibre fabrics appeared 1930 by superimposing on each other the webs from several
cotton cards and applying chemical hinder either on calender or by spraying to produce a
base for oil cloth and artificialleather. Next, the hinder like Iatex derivative was applied in a
pattern to give more soft band for interlinings and wood pulp was incorporated for
absorbent, hygienic pads. The blends of cotton and cellulose acetate fibers were bonded
uilder the influence of heat and pressure or by using a solvent for cellulose acetate resulting
in a product free from Iatex binder, suitable for medical purposes.
NON-WOVENS
The problern of changes in traditional methods of textile product manufacture is an old one as
it results from the 19th century patents taking into consideration a possibility of making
textile products by using gluing agents without spinning, weaving or knitting.
The term non-woven has been in general use since 1955. Jute and mainly bast fibers were
used to produce cheap blankets. Now needle looms produce blankets and floor coverings,
flltration, horticultural and geotextile products.
Nowadays the mostfrequent raw material to manufacture non-woven textiles are viscose and
naturallignocellulosic fibres.
SPUN BONDING
The idea of forming fabrics directly from spinneret (omitting cutting the tow), carding and
bonding is fairly obvious in principle, but difficult in practice (commercial product was
started by Du Pont in 1960). Now it is the fastest growing of all non-woven systems with
end uses: c~t backing, furniture, roofing, nappy linings, protective clothing, packaging,
and geotextiles.
This pr~cess is used to f?rm fibre~ on a conveyor by blowing ho~, low viscosity polymer
from spmnerets or by d1es, the au blast drafting the filaments m a somewhat irregular
manner, often producing very fine fibres.
CONCLUSIONS
In the last decades the growing impact of annual and biannual plants is observed on the
world economy and environment.
The lignocellulosic raw materials can be combined with man-made or natural polymers
giving a wide range of useful composites applied in textiles, particle- and other boards, pulp
and related products, composite non-wovens, geotextiles, chemo- and thermosetting
695
polymer-containing goods, filters, transportation, building industry and agriculture.
The authors are convinced that the future development of the lignocellulosic polymer
composites will be growing faster and will have a beneficial influence on the competition and
the coexistence of natural and man-made polymers.
In the future alllignocellulosic biocomposites have to be recyclable or biodegradable.
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698
LIQUEFACTION OF WOOD AND ITS APPLICATIONS
Nobuo Shiraishi
Dept. Wood Sei. & Technol., Kyoto University,
Kyoto 606- 01, Japan
INTRODUCTION
The term liquefaction of lignocellulosics has hitherto chiefly referred to those procedures for
producing oil-like materials from biomass under very severe conditions of conversion [1, 2]
. For example, Appel et al, [1] converted cellulosics to oil by using homogeneaus Na2C03
catalyst in water and a high-boiling-point solvent rnixtures (anthracene oil, cresol, etc) .at
pressures of 140- 240 atm with synthetic gas, CO/H2. Treatments for lh at 300- 350Ae
resulted in 40 - 60% yield of benzene solubles (oil) and a 95 - 99% conversion of the
starting materials. This type of liquefaction can be more precisely called the oilification of
lignocellulosics.
This review present recent progress on ligno~ellulosic liquefaction under milder treating
conditions? that is, at temperatures around 150Ae with acidic catalysts, or at temperatures of
240 - 270Ae without any catalysts. These can be compared with the organosolve pulping of
wood. While it can be pointed out that the conditions of the liquefaction are much severer
than those for the organosolve pulping, the difference is not so large when compared with
the case between the liquefaction and the oilification.
LIQUEFACTION OF UNTREATED WOOD
Recently, untreated wood has been found tobe liquefied in the presence of several organic
solvents [3- 21]. For example, after treating at around 250oC for 15-180 rnin, wood chips
and wood meals were liquefied at least in phenols, bisphenols, alcohols (benzyl alcohol),
polyhydric alcohols (1,6-hexanediol, 1,4-butanediol and glycerin), hydroxyethers (methyl
cellosolve, ethyl cellosolve, diethylene glycol, triethylene glycol and polyethylene glycol).
The liquefaction of untreated wood can also be achieved at a lower temperature of 150oC
and at atmospheric pressure in the presence of organic solvents and acid cata1ysts.
Phenolsulfonic acid, sulfuric acid, phosphoric acid, oxalic acid and hydrochloric acid having
been used as the acid catalyst [3 - 21].
lt is possib1e to obtain paste-like solutions with a high concentration of wood solute of up to

70% . After liquefaction, the wood components were found to have degraded and became
reactive, which will be shown more detail in a section of liquefaction mechanism for wood.
The obtained wooden solute can be used to prepared adhesives and other moldings, opening
a practical new field for utilization of wood wastes, the details of which will also be
explained later.
During the liquefaction of wood, especially in the presence of acid catalyst,

recondensation of degraded wood components also occurs, which has been also observed
in the explosion and autohydrolysis process for wood. Because of the recondensation, it
becomes very difficult to obtained a liquid with a large wood concentration, which is often
considered undesirable from the view point of biomass utilization. On the other hand,

Edited by P. N. Ptasad et al., Plenum Ptess, New York, 1998 699
starch is very easy to liquefy even at a very small liquid ratio and catalyst concentration,
even when the catalyst is necessary. Basedon these back ground, a combined liquefaction
process for wood and starch was proposed as a practical method for preparing large
biomass-content liquids [11]. That is, a stepwise-liquefaction procedure in which the wood
could be preliquefied alone at a relatively large liquid ratio followed by the addition and
liquefaction of the starch was proposed. By this procedure, a large biomass-content liquid
was prepared with relatively small unliquefied residue [11].
In order to find out an appropriate method for accurately determining the amounts of
unliquefied residues, the soluble properties of liquefied wood and starch were investigated
using a series of diluent solvents [13]. lt was found that the soluble behavior of a liquefied
biomass in a certain solvent was a kind of fractionation of the degraded and liquefied
biomass components. In most of the cases, any single solvent could not dissolved all of the
liquefied components completely. Several binary solvent mixtures composed of solvents
considerably different in polarity were found to be good diluent solvents for liquefied
biomasses. These phenomena can be illustrated by consulting with previous works on
physicochemical properties of the binary solvent mixtures. Among several satisfactory
binaries, the binary of dioxane and water has been studied in detail and found tobe widely
suitable for allliquefied biomass prepared in different liquefaction solvents. The range of
the dioxane/water mixing ratio usable for the complete dilution of liquefied biomasses was
wide enough for practical usage. Especially, a binary with a dioxane/water composition of
8/2 was recommended as a universal diluent for liquefied biomasses [13].
Phosphoric acid and even oxalic acid were found to be usable as catalysts for the
liquefaction of wood [12, 14- 16]. In the latter case, a small amount of hydrochloric acid
was tend tobe used simultaneously. These usages of catalyst were evaluated in connection
with the flow properties and reactivities or curing properties of the liquefied wood. In
these extension, phenolated wood/phenol/formaldehyde cocondensed resins were
proposed [19]. Wood was first liquefied in the presence of phenol by using an acid catalyst
to produce a phenolated wood, and after the liquefaction, formalin was added to conduct a
condensation reaction for converting the remaining nonreacted phenol into Novolac-type
resin components. It was found that this procedure can convert almost all the phenol
remained after liquefaction into resins, and therefore significantly upgrades the practical
value of the liquefaction technique. Another advantage of this cocondensation isthat it can
greatly improve the thermofluidity of the phenolated wood resins and the mechanical
properties of their molded products. The flow temperatures and melt viscosities of the
cocondensed resins were much lower than those of the phenolated wood resins. That is,
these two properties were more or less similar to those of the conventional novolac resin,
resulting in an excellent processability. The flexural properties of the molded products
made from the cocondensed resins, although this point should be discussed in the next
section, were much higher than those of the phenolated wood and also somewhat superior
to those of the conventional novolac resin [19].
APPLICATION OF THE LIQUEFACTION OF WOOD
From the liquefied solutions of wood, various products have been prepared. For example,
resol-type phenolic resin adhesives prepared from five parts of wood chips and two parts
of phenol did not require severe adhesion conditions and were comparable to the
corresponding commercial adhesives in their gluability. Acceptable waterproof adhesion
was attained from the adhesives after gluing wood veneers at 120-130 C with a hot-
pressing time of 0.5 min to 1 mm thick plywood. This adhesion temperature of 120 C is at
least 15 C lower than that ordinarily used for resol resin adhesives [9]. As a second
example, foams can be prepared from untreated wood-polyethylene glycol solutions [22].
Both soft and hard types of foams can be produced according to the preparation
conditions. An example of the foam thus prepared is shown in Fig. I. The prepared foams
had a density of around 0.04 g/cm3, substantial strength and strong restoring force against
deformation. These results imply that the wood components were not merely blended
within the foam bubbles, but also played an important role in maintaining the dimensional
stability of the foams.
700
Fig. 1 Foams prepared from liquefied wood in the presence of polycaprolactone.
Rigidpolyurethane foams from combined liquefaction mixtures of wood and starch were
proposed [17]. In this case, the !arge biomass-content polyols were first prepared from a
combined liquefaction of wood and starch, and the application of these polyols to the
preparation of polyurethane foam was studied. The viscosity of a biomass polyol was
influenced greatly by the composition of the biomass. At a constant total biomass content
of 50%, an increase in the wood content (i.e., decrease in starch content) drastically
increased the viscosity of the polyol. Rigid polyurethane foams have been prepared
successfully from the !arge biomass-content polyols. The foams had densities of about
0.03 g/cm3, compressive strength of 80 to 150 KPa, and elastic moduli of 3 to 10 MPa,
being comparable to those of the conventional rigid polyurethane foams. The biomass
composition in a biomasss polyol had a significant influence on the properties of the
resulting foams. The foams prepared from a biomass polyol containing only liquefied
starch showed the greatest compressive strength and elastic modulus, but they were brittle
and revealed poor restorability after deformation. The foams made from biomass polyols
containing both wood and starch had somewhat smaller compressive strength and elastic
moduli, but were much more resilient, revealing good balance in overall properlies.
Water-absorbing polyurethane foams were also prepared [20]. These were prepared from
liquefied starch polyols and diphenylmethane diisocyanate (MDI) by using a cell-opening
foaming surfactant. The liquefied starch polyols were obtained by the liquefaction of
starch in the presence of polyethylene glycol-dominant reaction reagents by using sulfuric
acid as a catalyst under either a refluxing condition or a reduced-pressure condition. The
influences of the liquefaction conditions on the properlies of the liquefied starch polyols
were investigated, taking into account the requirements for preparing appropriate
polyurethane foam. Feasible formulation for the preparation of the water-absorbing foams
were proposed and the properlies of the foams obtained were reporled [20].
The third application example is Novolac-resin type moldings prepared from untreated
wood-phenol solutions [23]. After one parl of wood meals had been liquefied in two parls
of phenol, the unreacted phenols were distilled under reduced pressure. The resulting
liquefied and reacted wood-phenol powder can be used directly after wood meal filler and
hexamethylene tetramine have been added and hot-pressed at 170-200 C. The flexural
strength of the moldingwas comparable to those made from the commercial novolac. An
example of the molded product is shown in Fig 2.
In connection with these moldings, it was described in the last parl of the previous section
that when the free phenol existing within the liquefied phenol solution was subsequently
701
F.g. 2 Sushi trays made from liquefied wood in the presence of phenol.
reacted with appropriate amounts of formaldehyde giving cocondensed resin, the thermal
fluidity, the curing property of the liquefied wood as weil as the mechanical properties of
the molding can be enhanced considerably [19]. Additionally, it was found that the
flexural properties of the liquefied wood moldings were enhanced with an increase in the
amount of combined phenol within the liquefied wood and became comparable to those of
the commercial novolac when the amounts of combined phenol were !arger than 75%.
Furthermore, with an increase in the content of wood fillers up to the amount of 70% the
flexural properties of the liquefied wood moldings were enhanced more effectively than
were the cases of the commercial novolac molding, exhibiting that the liquefied wood
resins could gain a greater reinforced effect from compounding with the wood fillers than
did the commercial novolac resins. And the greater the amount of combined phenol, the
higher the reinforcing performance of the wood fillers . In addition, water-sorption
measurements and the SEM observations of the moldings indicated that the liquefied
wood resins bad much greater hydrophilicity than that of the novolac and revealed greater
compatibility with wood fillers [18]. The carbon fiber could also be prepared from an
II' -0 II'
l(l::::=~~,)JII
I
R- O, R- 0
H ll
t
~<.-o,
~OR+ ~OH]
Maximirmr collvcr.vion Maximium com crsimr
rate to glucoside : 50% rate to gf11roside : 100%
Fig. 3 Fonnation of glucosides.
702
10 min.
Liqudicd Ccllol>iosc; 2 min.
20 min.
3 min.
II II
.1
61
Oll II II
:
" " " " O(\
~::
..-
.....,...
~ ~ b'A/J'JI~1li'c<ov
~
N
~~d~
NN C? C")
:cn..,~~~
(")
C!
;:1;
C!
::;;
~ ~
g ::!
5 min. 60 min.
f:
110~ ~Oll
~~
CII Ol1
110
Oll
Oll
Ul{JII
r,rI~ 1A_l -'{,

1 1\
Retention Time (min)

Fig. 4 HPLC chromatogra ms of cellobiose/phenol reaction products. Column: Shodex NH2P-50;
Eluent: acetonitrile/water=S/2; Flow rate: 1 ml/min; Column temp.: 30 C; Detector: RI.
703
untreated wood solution, and a tensile strength of up to 1.2 GPa has been obtained so far.
Even better physical properties can be expected with more development [24].
LIQUEFACTION MECHANISM FOR WOOD AND RELATED COMPOUNDS
As described above, liquefaction of wood and its application have been developed during
these ten and several years. More recently, there has occurred considerable studies for
elucidating the liquefaction mechanism for wood and its model compounds.
First, cellobiose was used as the model compound for cellulose, and its liquefaction
mechanism in the presence of polyhydric alcohol or phenol and catalytic amount of
sulfuric acid was studied [25]. As the conclusion, the followings were shown; (1)
liquefaction of polysaccharides in the presence of alcohols or phenol with catalytic amount
of sulfuric acid is accomplished via the alcoholysis or phenolysis in the glucosidic linkage
(Fig. 3); (2) during this liquefaction reaction in the presence of alcohols, the anomeric
hydroxyl groups of the reducing end group or that of the free glucose is protonated and
alcoholated resulting in the same glucoside as is yielded by the above alcoholysis (Fig. 3);
(3) the rate of liquefaction depends on the accessibility of the liquefaction solvent to the
polysaccharide. The liquefaction of an amorphaus polysaccharide, such as starch, is very
rapid, whereas that of crystalline cellulose proceeds in much slower rate, which obeys the
pseudo-first order kinetics; (4) the initial products of the liquefaction in the presence of an
alcohol or phenol is the corresponding alcohol or phenol glucosides (Fig. 4); (5) the
reaction between polysaccharide and phenol is more complicated compared with that
between polysaccharide and alcohols, because of the multi-functionality of phenol. As a
result,liquefaction products prepared in the presence of phenol tends to convert to higher
molecular weight substances with the increase in the reaction time [25].
On the other hand, liquefaction mechanism for Iignin in the presence of phenol was
studied in relatively wider ranges, that is, without and with acidic catalysts [26 - 28]. As
the model compound of Iignin, guaiacylglycerol --guaiacyl ether (GG) was used and the
range of the liquefaction studied was as follows: 1) under elevated temperature (200 -250
C) without catalyst, 2) under the elevated temperature of 200-250 C in the presence of
acetic acid (catalyst), 3) under the moderate temperature of 150 C in the presence of acetic
acid (catalyst), 4) under moderate temperature of 150 C in the presence of sulfuric acid
(catalyst) which is correspond to the study on the liquefaction of cellobiose described
above.
CONCLUSIONS
Conclusions obtained from this study are as follows; (1) the liquefaction of GG in the
presence of phenol under elevated temperature without catalyst proceeds very rapidly
through homolysis, producing coniferyl alcohol radical and guaiacol radical through
quinone methide as the initial main intermediates. However, there occurs various
homolytic cleavages which give various kinds of radical compounds. As the result,
considerable compounds are produced through reaction among these radical species, with
reactions among coniferyl alcohol radical, guaiacol radical and phenoxy or phenyl radicals
resulting in dominated reaction pathways (Fig. 5), (2) acetic acid can greatly promote the
homolysis reaction of GG, but not alters the reaction mechanism, that is, in the presence of
acetic acid, homolytic cleavage and coupling can occurs even at a mild temperature of 150
C, and the resulted reaction products are similar to those obtained under elevated
temperature without catalysts, (3) under the catalysis of sulfuric acid, GG is first
transferred into mainly benzyl cation. Benzyl cation rapidly condenses with phenol to give
four condensed products as the initial reaction intermediates which are produced so sooner
than they further subjected to the extensive cleavage in their -0-4 linkages and - y
bondings. The resulting cleaved fragments further react with phenol to form various
phenolated products. The characteristic of this liquefaction reaction is heterolytic, that is,
ionic, giving relatively small numbers of products when compared with the homolytic
reactions [26 - 28] (Fig. 6).
704
HCH~r
H(j=-0--/.0
OCH, ')-J (
HOHC
A ~ HOHCHG~(:~.../.) c;><,OH
Y-= t)_ ,", ] I l::
.
!ill ' V " 0 f'> e>,
{Ho-Q-o-Q -)J >-' j
(lll,) HO
~) OCH,= oyl
. ?-~~
I ?OCH~ ~6- HO~ l
~OH
H.,co>-i 'L{
OCH,
9-" . 1'1 "'
~ "0 '!'CH HOH:LQ CH OH ~:i;, o"' (lll,)
010 -+-- -HOl ' ' ' :-o
0- = VA ~ --" ~- ~ .,
Q. Q. 0 ):: ',
OH
~., ' ~~ HO (b) OH OCH, VoCH, OCH, OH
HOH1C-Q-1=a-tOOH
OCH,}
H,CO'()
9 ( (ItJ
~(Stilbene) ~) (1 ) OCH, 09 }
1 0 (iii) (d)
OHC-Qi=Q-iOOH
(I:t.)
~ . ,. , ! JO
.,. y%
H,CO~ ,Z:.o uJ. 'Y'o
~ ~~ +
;--...__ :,_Q ,~~ H,C
~0 Q ~.a~ A
V=.
L. Q.
(IV) CH OH (d) {H,1c f"l
(~) AVaCH, ~ OCH, Ui
'----y----' :1~.------> ,,,, q>- "' ,,
Q A, ~ ~
' ""' ,. , "'' V y
f:ri?k, "'F!?- l ~r-QOH Hbb/ 6 0
Ht' ~1~ ~:. Q::~-=Q:~-o-OH
A
V Q.
~ = ~..... ~."6, "~ =
~ ., "'' ~.= ,~ = &' , ,
l ;,= , \(=. 1 lf= Q ~ 1 ,,, ~-
" "'' . ,., ,.,':Q 6 o 0 cxOH
l o,
;i,--. ....:__ E' 0 6. rexx" =.}-
{ "' y. ('1 ' - '"'
09H ~ 9-0H {,t, , ,~ '(= Qe>, 1"".,.0:'
s~ 9s~} o.,.".._ y o .. 6 l ,", " ~ LVJ.o.=
(VtJ (V,) 6 Cr"" 6-""J o:CHY.:lmg (!,,) OH
(VI 1) (Vl,) (VI,)
05
~ oyCH=CHCH 0
H,CO t " GH (Ill)
Fig. 5 Reaction mechanism of GG in the presence of phenol under elevated temperature without catalysts.
~
HOH,~ -bOCH, HOH C OCHo
11-~-o
'I I
11~-o-Q
-o
HO-o-C-11
''AOoH
HOHz~ HOH,~
H~-0 90CH3
0-
HC-0-o OH
, _Q_
HOHC I OH VocH.
A
OCH, + +CH OCH OH
=--=-- (M~396)
(M~396)
ocH, VocH,
OH OH HOH C OCHo HOH C OCHo
(GG) 'I I 'I ,h"
bcnzyl cation 11-c-o-Q
11--e-0;::\_J
Q-!-11 IIJ-0
HO A A OH
VocH3 YocH3
OH OH
(M~J96)
(M~396)
A
(
HOH2 C O
J)
HOH 2C
HOH21 H?/
no
OH JH
Ho--Q-cH
HC- Q-OCH3
OH
~OCH3
HIC-o-OH
OH 90CHo
OH
c>-OCH 3
OH OH (M~272) Ho-Q +IIC110
p
(M~272)
jurno
oo{)l HO 4H,
"0----~2 OH
9
OH
I
OH
HCHO
6
(M= 230)
I OoH
"'~
"(J)
CH 2 0
H1C-o-OH
~
HC-
Q-OCH3
q-OH ~
Q
OH 90CHo
-~
OH
(M=336)
(M=348)
OH
(M=200) (M=200)
Fig. 6 Possible reaction pathway of GG in the presence of phenol under the

catalysis of sulfuric acid at 150"C.
REFERENCES
1. H. R. Appel, Y. C. Fu, E. G. Illig, F. W. Steffgen, and R. D. Miller: in 11 Conversion
of Cellulosics Wastes to Oil 11 , U.S. Bureau of Mines, 1957, RI 8013, 27.
2. C.Vanasse, E. Chomet, and R.P. Overend: Can. J. Chem. Eng., 66, 112 (1988).
3. N. Shiraishi: Mokuzai Kogyo (J. Wood Technol.Assoc., Japan), 42,42 (1986).
4. N. Shiraishi: in "Resent Research on Wood and Wood-based Materials" , Elsevier
Applied Science, London, 1993, 155.
5. N. Shiraishi: in "Handbook on Biodegradable Plastics 11 , STS Pub.,Tokyo, 1995, 139
706
6. N. Shiraishi, and M. Y oshioka: in "Handbook on Wooden New Materials " ,
Gihoudou Pub.,Tokyo, 1996,45, 62, 72, 79, 81, 118, 152.
7. N. Shiraishi, N. Tsujimoto, and S. Pu: Japan Patent Publication Unexamined 1986-
261358 (appl. May 14, 1985).
8. S. Pu, and N. Shiraishi: Mokuzai Gakkaishi, 39,446,453 (1993).
9. S. Pu, M. Yoshioka, Y. Tanihara, and N. Shiraishi: in "Adhesives and Bonded Wood
Products " , C.-Y. Hse and B. Tomita eds., Forest Products Soc. U. S. A., Madison,
1994,344.
10. S. Pu, and N. Shiraishi: Mokuzai Gakkaishi, 40,824 (1994).
11. Y. Yao, M. Yoshioka, and N. Shiraishi: Mokuzai Gakkaishi, 39,930 (1993).
12. L. Lin, M. Yoshioka, Y. Yao, and N. Shiraishi: J. Appl. Polym. Sei., 52, 1629 (1994).
13. Y. Yao, M. Yoshioka, and N. Shiraishi: Mokuzai Gakkaishi, 40, 176 (1994).
14. M. H. Alma, M. Yoshioka, Y. Yao, and N. Shiraishi: Mokuzai Gakkaishi, 41, 1122
(1995).
15. M. H. Alma, M. Yoshioka, Y. Yao, and N. Shiraishi: J. Appl. Polym. Sei., 61,675
(1996).
16. M. H. Alma, M. Yoshioka, Y. Yao, and N. Shiraishi: Holzforschung, 50,85 (1996).
17. Y. Yao, M. Yoshioka, and N. Shiraishi: Mokuzai Gakkaishi, 41,659 (1995).
20. Y. Yao, M. Yoshioka, and N. Shiraishi: J. Appl. Polym. Sei., 60, 1939 (1996).
21. M. H. Alma, M. Yoshioka, Y. Yao, and N. Shiraishi: Mokuzai Gakkaishi, 41,741
(1995).
22. N. Shiraishi: in "Cellulosics Utilization; Research and Rewards in Cellulosics
","Elservier Applied Science, London, 1987, 97.
23. N. Shiraishi: Japan Patent Publication Unexamined 1989-179483.
24. N. Tsujimoto: in "Recent Research on Wood and Wood-based Materials" ,
Elsevier Applied Science, London, 1993, 169.
25. Y. Yao, M. Yoshioka, and N. Shiraishi: J. Appl. Polym. Sei., submitted (1996).
26. L. Lin, Y. Yao, M. Y oshioka, and N. Shiraishi: Holzforschung, accepted.
27. L. Lin, M. Yoshioka, Y. Yao, and N. Shiraishi: Holzforschung, accepted.
707
Enzymatic Bonding Systems
Claus Felby and Per Oie Oiesen
Plant Fibre Laboratory,

Unit ofForestry,
Royal Veterinary and Agricultural University,
Agrovej 10, Taastrup
Denmark
Introduction
In conventional production of wood-based boards and panels, synthetic adhesives such

as urea- and phenol formaldehyde, are added during the production process. The adhesives
ensure good mechanical properties and dimensional stability upon exposure to water
However, some of the applied adhesives may cause environmental or health hazards, and
new less harmful adhesives are in high demand. A new approach for bonding of boards and
panels is to use environmentally friendly enzymes for cross-linking and polymerization of
wood-based materials.
The chemical structure of wood is called lignocellulose, and is the main consti-tuent of
all higher plants. Lignocellulose contains the two most abundant natural polymers; cellulose
and Iignin. Both polymers are along with hemicelluloses the main structural components of
cell walls in wood. The cells may have differrnt physio-logical functions such as fibers and
vessels, but each cell has a basic structure of a primary, secondary and tertiary wall
surrounded by a rniddle lamella, see Figure 1. The cells are joined by the rniddle lamella
which is mainly composed of Iignin, thus a physiological function of Iignin is therefore as
"natural" wood adhesive. Lignin comprises 20-30% of woody plant cells and is a highly
branched and heterogenaus 3-dimensional aromatic polymer made from crosslinking of
three precursors, all with a basic structure of 9 carbon atoms (C 9-units) arranged in a
phenolic ring with a propanoid side chain, see Figure 2.
In vivo the monomers are polymerized by an enzyme initiated radical coupling process.
Oxidation oflignin monomers by enzymes such as laccase and peroxidase produces a
multiplicity of different radical species which participate in the polymerization and form the
Iignin polymer.
Annually more than 90 rnill tons of spent sulfite Iiquor and kraft Iignin known as
Science anti Techno/ogy of Polymers anti Advanced Materials

technical Iignins are available as waste from the paper pulping industry. The !arge quantities
and Iow cost make Iignin attractive as a raw material for industrial applications. For bonding
applications Iignin has some interesting properties, as it will develop tack when subjected to
heat (Goring 1963) a phenomenon known as auto-adhesion. Similar to in vivo polyme-
rization Iignin will readily undergo in vitro polymerization through oxidation by enzymes.
These properties may be utilized for enzymatic catalyzed bonding of Iignocellulose e.g.
wood-based fiberboards or paper and packaging materials
Figure 1. Wood cell wall structure of a softwood tracheid. ML = middle lamella, P = primary layer, SI =
secondary wall, S2 = secondary wall, T = tertiary wall. Reproduced from Fengel and Wegener (1984).
CH 20H CH 20H
I
CH 2
I
CH 2
I
CH 2
I
CH 2
OCH.a
OH
Syrtngyl
Figure 2. The three Iignin precursors p-coumaryl, coniferyl and syringyl alcohol. The monomers are
polymerized to a 3-dimensional conjugated aromatic polymer through an enzyme initiated radical coupling
process.
The enzymes used for bonding applications are the phenol oxidases peroxidase (EC
I.l I.l.7) and Iaccase (EC I.l0.3.2). Both are available in commercial quantities and will
catalyze a one-electron oxidation of phenolic hydroxyl groups while reducing H20 2 or 0 2,
yielding phenoxy radicals and water, see Equation 1 and 2. The catalytic reaction for both
enzymes are two-substrate, two-product reactions.
Peroxidase
2Phe-OH + H202 ~ 2Phe-o + 2H20 (1)
Laccase
4Phe-OH + 0 2 ~ 4Phe-O" + 2H20 (2)
710
The concept of using phenol oxidases for bonding applications is based on the
reactivity of phenoxy radicals in wood, as shown by Glsser and Sandermann (1970). In
vivo phenol oxidases participate in polymerization of Iignin through radical formation, and it
may be possible in vitro to utilize the same type of reaction for bonding of Iignocellulosic
materials. Even though phenoxy radicals in !arge Iignin structures appear stable
(Hatakeyama and Nakano 1970), the stability is caused by immobilization in the Iignin
matrix rather than low reactivity, as radical reactions between aromatic compounds are
thermodynarnically favorable (Foti et al. 1994).
Enzymatic bonding
Enzyme catalyzed bonding of Iignocellulosic materials can be applied as a one-

component system on wood fibers where the Iignin is activated by phenol oxidases followed
by hot pressing to a board. A more conventional approach is to use the enzyme in
combination with technical Iignins. The enzyme/lignin rnixture is then applied to wood chips
or fibers as a conventional adhesive.
One-component systems
A one component system for bonding of wood fibers was described in a patent appli-
cation by Kharazipour et al. (1993). Fiberboards were made from laccase treated wood
fibers without any addition of adhesive. In the description of the invention unspecified wood
fibers from an unspecified fibration process were submerged in an aqueous laccase solution
at 25C. The fibers were incubated 2-7 days and drained to a maisture content of approxi-
mately 50%. The incubated fibers were either strewn on a sieve and hot pressed for wet-
process boards, or dried to 3% maisture content to make air-Iaid fiber mats for hot pressing
to dry-process fiberboards. Control boards were made in the same way by replacing the
enzyme solution with tap water. In both cases boards made from the enzyme treated fibers
had superior physico-mechanical properties compared to the controls.
The technique was investigated in further details by Felby et al. (1997). Wet and dry
process fiberboards were made from Iaccase oxidized beech (Fagus sylvatica) wood fibers
from a thermomechanical pulping process (T.MP). For dry process fiberboards the fibers
were suspended in waterat room temperature, 3 J.Lg enzyme protein/g fiberwas added and
the enzymetreatmentwas continued for 1 hr. The fibers were dried, air-laid fiber mats were
formed and 3 mm fiberboards were pressed at 200 C. The enzyme treated fiberboards had
significantly higher modulus of rupture and modulus of elasticity as weil as better dimen-
sional stability, see Table 1.
Table 1. Mechanical properties for fiberboards made from Iaccase treated, heat
inactivated Iaccase treated and untreated beech wood fibers. Thickness swell (T.S)
and water absorption (W.A) are measured following a 24 hr cold water soak.
Modulaus of rupture (MOR), modulaus of elasticity (MOE) and internal bond
strength (IB) are measured according to ASTM D-1037. Felby et al. (1997).
Treatment Density MOR MOE IB T.S W.A

(MPa) (GPa) (MPa) (%) (%)
(kg/m3)
Laccase 890 40.3 4.10 1.49 23 79
Inactive laccase 855 26.4 3.54 1.01 42 163
Untreated 900 27.1 3.42 0.97 47 147
711
The control series of boards made with heat inactivated enzyme did not show any
effect of the protein and carbohydrate content in the enzyme solution upon mechanical
properties and dimensional stability, thus the bonding effect is believed to be caused by the
catalytic effect ofthe enzyme only. Note that the laccase treatment is only 1 hr compared to
2-7 days reported in the patent by Kharazipour et al. (1993). Further investigations of the
bonding mechanism by electron spin resonance spectrometry (ESR) of beech wood fibers
revealed that oxidation by laccase increase the number of free radicals in the fiber Iignin
matrix by an order of decades. The laccase generated radicals had a high stability with a half
life of more than 2 weeks, and a theory was put forward that the bonding mechanism is
associated with crosslinking reactions of laccase generated radicals situated in the Iignin
matrix.
Two-component adhesive systems
Adhesives based on phenol oxidases and enzyme treated Iignins or phenolic compounds
have been investigated on several occasions. Nimz et al. (1976) studied the adhesive
performance of a horse radish peroxidase treated lignosulfonate, however, no polymeri-
zation effect of the enzyme was observed. Haars and Htter-mann (1983) applied for a
patent on a two component adhesive using laccase treated lignosulfonates to bind blocks of
solid wood, and further development of the adhe-sive system for particleboards and wood
Iaminates was described by Haarset al. (1989). The adhesive formulation was one part of
laccase solution and two parts oftechnicallignin known as spent sulfite Iiquor (SSL) from a
sulfite-based paper making process. For making the particleboards 150 g (50% w/w) of
adhesive was mixed with 1 kg of wood chips and pressed by 30 kg/cm2 Results of internal
bond strength measurements on particle boards bonded by synthetic adhesives and enzyme/
Iignin mixtures are shown in Table 2.
Jin et al. (1991) used an adhesive system of brown-rotted Iignin (BRL) made from
fungal degradation of wood in combination with laccase, peroxidase and hydrogen
peroxide. Wood Iaminates were made from three different wood species by the use of diffe-
rent adhesive formulations of enzyme and BRL. The results show a positive effect of the
enzyme treatments on dry shear strength. No investigation of the bonding mechanism was
made.
The use of peroxidase and laccase to improve the plybond strength of paper boards
was described by Yamaguchi et al. 1992. DHP (dehydrogenative polymer) synthetic Iignin
was made from vanillic acid using peroxidase as catalyst. The vanillic acid was polymerized
in dialysis tubes in the presence of TMP pulp, whereby the DHP Iignin precipitated on the
pulp surface. Paperboards made from the DHP treated TMP pulp had superior plybond
strength compared to TMP pulp without precipitated DHP. Yamaguchi et al. (1993) used a
similar technique to precipitate DHP made by poly-merization of vanillic acid, catechol and
different tannins onto a TMP pulp. The pulpwas either untreated or pretreated with laccase
for 72 hr. A positive effect on paperboard plybond strength was found both for the TMP
with precipitation ofDHP and for the TMP pulp subjected to a laccase treatment only.
In a study to reveal the bonding mechanism of enzyme treated DHP-Iignin and TMP
pulp Yamaguchi et al. (1994) suggest that the cross-linking of wood-fibers in the treated
paperboards is due to an increased bonding area and an enzyme generated depolymerization
or loosening ofthe 3-dirnensionallignin structure, thus improving the accessibility and reac-
tivity of the Iignin.
The use of technical Iignins in two component systems may be substituted by
hemicelluloses with phenolic substituents. In a patent application by Pedersen and Felby
( 1996) ferulated arabinoxylan (FAX) was used in combination with laccase as adhesive for
fiberboards, solid wood blocks and paper sheets made from unbleached mechanical pulp.
712
Table 2. Intemal bond strength ofparticleboards bonded by synthetic adhesives and
lignin!laccase-based two component adhesives. Note that different types oflignin are
used. Haars et al. (1989).
Type of resin IB (MPa) Press Temp. eq

A. Synthetic adhesives
Urea-formaldehyde 0.52 190
Phenol-formaldehyde 0.62 190
B. Controls
SSL (spray dried) 0.25 24
Enzyme 320 U/ml 0.00 24
SSL + inactive enzyme 0.25 24
C. Lignin-Iaccase adhesives
SSL (Ca) + 320 U/ml 0.64 24
SSL (Ca/Mg) + 320 U/ml 0.51 24
SSL (Mg) + 320 U/ml 0.60 24
SSL + organosolv Iignin + 320 U/ml 0.05 24
Ferulated arabinoxylan has a backhone of xylan units branched with arahinan and ferulic
acid substituents for approximately every 5 xylan units. The com-pound can be found in
most grass species and can readily be extracted from com bran. As the compound is almost
colorless it will not result in any darkening or discolora-tion as is the case for technical
Iignins, which makes it of interest for strength enhancement of paper and packaging
materials. In the patent by Pedersen and Felby (1996) handsheets were prepared from a
softwood (Pinus radiata) TMP pulp and submerged in a 2% solution ofFAX, whereupon 3
J.18 enzyme protein/g of fiber was added. The enzyme was allowed to react for 2-5 minutes
and the handsheet was removed and dried at I 00 oc for 5 min. The effect of the treatment
upon tensile strength of the handsheets show a drastic increase in both dry and wet strength,
see Figure 3. The bonding mechanism is believed to be a combination of radical cross-
linking ofFAX and softwood fibers as well as a locking ofthe fibers in a FAX matrix.
Applications
Enzymatic bonding systems can be used for bonding and strength enhancement of such
products as medium density fiberboards, masonite boards and paper and packaging
materials. For industrial implementation of enzymatic bonding, the enzyme process must be
adapted to existing manufacturing processes. A major part offiberboards (MDF-boards) are
made in a semi-dry process with a maximum moisture content of approximately 50% (wet
substance). These conditions arenot favorable for enzyme reactions, and the use of enzymes
will require development of new techniques for industrial use of enzymes. Future work
within the concept should emphasize upon the enzyme reaction at industrial relevant process
parameters.
713
Tensile trength (kNm/kg)
50
Control Laccase FAX Laccase + Laccase + Control

FAX (dry) FAX (wet) (wet)
Figure 3. Tensile strength of handsheets (200g/m2) made from unbleached TMP softwood fibers (Pinus
radiata) . The handsheets were either untreated, made with laccase only or immersed in a 2% solution of
ferulated arabinoxylan (FAX) with or without laccase present. Pedersen and Felby (1996)
Conclusion
Bonding of lignocellulosic polymers can be achieved through enzymatic catalyzed

oxidation of Iignin. The enzyme reaction generates stable free radicals in Iignin through a
dehydrogenative oxidation, and the bonding mechanism appears to be associated with
reactions of these free radicals. Enzymatic bonding can be applied either by a direct
activation of Iignin in wood fibers or by rnixing enzyme and technical Iignin or sirnilar
phenolic compounds with wood fibers or particles. The use of oxida-tive enzymes to
process and manufacture wood-based materials may yield new and more environmentally
safe products.
References
Felby, C., Pedersen, L.S., and Nielsen, B.R, 1997, Enhanced auto adhesion ofwood fibers using
phenol oxidases. Holzforschung 51:281.
Fengel, D . and Wegener, G., 1984, "Wood: Chemistry, Ultrastructure, Reactions" De Gruyter Berlin,
New York.
Foti, M . Ingold, K.U., and Lusztyk, J., 1994, The surprisingly high reactivity ofphenoxyl radicals.
J. Am. Chem. Soc. 116:9440.
G1sser, W.G., and Sandermann W., 1970, Die katalytischewirkungvon ligninradikalen bei
chemischen urnsetzungen. Holzforschung 24:73.
Glasser, W.G., and G1asser, H.R., 1981, The evaluation oflignins chemical structure by
experimental and computer simulation techniques. Paperii je Puu 63:71.
Goring D.A.I., 1963, Thermal softening oflignin, hemicellulose and cellulose. Pulp and Paper
Magazine ofCanada 64:517.
Haars, A., and Httermann, A., 1983, Verfaltren zur Herstellung eines Bindemittels fr
Holzwerkstoffe. German patent, DE 30,37,992,C2,
Haars, A., Kharazipour, A. , Zanker, H., and Httermann, A., 1989, Room-Temperature Curing
Adhesives Basedon Lignin and Phenolox.idases in: Adhesives from Renewable Resources. Eds.
R.W. Hemingway and A.H. Conner. ACS Symp. ser. 385. American Chemical Society
Hatakeyarna, H., and Nakano, J., 1970, Electron spin resonance studies on Iignin and Iignin model
compounds. Ce//. Chem. and Techn . 4:281.
Jin, L ., Nicholas, D.D., and Schultz, T.P., 199 1, Wood Iaminates glued by enzymatic ox.idation of
brown-rotted Iignin. Holzforschung 45, 467.
714
Kharazipour, A., Httermann, A., Khne, G., and Rong M., 1993, Verfairren zum Verkleben von
Holzfragmenten und nach dem Verfahren hergestellte Fonnkrper. European patent
0,565,109,A1,
Nimz, H.H., Gurang, 1., and Mogharab 1., 1976, Untersuchungen zur vernetzung technischer
sulfitablage. Liebigs Ann. Chem. 1421.
Pedersen, L.S., and Felby, C., 1996, Process for preparing a lignocellulose-based product, and
product obtainable by the process. International patent application PCT/DK95/00318
Yamaguchi, H., Maeda, Y., and Sakata 1., 1992, Application ofphenol dehydrogenative
polymerization by laccase to binding among woody-fibers. Mokuzai Gakkaishi 38:931.
Yamaguchi, H., Nagamor, N., and Sakata 1., 1993, Application ofthe dehydrogenative
polymerization ofvanillic acid to bonding ofwoody fibers. Mokuzai Gakkaishi 37: 220.
Yamaguchi, H., Maeda, Y., and Sakata 1., 1994, Bonding among woody fibers by use of enzyrnatic
phenol dehydrogenative polymerization. Mokuzai Gakkaishi 40:185.
715
PROPERTY ENHANCED NATURAL FIBER COMPOSITE
MATERIALS BASED ON CHEMICAL MODIFICATION
Roger M. Rowell
USDA Forest Service, Forest Products Laboratory, One Gifford Pinchot Drive,
Madison, WI 53705-2366 and Department ofBiological Systems Engineering,
University of Wisconsin, Madison, Wl 63706
INTRODUCTION
Agro-based resources, also referrered to as lignocellulosics, are resources that
contain cellulose, hernicelluloses, and Iignin. Lignocellulosics include wood, agricultural
residues, water plants, grasses, and other plant substances. When considering
lignocellulosics as possible engineering materials, there are several very basic concepts that
must be considered. First, lignocellulosics are hygroscopic resources that were designed to
perform, in nature, in a wet enviomment. Secondly, nature is programmed to recycle
lignocellulosics in a timely way through biological, thermal, aqueous, photochernical,
chernical, and mechanical degradations. In simple terms, nature builds a lignocellulosic
from carbon dioxide and water and has all the tools to recycle it back to the starting
Biological Degradation - Fungi, Bacteria, Insects, Terrnites

Enzymatic Reactions - Oxidation, Hydrolysis, Reduction
Chernical Reactions - Oxidation, Hydrolysis, Reduction
Mechanical - Chewing
Fire Degradation - Lightning, Sun,
Pyrolysis Reactions - Dehydration, Hydrolysis, Oxidation
Water Degradation - Rain, Sea, Iee, Acid Rain, Dew
Water Interactions - Swelling, Shrinking, Freezing, Cracking
Weather Degradation - Ultraviolet radiation, Water, Heat, Wind
Chernical Reactions - Oxidation, Hydrolysis
Mechanical -Erosion
Chernical Degradation - Acids, Bases, Salts
Chernical Reactions - Oxidation, Reduction, Dehydration, Hydrolysis
Mechanical Degradation -Dust, Wind, Hail, Snow, Sand
Mechanical - Stress, Cracks, Fracture, Abrasion
Figure 1. Degradation reactions which occur when lignocellulosics are exposed to nature.
chernicals. We harvest a green lignocellulosic (for example, a tree) and convert it into dry
products, and nature, with its arsenal of degrading reactions, starts to reclaim it at its first
opportunity (Figure 1).
In order to produce lignocellulosic-based composite materials with a long service
life, it is necessary to interfere with the natural degradation processes for as long as possible.
This can be done in several ways. Traditional methods for decay resistance and fire

retardancy, for example, are based on treating the product with toxic or corrosive chemieals
which are effective in providing decay and fire resistance but can result in environmental
concems. There is another approach which is based on the premise that the properties of
any resource are a result of the chemistry of components of that resource. In the case of
lignocellulosics, cell wall polymers, extractives, and inorganics are the components that, if
modified, would change the properties of the resource.
In order to make property changes, you must first understand the chemistry of the
components and the contributions each play in the properties of the resource. Following this
understanding, you must then devise a way to modify what needs to be changed to get the
desired change in property.
Properties of lignocellulosics, such as dimensional instability, flammability,
biodegradability, and degradation caused by acids, bases, and ultraviolet radiation are all a
result of chemical degradation reactions which can be prevented or, at least, slowed down if
the cell wall chemistry is altered [Rowell 1975, Rowell and Youngs 1981, Rowell 1983,
Rowell and Konkol 1987, Rowell et all 1988a, Hon 1992, Rowell 1992, Kumar 1994,
Banksand Lawther 1994].
FEATURES OF LIGNOCELLULOSICS
Lignocellulosics are three-dimensional, polymeric composites rnade up primarily of

cellulose, hemicelluloses, and Iignin. While all types of lignocellulosic fibers differ in
chemical composition, within certain Iimits, alllignocellulosics have very similar properties.
That is, they all swell and shrink as the moisture content of the cell wall changes, they burn,
they decay, and they are degraded by acids, bases and ultraviolet radiation. Because, as a
generat class, alllignocellulosics have similar mechanisms of environmental degradation, it
might be expected that all types of natural fibers would respond to the same types of
chemical treatrnents to overcome these degradation reactions.
To improve the resistance to the degradation forces acting on lignocellulosics, it is
frrst important to understand the mechanisms of degradation, which components in the cell
wall are responsible for these effects, and what can be done to slow down or stop the
degradation forces.
DEGRADATION OF LIGNOCELLULOSICS
Figure 2 shows the cell wall polymers involved in each fiber property as we
understand it today [Rowell 1990]. Lignocellulosics change dimensions with changing
moisture content because the cell wall polymers contain hydroxyl and other oxygen-
containing groups that attract moisture through hydrogen bonding [Stamm 1964, Rowell and
Banks 1985]. The hemicelluloses are mainly responsible for moisture sorption, but the
accessible cellulose, noncrystalline cellulose, Iignin, and surface of crystalline cellulose also
play major roles. Moisture swells the cell wall, and the fiber expands until the cell wall is
BIOLOGICAL DEGRADATION
Hemicelluloses >>>> Accessible Cellulose >> Non-CrystallineCellulose >>>>>>>
Crystalline Cellulose >>>>>>>>>>>>>> Lignin
MOlSTURE SORPTION
Hemicelluloses >>> Accessible Cellulose >>>> Non-Crystalline Cellulose >>
Lignin > Crystalline Cellulose
ULTRAVIOLET DEGRADATION
Lignin >>>>>>>>>>>>>>> Hemicelluloses >>> Accessible Cellulose >> Non-
Crystalline Cellulose>>>>>>>> Crystalline Cellulose
THERMAL DEGRADATION
Hemicelluloses > Cellulose >>>>>>>>>>>>>>> Lignin
STRENGTH
Crystalline Cellulose >>> Matrix [Non-Crystalline Cellulose + Hemicelluloses +
Lignin] Lignin
Figure 2. Cell wall polymers responsible for the properties of lignocellulosics.
718
saturated with water (fiber saturation point, FSP). Beyond this saturation point, moisture
exists as free water in the void structure and does not contribute to further expansion. This
process is reversible, and the fiber shrinks ~s it l?ses moisture below th~ FSP. .
Lignocellulosics are degraded bwlogtcally because orgamsms recogmze the
carbohydrate polymers (mainly the hemicelluloses) in the cell walland have very specific
enzyme systems capable of hydrolyzing these polymers into digestible units.
Biodegradation of the high molecular weight cellulose weakens the fiber cell wall because
crystalline cellulose is primarily responsible for the strength of the cell wall [Rowell et al
1988b]. Strengthis lost as the cellulosepolymer undergoes degradation through oxidation,
hydrolysis, and dehydration reactions. The same types of reactions take place in the
presence of acids and bases.
Lignocellulosics exposed outdoors undergo photochemical degradation caused by
ultraviolet radiation. This degradation takes place primarily in the lignin component, which
is responsible for the characteristic color changes [Rowell 1984]. The Iignin acts as an
adhesive in the cell walls, holding the cellulose fibers together. The surface becomes richer
in cellulose content as the Iignin degrades. In comparison to Iignin, cellulose is much less
susceptible to ultraviolet light degradation. After the Iignin has been degraded, the poorly
bonded carbohydrate-rich fibers erode easily from the surface, which exposes new Iignin to
further degradative reactions. In time, this "weathering" process causes the surface of the
composite to become rough and can account for a significant loss in surface fibers.
Lignocellulosics burn because the cell wall polymers undergo pyrolysis reactions
with increasing temperature to give off volatile, flarnmable gasses. The hemicellulose and
cellulose polymers are degraded by heat much before the Iignin [Rowell1984]. The Iignin
component contributes to char formation, and the charred layer helps insulate the composite
from further thermal degradation.
CHEMICAL MODIFICATION SYSTEMS
For this discussion, chemical modification will be defined as a chemical reaction

between some reactive part of a lignocellulosic and a simple single chemical reagent, with or
without catalyst, to form a covalent bond between the two. This excludes all simple
chemical impregnation treatments which do not form covalent bonds, monomer
impregnation that polymerize in situ but do not bond with the cell wall, polymer inclusions,
coatings, heat treatments, etc.
There are several approaches to chemically modifying the lignocellulosic cell wall
polymers. The most abundant single site for reactivity in these polymers is the hydroxyl
group and most reaction schemes have been based on the reaction of hydroxyl groups. Sites
of unsaturation in the Iignin structure can also be used as a point of reactivity as weil as free
radical additions and grafting. However, the most studied class of chemical reactions are
those involving hydroxyl Substitutions.
In modifying a lignocellulosic for property improvement, there are several basic
principles that must be considered in selecting a reagent and a reaction system [Rowell
1975]. Of the thousands of chemieals available, either commercially or by synthetic means,
most can be eliminated because they fail to meet the requirements or properties listed below.
If hydroxyl reactivity is selected as the preferred modification site, the chemical must
contain functional groups which will react with the hydroxyl groups of the Iignocellulosic
components. This may seem obvious but there are several failed reaction systems in the
Iiterature using a chemical that could not react with a hydroxyl group.
The overall toxicity of the chemieals must be carefully considered. The chemieals
must not be toxic or carcinogenic to humans in the finished product, and should be as
nontoxic as possible in the treating stage. The chemical should be as noncorrosive as
possible to eliminate the need for special stainless steel or glass-lined treating equipment.
In considering the ease with which excess reagents can be removed after treatment, a
liquid treating chemical with a low boiling point is advantangous. Likewise, if the boiling
point of a liquid reagent is too high, it will be very difficult to remove the chemical after
treatment. lt is generally true that the lowest member of a homologous series is the most
reactive and will have the lowest boiling point. The boiling point range for liquids to be
considered is 90-150C. lt is also possible to treat fibers with a gas system, however, there
may be processing challenges in handling a pressurized gas in a continuous reactor.
Accessibility of the reagent to the reactive chemical sites is a major consideration. To
increase accessibility to the reaction site, the chemical must swell the lignocellulosic
719
structure. If the reagents do not swell the structure, then another chemical or co-solvent can
be added to meet this requirement. Accessibility to the reactive site is a major consideration
in a gas system unless there is a condensation step in the procedure.
Almost all chemical reactions require a catalyst. With lignocellulosics as the reacting
substrate, strong acid or base catalysts cannot be used as they cause extensive degradation.
The most favorable catalyst from the standpoint of lignocellulosic degradation is a weakly
alkaline one. The alkaline medium is also favored as in many cases these chemieals swell
the cell wall matrix structure and give better penetration. The properties of the catalyst
parallel those of reagents, i.e., low boiling point liquid, nontoxic, effective at low
temperatures, etc. In most cases, the organic tertiary amines or weak organic acids are best
suited.
The experimental reaction conditions which must be met in order for a given reaction
to go is another important consideration. The temperature required for complete reaction
must be low enough so there is little or no fiber degradation, i.e., less than 150C. The
reaction must also have a relatively fast rate of reaction with the cell wall components. 1t is
important to get as fast a reaction as possible at the lowest temperature without
lignocellulosic degradation.
The moisture present in the lignocellulosic is another consideration in the reactjon
conditions. It is costly to dry lignocellulosics to less than 1 percent moisture, but it must be
remernbered that the -OH group in water is more reactive than the -OH group available in the
lignocellulosic components, i.e., hydrolysis is faster than substitution. The most favorable
condition is a reaction which requires a trace of moisture and the rate of hydrolysis is
relatively slow.
Another consideration in this area is to keep the reaction system as simple as
possible. Multicomponent systems will require complex Separation after reaction for
chemical recovery. The optimum would be a reactive chemical that swells the
lignocellulosic structure and acts as the solvent as well.
If possible, avoid byproducts during the reaction that have to be removed. If there is
not a 100 percent reagent skeleton add-on, then the chemical cost is higher and will require
recovery of the byproduct for economic and evnironmental reasons.
The chemical bond formed between the reagent and the lignocellulosic
components is of major importance. For permanence, this bond should have great stability
to withstand weathering. In order of stability, the types of covalent chemical bonds that
may be formed are: ethers > acetals > esters. The ether bond is the most desirable covalent
carbon-oxygen bond that can be formed. These bonds are more stable than the glycosidic
bonds between sugar units in the lignocellulosic polysaccharides so the polymers would
degrade before the grafted ether. It may be desired, however, to have the bonded chernical
released by hydrolysis or enzyme action in the final product so that an unstable bond may be
required from the modification.
The hydrophobic nature of the reagent needs to be considered. The chernical added
to the lignocellulosic should not increase the hydrophilic nature of the lignocellulosic
components unless that is a desired property.
If the hydrophilicity is increased, the susceptibility to micro-organism attack increases. The
more hydrophobic the component can be made, the better the moisture exclusion properties
of the substituted lignocellulosic will be.
Single site substitution versus polymer formation is another consideration. For the
most part, a single reagent molecule that reacts with a single hydroxyl group is the most
desirable. Crosslinking can occur when the reagent contains more than one reactive group
or results in a group which can further react with a hydroxyl group. Crosstinking can cause
the lignocellulosic to become more brittle. Polymer formation within the cell wall after initial
reaction with the hydroxyl groups of the lignocellulosic components gives, through bulking
action, dimensional stabilization. The disadvantage of polymer formation is that a higher
Ievel of chemical add-on is required for biological resistance than is required in the single site
reactions.
The treated lignocellulosic must still possess the desirable properties of
lignocellulosics. That is, the fiber strength should not be reduced, no change in color, good
electrical insulation properties retained, final product not dangeraus to handle, no lingering
chemical smells, still gluable and finishable unless one or more of these properties are the
object of change in the product.
A final consideration is, of course, the cost of chemieals and processing. In
laboratory scale experimental reactions, the high cost of chemieals is not a major factor. For
?W
commercialization of a process, however, the chemical and processing costs are very
important factors. Laboratory scale research is generally done using small batch processing,
however, rapid, continuous processes should always be studied for scale up. Economy of
scale can make an expensive laboratory process economical.
In summary, the chemieals to be laboratory tested must be capable of reacting with
lignocellulosic hydroxyls under neutral, mildly alkaline or acid conditions at temperatures
below 150C. The chemical system should be simple and capable of swelling the structure
to facilitate penetration. The complete molecule should react quickly with lignocellulosi~; _
components yielding stable chemical bonds, and the treated lignocellulosic must still
possess the desirable properties of untreated lignocellulosics.
CHEMICAL MODIFICATION FOR PROPERTY ENHANCEMENT
As was stated before, because the properties of lignocellulosics result from the
chemistry of the cell wall components, the basic properties of a fiber can be changed by
modifying the basic chemistry of the cell wall polymers. Many chemical reaction systems
have been published for the modification of agro-fiber. These chemieals include anhydrides
such as" phthalic, succinic, malaic, propionic and butyric anhydride, acid chlorides, ketene
carboxylic acids, many different types of isocyanates, formaldehyde, acetaldehyde,
difunctional aldehydes, chloral, phthaldehydic acid, dimethyl sulfate, alkyl chlorides, beta-
propiolactone, acrylonitrile, epoxides, such as, ethylene, propylene, and butylene oxide, and
difunctional epoxides [Rowell1983, 1991].
By far, the most research has been done on the reaction of acetic anhydride with cell
wall polymer hydroxyl groups to give an acetylated fiber. Many different types of
lignocellulosic fibers have been acetylated using a variety of procedures including wood
[Rowell 1983, Rowell et al 1986], bamboo [Rowell and Norimoto 1987, 1988], bagasse
[Rowell and Keany 1991], jute [Callow 1951, Andersson and Tillman 1989, Rowell et al
1991], kenaf [Rowell 1993, Rowell and Harrison 1993], pennywort, and water hyacinth
[Rowell and Rowell 1989]. Without a strong catalyst, acetylation using acetic anhydride
alone Ievels off at approximately 20 weight percent gain (WPG) for softwoods, hardwoods,
grasses, and water plants. While acetylation is not the only chemical modification procedure
that has been shown to improve properties of lignocellulosics, it has been studied the most
and will be used as an example in many cases.
Properties of Chemically Modilied Fiber

Moisture sorption. By replacing some of the hydroxyl groups on the cell wall
polymers with bonded chemical groups, the hygroscopicity of the lignocellulosic material is
reduced. Table 1 shows the equilibrium moisture content (EMC) of several types of
lignocellulosic fibers which have been reacted with several types of chemicals. Table 1
shows the EMC of pine wood fibers which have been reacted with different chemicals. In
all cases, the EMC has been reduced as a result of modification. Both reactions with acetic
anhydride and formaldehyde give the best results in lowering the EMC of the treated fiber.
Table 2 shows the results of acetylating several different types of fibers on the EMC of the
modified fiber. In all cases, as the Ievel of acetyl weight gain increases, the EMC of the
resulting fiber goes down. All types of fiber show the same Ievel in the reduction in EMC as
a function of Ievel of acetyl weight gain (Rowell et al 1986).
lf the reductions in EMC at 65% RH of acetylated fiber referenced to unacetylated
fiber is plotted as a function of the bonded acetyl content a straight line plot results (Rowell
and Rowell 1989). Even though the points represent many different types of lignocellulosic
resources, they all fit a comrnon curve. A maximum reduction in EMC is achieved at about
20% bonded acetyl. Extrapolation of the plot to 100% reduction in EMC would occur at
about 30% bonded acetyl. This represents a value not too different from the fiber Saturation
point for water in these fibers. Because the acetate group is !arger than the water molecule,
not all hygroscopic hydrogen-bonding sites are covered so it would be expected that the
acetyl saturation point would be lower than that of water. This finding would indicate that
it does not matter which type of Iignocellulosic resource is used to acetylate to make
composites.
The fact that EMC reduction as a function of acetyl content is the same for many
different lignocellu1osic resources indicates that reducing moisture sorption and, therefore,
achieving cell wall stability are controlled by a comrnon factor. The Iignin, hemicellulose,
721
Table 1. EMC of control and chemically modified pine fiber.
Chemical Weight Equilibrium Moisture Content at 27C

Percent
Gain 30%RH 65%RH 90%RH
Control 0 5.8 12.0 21.7

Acetic 20.4 2.4 4.3 8.4
Anhydride
Formaldehyde 3.9 3.0 4.2 6.2
Propylene 21.9 3.9 6.1 13.1
Oxide
Butylene 18.7 3.5 5.7 10.7
Oxide
Table 2. EMC of fiberboards made from control and acetylated fiber.

Fiber Weight Equilibrium Moisture Content at 27C
Percent
Gain 30%RH 65%RH 90%RH
Bagasse 0 4.4 8.8 15.8
9.4 2.0 5.3 9.5
13.0 1.7 4.4 7.7
17.6 1.4 3.4 5.8
Kenaf 0 4.8 10.5 24.3
18.4 2.6 5.8 11.3
Bamboo 0 4.5 8.9 14.7
10.8 3.1 5.3 9.4
17.0 2.0 3.7 6.8
Jute 0 5.8 9.3 18.3

16.2 2.0 4.1 7.8
Pine 0 5.6 12.1 22.6
6.3 4.5 10.2 19.5
13.8 2.7 6.8 13.2
18.2 2.1 5.1 9.9
Aspen 0 4.9 11.1 21.5
8.7 3.1 7.7 14.9
13.0 2.0 5.9 11.8
17.6 1.6 4.8 9.4
and cellulose contents of all the materials are different. Earlier results showed that the
bonded acetatewas mainly in the Iignin and hemicelluloses [Rowell1982] and that isolated
wood cellulose does not react with uncatalyzed acetic anhydride [Rowell et al1994b].
Because these materials vary widely in their lignin, hemicellulose, and cellulose
content, because acetate is found mainly in the lignin and hemicellulose polymer, and
because isolated cellulose does not acetylate by the procedure used, acetylation may be
controlling the moisture sensitivity due to the Iignin and hemicellulose polymers in the cell
wall but not reducing the sorption of moisture in the cellulose polymer.
Pyrolysis properties. Chemical modification of agro-based fibers has some

effect on the pyrolysis properties of lignocellulosics. In thermogravametric analysis, control
722
Table 3. Pyrolysis properties of control and chernically modified pine fiber.
Chemical Weight Temperature Heatof Rate of
Percent ofMaximum Combustion Oxygen
Gain WeightLoss Consumption
c KCallg MM/gsec
None 0 335/375 2.9 0.06/0.13

Acetic 21.1 338/375 3.1 0.08/0.14
Anhydride
Methyl 24.0 315/375 2.6 0.07/0.12
Isocyanate
Propylene 32.0 380 4.3 0.23
Oxide
Butylene 22.0 385 4.1 0.24
Oxide
and chemically modified pine fibers pyrolyze at about the same temperature and rate (Table
3) [Rowell et a1 1984]. Fibers reacted with propylene or butylene oxide have a slightly
higher temperature of maximum weight loss. Fiber that was reacted with acetic anhydride or
methyl isocyanate showed two peaks in the maximum weight loss data while both propylene
and butylene oxides resulted in only one peak. Since the smaller, lower temperature peak
represents the hemicellulose fraction in the fiber, the epoxide modified hernicelluloses seem
to pyrolyze in the temperature range of the cellulose fraction. The heat of combustion and
rate of oxygen consumption are higher for the epoxide modified fiber as compared to the
control, acetic anhydride and methyl isocyanate modified fibers. This data would indicate
that reacting fiber with acetic anhydride or methyl isocyanate is adding approximately the
same carbon, hydrogen and oxygen content as the cell wall polymers. Reactive fire
retardants could be bonded to the cell wall hydroxyl groups in reactions similar to this
technology. The effect would be an improvement in dimensional stability, biological
resistance as well as fire retardancy.
PROPERTIES OF COMPOSITES MADE WITH CHEMICALLY MODIFIED

FIBER
Dimensional Stability
Changes in dimensions, especially in thickness and in linear expansion, are a great
problern in lignocellulosic composites because they not only undergo normal swelling
Table 4. Equilibrium moisture content (EMC) and thickness swelling (TS) of fiberboards
made from control and acetylated fiber.
Fiber Weight EMC and TS at 27C
Percent 30%RH 65%RH 90%RH
Gain EMC TS EMC TS EMC TS
< ......................................... ........................ >
Pine 0 4.5 3.6 9.4 6.6 19.7 29.2
21.6 1.8 0.4 4.1 1.1 8.3 2.9
Bagasse 0 3.8 7.6 17.1
17.6 1.8 4.0 7.9
Kenaf 0 4.8 3.0 10.5 9.6 26.7 33.0
18.4 2.6 0.8 5.8 2.4 19.3 10.0
Bamboo 0 3.2 6.6 12.3
18.0 1.6 4.1 7.9
Remlock 0 3.3 1.0 7.2 3.1 19.8 11.2
22.5 1.6 0.2 3.9 1.7 9.3 3.1
723
(reversible swelling) but also swelling caused by the release of residual compressive stresses
imparted to the board during the composite pressing process (irreversible swelling). Water
sorption causes both reversible and irreversible swelling with some of the reversible
shrinkage occurring when the board dries. Dimensional instability of lignocellulosic
composites has been the major reason for their restricted use.
The EMC of different types of control and acetylated fibers are given in Table 2.
The EMC and thickness swelling at three relative hurnidities for boards made from these
fibers is shown in Table 4. Comparing the data in the two tables, it can be seen that the
EMC for boards is slightly higher than for the fiber alone. The adhesive is more hydrophilic
than the acetylated fiber.
Thickness swelling at the three Ievels of relative hurnidity is greatly reduced as a
result of acetylation. Linear expansion is also greatly reduced as a result of acetylation
(Krzysik et al1992, 1993).
The rate and extent of thickness swelling in liquid water of fiberboards made from
control and acetylated fiber is shown in Table 5. Both the rate and extent of swelling are
Table 5. Rate and extent of thickness swelling in liquid water of fiberboards made from
control and acetylated fiber and a phenolic resin [ Resin content ofboards: Kenaf- 8%,
Bagasse- 5%, Bamboo- 6%, Remlock- 8%, Pine- 8%]
Fiber Percent Thickness Swelling at--

<--- Minutes ----------><------------------------ Rours-------------------------------- >
15 30 45 1 2 3 4 5 6
Kenaf
Control 15.5 17.1 21.1 22.6 24.7 26.8 31.1 32.6 34.0
18.4 WPG 6.7 6.8 6.8 7.0 7.0 7.0 8.0 8.1 8.3
Bagasse
Control 19.2 20.2 21.0 21.6 22.0 22.7 23.0 23.6 24.0
17.6 WPG 1.8 2.0 2.2 2.3 2.7 2.9 3.3 3.5 3.8
Bamboo
Control 4.0 7.3 8.4 10.2 12.6 13.8 14.0 14.8 15.0
18.0 WPG 1.5 1.7 1.9 2.3 2.3 2.3 2.4 2.4 2.4
Remlock
Control 11.2 11.8 12.3 12.5 14.1 15.2 16.2 16.8 17.0
22.5 WPG 2.6 3.3 3.7 3.8 3.9 4.0 4.0 4.1 4.2
Pine
Control 25.7 29.8 30.7 31.6 32.9 33.5 33.8 33.9 34.0
21.6 WPG 0.6 0.9 1.1 1.2 1.6 1.9 2.1 2.2 2.5
Oven Weight loss
<------- Days ----------------------------> drying after test
---------------------- % ----------------------
1 2 3 4 5
Kenaf
Control 37.7 41.5 42.6 43.5 44.5 19.0 2.0
18.4 WPG 8.5 8.5 8.7 8.8 9.0 0.7 2.8
Bagasse
Control 25.0 25.2 25.3 25.4 25.5 16.0 1.2
17.6 WPG 5.0 5.0 5.1 5.2 5.2 1.5 1.4
Bamboo
Control 16.1 16.5 17.9 18.1 18.2 8.3
18.0 WPG 2.5 3.1 3.2 3.2 3.3 2.2
Remlock
Control 17.3 17.5 17.8 17.9 18.1 7.8 2.9
22.5 WPG 5.2 5.6 5.8 6.0 6.6 1.7 1.9
Pine
Control 35.0 35.6 35.9 36.0 36.2 24.9 0.5
21.6 WPG 3.7 4.0 4.2 4.3 4.5 2.6 1.1
724
greatly reduced as a result of acetylation. At the end of 5 days of water soaking, control
boards swelled from 18 to 45% whereas boards made from acetylated fiber swelled from 3
to 10%. Drying all boards after the water soaking test shows the amount of irreversible
swelling that has resulted from water swelli~g. Control boards show a greater degree of
irreversible swelling as compared to boards made from acetylated fiber.
The results of both water vapor and liquid water tests show that acetylation of
lignocellulosic fibers greatly improve dimensional stability of composites made from these
resources.
Biological Resistance
Partideboards and flakeboards made from acetylated flakes have been tested for
resistance to several different types of organisms. In a 2-week termite test using
Reticulitermes flavipes (subterranean termites), boards acetylated at 16 to 17 WPG were
very resistant to attack, but not completely so (Table 6) [Rowell et al 1979, 1988a]. This
may be attributed to the severity of the test. However, since terrnites can live on acetic acid
and decompose cellulose to mainly acetic acid, perhaps it is not surprising that acetylated
wood is not completely resistant to terrnite attack.
Chemically modified composites have been tested with decay fungi in several ways.
Control and chemically modified particleboards were exposed to a 12 week soil blocktest
using the brown rot fungus Gloeophyllum trabeum and the white rot fungus Trametes
versicolor (Table 7). Allboards were made using a phenolic resin [Nilsson et al 1988,
Table 6 Weight loss in chemically modified southern pine after 2 weeks exposure to
Reticulitermes flavipes
Chemical Weight WoodWeight

Percent Loss
Gain
<...... % ........ >
Control 0 31
Propyleneoxide 9 21
17 14
34 6
Butyleneoxide 27 4
34 3
Acetic anhydride 10.4 9
17.8 6
21.6 5
Table 7. Biological resistance of chemically modified pine agairrst brown- and white-rot
fungi
Chemical Weight Weight Loss After 12 Weeks
Percent
Gain Brown-rot White-rot
Fungus Fungus
< ............. % ......................... >
None 0 68 7
Acetic 17 <2 <2
Anhydride
Propylene oxide 25 <15 <2
Butylene oxide 22 <3 <1
Methyl
Isocyanate 20 <3 <1
Formaldehyde 5 <3 <1
Beta
Propiolactone 25 <2 <2
Acrylonitrile 25 <2 <2
725
Rowell et al 1988a]. All of the bonded chemieals at a WPG over about 20 show good
resistance to brown- and white-rot fungi except propylene oxide in the brown rot test.
Propylene oxide is not effective in preventing attack by brown-rot fungi even though the
same number of hydroxyl groups should be modified as were modified by reaction with
butylene oxide, methyl isocyanate, acetic anhydride, beta propiolactone or acrylonitrile
[Rowell et al 1988b]. This exception of propylene oxide to the protection rule is perhaps the
key to understanding the mechanism of the resistance to attack by fungi by chemical
modification. As was seen in Table 1, the EMC of propylene oxide modified fiber is higher
than any other modified fiber and this may be the reason for the lower biological resistance.
The mechanism of brown-rot fungi attack on lignocellulosics is thought to be as
given in Figure 3 [Nilsson 1986]. The first biological attack on a lignocellulosic is an
enzymatic reaction that results .in a metal/peroxide chemical oxidation system. This
oxidation system breaks down the large polymers into smaller pieces which results in an
early and rapid strength loss as the degree of polymerization of the cellulose molecule is
reduced. During this reaction phase, a second enzymatic system starts working in which
carbohydrates and Iignin are broken down. lt is in this phase that weight loss occurs.
This mechanism is consistent with the data that strength Iosses occur long before
weight Iosses in brown-rot fungi attacked wood [Rowell et al 1988b]. In this mechanism
the key to brown-rot fungi resistance lies in the protection of the hemicellulose polymers. If
that single component is protected, attack can not proceed.
Weight loss resulting from fungal attack is the method most used to determine the
effectiveness of a preservative treatment to protect wood composites from decaying. In
some cases, especially for brown-rot fungal attack, strength loss may be a more important
measure of attack since large strength Iosses are known to occur in solid wood at very low
wood weight loss [Couling 1961]. A dynamic bending-creep test has been developed to
determine strength Iosses when wood composites are exposed to a brown- or white-rot
fungus [lmamura and Nishimoto 1985].
Using this bending-creep test on aspen flakeboards, control boards made with
phenol-formaldehyde adhesive failed in an average of 71 days using the brown-rot fungus
T. palustris and 212 days using the white-rot fungus T. versicolor [Rowell et al1988b]. At
failure, weight Iosses averaged 7.8% for T. palustris and 31.6% for T. versicolor.
lsocyanate-bonded control flakeboards failed in an average of 20 days with T. palustris and
118 days with T. versicolor, with an average weight loss at failure of 5.5% and 34.4%,
respectively [Rowell et al1988b]. Very little or no weight loss occurred with both fungi in
flakeboards made using either phenol-formaldehyde or isocyanate adhesive with acetylated
flakes. None of these specimens failed during the 300 day test period.
Mycelium fully covered the surfaces of isocyanate-bonded control flakeboards
within 1 week, but mycelial development was significantly slower in phenol-formaldehyde-
bonded control flakeboards. Both isocyanate- and phenol-formaldehyde-bonded acetylated
flakeboards showed surface mycelium colonization during the test time, but the fungus did
not attack the acetylated flakes so little strength was lost.
In similar bending-creep tests, both control and acetylated pine particleboards made
using melamine-urea-formaldehyde adhesive failed because T. palustris attacked the
adhesive in the glueline [lmamura et al 1988]. Mycelium invaded the inner part of all
boards, colonizing in both wood and glueline in control boards but only in the glueline in
acetylated boards. These results show that the glue line is also important in protecting
composites from biological attack.
ENZYMES--> HEMICELLULOSES
[Energy source for
generation of
chemical oxidation
system]------------>ACCESSIBLE CELLULOSE
[Strength losses]
[Energy source for
generation of beta-
glucosidases]------>WEIGHT
LOSS
Figure 3. Mechanism of brown rot fungus attack on lignocellulosics
726
Table 8. Fungal cellar tests of aspen flakeboards made from control and acetylated
flakes [1 ,2]
Weight
Percent Rating at intervals (Months) [3]
Gain
2 3 4 5 6 12 24 36
0 S/2 S/3 S/3 S/3 S/4
7.3 S/0 S/1 S/1 S/2 S/3 S/4
11.5 0 0 S/0 S/1 S/2 S/3 S/4--
13.6 0 0 0 0 S/0 S/1 S/2 S/3
16.3 0 0 0 0 0 0 0 0
17.9 0 0 0 0 0 0 0 0
(1] Nonsterile soil containing brown-, white-, and soft-rot fungi and
tunneling bacteria.
[2] Flakeboards bonded with 5% phenol-formaldehyde adhesive.
[3] Rating system: 0 = no attack; 1 = slight attack; 2 =moderate attack; 3 = heavy attack;
4 = destroyed; S = swollen.
After a 16-week exposure toT. palustris, the intemal bond strength of control aspen
flakeboards made with phenol-formaldehyde adhesive was reduced over 90% and that of
flakeboards made with isocyanate adhesive was reduced 85% [lmamura et al1987]. After 6
months of exposure in moist unsterile soil, the same control flakeboards made with phenol-
formaldehyde adhesive lost 65% of their intemal bond strength and those made with
isocyanate adhesive lost 64% intemal bond strength. Failure was due mainly to great
strength reductions in the wood caused by fungal attack. Acetylated aspen flakeboards lost
much less intemal bond strength during the 16-week exposure to T. palustris or 6-month
soil burial. The isocyanate adhesive was somewhat more resistant to fungal attack than the
phenol-formaldehyde adhesive. In the case of acetylated composites, loss in intemal bond
strength was mainly due to fungal attack in the adhesive and moisture, which caused a small
amount of swelling in the boards.
Another test for biological resistance that has been done on acetylated composites is
with brown-, white-, and soft-rot fungi and tunneling bacteria in a fungal cellar (Table 8).
Control blocks were destroyed in less than 6 months while flakeboards made from
acetylated fumish above 16 WPG showed no attack after 1 year. [Nilsson et al 1988,
Rowell et al 1988a]. This data shows that no attack occurs until swelling of the wood
occurs [Rowell and Ellis 1984, Rowell et al1988a]. This is more evidence that the moisture
content of the cell wall is critical before attack can take place.
Table 9. Ratings of chernically modified southem pine exposed to a marine environment (1]
Chernical Weight Years of Mean rating due to attack

Percent Exposure by
Gain Limnoriid and Shaeroma
Teredinid Borers terebrans
Control 0 1 2-4 3.4
Propylene 26 11.5 10
Oxide 3 3.8
Butylene 28 8.5 9.9
Oxide 3 8.0
Butyl 29 6.5 10
Isocyanate
Acetic 22 3 8 8.8
Anhydride
[1] Ratingsystem- 10 = no attack; 9 = slight attack; 7 =some attack; 4 = heavy attack; 0 =

destroyed
727
Table 10. Weight loss and erosion of aspen fiberboards made from control and acetylated
fiber after 700 hours of accelerated weathering
Specimen Weight loss Erosion Reduction Depthof

in Erosion Penetration of
Weathering
%Ihr pmlhr % pm
Control 0.019 0.121 199-210
Acetylated 0.010 0.059 51 85-105
Table 9 shows the data for chemically modified pine flakeboards in a marine
environment [Johnson and Rowell 1988]. As with the termite test, all types of chemical
modifications of wood help resist attack by marine organisms. Control flakeboards were
destroyed in 6 months to 1 year, mainly because of attack by Limnoria tripunctata, while
chemically modified flakeboards show little or no attck after 8 to 10 years.
All laboratory tests for biological resistance conducted to this point show that
acetylation is an effective means of reducing or eliminating attack by soft-, white-, and
brown-rot fungi, tunneling bacteria, marine organisms, and subterranean terrnites.
Ultraviolet Resistance
Acetylation has also been shown to improve ultraviolet resistance of aspen
fiberboards [Feist et al 1991a]. Table 10 shows the weight loss, erosion rate, and depth of
penetration resulting from 700 hours of accelerated weathering. Control specimens erode at
about 0.12 pmlhr or about 0.02 %/hr. Acetylation reduces surface erosion by 50 percent.
The depth of the effects of weathering is about 200 um into the fiber surface for the un-
modified boards and about halfthat ofthe acetylated boards. Table 11 shows the acetyl and
Iignin content of the outer 0.5 mm surface and of the remaining specimen after the surface
had been removed before and after accelerated weathering . The acetyl content is reduced in
the surface after weathering which shows that the acetyl blocking group is removed during
weathering. UV radiation does not remove all of the blocking acetyl group so some
stabilizing effect to photochemical d,egradation still is in effect. The loss of acetate is
confined to the outer 0.5 mm since the remaining wood has the same acetyl content before
and after accelerated weathering. The Iignin content is also greatly reduced in the surface as
a result of weathering which is the main cell wall polymer degraded by UV radiation.
Cellulose and the hemicelluloses are much more stab1e to photochemical degradation.
In outdoor tests, flakeboards made from acetylated pine flakes maintain a light
yellow color after one year while control boards turn dark orange to light gray during this
time [Feist et al 1991 b].
Table 11. - Acetyl and Iignin analysis before and after 700 hours of accelerated weathering of
aspen fiberboards made from control and acetylated fiber.
Specimen Before weathering After weathering
Surface Remainder Surface Remainder

Acetyl Acetyl
<........................ % ..................................... >
Control 4.5 4.5 1.9 3.9
Acetylated 17.5 18.5 12.8 18.3
Lignin Lignin
Control 19.8 20.5 1.9 17.9

Acetylated 18.5 19.2 5.5 18.1
728
Table 12. Modulus of rupture (MOR), modulus of elasticity (MOE), and tensile strength
(TS) parallel to the board surface of fiberboards made from control or acetylated fiber and
phenolic resin [1].
Board MOR MOE TS

-MPa> -GPa> -MPa>
Pine
Control 37.1 3.7 19.0
21.6 WPG 27.9 3.3 13.6
Kenaf
Control 47.1 4.6 31.0
18.4 WPG 38.6 5.1 27.1
Remlock
Contro1 66.0 6.0 33.9
22.5 WPG 51.1 5.0 32.1
ANSI Stanard 31.0 10.3
[1] Resin content ofboards: Pine 8%, Kenaf 8%, Remlock 8%
Strength Properties
The modulus of rupture (MOR), modulus of elasticity (MOE) in bending and tensile
strength (TS) parallel to the board surface are shown in Table 12 for fiberboards made from
control and acetylated pine kenaf and hemlock fiber. Acetylation results in a small
decrease in MOR but about equal values in MOE and TS. All strength values given in Table
12 are above the rninimurn standard as given by the American Rardboard Association [ANSI
1982]. It has been shown that there is very little effect on strength properties ofthin flakes
as a result of acetylation [Rowell and Banks 1987]. The small decrease in some strength
properties resulting from acetylation may be attributed to the hydrophobic nature of the
acetylated furnish which may not allow the water soluble phenolic or isocyanate resins to
penetrate into the flake. The adhesives used in these tests have also been developed for un-
modified lignocellullsics. Different types of adhesives may be needed in chemically
modified boards [Vick and Rowell1990].
lt should also be pointed out that strerigth properties of lignocellulosics are very
dependent on the moisture content of the cell wall. Fiber stress at proportional Iimit, work to
proportionallirnit, fiber stress at proportional Iimit, and maximum eroshing strength are the
mechanical properties most affected by changing moisture content by only +/- one percent
below FSP [Rowell 1984, USDA 1987]. Since the EMC and FSP are much lower for
chernically modified fiber than for control fiber, strength properties will be different due to
this fact alone.
FUTURE OF LIGNOCELLULOSIC COMPOSITES

Fiber technology, high performance adhesives, and fiber modification can be used to
manufacture structural lignocellulosic composites with uniform densities, durability in
adverse environments, and high strength. Fiber modification can also be used to improve
properties in composites made of both natural and synthetic resources used for geotextiles,
filters, sorbents, packaging, and non-structural composites.
Products having complex shapes can be produced using flexible chernically modified
fiber mats, which can be made by nonwoven needling or thermoplastic fiber melt matrix
technologies. Within certain Iimits, the mats can be pressed into any desired shape, size,
thickness, and density. With fiber mat technology, a complex product can be made directly
from a lignocellulosic fiber blend. In general, the present technology requires the formation
of flat sheets prior to the shaping of complex parts.
All of this technology can be applied to recycled lignocellulosic fiber as weil as virgin
fiber, which can be derived from many sources. Agricultural residues, all types of waste
729
paper, yard waste, industrial fiber residues, residential fiber waste, and many other forms of
waste lignocellulosic fiber can also be used to make property enhanced composites.
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United States Department of Agriculture, Forest Service, (1987). Wood Handbook,. USDA
Agri. Handbook 72, Washington, D.C.
Vick, C. B., and Rowell, R. M., (1990). Adhesive bonding of acetylated wood, Internat.
J. Adhesion and Adhesives, 10(4), 263.
732
CHEMICAL MODIFICATION OF LIGNOCELLULOSICS USING
MICROWAVE TECHNOLOG V
Pia Larsson Brelid and Rune Sirnonsou
Dept. of Forest Products and Chemical Engineering

Chalmers University ofTechnology
S-412 96 Gteborg, Sweden
ABSTRACT
The property enhancement of lignocellulosics by means of chemical modification has
been studied for a long time. Most methods involve a reaction with wood polymer hydroxyl
groups. One ofthe most promising methods is acetylation with acetic anhydride which gives
a highly improved dimensional stability and improved biological resistance. The tendency of
wood to absorb moisture is reduced when the hydroxyl groups of wood polymers react with
acetic anhydride thus, forming covalently bonded acetyl groups. The equilibrium moisture
content (EMC) decreases along with an increase in the degree of acetylation. In this study,
the acetylation process was performed by using microwave energy as the heat source.
The use of microwave energy as a heat source in the acetylation process is likely to be
most beneficial when solid wood of large radial and tangential dimensions is tobe treated. In
a conventional reactor, the wood tobe acetylated is heated from the wood surface to the
interior and the heat transfer is slow. The larger the wood dimensions, the more time
consuming the process will be. In addition, heating the wood from the surface to the interior
could lead to a lower acetylation level in the center of the wood being treated, due to
temperature gradients within the wood.
Microwave energy effectively heats acetic anhydride and the microwaves have a
penetration depth of about 10 cm in acetic anhydride impregnated wood, which means that
wood samples up to dimensions of 20 by 20 cm (radial x tangential) can be evenly heated
during acetylation.
When two different spruce samples, 10.5 x 9.5 x 16.0 cm; (r x t x 1), were acetylated
in separate experiments under the same conditions the variation in acetyl content both within
and between samples were less than 2%. This result implies a high degree of reproducibility
in the process. Generally, a somewhat higher acetyl content was obtained in the middle of a
microwave acetylated wood sample than in the outer part of it. Further studies showed that
the reaction temperature (130 C) could be reached in about 10 minutes without any
formation of cracks in the wood due to the fast increase in temperature.
The potential for using microwave energy, not only for acetylation but also to getan
efficient removal of excess chemieals by evaporation under vacuum, was investigated.
During the vacuum step nearly 50% of the chemieals were removed after half an hour, and
70% after one hour. The remaining amount of excess chemieals requires a considerably
Ionger vacuum period in order to be removed under the conditions applied. Pine wood
samples acetylated for 3 hoUJ"S at 130 C followed by a vacuum step for two hours at 130 C,
showed an acetyl content of about 19% and the content of residual chemieals was about 5%
calculated on basis of dry acetylated wood. The temperature in the wood samples could be
maintained at 120 to 130 C even with a very low content of residual excess chemieals
Scumce and Technology of Polymers and Advanced Materillls

Edited by P. N. Prasadetal., Plenum Press, New York, 1998 733
without any formation of hot spots, which otherwise could cause a pyrolysis reaction. The
results obtained imply potential for further removal of excess chemieals from acetylated
wood by means of microwave heating.
INTRODUCTION
Acetylation
At our department, chemical modification of lignocellulosics has been studied for
almost ten years. The most promising method in achieving dimensional stability and
resistance to rotting is modification by means of acetylation. The treatment involves a
reaction between acetic anhydride and accessible hydroxyl groups in the lignocellulosic
material. The reaction Ieads to an increased content of acetyl groups in the material giving,
e.g., an acetyl content of about 20 wt-% in softwood compared with 1 to 2 wt-% for natural
wood. The equilibrium moisture content is considerably reduced, as weil as the swelling and
the shrinkage due to changes in relative humidity. A dimensional stability of 70-75%
(expressed as an ASE-value) is achieved, and at the sametime a rot resistance comparable to
that obtained for wood impregnated at a high retention Ievel with preservatives like arsenic,
chromium and copper.
Wood
Acetic anhydride
Acetylated
wood
Figure 1. Procerlure for acetylation of wood
The acetylation is done with a limited amount of acetic anhydride, and with acetic acid
present in the anhydride, without any addition of a catalyst or an organic cosolvent (Rowell
et al. 1986 a,b). When solid wood is acetylated, the wood is frrst impregnated with acetic
anhydride using a normal vacuum/pressure impregnation technique. Excess anhydride is
drained off, and the reactor containing the anhydride impregnated wood is heated to a
734
reaction temperature of 120-130 C. On a laboratory scale, the heating was performed by
means of electrically heated coils surrounding the reactor. Large dimensions of wood to be
treated, require a Iot of time before the inner parts of the wood reach the reaction
temperature, and normal reaction time is 2-8 hours depending on dimensions.
During the chemical reaction, acetic acid is formed as a by-product and, after completed
acetylation the acetic acid as weH as remaining anhydride must be removed. This step is done
by applying a vacuum to the reactor while it is still heated. When the chemieals evaporate
from the wood, the wood is cooled and a good heat transfer to the inner parts is needed in
order to compensate for the consumed heat of evaporation.
The chemical modification process is not yet brought to the state where it can be
industrially utilized, nor has acetylated wood been manufactured on a laboratory scale to
such an extent that enables different applications to be tested by potential consumers. The
project presented here was conducted with the intention of bringing the technique up to the
stage from which the timher industry and saw mills can start their own research and
development. The potential for using microwave energy as the source of heat in the
acety lation process was investigated, with the aim of reducing reaction time, of achieving an
efficient removal of excess chemieals after reaction and of obtaining a uniform distribution of
acetyl groups within the acetylated wood.
Dielectric Properlies
Microwaves are, simply, electromagnetic radiation consisting of oscillating electric and
magnetic fields, as are visible light, ultraviolet, infrared, and radio waves. The wavelength
used in most microwave ovens is about 12 cm, which corresponds to a frequency of 2.45
GHz. There is one great difference between conventional heating and microwave heating. In
a conventional installation with, for example, electrically heated coils surrounding the
reaction chamber, heat is supplied to the exterior of the chamber and, thus, must be
convected inside the chamber and then conducted into the product. By using microwave
energy, instead, the heat is generated directly inside the product since microwaves provide
volume heating. All polar molecules absorb microwave energy. The degree of heating
depends upon the polarity of the chemicals.
The interactions between a material and a microwave field are expressed by a complex
dimensionless number, the permittivity; E*. The real component, the dielectric constant, (E'),
expresses the ability to store energy in the material, and the imaginary component represents
the energy Iosses and is called the dielectric loss factor, (E"). Knowledge of the basic
parameters such as the dielectric constant and the loss factor is of great importance in order
to predict how deep into the material the microwaves will penetrate.
MATERIALS AND METHODS

Dieleclric Properlies
Dielectric measurements were conducted in co-operation with Per Risman at the
Swedish Food Institute, using a cylindrical TMo 12-cavity (Risman and Bengtsson 1971
a,b). The method is based on the shift in the resonance frequency and the signal
transrnission ofthe cavity when a small sample is introduced into the cavity. The frequency
shift is used to determine the dielectric constant, and the loss in power transrnission is used
to determine the dielectric loss factor. One advantage of this method is that the samples and
the measuring cavity can easily be placed in a temperature controlled cabinet, allowing
measurements to be made over a wide temperature range.
Microwave Reaclor
In the rnicrowave reactor used (Fig. 2), the microwaves come from the magnetron
(generator) and pass through a cerarnic window into the reactor. The cerarnic window cannot
withstand either vacuum or pressure and, therefore, the initial vacuum/pressure impregnation
with acetic anhydride was carried out in a separate vessel. The impregnated wood samples
were reacted directly after impregnation. For temperature measurements in a microwave
735
field, a conventional, straight rod thermocouple does not work. Such a device alters the
microwave field pattern, and may cause a change in local temperature, since the
thermocouple absorbs more energy than the surrounding medium, leading to the formation
of hot spots in the wood close to the thermocouple. For temperature measurements made in a
microwave field, Teflon coated fiber optic thermal measurement probes or indirect infrared
devices can be successfully used. Such equipment, however, is very expensive and the
probes are easy to break. For our purpose, a specially designed, helix shaped (copper-
constantan) thermocouple probe was found tobe a good alternative. The power input during
the acetylation step could, thereby, be controlled by measuring the temperaturein the center
of the anhydride impregnated wood sample.
Generator -
Thermocouplc
\
Figure 2. Lab-scale microwave reactor.
Heating Rate and Reaction Rate

1.5 kg of acetic anhydride and acetic acid were heated separately in the microvawe
reactor for 3 minutes, using a power input of 460W. The temperature rise was compared
with the temperature rise for water when heated under the sarne conditions.
Pine wood samples ( 4.5 x 12 x 14 cm; t x r x 1) were acetylated in the microwave
reactor for different lengths of time. The degree of acetylation obtained after a certain
reaction time was compared with the degree of acetylation obtained for pine wood flakes
acetylated by means of heating in an oil bath, for corresponding reaction times.
Determination of the Degree of Acetylation

One way to deterrnine the acetylation Ievel is by determining the weight percent gain
(WPG) due to acetylation, based on the oven-dry weight before acetylation. For solid wood
of !arger dimensions, however, where it may be difficult to remove excess chemieals during
the final vacuum step or by water soaking, this method of measuring may give a value that is
too high. The wood acetyl content was calculated from the amount of liberated acetat~
determined by HPLC after deacetylation of oven-dried wood particles with 1M sodium
hydroxide. The wood particles were obtained by drilling holes into the wood sample at
different positions.
736
Distribution of Acetyl Groups in Microwave Acetylated Wood
In order to determine the distribution of acetyl groups within microwave acetylated
wood, a spruce wood block ( 10.5 x 9.7 x 16.0 cm; r x t x I) was impregnated with acetic
anhydride and then heated in the microwave reactor for lh at 120 C. After the reaction, the
wood blockwas sliced longitudinally into 17 smaller pieces, and then "air-dried" for 7 days
at room temperature. The wood acetyl content was then calculated.
Removal of Residual Chemieals

A spruce wood block, (10.5 x 9.7 x 16.0 cm; r x t x 1), was acetylated in the
microwave reactor for 1 hour at 120 C. After the reaction, the wood block was sliced
longitudinally into eight pieces as shown in Figure 3. The four triangular pieces denoted "3",
"4", "5" and "6" were air dried at room temperature for about a week before sampling of
wood particles by drilling. The wood particles were then oven-dried for 6 hours at 105 C,
and analyzed for acetyl. Results from analyses of the air-dried wood pieces are believed to
represent the actual acetyl content after the reaction period. The two wood pieces "1" and "2"
were leached in water for 12 hours with an initial vacuum period of 30 min. Water leaching
was follawed by air-drying far 1 day. The water soaking and drying cycle was repeated
twice befare the wood pieces were finally dried at 90 C. The last two pieces denoted "7"
and "8" were placed in an aven directly after acetylation and dried at 90 C for about 3 days.
Waad particles were callected from each woad piece ( "1" ta "8") bathat a 2 cm surface
sectian and at a 2 cm middle section and the acetyl cantent was determined.
# 1 and 2 were leached in # 3 and 4 were air dried

water before drying at room temperature
\~~~/
8
'--------"1<.----'-~:::: ------ 2 cm middle section
/ \ 2 cm surface section
# 5 and 6 were air dried

at room temperature
# 7 and 8 were oven-dried
at 90 C
Figure 3. Test samples for studying of different methods for removing excess chemieals were prepared by
cutting a spruce wood block longitudinally into 8 pieces.
RESULT AND DISCUSSION

Dielectric Properties
Figures 4 and 5 show the dielectric canstant (c') and the lass factar (c") far various
cambinations af woad and acetic anhydride as a functian af temperature. Amang the
combinatians studied neat acetic anhydride exhibited the highest dielectric canstant and lass
factar irrespective af temperature. Pine wood flaur soaked in acetic anhydride shawed a
higher c' than pine waad impregnated with acetic anhydride aver the temperature range
studied. This result means that the degree af heating will increase with an increase in the
737
uptake of acetic anhydride in the wood. Both E' and E" decreased with increasing
temperature. This fact means that less energy will be absorbed in overheated areas of the
wood during acetylation, leading to a leveling of the heat within the wood sample,
promoting a more uniform heating pattem and probably also more uniform acetylation.
30.---------------------------~
E'
25
0 acetic anhydride
20 Ii pine wood tlour soaked
in acetic anhydride
15 0 pine wood impregmated
with acetic anhydride
10 0 pine wood (mc 6%)
5
o----~e~--~e~----0
0+-----~----r----,----~----~
20 40 60 80 100 120
Figure 4. Die1ectric constant (E') for various combinations of wood and acetic anhydride as a
function of temperature.
3.-------------------------~
E"
2 0 acetic anhydride
Ii pine wood flour soaked
in acetic anhydride
0 pine wood impregnated
0 pine wood (6%)
0~----~0~====~'~===='~====~'~--~
20 40 60 80 100 120
Figure 5. Loss factor (E") for various combinations of wood and acetic anhydride as a
function of temperature.
The penetration depth (d), plotted against the temperature is presented in Figure 6.
For all three combinations of acetic anhydride and wood, the penetration depth increases
with increased temperature, indicating that acetylation using microwave heating could, at the
least, be performed on solid wood of dimensions of approximately 20 by 20 cm (tangential x
radial). The acetylation reaction being exotherrnie will most likely contribute to additional
heating of the inner parts of the wood.
Further sturlies of microwave absorbing properties were performed with mixtures of
acetic anhydride and acetic acid in combination with wood acetylated to different degrees of
acetylation. The results presented in Figure 7 show that the depth of penetration decreases
with an increase in the amount of acetic acid in the impregnation mixture. The higher the
738
level of acetylation is, the lower this decrease in penetration depth will be. This fact indicates
that during acetylation, as the degree of acetylation increases and the by-product acetic acid is
produced, the microwave absorbing properties are essentially unaltered.
300
d (mm)
250
200
.__ 0
D
pine wood (mc 6%)
pine wood impregnated
---e~----~~----&
150 pine wood tlour soaked
in acetic anhydride
100 0 acetic anhydride
50
0
20 40 60 80 100 120
Figure 6. Depth of penetration (d) for various combinations of wood and acetic anhydride as a function of
temperature.
150.-----------------------,
d(mm)
100 0 WPG: 19
<> WPG: 8-9
D WPG: 4-5
50
0+------.-----.------r---~
0 25 50 75 100
%HAc
Figure 7. Depth of penetration (d) of pine wood as a function of different acetylation Ievels when
impregnated with mixtures having different acetic anhydride:acetic acid ratios.
Heating Rate and Reaction Rate

A comparison of the rate of heating for water, acetic anhydride and acetic acid showed
that acetic acid heated twice as quickly as water in a microwave reactor (Table 1). Acetic
anhydride was heated somewhat faster as compared with acetic acid.
Pine wood samples were acetylated in the microwave reactor and the reaction rate
was compared to the reaction rate obtained for pine flakes acetylated by means of heating in
an oil bath. Figure 8 shows that the more rapid heating obtained by the microwaves in
comparison with conventional heating gives a higher degree of acetylation during the initial
739
phase of the reaction. The degree of acetylation is about the sarne with prolonged reaction
time. The result indicates that the use of microwaves makes the process less dependent on
the timher size.
Table 1. The increase in temperature obtained when 1.5 kg of liquid is heated by

microwave energy for 3 minutes at apower Ievel of 460 W.
Liquid Time Temp. Boiling point Heat capacity

increase
(min.) (OC) (OC) (kJ/kg,o C)
Water 3 13 100 4.18
Acetic acid 3 31 118 1.36
Acetic anhydride 3 35 140 1.27
Pine wood hcated wnh

microwaves
Pine nakc' hcatcd in an
oil bath
0 100 200
Reaction time
(min)
Figure 8. Degree of acetylation as a function of reaction time for pine wood and pine wood flakes.
Acetylation in Lab-Scale Microwave Reactor
Figure 9 shows the effect of power input on the temperature rise during the acetylation
of a spruce sarnple, 7 x 7 x 15 cm; (t x r x 1). The time required to reach reaction temperature
(130 C) was 11 minutes with apower input of 230 W. The generatorwas turned off at
about 123 C. The temperature then increased to 130 C without any further energy input.
The temperature rise could be explained by the energy released from the exotherrnie
acetylation reaction, but it could also result from a leveling of temperature differences within
the wood sample. The acetyl content obtained when the temperature reached 120 C was
about 9% indicating a high reaction rate for some of the hydroxyl groups in the wood.
Earlier investigations have shown that Iignin hydroxyl groups, especially phenol groups and
740
time
(min)
40
30
reaction
20 time
T
generator
10 turned off
imeta
reaction
ernperatme
50 100 150 temp

(0 C)
Figure 9. Temperature rise during acetylation of a spruce sample.
Figure 10. Acetyl distribution in two different spruce wovd blocks treated in separate experiments under
equal conditions.
741
"(- OH, react faster than hydroxyl groups in hemicellulose and amorphaus cellulose
(Paulsson et al. 1996, Rowell et al. 1994).
Distribution of Acetyl Groups in Microwave Acetylated Wood

The results obtained for two different blocks treated in separate experiments under
equal conditions are given in Figure 10. In both cases a very uniform distribution of acetyl
groups was obtained within the wood block despite its large dimensions. The variation in
acetyl content both within and between the two samples was less than 2%, which indicates a
high degree of reproducibility in the performance of the microwave reactor. Generally, a
somewhat higher acetyl content is obtained in the middle of the wood block than in the outer
part of it. This is presumably a result of a higher temperature in the middle compared with
that close to the end surface where the evaporation of chemieals prevails.
Removal of Residual Chemieals

The final step in the acetylation process is the efficient removal of excess chemieals
from the wood. When treating small 1 x 1 x 1 cm samples on a Iabaratory scale, the removal
of excess chemieals is easily accomplished by either water leaching before drying or just
oven-drying at 105 C ovemight. The influence ofthese methods ofremoving excess acetic
anhydride and by-product acetic acid on the final degree of acetylation when treating wood
of large dimensions was studied. The acetyl contents obtained are given in Figure 11, which
shows that for air-dried samples the values around 18% found for the surface section were
somewhat lower than those found for the middle section where the acetyl content was 19%.
The two wood pieces that were oven-dried at 90 C showed an increased acetyl content,
especially in the sample taken from the middle of the original wood block. Obviously, there
was less acetic anhydride present close to the end surface of the block due to evaporation
than was present in the middle, thus, accounting for the difference in the obtained acetyl
content. When applying water leaching prior to drying at 90 C for the removal of excess
chemieals from the wood, a considerably lower acetyl content was obtained. The lower
content could be explained by deacetylation due to heat treatment under wet acidic conditions
(Rowell et al. 1993). In a removal step performed under acidic aqueous conditions, 25 to
30% of the acetyl groups formed during the reaction period at 120 C were split off due to
hydrolysis of the ester bonds.
, , , \ air dried at
, , , \ room temperature
leached in water \ \ , \ /
befure~ ~~,~~~~~~\~,~~~l
......_ 2 cm rniddle section

/
.::;.;..;;;;._:z....;=~"-:::-
\ 2 cm surface section
air dried at
room temperature dried at 90 C
after acetylation
Figure 11. Acetyl contents of acetylated spruce wood after treatments for removal of excess chemicals.
742
Use of Microwave Heating During Evaporation under Vacuum
As pertains to the final design of an industrial process for acetylation of solid wood, our aim
is to use microwave energy not only for acetylation but also to obtain an efficient removal of
excess chemieals by means of evaporation under vacuum. In order to do so, a Teflon
desiccator containing the wood to be acetylated was placed in the microwave reactor. After
the reaction step, the Teflon desiccator was evacuated and excess chemieals were removed
by means ofvacuum while still applying microwave energy. The influence oftemperature on
the removal of excess chemieals during the vacuum step was studied. Results are presented
in Table 2. Impregnated spruce wood blocks of 10.5 x 4.5 14.0 cm were reacted at 125 C
for 2 hours and at 130 C for 3 hours, respectively. For samples having a temperature of
110 C during the vacuum step, the amount of residual chemieals after acetylation was about
10%, based on the amount of chemieals present in the wood before reaction. By increasing
the temperature of 120 C during the vacuum step, the amount of residual chemieals was
reduced to half the value. With a reaction time of 3 hours at 130 C, a total acetyl content of
20.0 and 19.6% was obtained. Since unmodified spruce wood has a natural acetyl content of
1.2%, this corresponds to a weight percent gain (WPG) of 23.5 and 22.9%, respectively.
Pine wood samples of about the same size as the spruce samples, were reacted for 2 and 3
hours at 130 C, and obtained high acetyl contents ranging from 17.3 to 19.0%,
respectively. About the same amount of residual chemicals, less than 5%, was obtained for
all samples when calculated as a percent of total uptake of chemicals. When calculations are
made on basis of dry acetylated wood instead, the results show that the acetylated pine wood
samples contained between 3.2 and 6.1% of residual chemieals when removed after
completed acetylation process.
Table 2. Process parameters during acetylation of spruce samples (10.5 x 4.7 x 14.0 cm;
r x t x 1) and pine samples (9.7 x 4.5 x 14.0 cm; r x t x 1).
Reaction Vacuum Uptake Residual Residual Acetyl

time/temp. time/temp. during impr. chemieals chemieals content
(hi"C) (hi"C) (% of dry wood) (% ofuptake) (% of Ac.wood) (%)
Snruce
2/125 2/110 161 11.6 16.8 11.0
2/125 2/110 155 9.5 13.0 12.4
3/130 2/120 210 5.2 8.8 20.0

3/130 2/120 184 4.5 6.8 19.6
Pine
2/130 2/125 150 4.9 6.1 18.8
2/130 2/125 138 2.8 3.2 17.3
3/130 2/130 155 3.5 4.5 19.0
3/130 2/130 154 4.3 5.5 18.8
The temperature in the wood samples could be maintained at 130 C even at very low
residual excess chemical content without any formation of bot spots which could cause
pyrolysis reactions. The results obtained in this preliminary study imply a potential for the
removal of additional excess chemieals from the acetylated wood by means of microwave
heating.
The amount of excess chemieals collected in the condenser (expressed as weight
percent of the total uptake of chemicals) was shown to increase rapidly in the beginning of
the vacuum step (Fig.12). During the vacuum step, nearly 60% of the chemieals were
removed after 20 minutes, while the remairring amount of excess chemieals will require a
considerably Ionger vacuum period in order to be removed under the conditions applied. In
this trial the sample was acetylated at 130 C for 2 hours and gained an acetyl content of
16.9%. The uptake of acetic anhydride during impregnation was 141 % basedondry wood
weight and the amount of residual chemieals left in the wood sample when removed from the
reactor after the vacuum step was 2.4 wt-% basedondry acetylated wood.
743
rJl 100 6130
Cdu ~
..... Q)
s~
ctl
80 Q)
Q)
.-!::1..., 5110
uO..
'"O::s
1il...
Q)"-<
60 Q)
:> 0
0~ ~ 90
s rJl 40 Q)
E-<
~ctl
70
20
0 50
30 60 T"1me 90 30 60 90
Time
(min) (min)
Figure 12. Removed chemieals calculated as percent of uptake and, temperature as a function of time of
applied vacuum for pine wood samples 10.0 x 4.5 x 15 cm ).
CONCLUSION
Microwave heating has been shown tobe beneficial for the acetylation of solid wood in
1umber thickness.
Studies of microwave absorbing properties have shown a leveling of heat within the
wood during acetylation, thus, promoting a uniform heating pattem. The penetration depth
of microwaves into a wood sample impregnated with acetic anhydride was shown to be
about 10 cm, indicating that acetylation by means of microwave heating, could at the least,
be performed on solid wood in dimensions of approximately 20 x 20 cm (tangential x
radial).
Microwave acetylation trials have shown that the variation in acetyl content both within
and between samples was less than 2%, which implies a high degree of reproducibility in the
process. Generally, a somewhat higher acetyl content was obtained in the middle of a
microwave acetylated wood sample than in the outer part of it.
When applying water-leaching prior to oven-drying at 90 C for the removal of the last
traces of acetic acid in the wood after acetylation, 25 to 30% of the acetyl groups formed
during acetylation were split off due to hydrolysis of the ester bonds. This calculation is
based on the acetyl content determined after air-drying the wood for a week at room
temperature.
Microwave heating could be used for the removal of excess acetic anhydride and acetic
acid under vacuum. Pine wood samples acetylated for 3 hours at 130 C followed by a
vacuum step for 2 hours at 130 C showed an acetyl content of 19%. The content of residual
chemieals was about 5%.
FURTHER RESEARCH
A pilot plant microwave reactor was built in order to further investigate the optimum
parameters for a proper acetylation process and, in that way come further toward an
industrial production of acetylated wood.
ACKNOWLEDGMENT
Financial support from the Swedish National Board for Industria1 and Technical
Development (NUTEK) is gratefully acknowledged.
744
REFERENCES
Risman, P.O., Bengtsson, N.E., 1971 (a), Dielectric properties of food at 3 GHz as
determined by a cavity perturbation technique I. Measuiing technique, Journal of
Microwave Power 6 (2): 101-106.
Risman, P.O., Bengtsson, N.E., 1971 (b), Dielectric properties of food at 3 GHz as
determined by a cavity perturbation technique. ll. Measurements on food materials,
Journal ofMicrowave Power 6 (2): 107-123.
Rowell, R. M., Tillman, A.-M., Simonson, R., 1986 (a), A simplified procedure for the
acetylation of hardwood and softwood flakes for flake board production, J. Wood
Chem. Techno/. 6 (3): 427-448.
Rowell, R. M., Tillman, A.-M., Simonson, R., 1986 (b), A simplified procedure for the
acetylation of chips for dimensionally stabilized particleboard products, Paperi ja Puu
68 (10): 740-744.
Rowell, R. M., Lichtenberg, R. S., Larsson, P., 1993, Stability of acetyl groups in
acetylated wood to changes in pH, temperature, and moisture, Wood and Fiber
Science 25 (4): 359-364.
Rowell, R. M., Simonson, R., Hess, S., Plackett, D. V., Cronshaw, D.,
Dunningham, E., 1994, Acetyl Distribution in acetylated whole wood and reactivity
ofisolated wood cell wall components, Wood and Fiber Science 26 (1): 11-18.
Paulsson, M., Li, S., Lundquist, K., Simonson, R., Westermark, U.,1996, Chernical
modification of lignin-rich paper. Part 3. Acetylation of Iignin model compounds
representative of -0-4 structures of the -guaiacyl ether type, Nordic Pulp and Paper
Research Journal 11(2): 109-114.
745
NEW RESIN SYSTEM FROM LIGNIN
Bunichiro Tomita
Institute of Agricultural and Forest Engineering,

University of Tsukuba, Tsukuba-shi, Ibaraki-ken 305, Japan
INTRODUCTION
In kraft pulp process for producing chemical wood pulps, economics require that the organic
matters containing Iignin in the spent Iiquor is burned for recovery of chemieals and heat. Kraft
Iignin, however, is a highly branched phenolic-like polymer possessing a variety of functional
groups that provide potential reactive sites for chemical modification. Until now, many attempts
have been madeto utilize kraft Iignin as a component ofresins (Tomita etal., 1989; Yoshida et al.,
1990; Kajiyama et al., 1994). Lee et al. (1991) prepared ozonized kraft lignin/epoxy resins and
found that its wood gluability was satisfactory.
In this paper, lignin/epoxy resins were prepared by mixing the alkahne solution ofkraft Iignin
and water-soluble epoxy compounds with curing reagents. The lignin/epoxy resins were
synthesized by alternating the blend ratio or their chemical structure. The viscoelastic properties
of cured resins and some applica:tion as wood adhesive ofthese resins were investigated.
EXPERIMENTAL
Matel'ials
The kraft Iignin selected as the sample was INDULIN AT (SIGMA Chemical Co.). Phenolic
hydroxyl group contents ofsample determined by the UV method was 2. 70%. This Iignin sample
was used without further purification and chemical modification. The water-soluble epoxy
compounds used were polyethylene glycol diglycidyl ethers (PEGDGE, Nagase Chemieals Ltd.)
which are different in degree of polymerization (n) ; ethylene glycol DGE (n=1, epoxy
value[e.p.]: 0.89), tetraethylene glycol DGE(n=4, e.p.: 0.51), and nonaethylene glycol DGE
(n=9, e.p.:0.36). Emulsion type ofdiglycidyl ether ofbisphenol A (DGEBA, Nagase Chemieals
Ltd. e.p.:0.19) also was employed for blending. Two types ofaliphatic amines were used as the
curing reagent, triethylene tetramine and hexamethylene diamine (HMDA, Wako Pure Chemical
Industries Co. Ltd.). The chemical structures of epoxy compounds and curing reagents are
shown in Figure 1.
Science and Techno/ogy of Polymers and Advanced Malerials

H2\TH-CH2-(- O-CH2 -CH2)n-O -H2C -C~cfCH 2
n=l:Ethylene glycol DGE

n=4:Tetraethylene DGE
n=9:Nonaetbylene DGE
Polyethylene glycol diglycidyl ether (PEGDGE}
c~ c~
I I
H2G-CH-CH2-{o0cQ-o-CH2-cH-CH2 )n-o-O,Q-o-H 2C -cH-CH 2
\/ I I I \I
0 CH3 OH CH3 0
Diglycidyl ether ofbisphenol A CDGEBA)
(Emulsion type}
HiN+ CHrCH2-NH-h-CH2-CH2-NH2 H2N-{CH 2)6-NH 2

Triethylene tetramine (TETA) Hexamethylene diamine (HMDA)
Figure I. Chemical structure of epoxy compounds and curing reagents.
Preparation of Lignin/Epoxy Resins
The kraft Iignin was dissolved in 1% sodium hydroxide at 60C, and mixed with the epoxy
compounds, and then added by the curing reagents. The amount of curing reagent was set to 80%
of the stoichiometric amount of epoxy equivalent, because the functional groups of Iignin were
considered to consume at most 20% of epoxide. The epoxy compound without Iignin was added
by the curing reagent stoichiometrically. Curing was generally done by allowing to stand at room
temperature for one day, and then heating at 150 C for 3 hours. The cured films were brown-
colored, but had good rigidities and toughness as weil as transparencies. Lignin/epoxy resins
were examined in terrns offollowing factors.
{1) Effect oflignin content
In order to investigate the effect of the Iignin content, the resins were prepared at various Iignin
contents, and cured with TET A. The epoxy compound used was tetraethylene glycol DGE.
{2) Effect of epoxy compound or curing reagent
The effect ofdegree ofpolymerization (n) was examined using two kinds ofPEGDGE {n=l
and n=9). In addition, an attempt was made to study the effect ofthe curing reagent by using
TETAandHMDA.
(3) Effect of epoxy blending ratio
Two types of epoxy compounds, tetraethylene glycol DGE and emulsion type of DGE of
bisphenol A were blended at various mixing ratio, and cured with TETA.
In the cases of(2) and (3), Iignin contents in resins were maintained at 50%(w/w).
Measurement ofGel Time ofLignin/Epoxy Resins
Two kinds of experiments were performed: PE GD GE {n=4) was mixed with Iignin at various
contents; three kinds ofPEGDGE (n= 1, n=4 and n=9) were mixed with Iignin at the same content
of 50%. The samples were maintained at 50C with stirring and the gel time was determined as
the time when the mixture solidified.
748
Acetone Extraction from Cu red Films
Cured films were extracted with acetone for one week. Then the films were dried at 100C for
6 hours, and their weights were measured. The percentages of weight decrease were calculated
by weights before and after extraction.
Dynamic Mechanical Measurement
Sampies were prepared by molding the liquid lignin/epoxy resins into the film specimens
whose sizes were 5cm(length)x 0.2cm(width)x O.OlOcm(thickness), and by curing with the
same condition as mentioned above. The dynamic mechanical-spectra were measured in
tension with a Rheovibron DDV-II(Toyo Baldwin Co. Ltd.) at a frequency of 110Hz and a
heating rate of2C/min.
Adhesive Strength Test
The adherends were birch (Betula maximowicziana Regel). The sizes of tensile shear
specimens and bonding areas were as follows: 25mm( width)x80mm(length)x5mm(thickness)
and 3. 75 cm'. The hat press conditions were as follows: bonding pressure 10 kgf/cm'; press
time 3 hrs; temperature 150C. The specimens were conditioned at 20C and 65 RH for one
week before being tested. Two type oftests were applied. One isanormal test and the other a
water-soaking at 60C for 3 hrs. The tensile shear adhesive strengths were measured with a
Tensilon testing machine{Toyo Baldwin Co. Ltd.) und er a crosshead speed ofl Omm/min.
Reaction of Lignin and Epoxide
Gelation took place under the condition with and without curing reagent, and were
recognized in the broad range of Iignin contents of 20% to 80%. This result indicates that
functional groups oflignin react with epoxide. On the other hand, the geltime became shorter
with decrease of (n); that is, the epoxy compounds having a great amount of epoxide per a
same weight had a higher reactivity. The weight decreases of the cured films after the acetone
extraction were determined. The soluble parts ofthese resins were quite low, and cured films
were almostinsoluble in acetone. This result also supports that Iignin reacts with epoxide to
form three-dimensionallv cross-linked networks.
Effect of Lignin Content on Dynamic Mechanical Propeties of Lignin/Epoxy Resins
Temperature dependence of viscoelastic property of the three kinds of Iignin content are
shown in Figure 2. E' and E" indicate storage modulus and loss modulus, respectively. Figure 3
shows the relationship between the Iignin content and the peak temperature of loss modulus,
T(E"max), which roughly can be considered to correspond to the glass transition temperature
(Tg). From these figures, it can be recognized that, depending on the Iignin content, clear
differences are displayed for the temperature and the shape of absorption peaks attributed to the
glass transition. The absorption peak shifted to a greater temperature and spread as the Iignin
content increased. The increase in the peak temperature can be explained by the decrease of
molecular mobility owing to the steric hindrance effect caused from the addition oflignin which
mainly consists ofthe rigid phenylpropane unit. Only one primary dispersionpeakwas observed,
749
~ 1 011.,--~-,r---.-----.---.-,
60
"'Q;5 -....____E' : T(E"max)
E' ~\,tJLignln content
1: o%
c \\ 2:25%
>- :. 3'50% 40
~10 10 1 : \2 3 . 0
e \ ~.,
0
:;
~~ 20
l.u 1o9 E"
. ~
\
'
iii
Q;
\
~ ~ 0.
.,
~ ~
E
0
J I-

~--~ -20
I
0 100 200
0 25 50
Tamperature ("C)
Lignin content (%)
Figure 2. Temperature dependence of viscoelastic Figure 3. Plots ofT(E"max) at 110Hz vs. Iignin
property of lignin/epoxy resins cured with TET A. content for lignin/epoxy resins.
Note: PEGDGE(n=4) was used. Note: PEGDGE(n=4) was used.
and T(E"max) increased uniformly depending on the Iignin content. These findings suggested
that a lignin/epoxy resin system has complete compatibility. The glass transition peaks, however,
tended to spread widely as the Iignin content increased. The isolated Iignin obtained from a
cooking solution consists of molecules which have a broad molecular weight distribution
(Hatakeyama et al., I 975). This unusual broad relaxation is supposed to be caused from a broad
distribution of cross-linking density or a wide fluctuation of composition on a locallevel, which
may be derived from the addition oflignin.
PEGDGE PEGDGE
1:n=9 1: n=9
2: n=1
2:n=4
3:n=1
!I
0
0
0
w
:~
0 f, \ o
}---- w
\~-\-
. \ ~
\
10 7 -100 0 100 200 0 100 200
Temperature ("C) Tamperature ("C)
Figure 4. Temperature dependence ofviscoelastic Figure 5 Temperature dependence ofviscoelastic

property of epoxy resins different in degree of poly- property of lignin/epoxy resins different in degree
merization cured with TET A. of polymerization cured with TET A.
Note: PEGDGE; (I) n=9, (2) n=4, (3) n=l. Note: PEGDGE; (1) n=9, (2) n=l.
750
The rubber elasticity was observed at a higher temperature, which indicates that the resins
form a complex three-dimensional cross-linking structure. A secondary relaxationwas observed
between -80 and -20C in all the samples. lt was reported that the broad relaxation observed at
same temperature range for typical epoxy resins cured with aliphatic diamine could be
interpreted as the sum of contributions due to hydroxyether groups and other parts ofthe cross-
Iinking structures (Ochi et al., 1982). This relaxationalso was observed at the system without
adding the curing reagent. These secondary relaxations observed in this study, may be related to
the molecular motion of cross-Iinking structures which are formed by the reaction between epox-
ide and hydroxyl group or amino group.
EfTect ofStructu.-e ofEpoxy Compounds and Cuing Reagents
Figure 4 shows temperature dependence of viscoelastic property of resins cured with TETA
using three kinds ofPEGDGE different in degree ofpolymerization. T{E"max) became lower as
the degree of polymerization increased. Generally, the higher the Tg value of the three-
dimensionally cured polymer, the smaller the average molecular weight between the cross-
linking points (Murayama and Bell, 1970). The value of storage modulus at rubbery plateau
region is related to cross-linking density through the cross-linking theory (Nielsen, 1975). The
cross-linking density is calculated by the equation: E' = 3)/RT, where E' is storage modulus at
rubbery plateau regional, the cross-Iinking density; R, the gas constant; T, the absolute tempera-
ture. Accordingly, the cross-linking densities were 2.50 and 1.20 x 10' moVcm' for ethylene
glycol DGE and tetraethylene glycol DGE, respectively. Furthermore, the increase of degree of
polymerization made the rnaximum value ofloss tangent (E"/E') shift as follows: 1.0 for n=1; 1.3,
n=4; 1.6, n=9. It was reported that the height oftangent delta peak increases with an increase in
the molecular weight between cross-links, Mc, which corresponds to a lower cross-Iinking
density; the greater separation of cross-links permits greater mobility of chain segment
(Murayama and Bell, 1970). Accordingly, it was concluded that the property ofPEGDGE cured
under the same condition is affected by segmental structure, repeating units between epoxides.
w
oll Blend rotlo ol
1: HMDA DGEBA/PEGDGE(n=4)
J 2: TETA
1 : 0/10
2: 2/8
3: 4/6
1o 7 U-~o~~~~1~oo~~~~2do~o
0 100 200
Tamperature ("C) Tamperature ("C)
Figure 6. Tempersture dependence ofviscoelastic Figure 7. Temperature dependence ofviscoelastic

property of lignin/epoxy resins cured with (I) HMDA property of lignin/epoxy resins different in blending
and (2) TETA for Iignin content ofSO %. ratios cured with TET A for Iignin content of 50%.
Note: PEGDGE (n= I) was used. Note: Blend ratio of DGEBA/PEGDGE(n=4);
(I) 0/10, (2) 2/8, (3) 4/6.
751
On the basis ofthe above results, lignin/epoxy resins were prepared by using different kinds of
epoxy compounds. Figure 5 shows the temperature dependence of viscoelastic property of
lignin/epoxy resins different in degree of polymerization. The absorption peak due to the glass
transitionwas observed around ll0C when using PEGDGE ( n= I) as epoxy compound. To the
contrary, the lignin/epoxy resin from PEGDGE (n=9) had that at about 30C. On the other hand,
it was observed at 55C for the resin prepared from PEGDGE (n=4) at the same Iignin content of
50% (Figure 2). It was noted that the properties oflignin/epoxy resins also are influenced by the
kind ofPEGDGE, because the network flexibility is changed by the number ofrepeating units
(n). However, the cross-linking densities oftwo kinds oflignin/epoxy resins were almost similar
each other in spite of difference in degree of polymerization; n=l, 1.78 x 10-'; n=4, 1.62 x
10-'mol/cm'. Additionally, the maximum values ofthe loss tangentalso were almost constant.
These discrepancies are supposed to be attributed to the broad distribution of crosslinking
density derived from the nature of Iignin. Figure 6 shows the temperature dependence of
viscoelastic property of lignin/epoxy resins cured with TET A and HMDA, respectively. The
absorption peak due to the glass transitionwas observed at the lower temperature region when
HMDA was used. This phenomenon is considered tobe caused by loosening ofthe networks,
such molecular motions as a crank-shaft movement of six carbon atoms of HMDA (Schatzki,
1962). It was concluded that the glass transition temperature of lignin/epoxy resins can be
modified over wide range by alternating the kinds of epoxy compounds and curing reagents.
100------------------------, 100r-----------------------~
~
lL 50 -
~
0
0
0 ~--~______e______o______JLn__~ 0
0 ~--~0--------------------~
'f100 ..... 100

0 g
E
~
Ol
c
80-
~
E 80
Ol
c
f
f
~ ~
~ 60 ~ 60-
~
"'
Q)
<11
~
"'rn
Q)
Q) 40 - Q) 40 -
>
;;; >
;;;
Q) Q)
~ ~
~ 20- ~ 20-
QL-~L_ ___ L_ _ _ __ L_ _ _ _ ~,L_~
0/10 2/8 4/6 6/4

A B c D Blendratio
(DGEBAIPEGDGE)
Figure 8. Plots of adhesive strength and wood Figure 9. Plot of adhesive shear strength and wood
failure (WF) vs. lignin/epoxy resins for the failure vs. blending ratio of DGEBA/PEGDGE
Iignin content of 50 %. (n=4) for lignin/epoxy resins cured with TETA at the
Note: A; cured with TETA at 2oc. Iignin content of 50%.
8; cured without TETA at tsoc. e : normal test, 0: wet lest
C; cured with TET A at tsoc.
D; ozonized lignin,cured with TETA at 15oc.
e: normal test, 0: wettest
752
Effect ofEpoxy Biending
Figure 7 shows the temperature dependence ofviscoelastic property oflignin/epoxy blend

resins. The glass transition temperature also could be modified by addition ofthe emulsiontype
of DGEBA at Iignin content of 50%, and shifted to high er temperature as its mixing ratio in-
creased. Although the emulsion was employed more than 50%, the cured films also were
transparent, that is compatible. On the other hand, the glass transitions for the cured resins from
the emulsiontype ofDGEBA and tetraethylene DGE without Iignin were observed about 90
and -l5C, respectively. If polymer blending had two Tgs at the same temperature as those of the
parent raw components, its system can be considered tobe completely incompatible. However,
Lignin!epoxy blending resins had a single peak due to the glass transition. Accordingly, it was
suggested that the cured resins have compatibilities to form a kind ofiPNs.
AdhesiveStrength Test
Figure 8 shows the result of adhesive strength tests. The high tensile shear strengths were
recognized when curing agent and hotpress were employed. On the other band, the lower values
were observed when curings were done without curing agent or at room temperature. The wet
strength after soaking in water were generally low, accompanied with lower wood failure values.
Figure 9 shows the effect of blending ratio of DGEBA/PEGDGE on adhesive strengths. The
blending ratio did not influence greatly on the normal adhesive strength. However, the increase
of DGEBA improved the wet strength with increase of wood failure value. These preliminary
wood bonding tests on this new adhesive system indicate good potential.
CONCLUSION
The dynamic mechanical measurements showed cured resins had complete compatibilities. It
also was found that the glass transition temperature of cured resins can be modified over wide
ranges by selecting epoxy compound and curing reagent. It is significant from practical aspects
that the resinification ofthe kraft Iignin can be performed by the simple method using its higher
content. As is generally known, polymeric materials can convert mechanical energy to thermal
energy in their glass transition temperature region. Cured ligninlepoxy resins exhibited very
broad relaxations due to the glass transition, hence those resins have the possibility of extensive
application of adhesives or damping materials which reduce the emitted noise and vibration.
Refeences
Hatakeyama, H., Jwashita, K., Meshituka, J., and Nakano, J., 1975, Effect ofmolecularweighton glass transition
temperature of Iignin, Mokuzai Gakkaishi, 21:618-623.
Kajiyama, T., Sato, H., Sato, T., and Tomita, B., 1994, Developmentofwood adhesives from ozonized Iignins,
Proceedingsfrom the Adhesives & Bonded Wood Symposium. Eds., C. Y. Hse, B.Tomita and S . .1.
Branham,Forest Products Society, Madison, Wisconsin. pp. 405-414.
Lee, H. J., Tomita, B., and Hosoya, S., 1991, Development ofOzonized kraft lignin/epoxy resin adhesives,
Wood lndustry, 46: 412-417.
Murayama, T. and Bell, J.P., 1970, Relation between the network structure and dynamic mechanical
properlies of a typical amine-cured epoxy polymer, J. Polym. Sci.,Pal"l A-2: 8: 437-445.
Nielsen, L. E., 1975,Mechanical properliesofpolymersandcomposites, NY: Marcel Dekker Inc ..
753
Ochi, M., Okazaki, M., and Shimbo, M., 1982. Mechanical relaxation mechanism of epoxideresins cured
with aliphatic diamines, J. Polym. Sei., Polym. Phys. Ed., 20: 689-699.
Schatzki, T. F., 1962, Glasstransitionsin ethylenecopolymers,J. Polym. Sci.,57: 494-498.
Tomita, B., Kurozumi, K., Takemura, A., and Hosoya, H., 1989, Ozonized lignin-epoxy resins synthesis and
use, Lignin: Properlies and Materials, Eds. W. G. Glasser and S. Sarkanen, ACS Symposium Series,
No.397, Chapter 39, pp. 496-505.
Yoshida, Y., Kajiyama, M., Tomita, B., and Hosoya, S., 1990, Synthesisof ozonized Iignin/aminomaleimide
resins using the Diels-Aider reaction and their viscoelastic properties, Mokuzai Gakkaishi: 36: 440-
447.
754
APPLICATIONS OF NATURAL FIBERS IN AUTOMOTIVE INDUSTRY IN BRAZIL-
THERMOFORMING PROCESS
Alcides L. Leao 1; Roger Rowell2; and Nilton Tavares3;
1Professor- UNESP, FCA, Campus Botucatu, SP, Brazil- 18.603-970
2project Leader- USDA Forest Products Lahoratory, Madison, WI, USA

3R&D Manager- Toro Ind. e Com. Ltd., Diadema, SP, Brazil
INTRODUCTION
Environmental and economical concems are stimulating research in the development of

new materials for construction, furniture, packaging and autornative industries. Particularly
attractive are the new materials in which a good part is hased on natural renewahle resources,
preventing further Stresses on the environment hy depleting dwindling wood resources from
forests. Examples of such raw material sources are annual growth native crops/plants/fihers,
which are abundantly availahle in tropical regions. These plants/fihers (like jute and sisal) have
heen used for hundreds of years for many applications such as ropes, heds, hags, etc. If new
uses offast growing, native plants can he developed for high value, non-timher hased materials,
there is a tremendous potential of creatingjohs in the rural sector. These renewahle, non-timher
hased materials could reduce the use oftraditional materialssuch as wood, minerals and plastics
for some applications. There is a tremendous interest hy the pharmaceutical industry in
exploring the rain forest for new drugs, hut so far there has heen little interest in exploring the
rain forest for fast growing native plants as a fiher source. In applications such as ropes, new
materials, such as nylon, have replaced locally grown fihers like sisal and jute. Therefore,
increasing interest in saving the forest and at the same time creating rural employment means
that new materials have to he developed to use locally available non-wood renewahle resources.
The advantages of these plants are that they are fast-growing and renewahle, and sometimes
are also a source of food supply for animals and even humans.
The materials made through the comhination of native fihers with different plastics, such
as Polyvinylcloride (PVC), Polypropylene (PP), and Polyethylene (PE) are composites that have
wide application possihilities, having a potential of developing new industries in the near future
using local crops, wastes and Iabor, and helping to reduce the demand for tropical hardwoods
(housing, furniture, pellets, etc. ), and plastics.
The technology developed in this project could easily be applied in other tropical countries,
with similar ecosystems.
Science and Technology of Polymers and Advanced MateriJJ/s

LITERATURE REVIEW
Lignocellulosic fibers are a kind ofbiopolymer composite, with the following components,
in different proportions, depending on the species considered: cellulose, hemicellulose, Iignin,
and other components insmall proportions. Thesepolymersare the basic constituents ofthe
cell wall and are responsible for most of the physical and chemical properties, such as
dimensional instability to moisture, biodegradability, flammability, thermoplasticity, and
degradability by ultraviolet light, acids, and bases. All of these characteristics will result in
specifi.c end-use of lignocellulosics in composite formulation. Lignocellulosics, can also be
called phytomass, biobased fibers, or biofibers, including wood, agricultural residues, water
plants, grass, agricultural fibers, and any other plant substance (ROWELL, et al. 1993;
SCHNEIDERet al. 1994).
Lignocellulosics can be put together with one or more substances, using some kind of
matrix, that would hold the components together, resulting in a composite material. Several
options are available, with different processes, compositions and bonding agents.
Thermoplastics can be used to mak:e composites for nonstructural parts, and thermosetting
resins can be used for structural composites. These composites can be designed based on end-
use requirements, under the most important aspects nowadays: cost, availability, renewability,
recyclability, energy use, and environmental safety. Fiber technology, high performance
adhesives, and chemical modifi.cation for the fibers can result in a composite with uniform
properties, durable in adverse environments, and mainly with high performance, suitable to
compete with other man-made materials. This new technology can be applied to either virgin
or recycled fi.bers from any plant. Recycled lignocellulosic fibers can be used as a reinforcement
fi.ller in composites with polyolefins. Recycled plastics can be used as binders producing a high
performance -low cost composite material. (ROWELL, et. al. 1993).
Lignocellulosics can be used as reinforcing fi.llers in thermoplastics composites, which
would Iead to increasing strength, stiflhess, and heat distortion temperature, although a
decrease in impact resistance is expected. Fibers with high aspect ratio, such as cellulose, are
more convenient than flours. Other properties can be enhanced using small amounts of additives
or coupling agents, to aid dispersion of the polar fi.llers in the non-polar matrix polymer,
therefore increasing the bondability between the fi.ller and the polymer (SCHNEIDER, et al.
1994).
Thermoformahle polypropylene and lignocellulosic fi.bers can be extruded in sheet form for
use in autornative interior components, such as door panels, trunk Iiners, sealbacks, package
and speaker trays, reducing the consumption of petro-dependent materials in the thermo-
moldable plastics by less than 50% (BALATINECZ & WOODHAMS, 1993). Several
alternatives have already been reported with very promising results: bagasse, cereal straw,
kenaf, rice husks, rice straw, sunflower hull and stalks, jute, sisal, banana, etc. The USDA
Forest Service, Forest Products Labaratory surveyed worldwide for agricultural fi.bers and
residues utilization and selected a total of 1,039 citations from a vast number available, showing
a strong interest all around the world for these kind of materials, depending only on its local
availability (YOUNGQUIST et al. 1993, 1994) .. Most ofthe research has been conducted
using polypropylene, with good results (CLEMONS & MYERS, 1993).
There are, however, problems regarding the compatibility of surface energies between
hydrophilic (polar) cellulose and hydrophobic (non-polar) polyolefi.ns. Consequently this
characteristic, poor match of surface polarities results in poor bonding between polyolefins and
cellulose. Therefore, cellulose must be treated on its surface, or totally, by various methods to
increase its bondability (determined by e.g. contact angle -wettability determination).
Differences in adhesion between modified cellulose and polypropylene can be measured by
internal bond and peei tests. The use of sizing agents reduces the acidlbase (hydrogen bonding)
character ofthe cellulose surface. There is a corresponding relation between hydrogen bonding
756
and adhesion between cellulose and polypropylene. It is recommended to modify the
hydrophobic polymer in a way to introduce chemical modification in its surface, that could
result in strong acidlbase (hydrogen bonding) interactions (QUILLIN, et al. 1992). The
evaluation ofthe quality ofthe fiber-matrix bond is done by a macroscopic pull-out technique
that determines the interphase properties in lignocellulosicsllow-molecular-weight-thermoplastic
systems. It is also useful to evaluate the effect ofwater exposure over the dimensional stability
oflignocellulosics fiber based composites (SANADI, ROWELL & YOUNG, 1993).
From the over 1,500 citations found, related to agricultural fibers, 101 are.for coir, 14 for
areca, 12 for banana, 5 for cassava, 23 for jute, and 15 for palm, showing the potential for fibers
that are commonly found in the rain forest region. Any of these fibers, alone or in combination,
blended with man-made fibers, could replace wood as a major component in fiberboards, and
even replace plastics in several industrial and commercial applications (BENATTI & LEO,
1994; SCHNEIDER, 1994). Many plants with fibers yet unknown scientifically can be found
in the tropical regions that would replace wood and man-made fibers in several different
applications (YOUNGQUIST et al. 1994). Fibers from the Amazon and other tropical rain-
forests showhigh potential due to their mechanical and physical characteristics such as: curaua,
malva, pupunha, jute, banana, etc. (LEO & TAVARES, 1995). Among these tropical fibers,
one is ofparticular interest and will be studied in this project: the curaua, whose properties are
described below.
- CURAUA -Ananas erectifolius- This is a hydrophilaus species from the Amazon region. Its
leaves are hard, erect and have flat surfaces. The leaves are about one meter long, or more, and
4 cm wide. The plant requires 2,000 mm or more of annual precipitation, preferring silil-humus
soils, but also grows in clay-sillic soils. It is commonly used by the Indians as a favorite plant
for :fibers utilization for hammocks and fishing lines. Eight months old leaves can reach up 1.5m
in length, and 50-60 leaves per year. The dry :fiber content in leaves is about 5-8%. The fiber
is commonly extracted by a primitive process called "forca" (hanger), washed and beaten with
a circular rod and left in water in order to mercerize for 36 hours. They are again washed and
allowed to dry. Natural Curaua :fiber (wet) shows an average elongation of 4.5%, MOE of 10.5
GPa, and MOR 439 MPa. Dryfiber (OD) values are respectively 3.2%, 27.1 GPa, and 117
MPa. Cutted and defibred the values are respectively 3.7%, 9.7 GPa, and 428 MPa. Cutted,
de:fibred and dried (OD), the values are respectively 4.3%, 11.8 GPa, and 502 MPa. Curaua is
very competitive among the traditional fibers, always ranking in the top three for economical
analysis and top four for stiffness (TORO, 1994). It has been reported in a study using several
agricultural fibers, such as: jute, kenaf, abaca, sisal and henequem, that bast fibers composites
have higher properties than leaf fiber composites. On the other hand, impact toughness values
are higher for leaf :fibers compared to bast fiber composites (JACOBSON, ROWELL &
CAULFIELD, 1995).
METHODOLOGY
Several natural fibers, such as curaua, coir, jute, rarnie and sisal were studied in this
project. Several combinations of plastics and :fibers were studied with and without coupling
agent (Maleated Polypropylene - MAPP - G3002, from Bastman Kodak). Combinations of
three components were also studied, such as viscose~ute-polypropylene, in different ratios. The
density varies from 0.59 to 0.95. The thickness was between 1.75 up to 2.95 mm. The statistical
design used was an incomplete factorial. Three samples of each treatment were tested and
analyzed through the statistical package SAS. The forming process was the same for all
treatments, using a commercial industrial size machine located at the Toro Ind.& Com. Ltd.
plant, located in Diadema, SP, Brazil.
The fiber components were mixed on a dry weight basis and mixed by hand prior to the
picker, which cuts the fibers to 5 cm in length, also giving more mixing. After the picker, the
757
mixture goes to the cards, where more mixing can be obtained, and finally it goes to the needle
machine. The mats were cut and pressed at different temperatures, densities, pressure and time
ofheating and cooling. The heating time was 30 to 180 seconds. The pressure varies from 3.25
MPa up to 9.8 MPa. The pressuretime in the cold press was 20-30 seconds. The samples were
taken from the boards using a pressing knife. The parameters evaluated were EMC (Equilibrium
Moisture Content), bending (ASTMD790M-93}, tension (ASTM D638M-89} and dimensional
stability.
The moisture content (MC) in the air at uncontrolled conditions, after 10 days of pressing
was very low for all the treatments, and therefore it will not be considered as a variable. The
results obtained varied from 1.6 to 2.8%, showing that there was no significant variation among
the treatments, and according to the objectives of obtaining a stable composite.
It was used in some trials recycled materials that are resultant from parts with non
conforrnity, that are scrapped and retumed for the line. The use of recycled materials in the
tecnomix mixture was very deleterious for all properties tested, the maximum of recycled
material usable in the tecnomix mixture being 100/o. The mixture of viscose, jute and
polypropylene (25/30/45) gave poor results for tensile strength (20.26 MPa), but average
results for flexural strength (23.09 MPa), and flexural (2.07 GPa) and tensile modulus (1.83
GPa), showing that it can be used in some applications, where tension strength in not so
important.
Short fibers, as coir and sugar cane bagasse, are limited in their strength properties due to
the non-woven technologies, but can compete in prices with fibers such as jute, rarnie and sisal.
Curaua has no competition in performance, since the prices of all natural fibers are about the
samein Brazil (US$0.60/kg FOB).
The Iimit for natural fibers content, at the processing conditions, were 60% for all the
treatments, including curaua. For curaua, at 200/o polypropylene, a strong reduction in tensile
and flexural strength was found, much more than for tensile and flexural modules (Table 1).
For jute, the differences among the treatments were not so high as for curaua (Table 2).
Ratios of 30/70 and 40/60 for jutelpolypropylene showed very little differences, with low
values, compared to standard ratio considered of 50/50, mainly for flexural and tension
strength.
For sisal, high natural fiber content resulted in lower values compared to the standard
50/50 natural fibers/polypropylene. At 70/30, the values were similar to curaua (Table 3}. The
modules showed very little differences.
At standard ratio, 50/50, curaua was much higher than rarnie and jute, in this sequence
(Table 4). Again, values ofmodulus showed no significant differences.
Table 1. Effect ofNatural Fibers Content on Curaua/Polypropylene Composites.
RATIO TENSION TENSION FLEXURAL FLEXURAL

CURAUAIPP STRENGTII MODULUS STRENGTII MODULUS
(%) MPa GPa MPa GPa
80/20 19.98 1.56 14.67 1.44
70/30 21.83 1.63 24.13 3.03
60/40 50.75 3.34 24.97 2.53
50/50 46.38 3.78 33.10 2.51
758
Table 2. Effect ofNatural Fibers Content on Jute/Polypropylene Composites.

JUTE/PP STRENGTH MODULUS STRENGTH MODULUS
(%) MPa GPa MPa GPa
30170 23.21 2.17 24.47 2.24
40/60 24 2.72 26.74 2.38
50/50 16.52 2.63 27.33 2.9
Table 3. Effect ofNatural Fibers Content on Sisal/Polypropylene Composites.

SISAL/PP STRENGTH MODULUS STRENGTH MODULUS
(%) MPa GPa MPa GPa
80/20 11.12 1.25 16.36 1.36
70/30 25.41 2.35 23.76 1.83
60/40 23.25 1.97 32.3 2.78
Table 4. Effect ofSpecies on Standard Ratio 50150 Natural Fibers/Polypropylene Composites.

NAT. Fffi./PP STRENGTH MODULUS STRENGTH MODULUS
50/50% MPa GPa MPa GPa
RAMIE 34.67 3.43 29.33 3.02
JUTE 15.66 2.4 23.97 2.5
CURAUA 46.58 3.78 33.1 2.51
Heating time was a significant variable. It must be enough to heat and melt the
po1ypropylene inside the mats. The minimum observed was 60 seconds. The temperature cannot
go above 220C, to prevent buming of the natural fibers. The low results for jute 50150,
compared to the other fibers is explained by the short time of heating in this treatment.
The basic weight was a significant variable on the strength properties, although, at
differences of200 g/m2, the results showed no differences. Therefore, ifhigh values are needed
in modules, the basic weight must go above 2000 g/m2 . In this case the basic weight will make
a difference, more than the species of the fibers.
The thickness was not important for the Ievels studied {1.8-3.0 mm), showing, that it is
closely related to basic weight, but it is not so sensibletosmall variations. Above 3.0 and below
1.5 mm, the properties have a significant reduction.
The pressure at the values tested, varying from 3.25 MPa up to 9.8 MPa, at the forming
press (cool) were not significantly different. The heating pressure was used only to compress
the mats and carry the heat throughout, with values varying from 0.82 to 3.67 Kg/cm2 The
759
Table 5. Effect ofSpecies on Standard Ratio 50/50 Natural Fibers/Polypropylene Composites.

NAT. FIB./PP STRENGTH MODULUS STRENGTH MODULUS
80/20% MPa GPa MPa GPa
CURAUA 19.98 1.56 14.67 1.44
SISAL 11.12 1.25 16.36 1.36
COIR 9.25 0.45 9.23 0.43
cooling time at the forming press also was not significant at the values tested, showing that it
was above the minimum Iimit.
Values of80% ofnatural fibers were too high to get a good mat, resulting in composites
with poor properties for all the fibers tested, more for coir, due to be the shortest fiber tested,
as observed in Table 5. Even in this case, curaua showed much better values than coir. Sisal
showed values at rniddle range.
Further studies must be developed in accelerated aging, and IZOD impact resistance for
these composites. By the prelirninary results observed with curaua, this will be the only fiber
that could compete with glass fibers.
CONCLUSIONS
Curaua is by far the best natural fiber for composites applications at the conditions tested.
The others, showed a sirnilar behavior, indicating that price and availability will be the main
aspect. The natural fibers tested showed a very high competitiveness with traditional materials,
mainly wood and fiber-glass based composites. The applications ofthe composites tested are
ideal for sound insulation and structural parts for interiors in the automotive industry.
The temperature of processing, must be high enough to melt the polypropylene, but below
the technicallirnit of 220C. The basic weight was important, showing better properties for
denser materials. However, since it represents a technical and economical trade-off, values of
1550-1800 g/cm2 showed very sirnilar behavior. Other variables such as pressing, and cooling
time were not significant.
The use of recycled material in the mixture must be limited to I 0%, because the fibers are
shortened and damaged in each processing pass.
Further analysis has been developed with several natural fibers using injection molding
technique, which will be described in another paper.
ACKNOWLEDGMENTS
We are thankful to FAPESP -Fundacao de Amparo a Pesquisa do Estado de Sao Paulo,

for funding this project; to the USDA Forest Products Laboratory in Madison, for their
assistance and testing ofthe materials; and to Toro Ind. & Com. Ltda. for the financial and
logistic support for this study.
LITERATURE
BALATINECZ, J.J. & R.T.WOODHAMS. 1993. Wood-Plastic Composites- Doing More

With Less. Journal ofForestry, 91(11):22-26.
BENATTI, R. & A. LEAO. 1994. Natural Fibers Situation in Brazil. FAO Meeting-
Bangalore, India. 5p.
760
CLEMONS, C.M. & G.E. MYERS. 1993. Properties ofMelt-Blended Composites From Post-
Consumer Polypropylenesand Wastepapers. ANTEC'93. pp.3213-3215.
ENGLISH, B. and J. SCHNEIDER 1993. The Recycling ofPost-Industrial Jute-Polyester
Automotive Interior Substraste Panels. Final Report. USDA, FPL, Agreement FP-92-1850.
ENGLISH, B. 1994. Biobased, Biodegradable Geotextiles: USDAForest Service Research
Update. In: Proceedings ofthe Pacific Rim Biobased Composites Symposium.
ENGLISH, B; YOUNGQUIST, J.; KRZYSIK, A.M. 1994. Lignocellusic Composites. In:
Gilbert, RD. ed. Cellulosic Polymers, Blends and Composites. N. York: Hanser Publishers.
Chp. 6. pp.l15-130.
GOVERNO DO ESTADO DO PARA. 1993. Tecnologia de Produyao e Beneficiamento de
Fibras Naturais- Gerayao, Validayao, Difusao e Transferencia. Belem, PA. 22p.
JACOBSON, R.E.; RM. ROWELL; D.E. CAULFIELD. 1995. Mechanical Properties of
Natural Fiber/Polypropylene Composites: Dependence on Fiber Type. In: Proceedings Inside
Automotives ASBE'95 Conference & Exhibition. April25-27, Dearbom, Michigan, MI,
1995.5p.
LEAO, A.L. & N. TAVARES. 1995. Natural Fibers as Reinforcements for Plastics - The
Brazilian Potential and Perspectives. In: Woodfiber-Piastic Composites - Virgin and
Recycled Woodfiber and Polymers for Composites. May 1-3, Madison, WI, USA. 1995. 8p.
QUILLIN, D. et al. 1992. Surface Energy Compatibilities ofCellulose and Polypropilene. In:
Rowell, R et. al. Eds. Materials Ioteradions Relevant to Recycling of Wood-Based
Materials: Proceedings OfMaterials Research Society Symposium; 1992. Vol. 266. pp.113-
126.
SANADI, A.; R.M. ROWELL; R.A. YOUNG. 1993. Evaluation ofWood-Thermoplastic-
Interphase Shear Strengths. Journal ofMaterials Science, 28(6347-6352.
SANADI, A.; D.F. CAULFIELD; R ROWELL. 1994. Reinforcing Polypropylene with
Natural Fibers. Plastics Engineering, 50(4}:27, ApriV94.
SCHNEIDER, J.P. et al. 1994. Biofibers as Reinforcing Fillers in Thermoplastic Composites.
ANTEC/94 Proceedings, San Francisco, May 1-5, 1994.
ROWELL, R. et al. 1993. Results ofChemical Modification ofLignocellulosic Fibers for use
in Composites. In: Proceedings lst. Wood-Fiber Plastic Composite Conference; Madison,
WI. pp.121-127.
TORO IND. E COM. LTDA. s/d. Natural Fibers. Intemal Publication. 10p.
TORO IND. E COM. LTDA. 1994. Natural Fibers. Intemal Publication. 30P.
YOUNG, R. et al. 1993. Strength Properties ofComposites from Biobased and Synthetic
Fibers. In: Kennedy, J.F.; Phillips, G.O.; Williams, P.A. eds. Cellulose: Chemical, Biochemical
and Material Aspeds. New York: Ellis Horwood. Chapter 66.
YOUNGQUIST, J. et al. 1993. Agricultural Fibers in Composition Panels. In: Maloney, T.M.
ed. Proc. Of the 27th. International Partideboard Composite Materials Symp.; 1993,
Pullman, WA. pp.l33-152.
YOUNGQUIST, J. et al. 1994. Literature Review on Use ofNonwood Plant Fibers for
Building Materials and Panels. USDA Forest Service, Forest Products Laboratory, FPL-
GTR-80. Madison, WI, 146p.;
WEGNER, T.; YOUNGQUIST, J.; ROWELL, R 1992. Opportunities for Composites from
Recycled Wood Based Resources. In: Rowell, R et. al. Eds. Materials Ioteradions Relevant
to Recycling of Wood-Based Materials: Proceedings Of Materials Research Society
Symposium; 1992. Vol. 266. pp.3-15.
761
IMPROVEMENT IN SURFACE PROPERTIES OF LIGNOCELLULOSICS
USING COLD-PLASMA TREATMENT
F. Denes and R.A. Young

Engineering Research Center for Plasma -Aided Manufacturing and
Department of Forestry, University of Wisconsin-Madison
Madison, WI 53706
INTRODUCTION
Twenty-first Century technologies will require low cost, accessible and high
performance materials due to the following reasons:
Most of the components of future machinery will have to "survive" under extreme
conditions (thermal stability, mechanical strength, chemical inertness, etc.) while
meeting the miniaturization requirements;
Their bulk structures should be composed of low cost materials. The end of the
petroleum era at the beginning of the next rnillennium will "force" scientists to develop
new technologies and high performance materials based mainly on renewable
biomaterials;
Surface characteristics of these "hybrid" structures should exhibit properties which
would allow their use under extreme conditions. Light-weight, thermally- and
radiation-stable, chemically inert "skinned" materials will probably replace precious-
metal-based heavy and costly structures in space technology applications. Tailored,
special electrical and optical surface properties will also permit the creation of ultra-
miniaturized high speed circuitry. Molecular recognition will play a central role in future
technologies. Immobilized enzymes and oligonucleotides and other biologically
important macromolecules will Iead, in the next century, to the development of
molecular-selective technologies and to the creation of oligonucleotide libraries.
Unprecedented highways will open up on this way for the instant identification of
diseases and for the development of efficient novel therapeutics.
Composite structures should replace specific-materials-based-products for economical,
environmental and performance reasons. This approach will require novel surface-
compatibization technologies, in the absence of which, high performance composite
networks can not be prepared.

Lignocellulosics are the most significant renewable and biodegradable natural
polymeric resources. Their use in the synthesis and development of advanced materials will
totally be controlled by the effectiveness of novel surface functionalization approaches.
Cold-plasma chemistry has operred up highways for the synthesis of fundamentally
new macromolecular surface structures through deposition, grafting and surface
functionalization mechanisms. The energy Ievels of the active species in plasmas are
sufficiently high to dissociate a11 chemical bonds of organic and organometallic
compounds, and consequently the resulting multifunctional species can lead, through
recombination processes, to the formation of macromolecular structures. Plasma species
can also become attached to polymer substrate surfaces creating new functionalities and
characteristics. The possibility of modifying even the most inert inorganic- and organic-
material surfaces places macromolecular plasma chemistry in the sphere of advanced
technologies. Applications of this novel technique can be envisaged in the fields of
microelectronics (e.g. low dielectric constant layers, planarizing films), optics (e.g.
nonlinear optics, graded refractive index layers), barrier coating technologies (e.g.
controlled gas and liquid permeability, corrosion protection), mechanics (e.g. controlled
tribological characteristics) and biotechnology (e.g. enzyme and oligonucleotide
immobilization).
THE PLASMA STATE

The plasma state can broadly be defined as a collection of an equal number of
oppositely charged carriers with a net zero electric charge. It can be associated with the
high energy content of the matter; and it is consequently not surprising that that most of the
known Universe is believed to exist in the plasma state. All active celestial bodies,
including our sun, represent true plasmas. Interplanetary spaces are considered rarefied
plasmas, lightning, and the ionosphere are plasma states, as weil. Man-made plasmas can
be created by increasing the intrinsic energy content of the matter regardless of the nature of
the energy involved. Mechanical (e.g., shock waves), thermal, radiant and chemical
energies can generate plasma environments. Plasmas lose energy toward their surroundings
through radiation and collision processes, and as a result, energy must be supplied
continuously to the discharge in order to sustain the plasma state. The rate of ionization and
the rate of loss of ions and electrons must be equal. The most convenient way to supply
energy into a discharge in a continuous manner is with electrical energy; and this explains
why electrical discharges are the most common plasmas.
The degrees of ionization and the energies of plasma species allows the division of
the plasma state into two categories: 1) Hot plasmas (near-equilibrium plasmas),
characterized by high energy species including electrons, ions of either polarity, and by
high degrees ofionization (close to 100 %; total equilibrium can not be reached owning to
the radiant energy loss at the plasma boundary). 2) Cold plasmas (non-equilibrium
plasmas, glow discharges) are defined by much lower energy contents and very low
764
degrees of ionization (10"4-10' % ). The atmnic and molecular charged and neutral species
have low energies in this case, while the electrons have relatively high energies. These
energies are usually expressed in energy or temperature units (1 eV = 11,600 K) based on
the kinetic theory (E, = 112 mv /2 =3/2 kT; where m stand for the rnass of the molecule , v2
2
for the mean square velocity, k for the Boltzmann's constant and T for the absolute
temperature). The rnass of electrons are considerably smaller than those of molecular and
atomic species, therefore their velocities and consequently their kinetic energies are much
higher in comparison to ions, excited species or free radicals. Due however, to the low
heat capacities of the electrons these energies will not raise significantly the temperatures of
the surfaces which Iimit the discharge.
Electric energy sustained cold plasmas are initiated when in a low pressure gas
environment, omni-present free electrons (e.g. cosmic ray's created free electron) are
accelerated by electric or electrornagnetic fields to kinetic energy Ievels when continuously
sustained ionization, molecular fragmentation and excitation processes occur. Cold plasrnas
are characterized by the simultaneous presence of electrons, ions of either polarity, neutral
atoms and gas molecules, molecular fragments (e.g. mono- and multiple-free-radicals) ,
and their corresponding excited species, and photons.
Plasma Characteristics
Plasmas are characterized by the following main parameters: mean free path, Debye
length and plasma temperature. The free path is the distance a particle traverses between
two successive collisions, and due to the probabilistic nature of the collisions, it has a
specific distribution.
The electrical neutrality of a plasrna is true only in a macroscopic sense. The electric
field of each particle interacts with the electric fields of surrounding particles. A global
neutrality is only achieved when the field of each particle is negligible outside of plasrna
zone. The parameter at which the potential of each particle is shielded by the electric fields
of the surrounding particles is called the Debye length, and it defines the volume (Debye
sphere) in which the neutrality rule can be violated. Consequently, an ionized gas is
considered a plasma only if the Debye Iength is much smaller than the physical dimensions
of the plasrna region and if the number of particles within the Debye sphere is much larger
than unity.
Plasma temperature is the mean translational energy of the particles in the discharge.
Due however to the substantial mass differences between the electrons and heavy species
these particle populations can be considered as two systems in their own thermal
equilibrium. Due to the probabilistic nature of the collisions, electrons and charged and
neutral molecular species have specific energy distributions.
Since field-accelerated-electrons initiate all plasrna processes their temperature
Ievels, densities and energy distributions are the most important characteristics. The
electron energy distribution of non-equilibrium plasrnas can be described by a Druyvesteyn
approximation (Figurel) when the temperature of the electrons is considered much higher
that that of ions, and when it is assumed that the only energy Iosses are by elastic
165
0.25
~
t:; 0.2 3eV
ri
!u -----5eV
111
c 0.15
j
J
i 0.1
: ,
I ...
j

... ....
I
0.05
I
--- -
00 5 10 15
Energy, E/eV
Figure 1.
Druyvesteyn electron energy distribution for I eV and 5 eV average electron energies.
collisions. One can observe that a small number of electrons have a relatively high energy
range (5-15 eV) while most of the electrons belong to a low-energy domain (0.5-5 eV).
Since the primary ionization potentials of the atoms of common organic structures are in the
range ofthe tail section ofthe electron energy distribution function (e.g. c+ = 11.26; W =
13.6; o+ = 13.6; N+ =14.53, etc.), the low degrees of ionization of cold plasmas are
critical.
However, the energies of most of the cold-plasma electrons (0.5-5 eV) are high
enough to dissociate almost all chernicallinkages involved in organic structures (Tablel)
and to create mono- and multi-free radical species capable of reorganizing into ''micro" or
macromolecular structures.
Plasma Reactors
Most of the plasma reactors used for the synthesis of macromolecular structures and
surface modification of polymeric substrates are radio frequency (RF) installations. These
discharges can be excited and sustained even by using insulated electrodes located inside or
outside ofthe reaction chamber. They can be capacitively or inductively coupled and both
the reactors and the electrodes can have various geometrical configurations (Figure 2).
These are important features relative to DC discharges because dielectric depositions on the
electrodes and on the walls during the plasma reactions do not influence significantly the
regime of the discharge. RF-plasmas can also be operated at lower pressure conditions and
have higher ionization efficiencies than DC discharges. The flux direction and energies of
charged particles of RF plasmas can conveniently be controlled by adjustable negative bias;
while, these possibilities are lirnited by the breakdown voltage in the case of DC plasmas.
766
Table 1. Bond energies and enthalpies of formation of free radlcals*
Bond energies Enthalpies of formation of free radleals

Species Energy/eV Species Energyin Energyin
kJmol' eV
Diatornie molecules:
C-H 5.3 CH: 596.3 6.1
C-N 7.8 c~: 430.1 4.4
C-CI 4.0 C~ 146.0 1.5
C-F 5.7 HC=C 566.1 5.8
C=O 11.2 HC=C~ 300.0 3.1
C-C 6.3 NH: 352.3 3.6
Polyatomic molecules:
C=C 7.6 N~ 185.4 1.9
c.. c 10.0 :si: 456.6 4.7
CH3 -H 4.5 Si Cl: 195.0 2.0
<;H 5-H 4.3 SiCI 2 : -163.0 -1.7
CH2CH-H 4.8 SiCI 3 -318.0 -3.3
CHC-H 5.7 C6Hs 328.9 3.4
C6Fs -547.7 -5.0
*Handbook of Chemistry and Physics, 75th ed., CRC Press
RF
y
()) ) ([)) 0 ~llllll~)
RF
lnductivaly couplad glass-raactor
outsida-coil configuration
RF RF
Capacttlvely couplad paralle~

plata, inside-alectrode stainlass
steel reactor configuration
RF RF
Capacitivaly couplad glass-raactor lnductivaly coupled, planar

outside-electroda configurations outside-alsetrode stainlass steal
reactor configuration
Figure 2.
Inductively and capacitively coupled RF-plasma reactor configurations.
767
However, due to the extremely high diversity of RF electrode and reactor
configurations and to the large variety of geometrical locations of the electrodes in the
reactors and those of the substrate holders and deposition areas, comparison of
experimental results from different plasma installations are often difficult.
RF-plasma ruscharges involved for surface modification of various natural and
synthetic polymeric substrates are usually operated in the following extemal-plasma
parameter range: RF-power dissipated to the electrodes: 50-500 W; pressure in the reactor
in the presence ofplasma: 100-600 mTorr;
RF-PLASMA TREATMENT OF LIGNOCELLULOSICS
Lignocellulosics are the most significant renewable natural polymeric resources.
They include wood, jute, agricultural crops, grasses etc., and they are natural composites
built up of cellulose and Iignin. These materials are lightweight, strong, abundant,
biodegradable and relatively inexpensive which mak:es them ideal components for creating
advanced materials in conjunction with synthetic polymers. High lignocellulosic-content
composites combine the attributes of natural macromolecules (e.g. supramolecular order,
non-hazardous, renewability, etc.) with the chemical inertness, processability, high tensile
strength, etc., characteristics of the synthetic Counterparts. However, some composite
properties are reduced due to their dissimilar nature. Conventional approaches to
compatibilize or to functionalize these materials are expensive, heavily polluting and may
Iead to desaggregation of the supramolecular structure of the components.
Cold plasma conditions offer an unique way for efficient surface modification
(functionalization, grafting) of these dissimilar materials without altering the desired bulk
characteristics. The interaction of the active species of a plasma with polymer surfaces
involves in addition to the electron mediated processes (electrons play the most irnportant
role for driving chemistry in the plasma state), positive ion-induced reactions. Valence
ionized polymer chains from the action of 'heavy' charged- and neutral(excited)-species
lead, through neutralization reactions, to energy concentrations localized on
macromolecular chains (electronically excited states) which can promote homolytic bond
cleavages leading to the forrnation of free radical sites. These reactive centers lead to a large
variety of functionalization mechanisms depending on the reaction environments under in-
situ or ex-situ plasma conditions.
The predominant component of lignocellulosics is cellulose, therefore an
understanding of the plasma induced reaction mechanisms developed on various cellulose
substrate surfaces would be the logical frrst step for evaluation of the efficiency of plasma
chemistry for modifying lignocellulosic materials.
All plasma treatments of cellulosic substrates discussed in this paper have been
performed in a parallel plate, capacitively coupled, cylindrical, stainless steel, 30 kHz-RF-
plasma installation described earlier [1, 2].
Generation of High Surface Energy Cellulosic Substrates
This approach is generally directed to create polar functionalities other than
hydroxyl groups on cellulose substrate ( fibril) surfaces. Cellulose is built up of -D-
768
mc-oH D 0-C-0 Re-c-o l 0-C=O mo-co-o
(C=O)
Control sow 100W 300W soow

Argon Plasma Power (W)
Figure 3.
Percent surface areas of non-equivalent Cls carbon peaks from untreated and 50, 100, 300
and 500 W argon-plasma treatred cellulose (Whatman paper) substrates.
CH2 -0H THcOH

I
--o c--o o-- --0 c- 0 o-
\/~
c
\/
c _....:A..::.r_-J~
\I~
C
\I C
H
/\?" C--C
~i\H
Plasma
/\?-
H C
H H
I
C
\ H
I I I I
H OH H OH
CH 2 -0H CH 2 -0H
I ,-------.. I ,-------..
--o c- o o- --o c- o o-
\/~
c
\/
c
\/~
c
\/
c
/\?" ~ ~ /\?"c - ~c ~
" er- w
H 0
H
I
H
I
OH
Figure 4.
Suggested reaction mechanism for argon-plasma induced rnnolecular fragmentation of
cellulose.
769
Power= JOOW
Time= Imin.
-o-c-c
-<>- C-OH +C-0-C
0 0-C-0
----
-6--0-C=O
-- -IB--- 0-COO
.()0
o-
..
... .a.....
C
--~
------------~-----------;~-----~-----18-----iB
0~----------------r-------------~-----------------r------------~
!50 200 250 300 350
Pressure [mT]
Untreated
Figure 5.
Influence of pressure on the percent concentration of non-equivalent C 1s carbon linkages
from argon-plasma treated (100 W, 1 minute) cellulose.
glucopyranose rings with dominant hydroxyl groups which are very appropriate units for
functionalization reactions. However, the reactivity of these groups is strongly dependent
on the origin of the cellulose substrate and on its preparation history. The relative ratios of
crystalline and amorphous regions of the cellulose superstructure, determined primarily by
hydrogen bonding, control the accessibility of the OH groups [3]. The reactivities of
primary and secondary hydroxyls are also microstructure dependent. Both conventional
(e.g. chemical) and plasma techniques used for derivatization reactions are believed to
modify selectively the crystalline and amorphous topographies of cellulose. Chemical
reactions occur preferentially, for instance, at the surfaces of cellulose fibrils owning to the
nature of the polymer matrix.
0 2- and Ar-plasma treatment of Whatman fllter paper indicate that identical surface
functionalities are created but through different reaction mechanisms [ 4-8]. Relative
percent surface areas of non-equivalent carbon peaks of high resolution ESCA data
770
collected from argon-plasma treated sarnples, indicate that the trimodal pattem characteristic
for unmodified cellulose is replaced by a pentamodal structure (Figure 3). In addition to
the peculiar C-OH, C-0-C (286.6 eV) and 0-C-0 (288 eV) cellulose peaks, the existence
ofO-C=O (288.7 eV) and 0-C0-0 (290.4 eV) binding energy peaks can also be noticed.
Plasma induced surface modification even at higher RF-powers involve mainly the
diminution of 0-C-0 linkages of the pyranosidic unit through the cleavage of C 1-C2 bonds
(Figure 4). The formation of ketone or aldehyde functionalities as a result of the ring
opening process, demonstrated by high resolution ESCA data from Ar-plasma treated and
pentafluorophenylhydrazine-derivatized samples (the presence of fluorine atoms in the
surface atomic composition) substantiate the suggested reaction mechanisms. Certainly, the
oxidation processes of Ar-plasma treated substrates are related to plasma-created free
radicals which initiate oxidation reactions under open laboratory conditions.
Oxygen-plasma treatments of cellulose at various powers ( 100, 200 W) and
pressure (150-325 mT) similarly resulted in the formation of new 0-C=O; C=O and 0-C0-
0 functionalities on substrate surfaces. However, in this case C-OH and C-0-C linkages
are involved in the plasma induced reaction mechanisrns (Figure 5). It was suggested
that the relative increase of 0-C-0 concentration is related to the dirninution of C-OH and
C-0-C concentrations. The intensified reaction mechanisms involving C-OH and C-0-C
groups at higher pressure values were suggested to be associated with crosslinking
mechanisms. High resolution ESCA data collected from pentafluorophenylhydrazine-
derivatized sarnples also indicate the presence of C=O functionalities. This is a significant
finding because it is known that the presence of carbonyl groups on polymer surfaces play
an important role in improving adhesion at interfaces.
Halo-silicon ( e.g.Si,Cly) plasmas are of particular interest for creating high energy
polymer surfaces and surface graft-polymer layers. Molecular fragments of these
compounds (e.g. free radicals) and especially their silylium ions are extremely reactive due
to the existence of trigonal planar structure (e.g. SiCl 3+), for instance, to the large size of
silicon atom and to the presence of d orbitals in the atomic structure of silicon which allow
the extension of the valence of Si beyond four. Implantation of SiCl, functionalities into
polymer substrate surfaces allow the spontaneaus generation of Si(OH)x functionalities in
moisture environment or the initiating of graft-polymerization reactions in the presence of
"silicon monomers' (e.g. dimethyldichlorosilane). It has been shown in earlier studies that
silylium ions can conveniently be generated under SiC14- and Si 2Cl 6-RF plasma conditions,
and that these species are sufficiently active to functionalize natural polymeric substrates or
even inert synthetic polymers, like polypropylene and Teflon [9-11].
Comparative ESCA and contact angle evaluations performed on SiC14- and 0 2-RF-
plasma treated security paper [5] clearly indicate that silicon atoms are incorporated into the
surface structures of SiC1 4-plasma modified substrates (Figure 6) and that both the
presence of silicon/oxygen- and carbon/oxygen-based functionalities are responsible for the
very low contact angle values (Figure 7, 8, 9, 10). It was demonstrated that relatively
low RF-power values (60-70 W; electrode diarneter: 20 cm; gap: 3 cm) and treatment times
771
292 291 290 289 288 287 286 285 284 283 282
292 291 290 289 288 287 286 285 284 283 282
292 291 290 289 288 287 286 285 284 283 282
Binding Energy (eV)
Figure 6.
Highresolution ESCA diagrams of untreated and 1 and 5 minutes SiC14-plama treated
cellulose.
(30-40 seconds) are sufficient for achieving very low contact angles.
Generation of Low Surface Energy Cellulosic Substrates
Many applications of lignocellulosic-based materials are limited due to their
hydrophilicity. Composite-material preparations from thermoplastics and natural polymeric
components also are difficult because of their dissimilar nature. Plasma chemistry opens up
new ways for creating hydrophobic lignocellulosic surfaces.
CF4-RF-plasma exposure of security paper results in the surface irnplantation of
CFx functionalities, and as a result, contact angles higher than 100 degrees can be generated
[5] (Figure 11). Low power values ( 60-80 W) and extremely short plasma exposures
(10-50 second) arehigh enough to generate totally hydrophobic surfaces.
772
...
Cl
10
GI t-:1
=~
c 10
!C\1
li~
CIO
8
-
Cl
10
Figure 7.
Response surface of contact angle for SiCl4-plasma treated security paper (Factor time is
fixed at 52 seconds).
N
N
N
Cl!
ie~
0~
1\!
CD
c:i
Figure 8.
Response surface of Si/C for SiCl4-plasma treated security paper (Factor treatment time is
"Plasma-polymers" deposited from hexamethyldisiloxane (HMDSO) on cellullose

or wood surfaces, or generation of Teflon-like structures on lignocellulosic surfaces
through ring-opening mechanisms by starting from cyclic perfluoro compounds (e.g.
C6F 12, Cuf 18, etc.) isanother way to generate low surface energy lignocellulosic surfaces.
It was demonstrated that the water up-take of Whatman filter paper is dramatically reduced
as a result of HMDSO-plasma exposure, and that treatment times as low as 10 seconds
have a tremendous effect (Figure 12). Cyclic, perfluoro carbon derivatives result, under
773
Figure 9.
Response surface of contact angle for 0 2-plasma treated security paper (Factor time is ftxed
,
at 50 seconds).
_____........_............ ..............
Cll
ci
. ...............----
.,."-
I
:
............ .......
~~
-~
"":
c
Cll
8~ci
...ci --~~~-~ i
'
~
Figure 10.
Response surface of C/0 for SiC14-plasma treated security paper (factor treatmenttime is
RF-plasma conditions, in high fluorine content (>60 %) Teflon-like coatings with a

predominant CF2 content (Figure 13), [12]. However, these structures contain
significant quantities of CF and CF 3 groups as well. These coatings are very uniform
(Figure 14, 15) and exhibit contact angles around 120 degrees.
Creation of Tailored Surface Roughness Lignocellulosic Substrates
All plasma treatments alter the surface morphologies of polymeric substrates. This
is significant because increased surface roughness usually enhances adhesion
characteristics. In the case of quasicrystalline structures (e.g. cellulose) surface
topographies are selectively etched depending on the amorphous/crystalline surface
regions. Ten minutes oxygen-plasma exposed cellophane, for instance, clearly exhibits the
ordered regions (Figure 16, 17). Amorphous regions are more intensely ablated in
714
Figure 11.
Response surface of contact angle of CF4-plasma treated security paper (Factor time is
60~----------------------------~
20
-o-o-o
10
I
~8=8=8-o-o-a
--6--6 __ 4 __ 6 __6
0~~----~------~------~----~
0 10 20 30 40
Elapsed Time (minutes)
c Untreated Filter Paper

o 30 seconds
o 2minutes
4 10 minutes
Pressing Force: 200 grams
Figure 12.
Water uptake ofuntreated and hexamethyldisiloxane-plasma treated filter paper.
775
CF2 (291.7 eV)
297 296 295 294 293 292 291 290 289 288 287 286 285 284 283 282
Binding Energy (eV)
Suggested structures:
(a > 1)
Figure 13.
High resolution ESCA diagram of C6F12-RF-plasma treated paper, and the suggested
structure of the macromolecular layer.
Figure 14.
AFM image of untreated Whatman filter paper.
776
0 3,00 IJI
Data type AMPI i tude
2 range 7.00 nM
Figure 15.
AFM image of C6F 12-plasma coated Whatman filter paper.
2.00 IJM
Figure 16.
AFM image of untreated cellophane.
comparison to the crystalline zones due to their densely packed nature. Recently it has been
demonstrated that plasma-enhanced-crystallinity cellulosic Substrates can mediate template
polymerization reactions [8, 13,14]. This opens up new highways for creating ordered
polymeric layers on natural polymeric surfaces.
Continuous-flow-plasma-system and high capacity rotating plasma machines (pilot
777
2.00 j.llt
Figure 17.
AFM image of 10 minutes oxygen-plasma treated cellophane.
scale installations) have already been designed and developed. This will allow scaling up
laboratory plasma technologies and the development of novel approaches for improving
surface characteristics of natural and synthetic polymeric substrates.
CONCLUSIONS
Cold plasma treatments have been shown to be an efficient method for modification of
lignocellulosic materials for a wide variety of uses. Initial investigations were carried out
on cellulose samples to evaluate the effects of argon and oxygen plasmas on the surface
properties of the pure cellulose. ESCA analyses indicated oxidation and ring splitting
mechanisms at the cellulose surface both with oxygen and argon plasma treatment.
Treatment of cellulose paper with these plasmas was found to enhance the adhesion of ink
applied to the plasma-treated surfaces. Implantation of silicon chloride functionalities with
a silicon tetrachloride plasma also created a very reactive surface. The contact angles of the
silicon tetrachloride and oxygen plasma treated cellulose were drarnatically reduced
indicating enhanced hydrophilicity. In contrast, hydrophobicity was drarnatically increased
by treatment of the cellulose paper with a carbon tetrafluoride plasma. Treatment with
cyclic, perfluorocarbon derivatives resulted in high fluorine content, Teflon-like structures.
In addition to the chemical modification, the plasma treatments were found to create
increased surface roughness, which may be related to preferential removal of amorphous,
as opposed to crystalline, regions of the cellulose surface. Clearly, cold plasma treatment
of lignocellulosics offers a wide variety of options for creating high-tech rnaterials from
renewable, natural products.
778
REFERENCES
1. A.M. Sarmadi, T.H. Ying, and F. Denes, Eur. Polym. J., 31(9), 847 (1995)
2. M. Sarmadi and F. Denes, TAPPI Journal, Vol. 79, NO. 8, 189 (1996)
3. S. Tasker and J.P.S. Badyal, Polymer, 35(22), 4717 (1994)
4. Z.Q. Hua, R. Sitaru, F. Denes, and R.A. Young, Mechanism of Oxygen- and Argon-
RF-Plasma Induced Surface Chernistry of Cellulose, Plasmas and Polymers (subrnitted
for publication in August-1996)
5. F. Denes, Z.Q. Hua, E. Barrios, J. Evans, and R.A. Young, J.M.S.-Pure
Appl.Chem., A32, (8 & 9), 1405 (1995)
6. R.A. Young, X. Tu, and F. Denes, Cellulose, 1, 87 (1994)
7. F. Denes and R.A. Young, Cold Plasma State-A New Approach to improve Surface
Adhesion of Lignocellulosic Substrates, in Proceedings of Wood Adhesives-1995,
Sponsored by: USDA Forest Service, forest Products Laboratory, and The Forest
Products Society, Eds. A.W. Christiansen and A.H. Conner, Forest Products Society-
Proceedings No. 7296, p. 61-74 (1996)
8. L.D. Nielsen, PhD Thesis: A Comparative Study of Plasma-Induced Polymerization
and Plasma-State Polymerization of Acrylonitrile for Modification of Cellophane, UW-
Madison, Department ofForestry (1995).
9. Z.Q. Hua, F.Denes, and R.A. Young, J. Vac. Sei. Techno!., A 14(3), 1339 (1996)
10. F. Denes, Z.Q. Hua, C.E.C.A. Hop, and R.A. Young, J. Appl. Poly. Sei., 61, 875
(1996)
11. F. Denes, AR. Denes, and J.P. Kennedy, J.M.S.-Pure Appl. Chem., Polymerization
of Isobutylene by RF-Plasma Generated Cl,St Silylium Ions (accepted-1997)
12. Z.Q. Hua, D. Holm, P. Gatenholm, R. Rowell, and F. Denes, Hydrophobization of
Paper under Cyclic-Perfluorocarbons-RF-Plasma Conditions, presented t the Cellulose
Paper, and Textile Division ofthe 213th ACS National Meeting, San Francisco, April
13-17 (1997)
13. F. Denes and R.A. Young, Surface Modification of Polysaccharides under Cold
Plasma Conditions, in: Structural Diversity and Functional Versatility of
Polysaccharides, Editor: S. Durnitriu, Marcel Dekker (in press-1997)
14. F. Denes, L.D. Nielsen and R.A. Young, Cold Plasma State-A New Approach to
Improve Surface Adhesion in Lignocellulosic-Plastic Composites, Proceedings of the
First International Symposium on Composites Based on Lignocellulosics and Plastics,
March 13-15, 1996, Sao Paulo-Brazil, Eds. A. L. Leao, F. X. Carvalho, and E.
Frollini, UNESP, p.61 (1997)
779
TUE PETROCHEMICAL INDUSTRY AND NATURAL GAS
A Strategie Alliance
Jasern M. Al-Besharah
Division of Petroleum, Petrochemieals & Materials

Kuwait Institute for Scientific Research
INTRODUCTION
The petrochemical industry in the Gulf region has gained more momentum during the
last decade, whereby many major enterprises have either been newly established or expan-
sions on existing plants have been achieved. The development of the Gulf petrochemical in-
dustries over the past fifteen years or so has been a major success story. A world class industry,
competing successfully in international markets, has been created from scratch, and regional
Companies such as SABIC are known and respected world-wide.
This move has been successfully driven by the willingness of the GCC countries (a) to
diversify their income sources, so that to be able to overcome the main hurdle against long
term strategic development programs, that is the single source economy which heavily de-
pends on the sales of crude oil and refined petroleuro products; and (b ): to maximize the added
value from the natural resources, particularly the natural dry gas, LPG and Naphtha. In addi-
tion, the GCC Countries have many encouraging advantages that support the growing momen-
tum ofthese countries to go forward in the chemical industry. These include the followings:
1. The availability of relatively low cost feedstocks, especially the natural gas and the
light petroleuro products. This is considered the main driving force for any invest-
ment in this industry which strongly affects the economic feasibility of any petro-
chemical plant.
2. Low cost energy, whether in the form of electricity or fuel: Although in most ofthe
cases the energy is subsidized, yet, taking in consideration the present pricing poli-
cies, it is considered relatively eheaper than in many other regions.
3. The distinguished geographicallocation of the region has a direct impact in en-
hancing the competitiveness of the petrochemieals products in the International
markets.
4. The availability ofthe financing capabilities in the region encouraged both the gov-
emmental and the private sectors to invest in this industry, and to attract foreign in-
vestors, as weil. However, most ofthe initiatives that have been made are from the
States Govemments, which were mainly directed to the upstream industries and the

maga-size enterprises. Therefore, there is more room for stronger contribution
from the private section the region, which should play a bigger roJe in this growing
industry, particularly in establishing medium and small size enterprises for the
downstream and finished products.
5. The availability ofthe necessary infrastructure such as exporting facilities, water,
electricity, and other logistics. No doubt that the prime location ofthe GCC coun-
tries directly on the Gulf and the Red Sea facilitates the different national and re-
gional projects to strengthen these infra-structures or to improve the efficiency of
the utilization ofthe available facilities; which in turn positively affects the com-
petitiveness of the GCC Petrochemical Industries.
6. Most ofthe petrochemical plants that are existing at present, under construction or
planned tobe established are highly integrated with the existing LPG plants andre-
fineries. This of course, improves the economics of the plants and increases their
flexibility in logistics utilization.
7. Adequate capital and govemment incentives: In addition to the low pricing of raw
material, GCC Govemments have been encouraging the petrochemical develop-
ment in the region by offering various attractive incentives such as low utility
prices, soft loans, low land rents, relaxed taxation legislations.
8. A preferable economy of scale: The existing petrochemical industries or the ones
under consideration are, in general, !arge production plants, with the latest technol-
ogy resulting in substantial reduction in production cost, which gives the competi-
tive edge on this cost.
In addition, the increasing tendency of the petrochemical industries in the region to
obtain the needed technologies has even strengtherred the advantages mentioned before. This
is achievable through either joint venture projects or licensing agreements. However, there is a
growing momentum in the local concemed R&D institutions to build their indigenous techno-
logical capabilities. SABIC R&D center in Riyadh and KISR in Kuwait are good successful
examples.
lt is also worthwhile mentioning that the previous accumulated experience ofthe GCC
countries in marketing their crude oils, down-stream petroleum products and fertilizers prod-
ucts, participated in encouraging the States Govemments to invest in new petrochemical proj-
ects.
PETROCHEMICAL PRODUCTS
Petrochemieals are chemical compounds of different chemical structures manufac-

tured from the natural gas or petroleum products. Those feedstocks are vigorously treated in
high tech chemical plants whereby complexed chemical reactions take place, which at the end
produce wide range of chemieals that are of various applications.
The petrochemieals are generally classified into three main categories: Basic, Inter-
mediate and Finished or Downstream Products
1. The first category, Basic products (and sometime called main building block) in-
cludes:
a. Olefins : such as ethylene, propylene, butadiene, butene.
b. Aromatics: such as Benzene, Toluene, 0-xylene, P-Xylene.
c. Alcohols : such as Methanol, Ethanol
2. The intermediate products include many other products that are manufactured
from the basic products such as ethylene, glycol, styrene, ethylene chloride and
others.
782
3. The Down-stream products are manufactured either directly from the basic prod-
ucts or from the intermediate ones. This includes polymers such as polyethylene
(HDPE, LDPE, LLDPE), polypropylene, polystyrene, PVC and others. These
products can be molded, extruded or blown to form different finished consumable
commodities or products of industrial applications such as paints, detergents, insu-
lating materials and other plastics.
Figures 1-5 demoostrate the structure building blocks ofthe petrochemieals starting
from the natural gas and petroleuro to the downstream applications.
Petrochemical/Chemical products are highly diversified in their applications. They
are used nearly in every commodity and industry discipline. The main applications of the pet-
rochemical products are summarized in Figure 5.
The interesting feature ofthese chemical compounds is that, ifthe chemistry allows,
they can be engineeringly structured in order to meet different specifications, even for the
same compound. This phenomena gave these compounds advantageous over many other ma-
terials that do not have this flexibility ofthe molecular structure. This bad widerred their appli-
cations; and attracted many researchers all over the world to explore more combinations of
those compounds either by molecu1ar restructuring or by blending. This resulted in continu-
ous expansions in the applications ofthe petrochemical products.
In order to illustrate this phenomena we will examine the polypropylenepolymer which
is a plastic material produced from the polymerization of propylene gas obtained from natural
gas. Figures 6 and 7 demoostrate how the properties ofthe polypropylene can be changed by
simply changing the position ofthe methyl (CH3_) group in the molecule chain. This is a power-
ful tool enable the manufacturer to produce wide range of products of different properties.
THE FEATURES OF THE PETROCHEMICAL INDUSTRY MARKET
The chemical/petrochemical industry, world wide, has grown rapidly over the last
fifty years. The widespread use of natural gases and petroleuro products in manufacturing
chemieals first began in USA during the second and third decade of this century.
Traditionally, USA, Western Europe and Japan were the main producers with varying
tendency in the usage of natural gas or naphtha as feedstock. The main markets at that time
were the same regions, since they were experiencing a strong growth in chemical products
utilization particularly the new magic materials, plastics, that were ofwide range of applica-
tions. However, during the 1960's and 1970's new ernerging markets, namely Far East, started
to play a remarkable role in promoting the business of the main producers.
During the 1980's the chemical industry went through a fundamental change. The tra-
ditional producers--USA, W. Europe and Japan consolidated their position, but major addi-
tions to world production capacity occurred more widely in other areas such as the Far East,
Middle East and some Latin America Countries. This change was strongly enhanced by sev-
eral factors, which can be summarized as follows:
1. The desire of some major oil producers, (such as GCC countries, Mexico, Iran,
Venezuela), to maximize the added value oftheir natural resources before export.
2. The growth of consumption capacity in a few !arge, developing countries such as
China, Irrdia ... etc.
3. The tendency ofthe countries ofeconomy in transition, especially in South East
Asia, to reduce their import bills.
4. Exploitation of natural gas reserves to secure attractive feedstocks, as in GCC
states, Canada, New Zealand, ... etc.
5. Saturation of the markets in many industrialized countries, which has encouraged
some European companies such as BASF, Hoechst, UCC and others, to Iook for in-
vestment opportunities in new markets.
783
-.1
~
~- ~----- --- l
Basic 1 Intermediate I Downstream --~
Oietins Ethylene
I
Ethylene Chloride
I
LDPE I
Propylene Ethylene Glycol LDPE
Butadiene Styrene HDPE
Butene Vinyl Chloride Monomer PP
Formaldehyde
Aromatics Toluene
L Di-Methyltrephalate
PVC
PS
Benzene Phthalic Anhydride Melamine
0-xylene Ethyl Benzene Polyester Fibers
P-xylene Ethylene oxide Styrene Butadiene Rubber
Propylene mcide Butadiene Rubber
Acetic Acid Alkyl Benzene
Acrilonitrile MTBE
ExAlcohol Poly Vinyl Acetates
Vinyl Acetates
1 ""hls 1 1 Mctrumol 1S
Ethanol
Figure I. Main petrochemical building blocks.

NATURAL GAS & PETROLEUM j
I
BASIC PETROCHEMICALS
INTERMEDIATE
PETROCHEMICALS
Figure 2. Applications of natural gas and petroleum.
-.I
00
Ul
Figure 3. Applications of methane.
6. Strong and sustainable economic growth in the area ofhigh population and market
demand such as in China, Korea, Indonesia ... and other Asian Countries
As a future forecast ofthe chemical industry, it is believed that although the industry
suffers from up and down market cycles, yet it is expected that over the next 10 years, the
global chemical industry will provide growth opportunities. The growth is expected to be
I Others
1----1 Polyethylene , _ !ID:.:D: . :~:. :i:_ _ ___.
c..:l
1----+ Ethylene Oxide

-
Ethylenedi
Chloride -
Ethyl Chloride 1-L..;ITE=L_ _ _ ---J
~----;{!jE~th~yDtB~ei!inz~ei!in~e=:JI-1 Styrene- P. S.
1---- Propionaldehyde 1-1 Propienie Acid
a..;E::.t:::h=an::.:o;:"l_ _ __.l-1 Ethyl Acetates
Figure 4. Applications of ethane.
786
Transparent sheets Nitocellulose & vin}l Disinfcctant Housewares Coatings Bowlingballs
Aircraft windows solvents Fibre Fumiture Adhcsi\'es Showerstalls
Police car glass 1nks Autornativeparts Appliance parts Film& Tape Cements
..
Stonndoors Magnetic tapes Film. wire, & cable Electronic component Molded products Buttons
.. Bath & shower Lube oil dewaxing coating Electric components Hoscs Autoparts
doors Rubber processing Food wrap Polishes Wheels & rollers Solvent
. Lighting fixturesPolycarbonates Molded products Dyes lnsulalion High octane gasoline
Autoparts Recrcational products Apparcl Rccreational products compounds
Transparent plaslics
.. Carpct Tubing Explosives
Molding & extruding Epoxy resins Oil additives Upholstery Fumiture Flexible foams
Talllight Jenses Engineering plastics Plasticizers Tire cord Pipe Bedding
Dials & knobs Flame retardent Agricultural chemieals Conveyor belts Tanks Cushions
.. ..
. Bathroom plumbing Resins PrcseJYalive for fats & Horne fumishings Simulated marlJle . Car seats
oils
Material Plpvood adhesive Latex paints Beverage botlies Gel coats RigidFoams
Bottles Chemicallntermediate Floorpolish Marine products lnsulations
Medical/dental Pigment disbursement Refrigerators
..
parts Packaging (food) Trucks & rail cars
...
Pharmaceuticals Coatings
Adhesives Marine
Benzene
I I-I - I I ~X) Jene
I Tolene
Paint thinner/cleaner Vamishes
..
Solvent
Fiber spinning IPropelene II Coal- Natural Gas- Oil
II I Ethylene
Proteelive coatings
1nks Metltane Butanes Butylenes Butadiene
... I I I II II II
. Paper coatings
Reaction solvent Automotive parts Oiladditives Footware

Textile dry cleaning Furniture Leather finishes Adhesives & cements
Fire extinguishing Appliances Paper coating Sealants
Meta! degreasing Dinnenvare Floor polishing Molded products
Grainfumigant Plastics High octane gasoline component & Latexfoams
Packaging Solvent oxygenate Latex paints
Autoparts Gasoline component Sealant Footware
Appliance parts Single cell protein Caulking compound Hoses & seals
Plumbing & hardware Chemical intermediate Adhesives Gaskets, belts & packing
Pens & pencils Windshield wash Paper manufacture Adhesives
Lightcrs Ethyle alcohnl denaluring 1nk manufacture Wire & cable coating
Shavers Surface coating Lobe oil dewaxing Coated fabrics
Molding compound Latex paints Tires & tire products Paints
Particle board adhesive Lacquer resins Hoses & belts Carpet backing
Foam insulation Enamel resins Rubber goods Cement additive
Paper coatings
-.l Figure 5. Summary ofmain applications ofpetrochemical products.

00
-.l
H H
X "C=C /
H/ 'H
Ethylene Polyethylene
"Monomer" "Polymer"
Propylene Polypropylene
"Monomer" "Polymer"
Figure 6. Illustration of the basis of the polymerization processes.
around 3.5%/year which will bring it to - 1.9 trillion dollar. Business in year 2005 from its
present Ievel - 1.35 Trillion Dollar, i.e. - 40% increase in size.
Figure 8 demonstrates the expected global demand on the chemical products based on
the geographical distribution. It shows that the Far East market will maintain its growth to in-
crease its share from 8% to 13% on the expense of other traditional markets such as Western
Europe of25%, North America of24%, and Japan of 14%. However, Western Europe and
North America will continue to predominate the market.
Type Structure Properties
lsotactic CH3 on same side

fal ofC C plane
Highly crystalline
Commercial product
CH3 on opposite
Syndiotactic sides of plane
(bl Highly crystalline
Not commercially
available
Atactic
H.,
c
~~H
f.r -~
c
CH 3
H., - ; - CH3
c
H
'J'
H
1 ~CH 3
c ....._
Jr
CH3 random distribution
Soft, rubbery
(c) ...----L-...._c~ -...._c.-- -...._c.--/ Solution in organic
/. 'H /_ 'H L 'H solvents
H H H
Wustrates polypropylene polymer types

Figure 7. Relationship ofpolypropylene structures and properties.
788
lsotactic Notes:
CH 3 H CH 3 H CH 3 H CH3 groups an same
I I I I I I
side of chain
Crystalline
---c---c---c---c---c---c--- granular solid
~ I I I I I Good physical
H H H H H H properties
Atactic
CH3 groups randomly
CH H H H H H positioned an both
I3 I I I I I sides of chain
- - c ---c ---c ---c ---c ---c --- Amorphaus
1 I I I I I sticky and stringy
H H CH 3 H CH 3 H Paar physical
properties
Polypropylene cbemistry
Figure 7. (Continued)
The expected evolution ofthe industry in the forecasttime span, will be driven by five
main forces:
I. Macro economic and political force; mainly:
Differing regional growth rates
Formation of free trade zones
Privatisation programs
2. Market Dynamics force; mainly
Maturing product and regional markets
More demanding customers
Globalisation of customers
2 1.9
Other areas
Other Far East

Eastern Europe
c:
g Japan
....
;:
(h
~ '!;: ..~-~ .
16%
~:.;.~ ~.~# 24% North America
25%
28% Western Europe

o~----~----------~-----------L-- ________ _ L_ __ __ _
1994 2005
Figure 8. Expected global demand for chemical products based on geographical distribution.
789
Tecbnical
Specialties
Syntbesised specialty products, e.g.

Flame retardants Formulated
Antioxidants products
Pharmaceutical intermediates
PVC stabilisers
Additives, catalysts
Formulated specialty products, e.g.
Water treatment products
Basic Difl'erentiated Cleaning products
Chemieals Commodities LubricantsAdhesives
Basic utility-like chemical Difl'erentiated Commodities

builcling blocks, e.g. prodacts, e.g.
Oietins Linearalkyl benzene
Chlorine PolystyreneiPVC/PET/PE Performance
Caustic soda Elastomers and resins Materials
Soda ash
Sulphuric acid
Fabricated products, e.g.
Forward Fluoropolymers
Commodities Acrylic sheet
BOPPfilm
Fibres
Non-difl'erentiated commodity
products, e.g.
Ethylene oxidelglycol
Urea fertiliser
Aromatics
Methanol
Figure 9. Industry segments.
3. Industry Economics; mainly:

Rising costs to compete.
Declining value added
Increasing importance ofraw material costs (particularly for the natural gas).
Growing shareholder expectations
4. Technology: mainly:
Increasing pace of innovation
Need to master more complex technologies
Revolution in information technology
5. Social issues; mainly:
Increasing environmental concem
Growing health and safety legislations
lncreasing population
Pursuit of improved life style
As a result, the market will drive the industry for globalization; and will dictate on the
operating companies tobe more competitive. This will force some companies tobe of global
business portfolio and to Iook for easier access to low cost feedstock, especially the Natural
790
Force Drivers
Differing regional growth rates

I. Macro economic/political Formation offree trade zones
Privatisation
Maturing product and regional markets

12. Market dynamics More demanding customers
Globalisation of customers
IJ. ~
Rising costs to compete
Industry e<onomics Declining value added
~
lncreasing importance of raw material costs
Growin' shareholder ex ectations
Jncreasing pace of innovation

14. Technology Need to master more complex technologies
Revolution in information technology
is. Sotial isslies

lncreasing environmental concern
Growing health and safety legislation
Aging population
Pursuit of im roved lifes.t le
Figure 10. Five forces driving the evolution of the industry.
Gas. This is believed to be achievable by going through joint venture projects for selected
products with the feedstock owners. The marketwillalso force the major players tobe able to
market worldwide. Consequently, the Gulf region is expected to experience more joint ven-
ture projects with international mega-companies, such as the case of PIC/UCC EQUATE
project in the State ofKuwait.
The companies will also be forced tobe very responsive to market needs, and to intro-
duce new grades oftheir traditional products or brand new products and specialty chemicals;
which in turn may result in the introduction of new good process technologies, as weiL Conse-
quently, the companies will have to invest more in more focused applied R&D.
PETROCHEMICAL FEEDSTOCK: A STRATEGIC POINT
Although the amount ofNatural Gas used as feedstock for the petrochemical industry
is relatively small (around 10-15% world wide) compared with other usages particularly as
fuel andin power plants, yet the share of petrochemical industry in the Natural Gas utilization
is expected to increase exponentially, as the business size is expected to increase.
As has been described before, olefins (particularly ethylene and propylene) constitute
the main building blocks of the petrochemical industry. The two significant feedstocks for
olefin production areNatural Gas and Naphtha. The economics of olefin production and its
connections with its feedstock is one ofthe most strategic aspects oftbis industry. Despite the
huge complexity of the industry, this particular sector can be used to exemplify the type of
problems, options and decision-making variables that it contains, with respect to the feed-
stocks. 1t shows also the intrinsic linkage between this industry and the Gas & Petroleum In-
dustry.
The diagram shown in the Figure II simplifies the main unitary processes involved in
petrochemical feedstock production from natural gas and crude oil.
For produces of olefins, for example, the dehydrogenation of ethane or propane gas,
extracted from LPG, that takes place in the ethane cracking unit is much more attractive than a
791
Others
Naturalgas
,.. -- -- -------
Methane
- -----------..
Ethane
Natural
gas
Propane
liquid$ I
(Ethane.
propane,
butane)
LPG
I II
I
I
II
II
.J
II
Liquid petro leum gas (LPG )
II
II

(Propane, butane)
Ethylene

--- .,
Naphtha
I
II
II
II Propylene
Propylenes
I I
Gasoline I
Crude oil
01
c:
'5
c:
Q)
Medium
!I
Oisullates :
"C
Gasoline c:
ca
Fluid c:
-
Catalytic .Q I
Cracking ~ c4
,g I
. H=:v ygas ':l:l
0.
Atmesphene
gasoll
Others
wax
Figu re 11. Main unitary processes

involved in the production of petrochemical feeds
tock from natural gas and
crude oil.
792
cracker that uses naphtha as a feedstock. The chemistry is more selective and favourable to
produce high er yield ofhigher purity ethylene orpropylene gas for the polyolefins industry.
However, Naphtha cracking units also produce ethylene and propylene gas, but of
lower yield; together with other by-products, which require more vigorous high cost separa-
tion treatment. Consequently, the cost per unit of olefins production increases, which reflects
on the economics of the petrochemical plants under consideration.
Thus, it is always a strategic decision tobe tak:en by the petrochemical manufacturers:
which industry is more profitable?? Natural Gas or Naphtha based industry? The answer de-
pends heavily on the availability ofNatural Gas supplies ofpreferable composition.
On the other hand, for a C 1 petrochemical plants which produce methanol and its de-
rivatives, it is always the choice between dry Natural Gas (of70% to its constituents methane)
and LPG that contains less amount ofmethane as feedstock. Usually, the size ofthe plant de-
termines which route to go with.
The oil refining consists of several unitary processes designed to breakdown the com-
plex mixtures of substances and chemical functions into its constitutes. Most refineries have
conversion processes to crack the !arger molecules into a mixture of smaller ones. Fluid Cata-
lytic Cracking (FCC) is one of the main cracking units of interest.
The border between the petrochemical and oil industries is "steam cracking". This
process is used to produce some ofthe main basicpetrochemieals such as ethylene and propyl-
ene among others. As shown in the Figure 11 the main feedstocks to this process are ethane,
propane, naphtha and gas oil. The choice of one or more ofthese feedstocks is a major strate-
gic decision. The seasonal characteristics of these products, however, add some more com-
plexity to the equation. Usually, the gasoline demand exceeds the supplies. On the contrary,
heavier products, mainly fuel oils, are present in a much high er proportion than their demand.
Therefore, FCC is used to increase the refineries yield of gasoline and producing by-products
such as catalytic gas oil and liquefied petroleum gas (LPG). As the consumption of gasolinein
the northem hemisphere is greater in summer than in winter, the FCC operation peaks in the
early summer, fueled by gasoline price rises. As a Counterpart, gas oil and LPG prices fall as
they are over-produced. Thesevariations in price and demand became more accentuated dur-
ing the last few years following the phasing out of leaded gasoline which requires a !arger
amount ofnaphtha tobe reformed in order to produce the high-octane gasoline. In such a case,
a petrochemical cracker wanting naphthawill need to bid above its premium value in gasoline
production. On the other hand, when wanting LPG it will buy a likely surplus at low cost.
In the United States the volume ofnatural-gas production and its composition has since
the 1960's provided enough ethane, and later propane, for the production ofmost ofits ethyl-
ene. Also in the United States the high consumption of gasoline has prevented any excess of
naphtha for cracking, mak:ing gas oil their most usual option for feedstock flexibility. In Europe
due to the smaller availabilities of domestic sources of natural gas and the lower demand for
gasoline upto early 80's, naphtha became the natural choice for cracking. Since 80's however,
European refineries have to build FCC units to keep pace with motor-gasoline demand, gener-
ating some surplus ofLPG. European naphtha crackers have added LPG flexibility since the be-
ginning of the 1980's. The discovery of the North Sea reserves has helperl to change the
situation. However, due to the high costs involved in the transport and storage of natural gas in
one hand and the existing depreciated refining facilities in the other hand, it can be attractive
only in specific areas such as Scotland, North ofEngland and Norway. In general, European
crackers have a more limited flexibility than those in America, generatingwider seasonal price
differentials, the conditions of Japanese and other Asian producers in terms ofpetrochemical
cracking is even more dependent upon naphtha than the Europeans, and their flexibility is
srnaller. As the Asian countries are experiencing a faster growth in petrochemicals, the demand
for naphtha is expected to grow to a much tighter balance with production. This Situation is al-
ready stimulating fast changes in the Japanese industry, which intends to reduce its dependence
upon naphtha from 95% to 60% by swapping this capacity with NGL and LPG.
793
In a nutshell, the petrochemical feedstocks are one ofthe areas ofheavy R&D invest-
ment at the present. Since the first oil shock the industry has tumed its attention to the develop-
ment of substitutes for naphtha as fuel and feedstock. From a range originally consisting
mainly of natural gas, coal, tar-sands, oil-shale and fermentation of molasses this search re-
duced to a single-component, namely natural gas.
THE GCC PETROCHEMICAL INDUSTRY
Historically, GCC countries are the major producers and exporters of crude oils. How-
ever, the regionwas very small market for chemieals compared with other bigger regions such
as Europe, USA, Japan and other Asian Countries. Therefore, the chemical industry in the re-
gion was mainly fertilizers plants. In the early 80's Saudi Arabia started a very ambitious pro-
gram to build a strong industrial base in the field ofbasic and intermediate petrochemicals.
However, with the exception of Saudi Arabia, the GCC Petrochemical Industry is at
present dominated by two different streams: (a) Fertilizers (such as Ammonia, Urea); and (b)
Chemieals (such as Methanol Ethylene and its derivatives, and MTBE).
In Bahrain, the GulfPetrochemical Industries Company (GPIC), was the first petro-
chemical joint venture between three GCC member states (Bahrain, Kuwait and Saudi Ara-
bia). lt is operating since 1985. The GPIC at present is producing and exporting more than
400,000 MT/year of methanol. Sirnilar amount of ammonia is also produced. The new urea
project will utilize substantial amount ofthe produced ammonia.
In Saudi Arabia, SABIC was the pioneering company in the region in moving into
large-scale petrochemical production since early 1980s, main1y in Yanbu and Al-Jubil. Based
on the ethylene cracking unit which uses the ethane extracted from natural gas as feedstock,
SABIC p1ants, collectively, have a capacity of a1most 2 million tonnes of ethylene per year.
However, the SABIC is proceeding with a multi billion dollarexpansionsplan in order to raise
its annual capacity to 20 million MT of petrochemicals.
SABIC at present produces many petrochemica1 products in addition to the fertilizers,
among ofwhich the main five plastic polymers, namely, polyethylene (low density and high
density), polypropylene, polystyrene, PVC, and polyesters fibers.
SABIC also produces more than 2 MT of methanol and similar amount of MTBE
which is widely used as a gasoline additive. Recently a project was established to produce
140000 MT of po1yester fibers and PET pellets which is used in botdes manufacturing.
Terephthalic acidplant isanother example ofthe diversification policy ofpetrochemical in-
dustry in Saudi Arabia.
The other success story is in Qatar, where Qatar's Petrochemical Industry is repre-
sented through two state-controlled companies, in which the Qatar General Petroleum Corpo-
ration (QGPC) is the major shareholder. The Qatar Petrochemical Company (QAPCO)
established on 1980, with an annual design capacity of280,000 MT of ethylene, and 140,000
MT of LDPE. Qatar Fertilizer Company (QAFCO) was established by the Govemment of
Qatar in 1968, QAFCO produces 700,000 MT/year of ammonia and 800,000 MT/year of
Urea. QGPC is undertaking a huge development program ofthe north field gas resource into
petrochemical products such as methanol, MTBE, and to double the existing production ca-
pacity ofQAPCO and QAFCO.
In Kuwait Petrochemical Industries Company (PIC) which was established in 1963 is
the only govemmental operating company. PIC capacity is approximately l million MT/Y of
ammonia and 790,000 MT/Y of Urea. PIC is now developing the Shuaiba Petrochemical
Complex as a joint venture with Union Carbide. The new complex will be able by mid 1997 to
produce 650,000 TIY of ethylene from ethylene cracker which will use the ethane gas from
the LPG plant in Shuaiba district. The complex will also be producing 225,000 T/Y ofHDPE
and 225,000 T/Y ofLDPE together with 350,000 T/Y of ethylene glycol. PIC is building a
794
Table 1. Production and export values ofmajor petrochemicals. G.C.C. and world: 1993. Data
listed in descending order of G.C.C. export values
Production Exports
G.C.C World G.C.C World G.C.C World G.C.C. World
MillionS MillionS % % Million S Million S % %
LLDPE 581.1 5,408.0 14.56 3.74 529.3 2,343.4 22.56 7.72

409.2 10,822.2 10.26 7.53 366.0 4,001.2 15.60 13.18
HDPE
Methanol 343.2 2,598.0 8.60 1.80 312.7 1,111.1 13.33 3.66
279.7 2,377.5 7.01 1.64 270.7 935.1 11.54 3.08
Ethyl.Glycol
MTBE 168.9 3,017.8 4.23 2.09 168.9 957.6 7.20 3.15
218.7 7,533.5 5.48 5.21 151.7 1,625.6 6.47 5.35
Styrene
LDPE 145.7 10,779.8 3.65 7.46 145.7 3,909.3 6.21 12.87
175.8 11,735.6 4.41 8.12 108.0 2,807.7 4.60 9.25
PVC
Polystyrene 115.2 9,133.0 2.89 6.32 80.4 3,491.6 3.43 11.50
EDC 105.8 5,822.8 2.65 4.02 55.9 416.4 2.38 1.37

27.7 11,249.8 0.69 7.78 27.7 3,941.8 1.18 12.98
Polypropylene
Propylene 26.2 10,493.6 0.66 7.26 13.2 799.7 0.56 2.63
103.0 6,396.8 2.58 4.42 9.3 756.6 0.40 2.49
VCM
Benzene 99.7 7,044.4 2.50 4.87 8.2 77B 0.35 2.56
7.2 5,117.1 0.18 3.54 2.3 127.6 0.10 0.42
Formaldehyde
UFResins 7.8 6,648.3 0.20 4.60 2.0 863.1 0.08 2.84
9.7 1,408.1 0.24 0.97 1.0 286.9 0.04 0.95
Melam-Fonn
PFResins 0.8 1,100.0 0.02 0.76 0.3 121.4 0.01 0.40
Total 2,825.4 118,735.4 100.00 100.00 2,253.27 29,271.9 100.00 100.00
Ethylene 1,164.8 25,870.0 93.0 1,097.6
Note that the G.C.C. totals include, in addition to the Saudi Arabia Totals, data fortwo G.C.C. member States as follows:
Babrain -Methanol Prod: Mill S 49.2 Exports: Mill S 49.2
Qatar - Ethylene Prod.: Mi!! s 126.5 Exports: Mill S 54.7
Qatar-IDPE Prod.: Mill s 145.7 Exports: Mill S 145.7
SOURCE:GulfOrganization for Industrial Consulting (GOIC)
795
polypropyleneplant ofa total capacity of 150,000 T/Y which is completely owned by PIC. An
aromatic plant is another project being considered by PIC at present.
In Abu Dhabi, Ruwais Fertilizer Irrdustries (FERTIL) was established as ajoint ven-
ture between Abu Dhabi National Oil Company (ADNOC) and TCFP ofFrance. This was the
first chemical planttobe built in the UAE, which is export oriented. The capacity ofthe unit is
350,000 MT/Y of ammonia and 525,000 MT/Y ofUrea. ADNOC is also examining the possi-
bility of expanding into the Petrochemical field, such as building ethane cracker with down-
stream polymer units. Expansions in other petrochemical products based on the Omani
Natural Gas are also promising.
In Oman, there are not petrochemical or chemical fertilizer plants. However, a joint
venture with foreign partnerstoset up a world scale fertilizer plant is und er consideration. The
project will involve the production of approximately 1.5 MT of Urea and 315,000 tonnes of
ammonia.
Table I shows the contribution of the GCC petrochemical industry to the world indus-
try (excluding fertilizers ). lt is clearly demonstrated that although the industry in the GCC
countries is growing, yet its contribution to the world industry is still relatively small; which
call upon more expansions in selected products.
The demand for many ofthe GCC petrochemical products is believed tobe fairly elas-
tic and is expected to grow over time, as evidenced by the capacity expansions planned for by
the region's producers.
Formost ofthe products, the forecasts go in favour of a strong expansions trend. Thus
it is expected to see accelerating growth rate for a number of products, which include polypro-
pylene, ethylene glycol, polyethylene, PVC, polystyrene, styrene and ethylene di-chloride.
The demand for these products is likely tobe elastic and hence the WTO tariff reductions may
induce !arge increases in GCC exports.
However, with these encouraging scenarios, it became more necessary to establish
more concrete bases for better coordination and integration between all the operating petro-
chemieals companies in the GCC countries. Such coordination is inevitable due to:
Tightening competition in the international markets
Better utilization of the available feedstocks resources, taking into consideration
the availability of dry natural gas reserves in the southem GCC states (Qatar,
UAE, Oman) and the limited amounts of these in Kuwait and Saudi Arabia.
The necessity to be more selective in investing in new petrochemical plants that
are of sustainable competitiveness, among the wide range of available petro-
chemical products.
Better utilization ofthe available financing capabilities.
The necessity to promote the petrochemieals market in the region.
7%
PREPARATION OF Sll...ICA-BASED MEMBRANE FOR H 2 SEPARATION BY
MUL TI-STEP PORE MODIFICATION
Jae-Hyun So, Seung-Man Yang, Seung Bin Park

Korea Advanced Institute of Science and Technology
Taejon, 305-701, KOREA
INTRODUCTION
Because inorganic membranes have an excellent chemical and thermal stability, they
can be used in water desalination, ultrafiltration process in food industries, waste water
treatment and separation of gas mixtures. 1 Inorganic membrane can be classified into two
types; namely, non-porous(dense) membranes and porous membranes. 2 The important
factors in the membrane separation process are both the permeability and the selectivity.
However, the selectivity of a membrane decreases as the permeability increases. This
trend is confirmed by the corelation of selectivity versus permeability. 3 Since the polymer
membrane is non-porous, the fluxes and permeabilities are very small. However, as the
separation occurs via the so-called solution-diffusion mechanism, the selectivity of
polymer membrane is much high. 4 The mechanism of gas separation by a porous alumina
membrane or Vycor glass, is closely related to the membrane pore size relative to the
permeate molecule size as weil as other physical and chemical properties of the
membrane and the permeate species. 56
The important mechanisms of gas separation via a porous membrane are Knudsen
diffusion and surface diffusion. Knudsen diffusion occurrs when the mean free path ofthe
gas molecule is much )arger than the pore diameter and the collisions between the
permeate gas molecules and the pore wall become important.
On the other hand, surface diffusion is due to the concentration gradient of
adsorbed species on the pore wall. When the interactions beween the permeating gas
molecules and the pore walls are become significant, bulk transport models for gas flow
through the porous media are no Ionger valid. When the adsorption of gas molecules on
the pore wall is important, molecules adsorbed on the porous solid surfaces may have
considerable mobility, which gives rise to an additional gas transport mechanism. Surface
diffusion caused by migration of adsorbed molecules on the pore surface was confirmed
by many research groups. 6' 7' 8' 9 The surface diffusion rates are determined by the surface
diffusion coe:fficient and adsorption equilibrium, both of which are related with the
interaction between adsorbates and pore surfaces. 9 Therefore, in order to enhance
surface diffusion, membranes are frequently modified with palladium or silica, which

have selective hydrogen adsorption ability. Moreover, since surface diffusion becomes
more important when pore size is decreased6, it is important to reduce pore size to nano-
scale without pinholes or cracks.
In the present study, the multi-step pore modifications which are composed of in-
situ silica sol-gel, silica sol dip-coating and soaking and vapor deposition, were used to
prepare the membranes which can be effectively operated at a high pressure and used for
practical separation processes.
EXPERIMENTS
In this study, we used a porous a.-alumina support (Norltake Co.) with asymmetrlc
structure. The inner and outer diameters of the support are 7 mm and I 0 mm,
respectively, and its length is 50 cm. The inner layer ofthe supportisthin and dense with
the average pore size of 80 nm, and the outer layer is thick and coarse. To prepare a
porous inorganic membrane for hydrogen separation, both sol-gel and chemical vapor
deposition methods are adopted. The procedure of the membrane preparation is
composed of three steps of in-situ silica sol-gel, silica sol dip-coating and soaking and
vapor deposition method Two types of silica sol were made and used in both the in-situ
silica sol-gel process and the silica sol dip-coating procedure.
Membrane preparation by sequential pore modification method
As mentioned earlier, temperature distrlbution along the membrane durlog the

preparation step is important because homogeneous and narrow pore size distrlbution
requires the uniform temperature distribution. Yoon. et al made a dense silica layer in the
intermediate layer of the support. 10 However, because of typical geometry of our
membrane ( i.e., tube type support with 50 cm long}, uniform separation layer was not
able to be formed within the whole membrane. Therefore, the liquid phase silica sol-gel
reaction is adopted in this study. The reaction mechanism is similar to that of in-situ
hydrolysis of TEOS. However, the hydrolysis reaction and polycondensation take place
simultaneously in the liquid phase to create a homogeneaus temperature distrlbution.
TEOS (Aldlich. Co. 99.9%} and acidic alcohol-water mixturediffuse into the inside
ofthe porous alumina support counter-currently and reacts in the vicinity ofthe interface
between the two layers of the support. Distilled water and ethylalcohol were mixed at
25C (4:1 with molar ration) with vigoraus stirring. Small amount ofhydrochlorlc acid
(Junsei. Co.) was added as a reaction catalyst after 30 minutes. As the reaction proceeds
for 20 minutes, the silica sols are formed and partly gelled simultaneously in the
intermediate layer of the support. The temperature of the reactor is maintained at 80C
by a circulated water to aceeierate the hydrolysis and poly-condensation reaction. After
the reaction, the membrane was drled in atmospherlc condition and calcination was
carried at 400C by increasing temperature with rate of 0. 7C/min in the electrlc furnace
to prevent crack formation durlog calcination stage. This procedure was repeated 6 times.
To decrease pore size further down and thereby to increase hydrogen selectivity,
soaking and vapor deposition (SVD) method was adopted. In this case, it is still difficult
to maintain the temperature as high as about 350C over the whole part ofthe membrane,
because the tubular membrane support is quite long. Therefore, both the end parts of the
membrane {15cm from both the membrane ends) were modified additionally with another
type ofsilica sol by dip-coating method. To facilitate the penetration ofthe silica sol used
in the end treatment, the membrane was maintained under vaccum durlog dipping.
With this second modification, channeling through cracks and incomplete SVD can
be prevented. Dip-coating was conducted by maintaining the inner side of the membrane
798
under vacuum for two minutes on the silica impregnated porous alumina membrane with
the silica sol solution. One day drying in atmosphere is followed by calcination in an
electric furnace. The temperature was raised with rate of O.SOC/min to 500C for about
3hr to avoid crack formation. The dipping and calcination were repeated 6 - 7 times. Lee.
et al. reported that the membrane made by dipping the support in palladium impregnated
alumina sol solution showed high H2 permeability and high H2 selectivity, especially
under low transmembrane pressures. 12
Finally, to enhance the hydrogen selectivity of the membrane, we applied soaking
and vapor deposition (SVD) method to the membrane. In SVD method, the metal
precursor, O.Sg of palladium (II) acetate (Korean Engel-Hard. Co.) was dissolved in
20ml acetone (Merck. Co.), and hydrochloric acid (Junsei. Co.) was added to make the
palladium particles charged. The palladium acetate solution was stirred vigorously with
spinbar for Ihr, and soaked into the membrane pore for 30min. Before drying, the inside
ofthe membranewas maintained under vacuum (100-300 Torr) for 20min to facilitate
the penetration of the precursor solution fully into the inner layer. To evaporate the
solvents, the membranewas dried at 100C for 3hr in dry oven. After drying, palladium
(II) acetate was decomposed, as the temperature is gradually increased from room
temperature to 180C under reduced pressure within the pore wall. Lee et al. created an
intermediate layer of palladium in the vicinity of the interface between the two layers of
the support by SVD method. 13
Gas permeation experiments
The permeation of H2 and N2 experiment was carried out. The gas permeate rate
was measured by the mass flow conteoller (UFC-lSOOA, Unit Co.) in the permeate side
and the transmembrane pressure L1 P was measured by the differential pressure gauge
(7354 Series. Cole Parmer Inc.). The transmembrane pressurewas controlled by a needle
valve in the retentate side. In the pore modification step, the sol size relative to the pore
size of the membrane is very important. To identify the relation between the selectivity
change and the particle size during each modification step, TEM (Transmission Electron
Microscopy) was used. SEM (Scanning Electron Microscope) was also employed to
confirm the changes of the microporous structure during the sequential pore modification.
The ideal separation factor a* is defined as the ratio ofthe permeabilities for the species
of a binary gas mixture
a* = {}A!Qs (I)
RESULTS AND DISCUSSIONS
Gas permeation results
In the pore modification step, the silica sol or precursor must be smaller than the
pore size or at least the same in size to reduce the pore size of the membrane. As the
alumina support used in this study has asymmetric structure, the pore size distribution is
very broad ( O(Jlm) - 80 nm). Thus, it is very difficult to determine the exact pore size
distribution directly. Alternative way to determine the pore size distribution is a
measurement of the gas permeability and the particle size distribution used in the
modification step. From these results, the pore size can be estimated indirectly.
Permeability changes of the membrane with temperature and pressure difference
were shown in Figure I. In permeation experiments, p~re N2 and H2 gases were
799
permeated at 400, 200 and 25C, respectively. The gas permeabilities of the membrane
prepared by in-situ silica sol-gel method were shown to be independent of the pressure
difference up to 280kPa and decreased with temperature. It is obvious that the
permeability is independent of the transmembrane pressure and inversely proportional to
.,ft when the Knudsen diffusion is dominant. And the ideal separation factors defined as
the ratio of H2 and N2 permeabilities increased as the pressure difference decreased,
which have been observed in other investigations. 10' 11 ' 12 Thus, it can be concluded that
the in-situ silica sol-gel method can successfully replace both the alumina sol dip-coating
and the hydrolysis ofTEOS steps used in the procedures used by Yoon et a/. 10
By the silica sol dip-coating, N2 permeability was not changed, while H2
permeability was increased by I5% at 400C. This is due to the selective adsorption of
hydrogen on the silica within the modified pore wall. Since H 2 permeability was
increased and N2 permeability was not changed, the ideal separation factor was increased
over Knudsen diffusion Iimit (= 3. 74).
After 5 times of SVD were conducted, the ideal separation factor was increased up
to I0.8, and N2 and H 2 permeabilities were reduced to 5.3xl0'8 and 5.8xi0'7 m3(STP)/m2
sec kPa, respectively, which are shown in Figure I. Decrease in the gas permeability is
mainly due to the pore size reduction by the chemical vapor deposition of palladium.
Further, it can be noted that H2 permeabilities, which ~e IO times !arger than N2
permeabilities, are the results of the surface diffusion by the selective adsorption and the
adsorbate concentration gradient. Figure 2 shows the overall H2 selectivity changes
during the pore modification step at 400C. As the modifications are performed
sequentially, the permeabilities of H2 and N2 decrease and the ideal hydrogen selectivity
increases. Since the permeability of each gas is independent of transmembrane pressure
difference and hydrogen selectivities are far above the Knudsen diffusion Iimit (= 3.74),
the dominant separation mechanisms of the prepared membrane are the Knudsen
diffusion "and the additional surface diffusion.
Microstructural changes of membrane during sequential modification steps
In the modification step, there are two kinds of silica so! and Pd precursor solution
(palladium acetate dissolved in acetone) for SVD. Each sample was analyzed by TEM
(Transmission Electron Micrograpy). From these TEM results, the particle size
distribution was evaluated and the result is contained in Table I. Since the dense layer of
the a-alumina support has the average pore size of 80nm, the second type of silica sol
(used in the dip-coating step) and Pd precursor solution (palladium acetate dissolved in
acetone) for SVD soak easily into the membrane pores, while the firsttype of silica sol
(used in the in-situ silica sol-gel method) cannot penetrate. However, if the reactants
diffuse into the membrane pore and react within the porous structure, the !arge silica sols
which are comparable in size with the pore can be formed in the pore modification step.
To determine the distributions of the silica particles formed during the in-situ silica
sol-gel reaction, the overall distribution of the silica within the membrane cross-section
was shown by the dot-map image in Figure 3. It can be seen that the dense and
intermediate layers are effectively modified with the silica particles through the
modification method. It can be noted from this micrograpy that the silica sols could
reduce the pore size by forming a dense network structure within the macropores of the
support.
Through the in-situ silica sol-gel method, the Knudsen diffusion could be generated.
However, the hydrogen selectivity was only about 3-4 although the permeability was
sufficiently high. To raise the hydrogen selectivity, additional modification steps are
needed to further reduce the pore radius. Usually, narrow pore size distribution with
800
105 .----------------,------,
- - 400C
Ii
~ - - 200C
u - - 25C
Cl>
Cll ........_ in-situ
N.E - dipping
r; 106 --- SVD
!!?..
"'.
Cll
Cl>
~
:c<II
E
Cl>
1o-7
Cl>
a..
0 50 100 150 200 250 300 350

Pressure Difference [kPa)
Figure 1. Penneabilities of membrane modified by each sequential step with various

temperatures. (filled; H 2,unfilled; N2)
12.--------------.--------~
--e- in-situ
----- dipping
10 __.__ SVD#1
?:- --.- SVD#3
--+- SVD#S
..
;;:
"
-.;
8
.e
(/)
c
6
..,,..
C>
J:
4
2~~~~~~~~~~Lw~
0 50 100 150 200 250 300 350

Pressure Difference [kPa)
Figure 2. Selectivity changes by each sequential modification step at 400C
Figure 3. Dot map of silica within the cross-section of silica-modified membrane by in-situ silica
sol-gel method
801
Figure 4. Morphology of membrane surface modified by silica so I dip-coating step
Table I. Partide size distribution used in each modification step
type of particles silica sol formed in silica sol used in particles used in soaking
in-situ silica sol-gel dip-coating method and vapor deposition
method method
size distribution 80-40 nm 30-40 nm 3-5 nm
dense structure can be obtained through a chemical vapor deposition method. But, it is
difficult to maintain high deposition temperature for the entire zone of the membrane
since the membrane support in this study is as long as 50 cm. Therefore, both the end
parts ofthe membrane need an additional modification method. Silica sol dip-coating was
conducted 6 times with smaller silica sols on each end part (15 cm) of the membrane.
The morphology change of the membrane surface by the dip-coating was shown in
Figure 4. The white part ofthe micrograpy represents the membrane surface and the dark
part denotes the cross-section of the membrane. From this micrograpy, it can be easily
seen that the membrane surface was also clogged by the silica so I with some microcracks.
Figure 5. SEM micrograpy of the cross-section of palladium-modified membrane and

distribution of silica obtained by EDX (white peak Iine)
802
Thus, the thick and coarse outer Jayer of the membrane was modified by penetration of
the silica so! used in the dip-coating step. Consequently, the silica particles formed by the
silica so! dip-coating were distributed mainly on the outer layer ofthe membrane.
Finally, palladium which has hydrogen selective adsorption ability was deposited
into the membrane pore by soakimg and vapor deposition (SVD) method to improve
hydrogen selectivity. As shown in Table I, the SVD solution (palladium acetate
dissolved in acetone) has the particle size distribution in the range of 3~5nm. Thus, Pd
particles can be easily soaked into the membrane pore by capillary force. But as the
number of depositions increases, the amount of soaked solution decreases. Therefore, to
increase palladium content soaked into the membrane pore, vacuum was applied during
the soaking step. We simply called this procedure enhaneed soaking and vapor
deposition method. According to the permeation results, the membrane modified by SVD
method showed higher hydrogen selectivity. It is due to the surface diffusion mechanism
induced by palladium deposited in membrane pore. To evaluate the distributions of
palladium within the membrane pores, EDX was taken and its results were shown in
Figure 5. Palladium was deposited onto the whole cross-sections as well as the dense
skin layer and intermediate layer of membrane.
CONCLUSIONS
Porous inorganic membrane for hydrogen separation was prepared by the sequential
pore modifications, which are composed of silica sol-gel process and chemical vapor
deposition. Conclusions are as follows;
1. By the in-situ silica sol-gel method, the Knudsen diffusion was achieved and relatively
!arge silica sols were used in the pore modification step.
2. The silica so! dip-coating method induced the surface diffusion under low pressure
difference ( ~ 25 psi) and provided an effective pore reduction
3. The SVD method made the precursor soak effectively into the membrane pore
because the precursor particle had small in diameter (3~5 nm). The impregnated Pd
increased the hydrogen selectivity by forming a selective palladium layer
4. The present porous inorganic membrane prepared by the sequential pore modification
showed much higher permeability than typical polymeric membranes and could be
operated at high temperature (400"C) and high transmembrane pressure ( over 310 kPa).
REFFERENCES
1. A.F.M. Leenarrs, K. Keizer and A.J. Burggraaf, The preparation and characterization
of alurnina membranes with ultra-fine pores - part 1. Microstructural investigations on
non-supported membranes.l. Mater. Sei. 19 1077-1088 (1984)
2. J.G Wijmans and R.W. Baker, The solution-diffusion model : a review .1. Memb. Sei.
107 1-21 (1995)
3. L. M. Robeson, Cerrelation of separation factor versus permeability for polymeric
membrane.l. Memb.Sei. 62 165-185 (1991)
4. W. J. Koros and G. K., Flerning Membrane-based gas separation .1. Memb.Sei. 83 1-
80 (1993)
5. D. Li and S. T., Hwang Preparation and characterization of silicon based inorganic
membrane for gas separation.l. Memb.Sei. 59 331-352 (1991)
6. R. J. R. Uhlhorm, K. Keizer and A. J. Burrggaaf, Gas and surface diffusion in
modified g-alurnina systems .1. Memb.Sci. 46 225-241 (1989)
7. Y. K. Cho, K. W. Han, and K. H. Lee, Separation of C0 2 by modified y-Ah03
membranes at high temperature.l. Memb. Sei. 104 219-230 (1995)
803
8. K. Keizer, R. J. R. Uhlhorn, R. J. V. Vuren and A. J. Burrggaaf, Gas separation
mechanisms in microporous modified y-Ah03 membranes J. Memb. Sei. 39 285-300
(1988)
9. A. Yamasaki and H. Inoue, Surface diffusion of organic vapor mixtures through
porous glassJ. Memb. Sei. 59 233-248 (1991)
10. K.-Y. Yoon, J.-H. So, 1.-H. Cho, S. B. Park, W.-H. Hong, and S.-M. Yang,
Preparation of alumina membrane for hydrogen separation by multi-step pore
modification 7tJo World Filtration Congress, Budapest, Hungary (1996)
11. S.-J. Lee, S.-M. Yang, and S. B. Park., Synthesis ofpalladium impregnated alumina
membrane for hydrogen separation J. Memb. Sei. 96 223-232 (1994)
12. S.-Y. Lee, S.-J. Lee, S.-J. Kwon, S.-M. Yang, and S. B. Park, Preparation of sol-gel
driven alumina membrane modified by soaking and vapor deposition method J. Memb.
Sei. 108 97-105 (1995)
804
Application of Polymer Membranes to Alcohol Concentration
in Fermentation of Biomass
Tadashi Uragami
Chemical Branch, Faculty ofEngineering, Kansai University

Suita, Osaka 564-80, JAPAN
INTRODUCTION
It is required that aqueous alcohol solutions produced by a biomass fermentation technique are
concentrated and separated by some methods to use a concentrated alcohol as fuels. There are
many techniques for concentration and separation of aqueous alcohol solutions. Membrane separation
techniques are worth noticing to be able to concentrate and separate liquid and gas mixtures in low
energy consumption. In particular, pervaporation which is one ofthem is a very useful technique for
the concentration of organic liquid mixtures 1. When an aqueous ethanol solution produced by the
biomass fermentation is required to be concentrated by the membrane separation techniques, two
type membranes will be able to be applied. Namely, if an aqueous ethanol solution is distillated and
then an azeotropic mixture is given, water-permselective membranes are used to dehydrate water
from the azeotropic mixture. On the other hand, if an aqueous ethanol solution is concentrated
directly, ethanol-permselective membranes can be applied to concentrate ethanolinan aqueous
ethanol solution.
In this paper, structural design oftwo type polymer membranes such as water-permselective and
ethanol-permselective membranes on the permselectivity for aqueous ethanol solutions in
pervaparation and evapomeation23 are discussed from the viewpoints of an enhancement ofwater-
permselectivity based on a control of degree ofhydrogen bonds in a polymer membrane, a control
of permselectivity based on structures of microphase separations of graft copolymer membranes,
and an improvement of ethanol-permselectivity by surface modifications of polymer membranes.
WATER-PERMSELECTIVE MEMBRANES
F or purpose of investigating the relationship between the membrane structure and the permeation
and separation characteristics for aqueous ethanol solutions in evapomeation, chitosan was selected
as a membrane martial, because chiotsan has reactive functional groups and can be easily modified
by chemical reactions. In this study, a chemical modification ofthe chitosan membranewas carried
out using glutaraldehyde as shown in scheme 1. In this modification of chitosan, it was confirmed by
Science anti Technology of Polymers anti Advanced Materials

IR and 13 C NMR spectra that all glutaraldehyde took part in the reaction was used for the cross-
linking ofthe chitosan molecules as the glutaraldehyde content in a reaction mixture to the amino
groups in the chitosan molecules was low.
Effect of the feed vapor composition for aqueous ethanol solutions on the permeation rate,
ethanol concentration in the permeate through the chitosan and glutaraldehyde cross-linked chitosan
(GAC) membranes in evapomeation and degree ofswelling ofthese membranes are shown in Figure
1, in which the GAC membranewas the content of0.5 wt% glutaraldehyde in chitosan membrane.
As can be seen from Figure 1, the ethanol concentrations in the permeates through both the
chitosan and GAC membranes were very low. These results suggest that these membranes have a
high water-permselectivity.
1
CHzOH
0 0
II ~
+ H-C-CH ) II
2 3C-H
H NHz
Chitos an Glutaraldehyde (GA)
CH20H
! Crosstinking
CH20H
Schemel. Reaction of chitosan with glutaraldehyde under acidic catalyst.
There is a significant difference between the compositions in the permeates for the chitosan and
GAC membranes. Namely, the water-permselectivity ofthe GAC membranewas greater than that
ofthe chitosan membranein spite ofthe fact that the permeation rate ofthe GAC membranewas
greater than that of the chitosan membrane. Furthermore, the degree of swelling of the GAC
membranewas higher than that ofthe chitosan membrane. This tendency increased with decreasing
ethanol concentration in the feed mixture.
In general, when the polymer membranes are cross-linked, the permselectivity is improved but
the permeation rate is decreased because the degree ofswelling ofthe membrane is lowered. The
806
EtOH in feed ( wt"/o)
0 20 40 60 80 100
0 o-----'--'-.U:=..........__ _,
4 ~----------------~
0
0 20 40 60 80 100
EtOH in vapor (wt%)
Figure 1. Effect ofthe feed vapor composition on the permeation rate, ethanol concentration in the permeate through
the chitosan membrane ( e) and the GAC membrane ( 0 ) by evapomeation, and degree of swelling of these
membranes.
permeation rate, water-permselectivity, and degree of swelling ofthe GAC membrane, however,
are higher than those ofthe chitosan membrane.
In order to clear these results for the GAC membrane, crystallinity ofthe chitosan and GAC
membranes was determined by X -ray diffraction. The increase of the cross-linking with glutaraldehyde
in the chitosan membrane decreased the crystallinity ofthe membrane.
From the above results, a model structure for the chiotsan and GAC membranes is presumed.
Namely, the chitosan membrane has many intermolecular hydrogen bonds between hydroxyl groups,
amino groups, and hydroxyl and amino groups in the chitosan molecule. On the other hand, a few
ofthese hydrogen bonds in the GAC membrane are broken by cross-linking with glutaraldehyde
and consequently free hydrophilic groups such as hydroxyl and arnino groups are appeared. These
hydrophilic groups have a strong affinity to water molecules. Therefore, the GAC membranes are
moderately swollen by the water molecules and simultaneously increases the water-permselectivity.
The above discussion supports both the permeation rate and water-permselectivity increased by
cross-linking the chitosan membrane with glutaraldehyde.
807
If a deformation of the hydrogen bonds in the chitosan membrane gives a higher permeation
rate and higher water-permselectivity, it can be presumed that the cross-link is not necessarily need.
Thus, the chitosan membrane was modified using n-butyl aldehyde as a monofunctional aldehyde.
In this case also, both the permeation rate and water-permselectivity for aqueous ethanol solutions
in evapomeation increased with increasing n-butyl aldehyde content in the casting solution. Both
increase in the permeation rate and water-permselectivity are attributed to that n-butyl aldehyde
molecules reacted with the chiotsan molecules play a role ofprop for an inhibition ofthe hydrogen
bonds between the chiotsan molecule chains.
From the above results, it is found that the membrane performance for aqueous ethanol solutions
in evapomeation is significantly improved by the inhibition ofthe hydrogen bonds in the chitosan
membrane.
CONTROL OF PERMSELECTIVITY
In this section, a control of permselectivity for aqueous ethanol solutions based on the structures
of microphase Separations of graft copolymer membranes is discussed.
Figure 2 shows the permeation and separation characteristics in pervaporation for an aqueous
solution of 10 wt% ethanol solution through graft copolymer (P(MMA-g-DMS)) (I) membranes
prepared from copolymers ofmethyl methacrylate (MMA) and oligodimethylsiloxane macromonomer
(DMS) as shown in Scheme 2.
As can be seen from Figure 2, the permselectivity for an aqueous ethanol solution ofP(MMA-
g-DMS) membranes depended on the DMS unit content. Namely, the membranes with a DMS
content ofless than about 36 mol% preferentially permeated water but those ofmore than 36 mol%
predominantly ethanol.
It was observed by differential scanning calorimetry that all P(MMA-g-DMS) membranes had
two glass transition temperatures at about 120 C and -127 C. This result suggests that the P(MMA-
g-DMS) membranes have microphase-separated structures. Thus, in order to clari:fY the microphase-
separated structures, transmission electron micrographs (TEM) ofthe cross section ofthe P(MMA-
g-DMS) membranes were observed. The TEM ofP(MMA-g-DMS) membranes is shown in Figure
3. In these micrographs, dark part is for the DMS phase and bright part for MMA phase. From
these micrographs, it is found that the P(MMA-g-DMS) membranes had distinct microphase-
separated structures regardless of the DMS content. Furthermore, the DMS phase in the membranes
with a DMS content ofless than 36 mol% appeared discontinuous in the cross section but more
than 36 mol% tended to become continuous. From these results, it is presumed that the permeation
characteristics and permselectivity for an aqueous ethanol solution as shown in Figure 2 are
CH3 CH3
I I
CH2-~----+---+- CH2-~ --y-H3--+--
C-0-CH3
II
C
II
1 O-Si
I
1 CH3
0 0 CH3 st
m n
(I)
Scheme 2. Structure ofP(MMA-g-DMS).
808
DMS unit content (mol%)
Figure 2. Effect of the dimethylsiloxane unit content in the graft copolymer on the ethanol concentration in the
permeate ( 0) and normalized permeation rate ( e) for an aqueous solution of lOwt% ethanol through the P(MMA-
g-DMS) membranes by pervaporation.
significantly related to a change in the morphology ofthe microphase separation in the P(MMA-g-
DMS) membranes.
Ifit can be assumed that the P(MMA-g-DMS) membranes have the microphase separation
consisting of a continuous MMA phase and discontinuous DMS phase or a discontinuous MMA
phase and continuous DMS phase, the theoretical normalized permeation rates of an aqueous
ethanol solution through the P(MMA-g-DMS) membranes can be calculated from Maxwell's model
equation4 5 . In Figure 4, the theoretical normalized permeation rates are compared with the
experimental normalized permeation rates.
As can be seen from Figure 4, in the P(MMA-g-DMS) membranes with a DMS content ofless
than 36 mol%, the experimental normalized permeation rates were good agreement with the
theoretical curve calculated when the MMA phase was assumed to be continuous. On the other
band, in the P(MMA-g-DMS) membranes with a DMS content of more than 36 mol%, they
approached the theoretical curve calculated when a continuous DMS phase was assumed.
From the above results, the changes of the permselectivity with the DMS content can be explained
on the basis ofthe microphase-separated structures in the P(MMA-g-DMS) membranes as shown
in an illustration ofFigure 5. Namely, in the membranes with aDMS content ofless than 36 mol%,
the DMS component is discontinuous in the direction ofthe membrane thickness. Therefore, as the
permeants are mainly diffusing through the continuous MMA phase, the membrane becomes water-
permselective. On the other band, the DMS phase grows to be continuous gradually with increasing
DMS unit content as revealed from the TEM observations. The permeants are predominantly
diffusing through the continuous DMS phase, this DMS phase has high affi.nity to ethanol molecules
and consequently the membrane becomes ethanol-permselective.
ETHANOL PERMSELECTIVE MEMBRANES
It is well known that poly [1-(trimethylsilyl)-1-propyne] (PTMSP) (II) membranes have high
809
DMS30mol% DMS 34mol%
DMS52mol% DMS 68mol%
Figure 3. Transmission electron micrographs ofthe cross section ofP(MMA-g-DMS) membranes stained by Ru04.
The dark and bright parts show the DMS and MMA phase, respectively.
ethanol-permselectivity and high permeation rate in pervaporation6 7 This high ethanol-

perrnselectivity of the PTMSP membrane is attributed to a high solubility of ethanol into the PTMSP
membrane.
When further improvement of the ethanol-perrnselectivity of the PTMSP membrane is required,
it is very difficult to improve the selectivity on the basis of differences in ditfusivity attributable to
the molecular size of the water and ethanol molecules. Therefore, it is required to modify the
membrane surface which raise the solubility of ethanol molecules into the membrane relative to that
of water molecules. As the solubility of ethanol into the membrane is improved, the membrane
surface is swollen and consequently water solubility at the membrane surface is also increased.
Accordingly, it is very important to lower the affinity ofwater molecules for the membrane.
For such a purpose, a polymer surface reforming agent with both a hydrophobic part to repel
water at the membrane surface and an anchor part to become familiar with the membrane matrix
810
I
/
I
I
I
//
_,/ ~
./.~0
, ... ~~
. . . . . . . . . . . . . . . --fr:P
0
20 40 60 80 100
DMS unit content (mol%)
Figure 4. Relationship between the DMS unit content and the normalized penneation rate for an aqueous solution of
IOwt"/o ethanol through the P(MMA-g-DMS) membranes by pervaporation: -----; theoretical nonnalized penneation
rate caluculated by Maxwell's equation.
DMS unit content

<36mol% Water selectivity
DMS unit content

Ethanol selectivity
>36mol%
Figure 5. Tentativeillustration on the microphase separation structure ofthe P(MMA-g-DMS) membranes.
811
CH3 CH3
I
c=cH
I Catalysis: TaC15 -fb=~Ht
CH -Si-CH CH -Si-CH
3 I 3 Solvent: toluene 3 I 3
CH3 CH3
1-(trimethy1silyl)-1-propyne PTMSP(II)
Scheme 3. Synthesis ofPTMSP
synthesized. In this study, a graft copolymer P(F A-g-DMS) consisting of perfluoroalkyl acrylate
(FA) and oligodimethylsiloxane macromonomer (DMS) was prepared as shown in Scheme 3.
yH3
-f
~]ll
CH=CHz
I + C=CHz
I
TH-CHzH T- CHz-t,;--
C=O C=O Initiator: AIBN C=O C=O
I I Solvent:toluene I I
0 0 0 0
I I I I
(CH2)2 (CH2)3 (CH2)2 (CH2)3
I I I I
L
CsFI7 CH3- Si-CH3 CsFI7 CH3- Si-CH3
I
[ Clli J_
I
Clb ] " [CTh-LIUI
C4H9 C4H9
FA DMS P(FA-g-DMS)
Scheme 4. Synthesis ofP(FA-g-DMS)
Figure 6 shows the effect ofthe additional amount ofP(FA-g-DMS) on the contact angle for
water on the air side during the membrane preparation and permeation characteristics in pervaporation
for an aqueous solution of 10 wt% ethanol ofthe surface modified PTMSP membranes.
The contact angle for water was increased with increasing additional amount ofP(F A-g-DMS).
This increase in the contact angle suggests that P(FA-g-DMS) added to improve the surface ofthe
PTMSP membrane was localized to the membrane surface and consequently the smface of modified
PTMSP membranes became remarkably water repellent.
The permeation rate decreased slightly but the ethanol-permselectivity increased considerably
with an increase ofthe P(FA-g-DMS) content. The results in this figure indicate that the ethanol-
permselectivity is strongly dependent on the contact angle for water at the membrane surface.
Namely, the ethanol-permselectivity increased with an increase in the contact angle for water.
These results suggest that the ethanol-permselectivity of these membranes was more significantly
governed by the solubility of the permeant into the membrane than the diffusivity of the permeant in
the membrane.
812
f~~ fo
U
80
0 0
L--------------------------~
I 1.0
0.8?
~11)
0.6 !~
10
11)
0.
.::
.s 0.4 ~
11)
::r::
0
Cil 0.2 ~
60 0
0 1.0 2.0 3.0 4.0 5.0
Additional amount ofp(FA-g-DMS)(wt%)
Figure 6. Effect of the additional amount of P(FA-g-DMS) on the contact angle for water of air side, permeation rate
and ethanol concentration in the permeate for an aqueous solution of 1Owt% ethanol in PV of the surface modified
PTMSP membranes.
Tabl. Surface composition ofthe surface modified PTMSP membranes determined by XPS.
Additive Atomic ratio

Membrane content Surface
(wt%) F/C 0/C Si/C
Air 0.164
PTMSP
Glass 0.177
Air 0.107 0.087 0.205
0.1
Glass 0.021 0.031 0.170
PTMSP/P(FA-g-DMS)
Air 0.137 0.115 0.184
0.5
Glass 0.025 0.071 0.199
PTMSP* 0.167
P(FA-g-DMS)* 0.351 0.332 0.302
*Theoretical values
In order to investigate the characteristics of the surface modified PTMSP membranes, the
elemerttary analysis of the membrane surface of these membranes was measured by X-ray
photoelectron spectrometry (XPS).
813
Table I summarizes the surface composition ofthe PTMSP and surface modified PTMSP/P(FA
g-DMS) membranes. This table also includes theoretical atomic ratios ofPTMSP and P(FA-g-
DMS).
As can be seen from this table, the ratios ofF/C in the membrane surface on the air side ofth~
surface modified PTMSP membranes were considerably higher than those in the membrane surfac~
on the glass plate side used in the membrane preparation. Also, the F/C ratio in the membran~
surface on the air side increased with increasing additional amount ofP(F A-g-DMS) but that on th~
glass plate side was not changed.
Comparing the ratio ofF/C ofthe surface modified PTMSP membrane with 0.1 wt% ofP(FA
g-DMS) with that ofthe P(FA-g-DMS) membrane, it was found that the addition of only 0.1 wt%
of P(FA-g-DMS) could modicy about 30% ofthe PTMSP membrane surface. These XPS analyse!
can support that the surface ofthe PTMSP membranewas modified by the addition ofP(FA-g
DMS) and became water repellent. Consequently, the surface modified PTMSP/P(FA-g-DMS;
membranes were improved much more higher ethanol-permselectivity than the PTMSP membrane
HEFERENCES
1. R. Y. M. Huang, Pervaporation Membrane Separation Process, Elsevier Amsterdam, 1991.

2. T. Uragami, M. saito, K. Takigawa, Makromol. Chem. Rapid Commun. 9: 361 (1988).
3. T. Uragami, T. Morikawa, H. Okuno, Polymer, 30: 1117 (1989).
4. J. Crank, G. S. Park, Diffusion Polymers, Academic Press, New York, 1968.
5. A. E. Barnabeo, W. S. Creasy, L. M. Robenson, J. Polym. Sei. Polym. Chem. Ed. 13: 1979 (1975).
6. K. Ishihara, Y. Nagase, K. Matsui, Makromol. Chem. Rapid Commun. 7: 43 (1986).
7. T. Masuda, B.-z. Tang, H, T. Higashimura, Polym. J. 18: 565 (1986).
814
PERVAPORATION OF ALCOHOLS BY USING TUBULAR TYPE
CELLULOSE ACETATE AND POLYSULPHONE MEMBRANE WITH
CERAMICSUPPORT
Kyu Min Song, Yeon Ki Hong, and Won Hi Hong

Korea Advanced Institute of Science and Technology
373-1, Kusong-dong, Yusong-gu, Taejon, 305-701, Korea
INTRODUCTION
Liquid mixture can be separated by partial vaporization through a non-porous

permselective membrane. This technique which was originally called 'liquid
permeation', has subsequently been termed 'pervaporation' in order to emphasize the
fact that the permeate undergoes a phase change, from liquid to vapor, during its
transpoft through the barrier.
Pervaporation is the membrane separation process which has inherent advantage
of excellent selectivity for a number of mixtures that are otherwise difficult to
separate (e.g. azeotropic mixture or mixtures of liquids with only small differences in
vapor pressures).
Because ethanol/water and isopropanol/water system are the azeotrope, special
separation processes are needed. So we used a pervaporation process with prescribed
advantages in ordertoseparate these systems in this study.
In the pervaporation process, there are various mass transfer steps such as
diffusion in bulk, Sorption into membrane, diffusion and evaporation. One of these
mass transfer steps, diffusion in bulk, is dependent on the concentration polarization.
which is often the reason for the Iimitation of the membrane processes.
EXPERTIWENTALAPPARATUSANDPROCEDURE
The liquids used in this study were water, ethanol and IP A (isopropanol)
Ethanol and IP A were of guaranteed gradientgrade of the Merck Co. Allliquids were
used after boiling and sonication to remove the gas dissolved in them. CA (cellulose
acetate) was 39.8% acetyl content and the molecular weight was ca. 30,000. The
molecular weight of PSf (Polysulphone) was ca.30,000. CA and PSf was coated on

Table 1. Conditions of preparing the tubular membrane
Polymer solution:
Polymer cellulose acetate polysulphone
Solvent acetate tetrahydrofuran
Weight percent of polymer 20 20
Temperature 50C so Oe
Coating:
Immersing velocity 3 crnlmin
Drawing-out velocity 20 crnlmin
Rotating speed 750 rpm
...!~~~~~:..~~-~~~~---~~~-~-~-~~~~~~~~~~~--~~~-~-~--~----~~-:~----~-----~---~--
the tubular support for dehydration of alcohols. Acetone was used as solvent for CA.
and Tetrahydrofuran was used as solvent for PSf.
The tubular type membrane was prepared by the dip-coating and rotation-drying
technique. The dip-coating and rotation-drying technique are summarized in Table 1
and these conditions were determined by a preliminary examination.
The effective area of the membranewas about 26.4 cm 2 . The feed temperatures
were 25, 45 and 65C and the downstream pressure about 4.0 mbar. The liquid phase
was circulated inside the tube and the feed amount was 500ml. The mole fractions of
water in the feed were about 0.10 in the ethanol/water system and about 0.16 in the
IPA/water system. The permeate was collected by liquid nitrogen condensing and
analyzed by the gas chromatography with TCD detector. The effect of the feed flow
rate on the mass transfer rate was investigated by using the inner coated membrane.
The uncoated surface of the porous support, the coated surface and the cross
section of the prepared membrane and the surface of the active layer in contact with
the ceramic support were observed by using SEM photographs. The pore size of the
ceramic support measured by mercury porosimeter is about 0.1 J.Lm. The state of the
coated surface of the CA and PSf membrane is the same as that of the surface of a
nonporous membrane generally used in pervaporation. This membrane was prepared
according to the conditions in Table I. The thickness of the active layer of the CA
membrane is about 30 J.Lm. The intermediate layer exists between polymer and
ceramic support and its thickness is estimated tobe about I J.Lm. It is difficult to strip
the coated polymer from the ceramic support due to the existence of the intermediate
layer, which could play a better role in membrane durability. The CA membrane is
stripperl off by force in order to observe the contact surface of the intermediate layer.
The thickness of the intermediate layer can be controlled by concentration of polymer
solution, dip-coating velocity, rotation speed and pretreatment methods ofthe ceramic
SUpport.
Fig 1 illustrates the characteristics of pervaporation and the selectivity of water
in the ethanol/water and IPA/water system at 25C. The selectivity ofwater is defined
by the following equation:
. .
SeIectJvity = -_,_x__"w_/
( .:.....(1_-__,xw'-"'))'-"-p
(xw /(1-xw))R
816
10 0
)
Ethanol
g.,_ Q) 08
IPA
=:::
~ E o6
0 Q)
ca.
.2 <=
ti;;;: 04 / __
~~
-5 5 02
o/u
:E
---
r
12 200
E
._ E
-"'
Q)
Cii
.2!... "' 9 Q) Q)
150 ....
~
"'l:-2!...
V>
-....-. "' V>
;:
-0 V>
...
-ns 6 100 "..-2!
0 ;:
"..:::: .~ ra
-~ 0 / > ;:
> <= /
t;<t
.,o.s::
/
-:.;:"' 3 / 50 Q)Q.
.... _"/[] Qi~
- Q)
Q) <= /
/
Vl -
Vl - _;:]- ~
0 ~-- 0
00 02 04 06 08 10
Mole fraction of ethanol or IPA in retentate
Figure 1. The characteristics of pervaporation of ethanol/water and IPA/water system

at 25 C.
where xw is male fractian afwater in R (retentate) and P (permeate).

In the ethanol!water system, the selectivities af water are in the range af 4-11 .
The selectivities abserved in the IP A/water system range of 8-240, !arger than in the
ethanal/water system. At the same temperature, the selectivities abtained by
Rautenbach and Albrecht in the ethanal/water system were 3.5 and 13.1. The used a
flat type af CA membrane.
Fig. 2 shaws the selectivity af water at variaus temperature in ethanal
dehydratian using a membrane caated an the inner surface. The selectivities af water
are abaut 4 at 25C, 7 at 45C and 12 at 65C. As the temperature increases, the
selectivity increases. This behaviar is explained in Fig. 3 where the fluxes af pure
campanents are illustrated. Fig. 3 shaws that an the whale the fluxes af all
campanents increase with increasing temperature. Hawever, the flux increments af
each campanent are different. The flux increment af water is !arger than that af
ethanal and IP A Especially the flux increment af IP A is sma!L Thus the selectivity af
water increases as temperature increases, as it can be seen in Fig. I . Considering this
behavior, the operation at high temperature becomes more efficient far the
dehydration af ethanal and IP A
In Fig. 4 the cancentration af water in retentate is platted as a functian af time
far the ethanal/water system. The feed flaw rates are in the laminar flaw regian and
the feed male fraction af ethanal is near 0.9. It can be seen that the fluxes af pure
companents are independent af the feed flaw rate in Fig. 3. Since there is na
resistance af a baundary layer in a pure campanent system, these results can be
predicted. As the feed flaw rate and the temperature increase, the slape becomes
steeper.
817
16
14
12
...
Q)
iV
~
._ 10
0
~
"> 0
t; 8 0 0
mP
GI
4i 0
cn
0 ~0
6 0
0
4
2
0.72 0.74 0.76 0.78 0.80 0.82
Mole fraction of ethanol in retentate
Figure 2. Selectivity of water in ethano/water system at 25, 45, and 65 C.
25 45 65 C
2.0
0 'l-1\- water
0 0 -6 ethanol
e IPA
-1\
:!:. 1.0
fr ..... 6..._
..._ /
0 .5 ............. ......'tf.
o- --CF-:::::::::g--:iJ -==- . -=fl
. . i - ---

0.0
0 2 3 4 5 6 7
Feed Flow Rate [cm 3/sec)
Figure 3. Flux ofpure water, ethanol and IPA vs. feed flow rate at 25, 45, 65C.
818
4 ,1-----,-----,----,--- --,-----,-----.
0 1.66 cm3 /sec
:::J 5.74 cm3/sec
D
3
0
3
u
0
:s: 2
u D
::E
<(
~
1 I-
t
~
12
Time [hr]
Figure 4. Effect of feed flow rate and temperature on IPA/water pervaporation
CONCLUSION
The tubular-type membrane with ceramic supportwas used for the dehydration
of ethanol and isopropanol in pervaporation. The membrane was prepared by a dip-
coating and rotation-drying technique with CA and PSf. It was observed by SEM
photography that the membrane consists of a nonporous active layer, an intermediate
layer and a porous support. The intermediate layer strengthens the membrane' s
stability. In pervaporation using a membrane coated on the outer surface of the
ceramic support, the selectivities of water were in the range of 4- ll in the
ethanol/water system and 8-240 in the IPA/water system. In the case of PSf, it was
difficult to obtain data because of its low flux.
REFERENCES
K.M. Song and W.H. Hong, 7th APCChE Conferenee, Taipei, 1996
R. Rautenbach and R. Albrecht, J Membrane Sei., 19 (1 984) I.
Jeen NEEL, lnlroduetion to pervaporation, in:Pervaporation Membrane Separation Processes.
Robert Y.M. Huang, ed., ELSEVIER, Amsterdam (1991)
K.M. Song and W.H. Hong, J Membrane Sei, 123 (1997) 27
819
THE HIGHEST GAS PERMEABLE MEMBRANES OF
POLY[l-(TRIMETHYLSILYL)-1-PROPYNE]
- THEIR GAS PERMEABILITY AND MODIFICATION
Tsutomu Nakagawa
Department of Irrdustrial Chemistry, Meiji University

Higashi-rnita, Tama-ku, Kawasaki 214 Japan
INTRODUCTION
The industrialization of polymeric membrane processes has grown rapidly since the
1970's because of an increase in our commercial needs. The development of new membrane
materials has been expected produce both high permeability and high selectivity. Masuda's
group reported the excellent permeability for gases in a poly[l-(trimethylsilyl)-1-propyne]
(PMSP, PTMSP) membranein 1983. 1 Now, PMSP membrane is the highest gaspermeable
membrane of all synthetic membranes.
Membranes used for gas separation are required to have the following properties: (a)
high gas permeability coefficient; (b) high separation factor which is defined as the ratio of
permeability coefficients; (c) formation of non-porous thin layer, and (d) durability of
permeability coefficients. Oxygen/nitrogen separation by membranes, which are able to achieve
the oxygen enrichment of 40% concentration from air, have already commercialized for
medical use. More attractive use of membranes in oxygen enrichment for combustion, however,
has been difficult because of rather low oxygen permeation rates. While silicone rubber,
poly(dimethylsiloxane) membrane has the highest oxygen permeability of all non-porous
membranes synthesized on an industrial scale, it has certain defects - low separation factor
and difficulty in forming a thin membrane (thickness less than one micron).
Many groups have reported various modification and fundamental studies of this
polymer. 1 22 PMSP is a glassy polymer, whose glass transition temperature is shown at
250C by a viscoelastic measurement. The PMSP membrane's biggest problern is the
deterioration of its high permeability with time or thermal hysteresis. This suggests the
physical aging of its large excess free volume in the unrelaxed domains of this glassy
polymer. Here, the following items will be presented through our research of this polymer:
(a) very unique gas permeability including aging phenomena, (b) various modifications of
PMSP for gas permeability, (c) modifications for the effective separation membranes with
both high gas and liquid permeabilities and selectivity.
SYNTHESIS OF PMSP AND PREPARATION OF ITS MEMBRANE
PMSP was synthesized under dry nitrogen using TaC1 5 or NbC1 5 or TaC1 5-Ph 3Bi as
catalyst in toluene at 80C for 24 hrs; [1-(trimethylsilyl)-1-propyne] = 0.3M, [catalyst] =

0.02M. 23 ' 24 The product precipitated from a large amount of methanol. The yield was about
80%. The molecular weight and [11] are summarized in Table I. The synthesized PMSP was
dissolved in toluene ; then the solution was cast onto a glass plate and dried in the air. All
membranes were immersed in methanol to keep the membranes fresh. Chernical structure of
monomerandpolymer are shown in Fig. I.
Table 1. Weight average molecular

weight and intrinsic viscosity of
synthesized PMSP. CH3 CH3
I I
Catalyst MI [11]2 c=c +c=C+-
w I I
H3C-Si-CH3 H3C-Si-CH3
TaCl5 (A)3 860,000 6.0 I I
TaCl5 (Bt 540,000 1.6 CH3 CH3
TaCl5 -Ph3 Bi5 2,600,000 9.3
NbC15 3 350,000 0.7 TMSP PMSP
1Weight average molecular weight
2Intrinsic viscosity : [dL/g] Figure 1. Chemical structure of 1-trimethylsilyl-
3[monomer]: [cat.] =IM: 0.2 M 1-propyne, TMSP, and poly( 1-trimethylsilyl-1-
4 [monomer] : [cat.] = 0.3 M : 0.2 M propyne, PMSP.
5[monomer] : [cat.] : [cocat.] = I M: 0.2 M :
0.2M
GAS PERMEABILITY OF PMSP MEMBRANE

Effects of the Less Volatile Organic Vapors and Temperature in the Gas
Permeability
The general theory of gas transport in polymers and detailed discussion of the methods
of measurement and calculation of the permeability, diffusion and solubility coefficients have
been published elsewhere. 23 The experimental method used in our study was an adaptation of
the high vacuum gas transmission technique with an MKS Baratron Model 310BHS-100S
pressure uansducer. Nmmally the gasket is used in order to fix airtightly the membrane
sample in the permeation cell. In the early stage of our experiment, a nitrile rubberwas used
as a rubber gasket. Then silicone rubber with no additives was used, unless otherwise
mentioned.
The Arrhenius plots if the permeability coefficient, the apparent diffusion coefficient and
the permeative solubility coefficient of PMSP membrane to xenon are shown in Fig. 2 for the
case where a niuile rubber gasket were used. When the rubber was used, no reproducible
data were obtained and data were always lower than those of virgin membrane. An analysis
with IR spectra of the virgin PMSP membrane and the membrane which was used for the gas
permeation experiment showed the different absorption spectra, suggesting the presence of
dioctyl phthalate in the latter membrane. The result showed that the dioctyl phthalate was
absorbed in the PMSP membrane from the nitrile rubber gasket in spite of the very low vapor
pressure of dioctyl phthalate. When the silicone rubber gasket was used, reproducible data
were obtained during the short term experiment. This phenomenon is the very special case
which has never been found in other polymer membranes and suggests that PMSP membrane
gas a strong affinity to the less volatile vapors. 6 Such a phenomenon was also observed in
the evacuated atmosphere by the rotary vacuum pump and/or oil diffusionpump with liquid
nitrogen trap, and was emphasized in the case that the thickness of the PMSP membrane was
very thin. On the other hand, no deterioration of the permeability was shown when the
membrane was kept in an oil free chamber evacuated by a turbo-molecular pump to the same
822

o.:-o-
.,..:_.L..... -o--o
~ -o
2.9 3.0 3.1 3.2

1/f X 103 [K 1]
Figure 2. Effect of rubber gasket on the temperature dependence of permeability, P, diffusion, D, and
solubility, S, coefficients for xenon in PMSP membrane. Gasket: Nitrilerubber (e. ..6.); Siliconerubber
(0.0,6).
Table 2. Fermeability (P), effective

diffusion (D), and permeative solubility
coefficient (S) at 30C of PMSP to gases.
Gas p 1 X 108 Dzx105 S3 X 103
He 50.8
H2 132 68.9 1.91
Ne 32.9 10.2 3.23
~ 77.3 3.58 21.6
Ar 69.7 2.65 26.3
CH4 130 2.27 57.3
N2 49.7 2.55 19.5
co2 280 2.17 129
Kr 90.8 1.33 68.3
Xe 117 0.443 264
1[cm 3(STP)cm/cm2seccmHg] Figure 3. Temperature dependence ofpermeability
2[cm 2/sec] (open) and diffusion (filled) coefficients for oxygen
3[cm 3(STP)/cm 3(polym.)cmHg] (circle) and nitrogen (square) in PMSP membrane.
823
degree of vacuum. 10 This is very important properties of the PMSP membrane.
The effect of temperature on the permeability coefficient or effective diffusion coefficient
of N2 and 0 2 through PMSP membrane, which was thermally treated at 50C for a few days
just before the permeation experiments, is shown in Fig. 3. As can be seen in Fig. 3, the
apparent activation energies for permeation, Ep. are negative, while those of diffusion, E 0 ,
are positive. This means that the transport of gases through PMSP membrane occurs by an
activated diffusion process. According to the solution-diffusion theory, Ep is the summation
of Eo and the heat of solution, ~H. The negative value of ~H were frequently found in
polymelic membrane-gas or vapor systems, which have high solubility coefficient, such as
poly(dimethylsiloxime)-trimethyarnine systems. 24
Permeability, Diffusivity and Solubility of PMSP Membrane to Gases
The permeability coefficient P, the effective diffusion coefficient D calculated by the

time-lag and the permeative solubility coefficient S at 30C of PMSP membrane to gases are
summalized in Table 2. Diffusion coefficients of gases in PMSP membrane were also compared
with those in poly(dimethylsiloxane) (PDMS) membrane. The diffusion coefficients in both a
rubbery state PDMS and a glassy PMSP membrane are quite sirnilar. From Table 2, the
higher permeability of PMSP could be correlated with the higher solubility coefficient. The
higher diffusivity is due to the forrnation of large spaces between polymer segments by bulky
side chain of trimethylsilyl group. Later an analysis of the dual-mode sorption mechanism
will be discussed.
Aging of the Gas Permeability
Fig. 4 shows the detelioration of the permeabilities of C02 , H 2 , 0 2 , CH 4 , and N2 at

30C for PMSP membrane synthesized by TaCl 5 The membrane thickness is 61j.lm. The
membrane was kept in the evacuated vessel at room temperature. All gas permeabilities
decreased with time.
--D--Nz
~----~----~----~----~~ --*-CH
4
--tr-C02
--<>-Hz
~02
0 5 10 15 20 25 30
Time [day]
Figure 4. Deterioration of gas penneability ofPMSP with time at30C. Membrane thickness: 6l11m.
824
---o-- NbC15 (170 j.Lm)
- t - - TaC15 -Ph3Bi (163j.Lm)
--o- TaC15 (A)(6lj.Lm)
~ TaCI5 {A){257 j.Lm)
__s;;;.- TaC1 5 (8)(69 j.Lffi)
w- 7 L....L.._.__._._.........__.__._._.........__.__._._.........___.__.._.__._._._.__._-'-L._._.._.__.
0 5 10 15 20 25 30
Time under vacuum [day]
Figure S. Effect of aging time on the gas permeability coefficient for 0 2 at 30C in the PMSP
membranes synthesized with various catalysts. Conditions: stored in a vacuum vessel at 30C.
Fig. 5 also shows the aging effect on the oxygen permeability coefficients in the PMSP
membranes synthesized with TaC15 , NbC1 5 and TaC15 -Ph3 Bi. 25 Time 0 was when a membrane
was taken out of the methanol. An oil rotary vacuum pump was used, and cold trap with
liquid nitrogen was placed between the pump and the membrane during storage under vacuum.
As is evident from Fig. 5, catalyst dependence of the gas permeability was observed.
The configuration of the PMSP could be controlled by the polymerization catalysts. Therefore,
this indicates that the aging of the gas permeability would be dependent on the chain configuration
of the PMSP. The cis/trans ratio was not been quantitatively determined,; however, Costa et
al. 26 reported that the PMSP synthesized with NbC15 had a higher content of long cis or trans
sequence compared with TaC15 Izumikawa et al. 27 described that the PMSP synthesized with
NbC15 was a cis-rich structure compared with TaC15 , and polymerization conditions, e.g.
solvent, temperature and catalyst, hardly affected the geometric structure. Under the aging
conditions used, the gas permeability in the PMSP membrane synthesized with NbC15 was
more stable compared with TaC15 and TaC15 -Ph 3 Bi; that is, a quasistable state of an as-cast
membrane with NbC15 would be more stable compared with others. Using the same catalyst,
i.e. TaC15 (A) and TaC15 (B) in Fig. 5, the aging behavior differed slightly. Wehave already
described the thickness dependence of the gas permeability of the PMSP membranes25 The
gas permeability of the thinner membrane was more sensitive than that of the thicker rnembrane.
Additionally, these initial permeabilities differed slightly. The effect of membrane thickness
on the determination is also seen in Fig. 5. The reason for these difference will be discussed
later.
GAS SORPTION IN PMSP

Analysis of the Sorption Isotherm Using the Dual-Mode Sorption Model
As has already been shown, PMSP has the rigid main chain composed of the alternative
C=C double bonds and the bulky side chain trimethylsilyl group and methyl group. The
density ofthispolymer is 0.72-0.76, which is the lightest density of all synthetic polymers.
825
30
--o-- 0 2 (PMSP)
25
t - - - - N2 (PMSP)
a
......
---<>--- 0 2 (PDMS)
0 20 - - - - N2 (PDMS)
8
"'a 15
~
6:'
E-<
rn
..._, 10
"'a
~
u 5
0
0 5 10 15 20 25 30
Pressure [atm]
Figure 6. Sorption isotherms for 0 2 and N2 of PMSP and PDMS membranes at oc.
PMSP is the typical glassy polymer.

Solubility isotherms for N2 and 0 2 at 35C are shown graphically in Fig. 6. 4 in the fmm
of plots of the concentration c of the penetrant dissolved in the polymer versus the peneuant
pressure p. The isotherms have the typical concave shape to the pressure axis with light gases
in a variety of glassy polymers. Such isotherms are accurately described by the "dual-mode"
sorption model. 28 - 32 This model postulates that peneuant gases dissolve in glassy polymers
by different but simultaneaus modes: (a) by ordinary dissolution in mbbery part of the glassy
polymer, in other wards in the Henry's domain; (b) by entrapment in unrelaxed domains
which may contain an "excess" free volume, perhaps in the fmm of pre-existing rnicrocavities,
in other wards in the Langmuir domain. Penetrant molecules dissolved are partially or totally
immobilized.
When the concenuation of the peneuant population dissolved by the fmmer mode, c0 , is
sufficiently low, it can be related to tl1e peneuant pressure p by Heruy's law. The concenuation
of the penetrant population dissolved by the latter mode, eH , can be related to the pressure by
the Langmuir isotherm equation. Accordingly, the overall penetrant concentration, c, or
solubility, can be expressed as a function of p by the relation:
(1)
where k0 is a solubility coefficient in the Henry's law Iimit, herein units of cm3 (STP) I (cm 3
polymer-atrn); C H is a "hole saturation" constant, in cm 3 (STP) I (cm 3 polymer); b is a
"Langmuir affinity" constant, in atm 1 The total concentration of the dissolved penetrant, c is
therefore in units of cm 3 (STP) I (cm 3 polymer) and the pressure is in atm. parameter C' H
represents the maximum concenuation of penetrant gas in unrelaxed (Langmuir) domains of
glassy polymers, and therefore can be taken as a measure of the excess free volume in these
domains. 28 - 32
Fig. 6 shows the sot-ption isotherms for 0 2 and N 2 in PMSP, comparing with those of
PDMS. This figure also shows the concentration of these gases in PMSP is higher than that
of PMSP by over one order of magnitude. Considering with the diffusivity of these gases in
Fig.3 and Table 2, the main reason of the highest gas permeability of PMSP is the highest
gas solubility of PMSP in addition to the highest gas diffusivity in PMSP with the same
magnitude as that in PDMS.
826
Table 3. Dual-mode Sorptionparameters for co2 of typical glassy polymers.
Polymer Temp. [0 C] k D1 C'l

H bJ
Polystylene 25 0.65 7.7 0.37
Poly(ethyleneterephthalate) 35 0.33 5.76 0.322
Polycarbonate 35 0.685 18.805 0.262
Cellulose acetate 30 1.43 34.2 0.179
Ethyl cellulose 35 1.19 4.85 0.365
Poly(acrylonit:tile) 25 0.206 3.67 0.186
PMSP 35 1.497 112.9 0.058
1Solubility coefficient in Henry's Iaw Iimite : [cm3(STP)/cm3(polym.)atm]
2Hole saturation constant : [cm 3(STP)/cm 3(polym.)]
3Hole affinity constant : [atm" 1]
The c Hof co2 was calculated from the Sorption isotherm of PMSP and compared with
the C'H of other typical glassy polymers in Table 3.4 Table 3 provides a possible reason for
the high gas solubility in PMSP: the parameter c Hin eqn. (1) is much larger for co2 in
PMSP than vatiety of other glassy polymers. This is also the case for the other penetrant
gases studied. The high values of c Hfound for different gases in PMSP suggest that this
polymer contains an unusually large excess free volume. The excess free volume of PMSP is
due, in turn, to its structure. PMSP contains of relatively tigid molecules separated by very
bulky trimethylsilyl side chain. The excess free volume of PMSP is also responsible for the
high diffusivity of gases in this polymer.
Relationship between the Ageing and the Excess Free Volume
The unusual large excess free volume should be responsible for the unusual aging
phenomena. Fig. 7 shows the sorption isotherms for propanein the aged PMSP membranes.
The PMSP membranes were storedinglass tube at 10" 2 - 10" 3 mmHg for 12 h using a liquid
so~----------~~~~~~~~~
-o-- Vac. 1 day
---6-- Vac. 14 days
~
---+-- Vac. 30 days
-;::;- 40 ---SiJ-- Vac. 1600 days
~ 0
-o-- Air. 2200 days
,.,.e 30
E
u
~ 20
tn
'-'
~ 10
u
o~~~~~~~~~~~~~~~~~
0 20 40 60 80 100
Pressure [cmHg]
Figure 7. Sorption isotherms for C3Hg of aged PMSP membranes at 35C. Conditions: stored in a vacuum
vessel for 1. 14, 30, and 1600 days (thickness: 70 ~m) and in air at room temperature for 2200 days
(membrane thickness: 106 ~m).
827
Table 4. Dual-mode sorption parameters for C3 H8 in aged PMSP membranes at 35C.
Condition kD 1 C'H2 b3 Thickness4

20 hrs under vacuum 0.0912 50.1 0.0283 70
14 days under vacuum 0.113 40.0 0.0355 70
30 days in air 0.182 36.4 0.0432 70
2200 days in air 0.121 19.2 0.0762 106
1Solubility coefficient in Henry's law Iimite : [cm 3(S1P)/cm 3(polym.)atm]
2Hole saturation constant: [cm 3(STP)/cm 3(polym.)]
3Hole affinity constant: [atm. 1]
4(Jtm]
nitrogencold trap between the membrane and the pump. These tubes were then heat sealed at
both ends using a flame, wrapped in aluminum foil, and stored at room temperature. When
the membranes were stored in air, the membranes were sandwiehed between filter papers.
With continuing storage time, the sorption concentration decreased, and the C' H value also
decreased as shown in Table 4. 25 From 30 days to 1600 days, the decrease in the sorption
concentration was small compared with that from 1 and 30 days. This means that the glassy
state should approach the stable state. After storage for 2200 days, the sorption concentration
decreased along with a decreased in the gas permeability. The initial PMSP membranes were
colorless and transparent. The membranes stored in vacuum vessel for 1600 days maintained
this appearance; however, those in air for 2200 days became light yellow and transparent.
Witchey-Lakshmanan et al. 15 mentioned that the PMSP become yellowed due to sorbing
vacuum oil vapor. Therefore, these Observations suggest the sorption the sorption of
contaminants during storage in air. Based on these results, in the ease of Storage for a long
time period, the aging behavior under vaeuum is dependent physical aging, whieh would be
influeneed by a small amount of vaeuum pump oil vapor as an aceelerator. On the contrary,
the aging behavior in air at atmospheric pressure was probably determined by a eombination
of physical aging, oxidation effeet, 33 i.e., ehemieal aging, and especially the sorption of
contaminants in air.
MODIFICATION PMSP MEMBRANE

Control of the Excess Unrelaxed Free Volume
The physical aging is the phenomena of relaxation of the unrelaxed free volume, especially
the relativity large size of micro voids. There are several methods in order to control the
exeess free volume: (a) Physieal modifieation, namely the filling of additives, espeeially
polyorganosiloxane61\ or blend with other polymers34; ehemieal modifieation by halogenation 35
or eopolymerization with another acetylene monomer 4
Physical Modification by Filling of PDMS
PDMS ofviseosity 1000 es, MW =2.5 x 10\ 100 es, MW = 6 x 103 , and 10 es, MW
= 1.2 x 103 , were used for filling. Filling with PDMS was earried out by immersing the
PMSP membrane in a solution of methyl ethyl ketone eontaining liquid PDMS at room
temperature for about two days, followed by being taken out from the solution and then
wiped and dried under vaeuum. Only PDMS was left in the membrane. As one of the results,
the sorption isotherms of C02 for PMSP filled with PDMS of 1000 es are shown in Fig.
828
150 ----PMSP
- D - - PMSP filled with 3.19 wt% PDMS
--<>--- PMSP filled with 8.43 wt% PDMS
--..sv---- PMSP filled with 25.1 wt% PDMS
-o-- PMSP filled with 36.3 wt% PDMS
10 20 30 40
Pressure [atm]
Figure 8. Sorption isotherms for C0 2 at 35C of PMSP membrane and PMSP membranes filled with
different contents of PDMS (1000 es).
w-s
~
';fj
..... * .. "
c ::r:E w-6
-~
u
<;:::
"""'0Q)
'-?
u
Q)
~
~
E f:r----.fr----.
N
u
'~
.0 u w-7 ~- - - -~-- - - ~
.
~ A
~
Q) cn ~
- - .
---- ....
0.. "''--'
E - -- -- -
----- -..
~
10-8
2.9 3.0 3.1 3.2 3.3 3.4

l{f x 10 3 (K 1]
Figure 9. Temperature dependence of gas permeability coefficients for various gases in PMSP membrane
(filled symbols, solid lines) and PMSP membranes filled with different contents of PDMS (1000 es): 13.3
wt% PDMS (open symbols. solid lines). 42.9 wt% PDMS (filled symbols, dotted lines).
8_22 In Fig. 8 the convex shape gradually decrease and finally yields a straight for the filled
PMSP. The disappearance of the hole-filling concentration with increasing content of PDMS
below Tg was attributed to the fi.lling of PDMS in the Langmuir domain. From the view poi.nt
of the sorption isotherm, the straight line to the pressure axis suggest the filled PMSP became
rubbery. Fig. 9 shows the AtThenius-type conelations of the permeability coefficient of H,,
0 2 and N2 with temperature in PMSP and two filled PMSPs. 22 The apparent activatio~
energies change from negative value to positive value for pure PMSP membrane to the filled
829
100 ,.----
Il '---
0 50 100 150 200

Time [hour]
Figure 10. Effect of thermal hysteresis on gas permeabilities at 30C in PMSP membrane (open) and
PMSP membranes filled with 0.7 wt% PDMS (filled). Membrane thickness: 60 J.lffi.
PMSP membranes. The permeability coefficient decrease with increase of PDMS content in
the filled PMSP membranes.
For the stabilization of the gas permeability, the filling of only I wt% of PDMS was
found to be enough in Fig. 10? 5 in which the effect of the thermal hysteresis on the
permeability coefficients of PMSP and the filled PMSP with 0.7wt% PDMS (1000 es) to H2 ,
0 2 and N2 are shown. The measurements of all the permeability coefficient were canied out
at 30C for membranes being thermally treated successively at 50, 100 and then 75C for
-12h. The initial permeabilities appear to be equivalent in Fig. 10, because of very small
amount of PDMS filled, which does not decrease the permeabilities. The permeability
coefficients of the PMSP membrane to these gases decreased significantly, whereas those of
the modified PMSP membranes were quite stable throughout such thermal hysteresis. It is
considered that such a small amount PDMS selectively filled the large microvoids, which
probably decay first of all and stimulate the decay of the other voids. In another wards, the
relaxation of the unrelaxed excess free volume was controlled. This is supp01ted by the fact
that abrupt reduction of C' H occurs by a small amount of PDMS (1000 es) filled.
Chemical Modification by Copolymerization for Stabilization
The polymer used were the same PMSP, poly(TMSP-coPP) and PPP, having as average
molecular weight between 80 x 104 g/mol. Only the PMSP synthesized with TaC1 5 -Ph 3Bi as
a catalyst had an average molecular weight of 260 x 104 g/mol. Here, PP and PPP stand for
1-phenyl-1-propyne and poly(l-phenyl-1-propyne), respectively. These structure are shown
830
CH3 CH3
I I
c=c
I
+c=c+
I
Ph Ph
PP ppp
Figure 11. Chemical structure of l-penyl-1-propyne, PP, and poly(l-phenyl-1-propyne), PPP.
in Fig. 11. All membranes, including blends of PMSP and PPP were cast on horizontal glass
plate from a solution of toluene. They were immersed in methanol just before the measurement
of gas permeability to prevent hysteresis of the membranes. The compatibility of PMSP and
PPP was not good and the phase separation was found in the blend copolymer that the
content of PPP was more than 10 wt%.
Fig. 12 illustrate the SOrption isotherrns for co2 in the initial and aged poly(TMSP-co-PP)
and PMSP/PPP blend membranes at 35C. 35 These samples had same membrane thickness
and the aged membranes were stored in a vacuum vessel for 14 days at 30C. The gas
concentration of the PMSP dramatically decreased, but the PPP and blend membranes had
the same cmves. The copolymer's value slightly decreased. The C'H values were calculated
from this figure. The C'H value of the PMSP was dramatically reduced as was the gas
permeation behavior. The blend and PPP had stable gas perrneability and their C' H values
were the same after aging. On the other band, the C'H value of the copolymer decreased as
did the gas permeation behavior. The C'H value was strongly related to the gas permeability
and the stability of the perrneability of these membranes.
Interestingly, although the initial C' H value of C 3H 8 in the copolymer was larger than
that of the blend, the opposite results appeared in the C02 case; that is, the initial C' H value of
C02 in the copolymer was smaller than that of the blend. The microvoids of a glassy polymer
have the size and distribution. C02 and CH4 molecules have different molecular shapes and
200 --o-- PMSP (initial)

----.-- PMSP (aged)
--<>-- Copolymer (95:5) (initial) Gas: C02
--+-- Copolymer (95:5) (aged)
- - l l - Blend (95:5) (initial)
~ 150 ---.-- !end (95:5) (aged)
--v-- PPP (initial)
.a-
s
---9---- PPP (aged)
1. 100
~
~
]. 50
u
o~~~~~~~~~~~~~~~~~
0 10 20 30 40 50
Pressure [atm]
Figure 12. Sorption isotherm for C0 2 in the initial (open) and aged (fliled) PMSP, PPP. poly(TMS-co-PP)
(95 : 5). and PMSP/PPP blend (95 : 5) membranes at 35C. Aging condition : stored in a vacuum vessel at
30C.
831
diameters. A CH4 molecule is too large relative to C02 molecule to be sorbed in smaller
microvoids in a glassy polymer. However, the C'H value can provide only the total volume.
This results is probably due to a difference in the size and distribution of microvoids in the
copolymer and blend membranes. lt is assumed that the blend membrane has smaller microvoids
relative to the copolymer membrane and this is the mail reason of the stability of the gas
permeability.
Modiflcation for the Selective Permeation of Sour Gases of PMSP Membranes
One of the subjects in the gas membrane separation field is to remove sour gases from
the CQ2 emission SOurceS SUCh as power Stations steelworks and chemical industries, which
are burning fossil fuels such as coal, oil and natwal gas.
lt is generally known that polymeric membrane which has high gas permeability may
exhibit low selectivity and vice versa. One technique to achieve high values frr these properties
to modify high flux membrane materials in the form of blending or impregnation using
modifiers. 21 The 3-methylsulfolane modified PMSP membranes were p1-epared by impregnating
PMSP membranes in a saturated 3-methylsulfolane vapor. The content of 3-methylsulfolane
in the membranes were controlled by the sorption time.
The PMSP membranes modified by 3-methylsulfolane showed good selectivity for C02
with the trade-off relationship, namely the C02 permeability coefficient of PMSP/3-
methylsulfolane decreased and the separation factor for N2 increased with the increase in the
3-methylsulfolane content, but the permeability coefficient was still over 1,000 Barrer. Mm-e
influence of 3-methylsulfolane in the PMSP membranes for sour gas separationwas found
for S02 separation. Fig.13 shows the effect of 3-methylsulfolane content in the PMSP
membranes on S02 permeability coefficient and the separation factor of SO/N2 at 30C. As
can be seen in Fig. 13, both the permeabilities of S02 and N2 decreased with the increased in
3-methylsulfolane in the membrane. However, the solubility of S02 increased in the modified
160
140
'"'' 120
~
~'wo
~
.Mc:: 80
0
a 60
~
fr
Cl:l
40
20
I----- P (SOz}/P (Nz} I
L...-J--.L-.L-_.___.___.___,___,__........__. 10-9
00 10 20 30 40 50
3-methylsulfolane content [wt%]
Figure 13. Plots of gas permeability coefficient for S02 and separation factor for SOjN2 at 30C v.s.
3-methylsulfolane content in PMSP membrane.
832
membranes. Therefore, the diffusion coefficients of S02 and N2 of modified membranes
decreased remarkably. As the results, the permeability coefficient of S02 became much
higher than that of N2 in the modified membranes and the high ideal separation factor for
SOzfN2 of about 150 was obtained.
SUMMARY
The PMSP membrane gas the highest gas permeability of all non-porous polymer
membranes. The diffusion coefficients of gases were 10 5 cm2/sec order, which is also the
highest value, and especially the solubility coefficients of gases in PMSP membranes are
very high, comparing with those in the other polymers. The PMSP membranes has the very
high excess unrelaxed free volume.
The declining of the PMSP membranes is caused by the absorption of non volatile
organic vapors and physical aging. During aging, the unrelaxed volume of the PMSP membrane
was relaxed, suggesting that the decrease in the microvoids caused a tighter chain packing.
The effect of the absorption on the decrease of the gas permeability was remarkable for the
thinner membranes, and PMSP has a strong affinity for organic vapor. The physical aging
also depends on the catalysts which were used for polymerization.
The stabilization of the gas permeability is important. To control the unrelaxed excess
free volume, microvoids, may be the basic idea for the stabilization. For that, there is the
filling of a small amount of poly(dimethylsiloxane), Silicone-oil, in the PMSP membrane. As
another methods the copolymerization and with PP structure were novel strategy aimed at
improving the stability of the gas permeability of PMSP membranes. In particular the addition
of small amount of the PP structure provided excellent stability high gas permeability. The
gas permeation properties were cotTelated with the behavior of C'H, relating to the volume of
microvoids. The addition of the special chemieals which have affinity for a special gas is also
one of the very impmtant modification methods for the high effective membranes for the gas
separation.
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polymer synthesized with transition-meta! catalysts and characterized by extremely high gas
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poly[l-(trimethylsilyl)-1-propyne], Kobunshi Ronbunshu43:747 (1986).
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trimethylsilyl-1-propyne). J. Memb. Sei. 34:5 (1987).
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6. T. Nakagawa, T. Saito. S. Asakawa and Y. Saito, Polyacetylene derivatives as membranes for gas
separation, Gas Separation and Purifieation 2:3 (1988).
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modification ofpoly[1-(trimethylsilyl)-propyne) for gas separation membranes. Gas Separation and
Purifieation. 2:162 (1988).
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polyacetylene membranes, Polymer 29:2041 (1988).
10. S. Asakawa. Y. Saito. K. Waragai and T. Nakagawa. Composite membrane of poly[l-(trimethylsilyl)-
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833
11. K. Takada. Z. Ryugo and H. Matsuya, Studies on the applications of substituted poly(acetylene). VI.
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and its composite membrane. Kob1mshi Ronbunshu 46:1 (1989).
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13. K. Takada, Z. Ryugo and H. Matsuya. Studies on application of substituted polyacetylene. VIII. study of
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14. T. Nakagawa, H. Nakano, K. Enomoto and A. Higuchi, The highest gaspermeable membrane of
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Series, No. 272 85: I (1989).
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in poly[l-(trimethylsilyl)-1-propyne], J. Memb. Sei. 48:321 (1990).
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poly(dimethylsiloxane) graft copolymer,J. Polym. Sei., Polym. Phy. Ed. 29:171 (1991).
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Yampol'skii, Gas and vapor permeation and sorption in poly(trimethylsilylpropyne), J. Memb. Sei.
60: 13 (1991).
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of free volume in poly(trimethylsilyl propyne) by positron annihilation and electrochromism
methods,J. Appl. Polym. Sei. 47:85 (1993).
20. K.K. Hsu, S. Nataraj, R.M. Thorogood and P.S. Puri, polytrimethylsilylpropyne membranes by
UV -irradiation and further enhancement by subambient temperature. J. Memb. Sei. 79:1 (1993).
21. G. Chen. H.J. Griesser and A.W.H. Mau. Gaspenneability of poly[l-(trimethylsilyl)-1-propyne]
membranes modified by hexafluorobutyl methacrylate,J. Memb. Sei. 82:99 (1993).
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propyne) membranes for gas separation,J. Memb. Sei. 94:183 (1994).
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membrane, Kobunshi Ronbunshu 34:725 ( 1977).
25. K. Nagai and T. Nakagawa. Effects of aging on the gas permeability and solubility in poly(l-
trimethylsilyl-1-propyne) membranes synthesized with various catalysts,J. Memb. Sei. 105:261
(1995).
26. G. Costa, A. Grosso, M.C. Sachi, P.C. Stein and L. Zetta, A study by solid-state and solution 13C NMR
on silicon-containing polyacetylenes. Macromoleeules 24:2858 (1991).
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poly[1-(trirnethylsilyl)-l-propyne] by 13C and 29Si NMR spectroscopies. Polm. Bu/1. 27:193
(1991).
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29. D.R. Paul. Gassorption and transport in glassy polymers, Ber. Bausenges. Phys. Chem. 83:294 (1979).
30. D.R. Paul and W.J. Koros, Effect ofpatially immobilizing sorption on permeability and the diffusion
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31. D.R. Paul and W .J. Koros. Transient and steady-state permeation in poly(ethylene terephthalate) above
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20:956 ( 1979).
33. K. Nagai and T. Nakagawa, Oxidation ofpoly(l-trimethylsilyl-1-propyne),J. Appl. Polym. Sei. 54:1651
(1994).
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Phys. Ed. 35:119 (1997).
35. K. Nagai, A. Higuchi and T. Nakagawa. Gas permeation and sorption in brominated poly(l-
trimethylsilyl-1-propyne) membrane,J. App. Polym. Sei. 54:1353 (1994).
834
SOL-GEL-DERIVED MATERIALS FOR ANALYTICAL SEPARATIONS
Luis A. Colon
State University of New York at Buffalo
Buffalo, NY 14260-3000
INTRODUCTION
The use of fused silica capillary columns (<500 11m i.d.) to perform liquid phase
analytical Separations the offers numerous and very attractive features. 14 These include an
increased mass sensitivity, high efficiency, short analysis times, low solvent consumption,
low operational cost, and the capability of handling extremely low volume samples (<l!lL).
Open tubes and packed capillaries are the typical columns used to separate the solutes in a
sample. The open tubular format is used in capillary electrophoresis (CE),5 capillary
electrochromatography (CEC),6 and open tubular liquid chromatography (OTLC). 1 In the
case of CE, analytes are separated based on their differential migration under an applied
electric field; in most cases, a net solvent flow is also generated due to electroosmosis. In
OTLC, separation is based on distribution ratios between two phases (mobile and stationary
phase). The mobile phase is pumped through the column while the stationary phase is fixed
at the walls of the capillary. Open tubular capillary electrochromatography (OT-CEC),
however, is a relatively new technique that combines CE and OTLC. In this technique, an
electric field is applied across a capillary column which contains a stationary phase at the
inner walls. The electric field generates an electroosmotic flow (EOF), which possesses
unique properties, to drive the solvent and solutes through the column. CE is the most
commonly practiced of these techniques.
One of the major difficulties in OTLC and OT-CEC is the preparation of capillary
columns (<15 11m i.d.) with sufficient retentive characteristics. Although efforts in this area
have increased,6-9 several problems remain. The most common approach to column
preparation has been to chemically bond the stationary phase onto the inner walls of fused
silica capillary tubes. Because of the low surface area of the tube, this approach Ieads to low
phase ratios, which translates into low retention and low sample capacity. The methods
developed to increase surface area are time consumingY Other procedures using polymeric
phases9- 11 suffer from poor efficiency because of the slow diffusivity of solutes in such
polymeric phases. Furthermore, these types of phases cannot be used for OT-CEC since the
EOF is suppressed.
Scknce and Technology of Polymers and Advanced Materials

We are using sol-gel technology to fabricate coating materials on the inner walls of
fused silica capillaries for OTLC and OT-CEC. 12- 14 The sol-gel method produces porous
silica glasses at room temperature, and has been used in a variety of applications, from
nonlinear optical composites to chemical sensing platforms_ 15- 17 Herein, we describe the use
of the so I-gel process to fabricate silica-based coating materials suitable for OTLC, OT-CEC,
and CE. The Separation performance of capillary columns prepared by this means is also
presented.
EXPERIMENTAL
The equipment required for OTLC and OT-CEC was constructed in our laboratory, as
previously described. 12- 14 The CE experiments were performed in a P/ACE Model2200 CE
unit (Beckman, Fullerton, CA, USA). Fused silica capillaries were purchased from
Polymicro Technologies (Phoenix, AZ, USA). The organosilane compounds used as
precursors to prepare the sol-gel solutions were tetraethoxysilane (TEOS), n-
octyltriethoxysilane (C8-TEOS), and aminopropyltriethoxysilane (APTEOS), which were
obtained from United Chemical Technologies (Horsham, PA, USA). Solventsand reagents
were purchased from Fisher Scientific (Pittsburgh, PA, USA) and Aldrich (Milwaukee, WI,
USA), respectively. Water was purified with a Milli-Q UV Plus water purification system,
fed from a Milli-RO 10 Plus reversed osmosis system (Millipore, Bedford, MA, USA). The
mobilephasewas filtered through 0.45J-Lm nylon membrane filters (Supelco, Bellefonte, PA,
USA) and degassed prior to use.
The procedures to prepare the fused silica capillary columns containing the sol-gel
material have been described previously. 12- 14' 18 Generally, capillaries are rinsed with IM
KOH to expose the maximum number of silanol groups at the inner surface; then, they are
rinsed with water before drying at 180C ovemight. The coating material is prepared by
adding appropriate amounts of the organosilane precursors, water, ethanol (solvent) and the
catalyst (HCI). The water added corresponds to the stoichiometric quantity required to
completely hydrolyze the silane precursors. For example, to prepare a sol-gel solution
containing a C 8- TEOS/TEOS molar ratio of 0.3 the following quantities are mixed: 0.5 mL
of TEOS, 0.21 mL of C8 - TEOS, 0.33 mL of ethanol, 0.19 mL of water, and 6 J.lL of 0.1M
HCI. The solution is stirred for 6 hrs. The liquid-like sol-gel solution is then used to coat
the capillaries by means of a syringe. The excess material is removed by pressure. The
coated capillaries are allowed to dry overnight at 120C under nitrogen flow. The columns
are washed with acetone and methanol, and then equilibrated with the mobile phase for 30
minutes before use.
A Sol-Gel Derived Stationary Phase
The sol-gel method provides a new means to fabricate a stationary phase on the inner
walls of capillary columns. In our procedure, the commonly used sol-gel precursor TEOS
is hydrolyzed in conjunction with another precursor that contains an alkyl substituent (C 8-
TEOS). This approach allows the fabrication of an organically modified silica glass material
that can act as the stationary phase for OTLC and OT-CEC. The C 8 groups become an
intrinsic part of the glass matrix, as the hydrolyzed C8- TEOS molecules are incorporated in
the glass network. The surface silanols on the inner walls of the silica capillary are
incorporated into the polycondensation reactions, thereby anchoring the coating to the
836
1,2,3
A B
0 5 10 15 0 5 10 15
Times (minutes)
Figure I. Separation of three model compound by OT-CEC in (A) a capillary coated with a C8-
TEOSffEOS ratio of 2 and (B) capillary coated with TEOS only. Conditions: capillary, 13 !Jffi i.d. x 50 cm
length; mobile phase, methanol/lmM phosphate (67:33); separation voltage, 30 kV; electrokinetic
injection, I s at 30 kV; detection, UV at 220 nm. Testmixture contained (I) naphthalene, (2) phenanthrene,
and (3) pyrene. (Reprinted with permission from ref. 12, copyright American Chemical Society, 1995)
capillary walls. The C 8 groups exposed on the surface serve as the stationary phase in the
separation process. Figure 1 shows the separation of three model compounds in two different
columns, one containing a C 8- TEOSffEOS coating and the other containing only a TEOS
coating. The probe compounds are completely separated inside the column with the
C 8- TEOSffEOS material. However, no separation is achieved in the column prepared with
TEOS. This is an indication that the C 8 groups are chromatographically accessible to the
probe compounds, serving as the stationary phase for the separation process.
Figure 2 shows OT-CEC separations of a test mixture in two different columns using
sirnilar separation conditions. One of the capillary colurnns was coated with a sol-gel-derived
phase. The second capillary was prepared by a conventional procedure (reacting
octyldimethylchlorosilane with the capillary walls). All the components in the test mixture
were separated using the capillary containing the sol-gel derived phase. The capillary
prepared by the conventional method, however, was not able to resolve all the components
837
3
4
u1
1,2,3
u 4
0 2 4 6 8 10 12 14
Time (minutes)
Figure 2. OT-CEC separations in capillary columns with (A) a sol-gel-derived phase (C8-TEOSrrEOS = 0.3)
and (B) a conventionally prepared phase. Conditions: capillary, 10 11m i.d. x 48 cm Iength; mobile phase,
methanol/lmM phosphate (55/45), containing 0.5% triethylamine; separation voltage, 30 kV; electrokinetic
injection, 3 s at 6 kV; detection, UV at 210 nm. Testmixture contained (u) impurity, (I) phenol, (2) toluene,
(3) naphthalene, and (4) biphenyl. (Reprinted with permission from ref. 13, copyright John Wiley & Sons,
Inc., 1995)
838
2
3
1
" ... l,j ~... ........... ......

I "'
0 10 20 30 40
TIME (minutes)
Figure 3. OTLC separation of anthracene derivatives on a capillary containing a sol-gel derived phase (C8-
TEOS/TEOS = 2.5). Conditions: capillary, 12.6 J.lffi i.d. x 60 cm length; mobile phase, acetonitri1e/water
(60/40), flow rate, 5.6 nL min 1 LIF detection. Mixture, (l) silicylate, (2) anthracenecarbonitrile, (3)
anthracene, (4) fluoranthene, (5) 9-methylanthracene, (6) benz[a]anthracene, (7) 9-phenylanthracene.
(Reprinted with permission from ref. 14, copyright Friedr. Vieweg & Sohn Verlagsgesellschaft mbH, 1996)
present in the mixture. The materials fabricated by the sol-gel technology have an
intrinsically high porosity and large surface area. 15 These characteristics offer increased
phase ratio and sample capacity in capillary columns. Therefore, the sol-gel approach
overcomes the insufficient retention of the capillaries prepared by conventional procedures.
In addition, the so I-gel method increases the surface area while incorporating the stationary
phase in the same fabrication step. This reduces the time required to prepare a column with
increased surface area. Other methods require at least two different steps to obtain high
surface area. 6-8 Figure 3 shows the performance of a capillary colurnn containing the sol-gel
derived stationary phase in OTLC. Wehave shown that such separation performance is
similar to that obtained with columns prepared by the more time-consuming methods. 14
The amount of C 8 material available for separation can be varied by adjusting the
amount of the C8- TEOS precursor in the original solution; this is a means to vary the
retention of the sol-gel-derived phases. The effect of varying the C8- TEOSffEOS ratio in
839
(A)
Q)
(.)
c:
ctl
.0
0
Cl)
.0
<(
Q)
>
~
Q5
a::
2
4
5
0 5 10 15
TIME (minutes)
Figure 4. OTLC separation of five toluene homologues on three sol-gel-derived capillary columns prepared
by using different C8-TEOSffEOS ratios: (A) C 8-TEOSrrEOS = 0.5, (B) C8-TEOSffEOS = 1.5, (C)
C 8-TEOSffEOS = 2.5. Conditions: capillaries, II f.lill i.d. x 40 cm length; mobile phase, methanollwater
(70/30), flow rate, 7.8 nL min 1. UV detection at 210 nm; mixture, (I) toluene, (2) ethylbenzene, (3)
propylbenzene, (4) butylbenzene, (5) pentylbenzene. (Reprinted with permission from ref. 14, copyright Friedr.
Vieweg & Sohn Verlagsgesellschaft mbH, 1996)
the original solution on a separation is illustrated in Figure 4. The figure shows the
separation of five toluene homologues performed in three different sol-gel-derived stationary
phases, which were prepared by varying the C 8- TEOSffEOS ratio in the original solution.
The retention of the model compounds increases as the precursor ratio is increased from 0.5
to 2.5. The capacity factors (a measure of retention) for the first eluting compound (toluene)
and the last eluting compound (pentylbenzene) increased from 0.06 and 0.56 to 0.13 and
1.06, respectively. This indicates that the phase ratio increases as more C8- TEOS is used to
prepare the coating material.
Amino-Silica Coating for CE
We have also prepared an amino-silica coating material for CE using sol-gel

technology. 18 The material is prepared using APTEOS as the precursor for the coating. The
840
incorporation of amino groups on the surface of the fused silica capillary allows change in
the net surface charge. The pH of the running electrolyte in CE controls the protonation of
the amino groups and the dissociation of the silanals present at the surface. The net surface
charge controls the EOF through the capillary column. Therefore, by controlling the pH of
the running electrolyte, the direction and magnitude of the EOF can be manipulated. The
electroosmotic mobility in a capillary column coated with APTEOS is affected by the pH of
the running electrolyte. This effect is shown in Figure 5 in the pH range of 2-11. It can be
seen that the magnitude and direction of the EOF changes as the running electrolyte is
changed. Above pH 6.3, the direction ofthe flow is from anode to cathode, while below pH
6.3, the direction of the flow is cathode to anode. At pH-6.3, the EOF is suppressed (no net
flow). These characteristics facilitate the use of a single capillary column for different
applications in CE, where reversal of the EOF is required.
Stability
The sol-gel coating material inside the capillary columns has shown excellent hydrolytic
stability. Capillary columns with the C 8 coating have been exposed to acidic and basic
"'i 4
0
-r-
-<:
X
rn
C\1
3
-
E
u
~
:.0 0
0
:aE -1
u
~ -2
rn
g,_ -3

Q) -4
w
-5
2 3 4 5 6 7 8 9 10 11
pH of Running Electrolytes
Figure 5. Electroosmotic mobility vs. pH of the running electrolyte (20 mM phosphate) in an amino-silica
coated capillary: 50 11m i.d. x 47 cm length. Upper panel EOF towards the cathode, lower panel EOF towards
the anode. (Reprinted from ref. 16, Journal of Chromatography A 744, copyright 1996 with kind permission
ofElsevier Science- NL, Sara Burgerharhartstraat 25, 1055 KV Amsterdam, The Netherlands)
841
conditions to test their stability as follows. At low pH, a capillary column was washed with
1% trifluoroacetic acid (pH -0.8) for a period of time, after which the acid was flushed out
of the column. The column was then equilibrated with a mobile phase consisting of
methanol: 1 mM phosphate buffer (70:30) for 20 minutes. A test mixture containing two
probe compounds (naphthalene and phenanthrene) was injected into the column to evaluate
its performance. This procedure was repeated until the column was exposed to 1%
trifluoroacetic acid for a period of 32 hours. At high pH, the pH of the mobile phase was
adjusted to 11.4 with Na3P04 . The mobile phase was continuously run through the capillary
column for a period of 48 hours. The column performance was examined by injecting the
test mixture at several time intervals. In both cases, the capacity factor was obtained for each
component of the test mixture.
As shown in Figure 6, the capacity factors remained relatively constant throughout
the test. Even after exposure to high- or low-pH conditions, a retentive layer was still on the
surface of the capillary to effect separation. The stability of the sol-gel-derived phase can be
attributed to the fact that the phase is not prepared by modifying a silica surface through
siloxane bonds, as in the conventional procedure. Instead, the stationary phase is obtained
by bulk modification of the silica glass prepared through the sol-gel method. The C8 groups
(i.e., the stationary phase) on the sol-gel coating are linked to the silica support through Si-C
bonds. Such bonding is more hydrolytically stable than the 0-Si bond obtained during
surface modification. 19 At high-pH, the performance degradation of stationary phases
0.28 A B
-~
0.21
~
....
u..
........... _
0.14
~
-~
c.
1'11
--
(.)
0.07
~
0.00 '----'--.l..---I..-..J..._--L_....J....J
0 10 20 30 0 10 20 30
Time (hours)
Figure 6. Retentive characteristics of capillary colwnns prepared by the sol-gel method exposed to (A) acidic
conditions and (B) basic conditions, for naphthaJene (triangles) and phenanthrene (circles). (Reprinted with
permission from ref. 12, copyright American Chemical Society, 1995)
842
..,.
,...
0-1
X
Ui
~
E -2
~
-~
:.0
0
~ -3
:aE
0
C/)
e -4
0
u
Q)
LU
-5
0 10 20 30 40 50
Time (hours)
Figure 7. Electroosmotic mobility measured at pH 3 (20 mM phosphate) as a function of the time the capillary
was exposed to 1% trifluoroacetic acid, filled circles for a sol-gel amino-silica coated capillary, open circles
for an amino-silylated capillary .. (Reprinted with permission from ref. 18, Journal ofChronwtography A 744,
copyright 1996 with kind permission of Elsevier Science - NL, Sara Burgerharhartstraat 25, 1055 KV
Amsterdam, The Netherlands)
prepared conventionally is a result of hydrolytic dissolution of the silica surface, rather than
siloxane bond cleavage. 20 Because of incorporation of the C8 - TEOS precursor
into the sol-gel network, the modification becomes an intrinsic property of the glass matrix.
Therefore, if a layer of the coating material is removed through hydrolytic processes, the new
exposed layer will exhibit the corresponding characteristics of the glass material; 21 this
accounts for the performance at high-pH conditions.
Capillaries with the amino-silica coating exhibit a strong EOF (from cathode to anode)
in the low pH range (pH<4.0). To maintain a reliable EOF, it is important that the material
remains stable in the Jow pH range. Figure 7 shows that exposing the coated capillary to
harsh conditions (1% trifluoroacetic acid) for a period of 45 hours does not affect the EOF.
An amino-silylated capillary (conventional procedure) subjected to similar conditions
showed a significant decrease in EOF (-80% in 18 hours ). This is an indication that the
amino groups chemically bonded through the silylation method were removed from the silica
surface. The sol-gel derived amino-silica glass, on the other hand, exhibited excellent
stability. As with the C 8 material, the aminopropyl groups in the amino-silica coating are
introduced by bulk modification during the glass formation process. They are not attached
to the surface through hydrolytically unstable siloxane bonds, as is the case in the amino-
silylated capillary. The aminopropyl groups are attached to the coating surface through Si-C
bonds, which are hydrolytically stable at low pH values?2
843
CONCLUSION
The sol-gel method allows for the fabrication of coating materials inside capillary
columns in a relatively simple manner. This approach can be used successfully to fabricate
organo-silica glasses as the stationary phase for reversed-phase OTLC and OT-CEC. The
sol-gel process provides for an increase in surface area, resulting in a higher phase ratio. The
material shows hydrolytic stability at high and low pH. A sol-gel amino-silica material
produces a very stable coating that allows the switching of the EOF in CE. It is quite clear
that sol-gel technology has great potential for capillary separation techniques.
ACKNOWLEDGEMENT
Financial support from the National Science Foundation (U.S.A.) is greatly

acknowledged.
REFERENCES
I. M. Novotny, Anal. Chem. 60:500A (1988).

2. J. W. Jorgenson;, K. D. Lukacs, Anal. Chem. 53:1298 (1981).
3. R. T. Kennedy, M. D. Oates, B. R. Cooper, B. Nickerson, B.; J. W. Jorgenson, Science, 249:57 (1989).
4. J. P. Chervet, M. Ursem, J. P. Salzmann, Anal. Chem. 68:1507 (1996).
5. R. Weinberger, Practical Capillary Electrophoresis, Academic Press: Boston (1993).
6. J. W. Jorgenson, E. J. Guthrie, J. Chromatogr. 255:335 (1983).
7. Tock, P. P. H.; C. Boshoven, H. Poppe, J. C. Kraak, K. K. Unger, J. Chromatogr. 477:95 (1989).
8. A. L. Crego, J. C. Diez-Masa, M. V. Dabrio, Anal. Chem., 65:1615 (1993).
9. K. Bohlin, M. Larson, J. Chromatogr. 645:41 (1993).
10. R. Swart, J. C. Kraak, H. Poppe, J. Chromatogr. A, 640:25 (1990).
II. P. R. Dluzneski, J. W. Jorgenson, J. High Resolut. Chromatogr. Chromatogr. 11:332 (1985).
12. Y. Guo, L. A. Col6n, Anal. Chem. 67:2511 (1995).
13. Y. Guo, L. A. Col6n, J. Microcol. Sep., 7:485 ((1995).
14. Y. Guo, L. A. Col6n, Chromatographia 43:477 (1996).
15. C. J. Brinker, G. W. Scherer, Sol-Gel Science, Academic Press, New York (1990).
16. C. B. dave, B. Dunn, J. S. Valentine, J. I. Zink, Anal. Chem., 66:1120A (1994).
17. 0. Lev, M. Tsionsky, L. Rabinovich, V. Glezer, S. Sampath, I. Pankratov, J. Gun, Anal. Chem., 66:22A
(1995).
18. Y. Guo, Y, G. A. Imahori, L. A. Col6n, J. Chromatogr. A, 744:17 (1996).
19. K.A. Cobb, V. Dolnik, M. Novotny, Anal. Chem. 62:2478 (1990).
20. J. J. Kirkland, M. A. van Straten, H. A. Claessens, J. Chromatogr., 691:3 (1995).
21. H. Schmidt, H. Bttner, in: The Colloid Chemistry of Silica, H. E. Bergna, Ed., American Chemical
Society, Washington, Chapter 20 (1994).
844
TRANSPORT OF MULTICOMPONENT GAS MIXTURES
THROUGH POLYMERIC MEMBRANES
Mohammad Soltanieh and Mahta Momeni
Departmant of Chemical Engineering

Sharif University of Technology
P. 0. Box 11365/8639
TEHRAN - IRAN
INTRODUCTION
Development of high pedormance polymeric membranes for

separation of gases has resulted in significant competition with traditonal
processes for gas separationssuch as absorption and adsorption [1].
Membranes which are used for gas separation may be either symmetric
or asymmetric [2]. In the symmetric type pore size and pore distribution are
uniform across the membrane thickness, whereas in asymmetric membranes
the structure varies in different layers across the thickness. Asymmetrie
membranes may be of the phase inversion or composite types, the latter
being preferred due to its ability to be designed for optimum permeability
and selectivety. The polymer types that are used to make membranes may be
rubbery or glassy.
In recent years many different types of polymeric membranes, both
asymmetric and composite, have been developed for gas separation
applications such as oxygen enrichment in air, hydrogen recovery from
hydrocarbons in refinery operations, and natural gas sweetening (H2S and
C02 separation from hydrocarbons).
Depending on the structure of the membrane and the nature of the
gases to be separated, different mechanisms describe permeability and
selectivity of the membranes. Both asymmetric and composite membranes
have two layers of dense and paraus structure. In the dense layer, solution -

diffusion mechanism and in the paraus layer pore flow mechanism describe
the behavior of the membranes. In this paper these two mechanisms are
presented for prediction of separation and permeability of the dense and
paraus membranes. It is shown that for rubbery membranes absorption
based an Henry's law and diffusion by Fick's law describe transport of gases
thraugh the dense ( nonparaus) layer of the membrane, whereas for glassy
membranes transport thraugh the dense layer of the membranes is described
by Henry's law for absorption, Langmuir isotherms for adsorption and Fick's
law for diffusion. In the paraus layer, Knudsen- Poiseuille flows are used to
describe transport of gases through the membranes. Pore characteristics and
physicochemical praperties of gases are used to predict membrane
permeability and selectivity. The predictions of the models are compared
with the data reported in the Iiterature for pure gases and where possible for
multicomponent gas mixtures.
TRANSPORT MODELS
a. Nonporous (Dense) Membranes
For nonparaus rubbery membranes where T > Tg' the gas molecules
from upstream side dissolve in the membrane matrix by absorption according
to Henry's law, diffuse through the membrane by Fick's law, and then desorb
fram the downstream side of the membrane. Based an this mechanism which
is usually called the solution - diffusion model, membrane permeabilities
have been calculated [3, 4, 5]. The difference in the thermodynamic activity
acrass the membrane is the driving force for separation [6].
Based an the above mechanism for rubbery membranes, the gas
concentration in the membrane is given by
C = Sp (1)
The diffusion flux of the gas is given by Fick's law
(2)
The permeability is therefore defined as
P=DS (3)
For nonparaus glassy membranes where T < Tg' permeation

mechanism is different and follows the dual-mode sorption mactel [7, 8].
846
According to this model there are two types of adsorption sites in the glassy
membranes namely the Henry's sites and the Langmuir's sites. The former
sites refer to the dense - nonparaus sites of the membrane while the latter
sites refer to the microvoids (free volume). Paul and Karos [9] have used the
dual - mode sorption model to describe gas permeation through membranes.
This modelwas further developed by Barrer, aL [10].
According to the dual - mode sorption model, the total solubility of the
gas in the membrane is given by
C=~+Cr_=Sp+
cs bp (4)
1+bp
In Eq.( 4), b is the pore affinity constant which shows the tendency of the gas
for Langmuir adsorption, and e8 is the pore Saturation COStant which ShOWS
the adsorption capacity of the membrane and it increases with decreasing
temperature. At low pressures, bp 1, the adsorption isotherms reduce to a
Henry's type linear form
C = (S + C8 b) p (5)
whereas at high pressures, bp 1, the Langmuir sites become saturated and

the adsorption isotherms reduce to
(6)
which indicates that at high pressures the gas solubility in the membrane also
varies linearly with pressure.
lt can be shown that the total concentration of the gas in the membrane
is given by
c = ~ + Cr_ = [1 + es b I s ]~ (7)
1 + (b/S) eH
The dissolved gas is diffused through the membrane by the Fick's law.
Assuming that : (a) the molecules adsorpted onto the Langmuir's sites have
lower mobility than those adsorpted onto the Henry's sites [9], (b) there
exists equilibrium between the mobile and stationary gas molecules, and ( c)
the diffusion coefficients are not dependent an concentration or position [8],
the diffusion flux is given by
(8)
where DH and DL are the diffusion coefficients of molecules due to Henry

and Langmuir contributions which are functions of temperature. Let F = DL
847
I DH and DH = D, then Eq. (8) can be written as
Q = -0[1 + F~]~ (9)

d~ dx
Assuming that (a) the total concentration of the gas can be divided into
two portians , namely the mobile portion, em with diffusion ciefficient D and
the immobile portion with residual concentration e - em, and (b) the gas
adsorpted on Henry's sites, with concentration eH and the fraction F on the
Langmuir sites are mobile and diffuse with diffusion coefficient D,
0=-D~ (10)
dx
with
(11)
the diffusion equation at steady state is integrated to
e = em] - em? +e (12)

m 1 x m2
where emt and em2 are the downstream (x = l, p = Pt) and upstream
(x = 0, p = p 2) concentrations, respectively. The diffusion flux is then
(13)
Accordingly, the permeability coefficient is defined by
p = _QJ_ = D (em 2 - em 1) (14)

Pz-Pt Pz- Pt
a. 1 Pure Gases. For pure gases, Eq. (1) along with Eq. (4) is written as
e =S +F esbp (15)
m p 1+bp
Thus from Eq. (13), the permeability of pure gases through dense
membrane with dual - mode sorption model is given by
P =SD [ 1+ F K ] (16)
(1 + b p2) (1 + b Pt)
where K = es b/S.
a. 2 Gas Mixtures. For gas i in an n-component mixture, Eq. (11) along with
Eq. (15) can be extended to
848
Csi bi Pi
Cmi = ~i + Fi Crj = Si Pi + Fi --=n-- (17)
1+}: bj Pj
j=l
and the permeability of component i in the mixture is given by
or
(18)
RESULTS FOR NONPOROUS (DENSE) MEMBRANES
For dual - mode sorption model [Equations (4) and (8)], parameters S,
C8 , b, and diffusion coefficients DH and DL are available for polysulfone and
polycarbonate membranes for pure gases C02, CH4, N2 and Ar [11].
Permeabilities of these gases in pure state have also been measured From
Eq. (16), the permeabilities of these gases in polysulfone film have been
calculated and compared with measured data from the Iiterature as shown in
Figures 1 and 2. Good agreement between the predicted and measured
values are observed. Although experimental data for permeabilities of the
same gases in mixture were not available, it is interesting to compare the
predicted permeabilities in a multicomponent gas mixture and compare with
pure systems.
From Eq. (18), the permeabilities of the same gases in the mixture
were calculated and compared with the permeabilities of the pure gases as
shown in Figures 3 to 6. lt can be seen that for gases with high permeability
such as C02, the difference between the pure and multicomponent
permeabilities is rather low (see Fig. 3) whereas for gases with low
permeabilities the difference is significant. When permeability is low, the
competition for the Langmuir sites is high and interaction between gases
becomes more important. Furthemore, the difference in permeabilities is
higher as the upstream pressure increases.
b. Porous Membranes
Since the final objective of this work is to propose transpoft model for
multicomponent gases in asymmetric and composite membranes, the model
849
7
CD 6.5
J:
E
0
ui
c:\i
< 6
E
e
0
0
a:-
1-
5.5 D
~
.!!. 5
0
<
0
4.5
~
"Q.
4
0 2 4 6 8 10 12 14 16 18 20
p2 (atm)
Figure 1. Comparison of the predicted permeabilities by the dual - mode sorption model
and experimental permeabilities of pure C02 in polysulfone film [11).
0.55
0.5
CD
J:
E 0.45 Ar
0
ui
c:\i
< 0.4
E
.!:!. 0.35
E
0
a:-
1- 0.3
~
.!!.
0
0.25
<
0 0.2
:;;-
Q.
0.15
0.1
0 2 4 6 8 10 12 14 16 18 20
p2 (atm)
Figure 2. Comparison of the predicted permeabilities by the dual - mode sorption model
and experimental permeabilities of pure CH4 , Nz and Ar in polysulfone film [11).
described above for dense membranes is not sufficient and not applicable to
all membranes. As discussed in the intraduction, both asymmetric and
composite membranes have two layers, a dense nonparaus skin layer,
supported by a paraus layer.
850
7
Ci 6.5
J:
E
0
ui
C\i
< 6
E
.g
'[ 5.5
a:-
1-
~
.2. 5
0
<
0
;- 4.5
D..
4
0 2 4 6 8 10 12 14 16 18 20
p2,pi2 (atm)
Figure 3. The predicted permeabilities of pure C0 2 and COz in a mixture of C~ , Nz and

Ar for polysulfone film.
0.24-r---------------------------,
Ci 0.22
J:
5
00
C\i
0.2
<
E
......
0
0.18
"E
0
a:-
1- 0.16
~
0
.2.
0 0.14
<
0
;-
D.. 0.12
0.1
0 2 4 6 8 10 12 14 16 18 20
p2,pi2 (atm)
Figure 4. The predicted permeabilities of pure CH4 in a mixture of C02 , N2 and Ar for
polysulfone film.
Therefore, it is desirable to have appropriate models for each layer. Upon

combination of the two models for the whole membrane, the transport of
gases can then be fully described.
For paraus membranes, with normal (Gaussian) pore size distribution
between R = 0 and R = Rmax , based on kinetic theory of gases, four
mechanisms may be postulated for transport of gases in capillaries (pores),
namely:
851
0.2
o; 0.19
I
E
0 0.18
uj
C\i
< 0.17
E
.g
E'
0
0.16
1-
a:- 0.15
~
1t
0
0.14
<
0 0.13
;;-
w
a. 0.12
0.11
0 2 4 6 8 10 12 14 16 18 20
p2,pi2 (atm)
Figure 5. The predicted permeabilities of pure Nz and Nz in a mixture of co2 , CH4 and
Ar for polysulfone film.
0.52
o; 0.5
I
E
0 0.48
uj
C\i
< 0.46
E
.g
E'0 0.44
a:-
1- 0.42
~
~
0
0.4
<
0 0.38
;;-
w
a. 0.36
0.34
0 2 4 6 8 10 12 14 16 18 20
p2,pi2 (atm)
Figure 6. The predicted permeabilities of pure Ar and Ar in a mixture of C0 2 , C~ and

N2 in polysulfone film.
1. If the ratio of the pore radius to the mean free path of the gas,
R I < 0.05, then Knudsen flow exists.
2. If R I > 50, viscous flow exists
3. If 0.05 < R I A. < 50, slip flow prevails
852
4. In addition to transport of the gas through the pores by the above three
mechanisms, a portion of the gas flows by surface flow which results from
the gas-membrane interaction at the pore wall of the membrane.
Since a real membrane may have all types of pores, the proposed
transport model includes all four mechanisms mentioned above. In what
follows a brief descrption of these models will be described, the details is
given elsewhere [12].
Forasingle pore of radius R, the contribution of Knudsen flow to flux
is [13]:
_ ( 32n )1{2 R 3 p
qk- 9M R T 6 (19)
The contribution of Poisuille viscous flow is [13]:
_ n R4 p p (20)
qv- s"RT6
The contribution of slip flow is [13]:
_ n R 3 p
qsl- M c6 (21)
And finally the contribution of surface flow is given by [14]
0s
_
-
RT p
2000 i (f_P 62
_.&_
S
f -P
X
2
dp (22)
R s
where ~ and S8 are the cross sectional area and the pore wall area,
respectively given by
Ap =n J N(R) R
Rmax
2 dR (23)
R=O
S8 = 2n6 J N(R) R dR
R=O
Rmax
(24)
In Equations (23) and (24) N(R) is the pore size distribution function
defined by [15]
N(R) = ~ exp [- _1 ( R - R )2] (25)

v na 2 a
which is a normal Gaussion distribution.

The total contribution of the first three mechanisms is calculated from
0.05). 51M Rmax
Qg = Qk + Qsl + Qv = L N(R) qk + L N(R) qsl + L N(R) qv (26)
R=O R=0.05J. R=50A
and the contribution of surface flow can also be added from Equations (22)
to (24), [12].
853
7
Ii!
a.
111 6
C\1
(
.
0
5
E
~
0 4
-..
(
+
0
3 +
~ + CH4ATCA-3
+
~ + +
::J 2
-- -
iii
<
w
:::!;

c:
w CH4ATCA-4
a.
0
0 0.5 1 1.5 2 2.5
PRESSURE, ph*10"-6 (Pa)
Figure 7. Comparison of the predicted permeabilities and experimental permeabilities of

pure Cl4 for porous membranes [15).
15
Ii'
a.
111
C\1 H2ATCA-3
(
12
.
0
+
E
~
0
9 +
-.. H2ATCA-4
(
0 + +
(!)
< 6
~
:::::i
-----:----- -
iii
<
w
:::!;
3
H2ATCA-5
...
c:
w
a.
0
0 0.5 1 1.5 2 2.5
PRESSURE, ph*10"-6 (Pa)

pure H 2 for porous membranes [15).
RESULTS FOR POROUS MEMBRANES
From the available transport model parameters [15], the permeabilities

of pure CH"' C:zH6, N2, H 2, He, and Ar in polysulfone (PS), cellulose acetate
(CA), and hydrolysed cellulose acetate propionate (HCAP) membranes were
854
5~----------------------------------------------------------,
~
.,
~ 4
.E.
0
g
0 3
(
.. I
0
~
Ar AT CA-3
~ 2
~
::i
~ + + + +
I
-
iii
-
Ar AT CA-5
U1 ....
1
---..__ -.... ....
j
::!;
a:
w
Q.
Ar AT PS-3
0'~========~--------~--------~--------~--------~
0 0.5 1 1.5 2 2.5
PRESSURE, ph*10~-6 (Pa)

pure Ar for porous membranes (15].
calculated by the model described by Equations (19) to (26) and compared

with the experimental data reported for these pure gases [15]. Same results
are shown in Figures 7 to 9 which indicate that reasonable agreement
between the model and the data. Further work is needed to predict the
permeabilities of gases in multicomponenet systems for paraus membranes
[12].
CONCLUSIONS
Transport of pure and multicomponent gases in rubbery dense
(nonporous) membranes where T>Tg, can be described by by the solution-
diffusion model. For glassy dense membranes where T<Tg, the dual- mode
sorption model properly describes the transport mechanisms. It was shown
that there exists significant differences in permeabilities of pure and
multicomponent gases, the difference is more pronounced for less permeable
gases. For porous membranes, transport of gases by Knudsen - Poiseuille
flow, slip flow, and surface flow is adequate for description of permeabilities.
For asymmetric and composite membranes a combination of transport
models for nonparaus and porous membranes will be required. More
experimental data are needed for such membranes especially for
multicomponent gases.
Acknowledgement
The authors are grateful to the Vice - ChanceUar for Research at Sharif
University of Technology for the financial support of this research work.
855
Notations
b Langmuir affinity parameter (1\atm)

C concentration of gas in the membrane (cc (STP)Icc polymer)
~ coefficient of resistance for the transport of absorbed molecules
(kg/cm2)
Cs pare saturation constant (cclsTpy cc polymer)
c mean speed of the gas molecules (m/s)
D diffusion cofficient (cm%)
l membrane thickness (cm)
M molecular weght of gas (kg/ kmol)
Nt total nurober of pores, having a radii from Zero to Rmax
P pressure (atm)
L\p pressuredifferential across the membrane (pa)
p mean pressure across the membrane (pa)
P permeability of gas in membrane (cc (STp ). cm/cn2 s. cmHg)
q quantity of gas transported through a single copillary (kmol 1/s)
Q permeation tlux (cc (STP) I S.cn2)
R pore radius (m)
R mean pore radius (m)
Rmax pore radius of the largest pore (m)
R Gas Constant
S Henry's law Constant (cc (STp) I cc polymer.atm)
T Temperature (K)
Tg glass transition temperture (K)
x coordinate direction of permeation in the polymer film (cm)
X amount of gas adsorbed in a given amount of membrane material
(kmol/kg)
Subscripts
1 low pressure side
2 high pressure side
H Henry's type
L Langmuir's type
m mobile part
K Knudsen tlow
sl slip tlow
V viscous tlow
g gas phase
s surface tlow
ij component i and j
856
Greek Letters
c5 equivalent thickness of the membrane (m)
'fJ coefficient of viscoosity of gases (pa.s)
l mean free path of gases (m)
Papp apparen density of the membranc (kg!m3)
a standard deviation for the pore size distribution (m)
-r tortuosity factor for the poves
Keywords: Membranes, gas separation, transport models.
References
1 - R.E., Kesting, and AK Fritzshe, "Polymerie Gas Separation Membranes, John Wiley
and Sons Ine., (1993).
2 - R. Rautenbaeh, and R. Ulbreeht, "Membrane Processes, John Wiley, (1989).
3- G. J. van Amerogen, J. Appl. Phys., 17: 972 (1946).
4 - W. R. Vieth, J. M. Howell, and J. H. Hsieh, "Dual Sorption Theory J. Membrane Sci.,
1 : 177 (1976).
5 - R. T. Chem, W. J. Koros, H. B. Hoffenberg, and V. T. Stannet, in Materials Seienee of
Synthetic Membranes, D. Lloyd, Ed., American Chemical Soeiety, Washington, D. C., P.
25 (1985).
6 - W. J. Koros, and R. T. Chem, in Handbook of Separation Process Teehnology, R. W.
Rousseau, Ed., Wiley Ine., New York, P. 802 (1983).
7 - R. M. Barrer, J. A Barrie, and J. Siater, J. Polym. Sei., 27 : 177 (1958).
8- W. R. Vieth, and K J. Sladek, J. Colloid Sei., Phys. Ed. 20: 014 (1965).
9 - D. R. Paul and W. J. Koros, J. Polym. Sei. Polym. Phys. Ed., 14 : 675 (1976).
10- R. M. Barrer, "Diffusivities In Glassy Polymers For The Dual Mode Sorption Model", J.
Membrane Sei., 18 : 25 (1984).
11- AJ. Erb and D.R. Paul, "Gas Sorption And Transport In Polysulfone", J. Membrane Sci.,
8:11 (1981).
12-M. Momeni, "Transport of Multicomponent Gas Mixtures Through Membranes", M.S.
Thesis, Department of Chemical Engineering, Sharif University of Technology, Tehran,
Iran (1997).
13- R.D. Present, "Kinetic Theory of Gases", MeGraw - Hili, New York, P. 61 (1958).
14- F.R. Gilliland, R.F. Baddour and J. L. Russe!, "Rates of Flow Through Microporous
Solids", AIChE, vol.4, N0.1, 90 (1958).
15- R. Rangarajan, MA Mazid, T. Matsuura, and S. Sourirajan, "Permeation of Pure Gases
Under Pressure Through Asymmetrie Porous Membranes. Membrane Charaetrization and
Prediction of Performance", lnd. Eng. Proc. Des. Dev. 23:79 (1984).
857
BENEFITS OF CAPSTONE DESIGN COURSES
IN MATERIALS EDUCATION
R. W. Heckel, W. W. Milligan, C. L. Nassaralla,

J. Pilling and M. R. Plichta
Department of Metallurgical and Materials Engineering
Michigan Technological University
Houghton, MI 49931, USA.
INTRODUCTION
The many educational benefits of capstone design courses are being realized in the
rapidly growing number of universities whose engineering departments are inserting such
courses into their curricula. As a part of a complete revision of the upper division
curriculum, our department added a senior year (three academic terms at four credits per term
(approximately 25% effort per term)) capstone course entitled "Materials Processing and
Design" (MP&D). We have just completed the third offering of this course as of this
writing. Previous papers focused on the development of MP&D were written and presented
during the firse and second2 years in which the course was offered.
MP&D is team-taught with designated faculty responsibilities. Although some
traditional academic format is included in the first term (Fall), the course emphasizes student
teamwork with one or two faculty advising each student group. There have been six to nine
student teams each year with four or five students per team. The hallmark of this course is
the association of each team with an Industrial Participant (IP). The IPs offer topics for
student selection at the end of the junior year and teams are constituted by the faculty on the
basis of topic interest. Topics are subdivided by teams into several projects in the first term
(first third of the course) of the senior year and a proposal for team activity is written and
presented orally at the end of the first term. The second and third terms (the remainder of the
course in the Winter and Spring) are devoted entirely to activities proposed by the team;
faculty advisors meet with teams at least weekly; IPs are also involved in various forms of
communication and in sponsoring plant trips. The highpoints of the course are the team
reports and presentations at the end of each term. The presentations are in a formal setting;
the students organize and chair the sessions. The audience includes junior and senior
students in the departrnent, IPs, faculty, members of the Extemal Advisory Board of the
department and administrators of the University. Most students attend national professional
society meetings at various times throughout the year. Some student team accomplishments
have been presented at national meetings and have resulted injoumal publications.
The faculty advisors are enthusiastic about the very positive impact of this capstone
course. To date, eleven faculty have served as organizers, instructors and team advisors to at
least one student team during the three years in which MP&D has been offered. Several
faculty have been team advisors every year, often to more than one team. The students and
IPs have also responded very favorably to the course. The IPs add engineering reality to the
course. Faculty are welcomed by students as resource persons and are not viewed as being
in the traditional "teach and evaluate" mode since there are no exarninations throughout
Science and Techno/ogy of Polymers and Advanced MateTlls

Edited by P. N. Prasad et al., Plenum Press, New Y ork, 1998 859
MP&D. Further, students perceive the course as being a very important link between their
formal education and their professional careers.
This paper will focus on the nature of MP&D, the IPs, the topics selected by the
students, successful topic outcomes, educational benefits, technical successes and several
areas where improvements are desired.
COURSE ORIGIN AND DESCRIPTION

Development Of A New Department Curriculum
The department embarked upon a substantive revision of its undergraduate curriculum in
the early 1990s. Initial discussions clearly indicated the need for a document defining
educational objectives. lt was decided to focus on the expected outcomes of the
undergraduate educational experience and to use those goals to guide the development of the
new curriculum. These goals in a slightly abbreviated form are shown in Table 1.
Table 1. Goals of the new curriculum of the department.
Graduates who:
Appreciate and understand scientific and technical principles.
Are aware of developments and challenges in their field.
Are prepared for productive, competitive careers.
Are prepared for lifelong learning.
Understand the continuing impact of computers in technology.
Are capable of using computers for communication, control and problern solving.
Are capable of working in groups as weil as independently.
Are capable of communicating skillfully and effectively in writing and oral presentations.
Are capable of addressing unstructured engineering problems.
The use of student outcome goals greatly facilitated faculty discussions, resulted in more
effective communications and served to rninirnize nonessential discourse. The goals also
indicated quite clearly that the typical array of lecture, recitation and laboratory courses would
not provide the basis for a successful program. lt was decided to include a new, one-year,
capstone design course (MP&D) in the senior year of the curriculum.; the goals shown in
Table I, especially those difficult to achieve via conventional courses, guided the formulation
of the capstone course.
Description Of The MP&D Course

The first term (Fall term) of MP&D is divided into two parts; one (Fl) involves
"traditional instruction" of subjects associated with teamwork and design and is presented to
students in small recitation sections to encourage interactions. The second part of the first
term (F2) is devoted to team activities directed toward progress on team topics. The Winter
and Spring terms deal exclusively with student team activities. A detailed view of each of the
three terms of MP&D is provided in Table 2.
The nature of MP&D differs significantly and purposefully from traditional courses.
The overall curriculum goals (see Table 1) dealing with group activities and teamwork,
communication skills, problern solving (especially unstructured problems) and lifelong
leaming have relied heavily upon MP&D, making it a course. with unique characteristics.
Some ofthese nontraditional aspects are listed in Table 3.
Topics For Student Teams And Their lndustrial Participants

The Industrial Participants play a key role in the operation of MP&D. They provide
topics for the individual Student teams, provide tours of their industrial facilities, usually
provide financial support, receive and comment on memoranda and reports and attend student
presentations at Michigan Tech. Overall, they provide a "real world" atmosphere to the
course, an atmosphere that has the students focus on their engineering careers, extending the
860
Table 2. Format, organization and activities in MP&D.
Fall Term (1996-97)

F1 Text: M. Ashby, Materials Selection in Mechanical Desi~:n. Pergamon, 1992.
References: G. E. Dieter, En~:ineerin~: Desjgn: A Materialsand Processin~: Ap_proach, 2nd edition,
McGraw-Hill, 1991
R. Tepper, Model Letters and Memos: A Handbook for Seienrists and Enllineers, Wiley,
1996.
Topics: Ethics, teamwork, brainstorming, communications, experiment design, data analysis,
materials selection.
Grading for students based on homework.
No quizzes or examinations.
F2 Team activities; 4 or 5 students + 1 or 2 faculty.

Transform "topic" into "team projects" (problem definition/selection).
Information gathering, interaction with Iudustrial Participant, brainstorming, equipment
tutorials, safety.
Periodic memoranda to Iudustrial Participant.
Written proposal preparation.
Oral proposal presentation (20 minutes including discussion) to students & faculty.
Team grades based mainly on quality and content of communications (proposal and oral
presentation).
Winter & Spring Terms (199697)

Project activities by teams according to the proposal report of F2, probably with revisions.
Weekly progress meetings with faculty advisors.
lnteractions with IPs.
Team responsibility is stressed:
Teams control activities.
Teams correspond (letters, memos & reports) directly with IPs with copies to advisors
and staff (minimal faculty editing).
Milestone memos required:
Winter term: 4th wk: Describe initial experimental or analytical project.
7th wk: Results, analysis & conclusions from initial activities.
Spring term: 4th wk: Summarize all work to date.
7th wk: Projects end; summarize all work.
Reports: Interim/progress report for Winter term; Final report for Spring term.
Oral presentations (formal):
Each team has 45 minutes (including discussion).
Students plan and present a professional-style meeting.
Audience: Senior & junior class, IPs, faculty, staff & special guests.
Grading:
Winter term: Bach student gets a "P" (progress) and a memo from the faculty advisor with
team & individual student assessments.
Spring term: Team grades assigned; apply also to Winter term (conversion of "P").
horizon substantially beyond that of the MP&D course itself. The topics and IPs for the first
three years of MP&D are shown in Tables 4, 5 and 6.
Topics for incorporation into MP&D are solicited in the Winter and Spring terms in the
academic year prior to that in which they will be used. It is emphasized to potential IPs that
topics associated with important problems needing solution and opportunities for possible
commercial gain are sought. We believe that student teams, with IP and faculty advice,
should have the experience of analyzing the topics and subdividing them into specific areas
for team investigation. This procedure has been found tobe very effective in achieving "team
ownership" of the topics; the students, not the IPs or the faculty, decide on the program of
action. We do not want projects already defined by industry and in which the students
function only as technicians.
861
Table 3. Some characteristics of MP&D.
There are no quizzes or exarninations.

Classes are scheduled only for Fl.
Group (for Fl) and team (for F2, Winter and Spring) assignments are the norm.
The only assignment that can be given to an individual student can come from a team.
Cooperative student activity in problern solving is strongly encouraged, ifnot mandatory.
The terms cheating, copying, etc. carry little meaning (although plagiarism is not tolerated).
Specific information from the previous year' s course is definitely not applicable.
Behavioral traits can be more critical than intellectual strengths.
Faculty-student communication takes place by e-mail and informal office and Iabaratory discussions rather
than by typical classroom exchanges.
Student tearns organize Iabaratory exercises rather than faculty.
Student tearns define goals and methods for achievement.
Faculty advisors avoid giving specific directions to teams.
Faculty advisors "teach" only when they are requested to do so by the teams.
Faculty advisors do not "know the answers" which the students are seeking.
Although grading criteria are stated specifically, teams are often told that the "bottom Iine" is quality,
content and manner of presentation in written and oral communications.
Table 4. Topics and industrial participants in 1994-95.
Topic lndustrial Participant
Processing Steel for Spheroidized Carbides and Minimum Decarburization Charter Steel
Thermoplastic Matrix Composites for Automobile Bodies Ford Motor Co.
Non-Contact Magnetostrictive Sensors for Torque Measurement General Motors
Ferrosilicon: Extent of Hazardous Behavior Hickman, Williams
Characterization of TiN Coatings on Polymer Substrates Gold Star Coatings
Optimization of a Cast/Wrought Recycle Process for Al Alloys Ford Motor Co.
A Centralized Foundry Sand Reclamation Facility Hickman, Williams
Design of a Non-Leaking, Long-Lifetime Stopper System for Tundishes Howmet
A New Fracture Splitting Process for Diesel Engine Connecting Rods Cummins Engine
Topic Industrial Participant
Surface Roughness Control of Directed Light Fabricated Components 3M

Reduced Processing Costs for Copper-Beryllium Rolling Mill Products Brush-Weilman
Altemate Materials Systems for Roller Hearings N1N
Dispersion-Hardened Cu Alloys for Reduced Friction Applications SCM Meta! Products
Aluminized Coatings on Stainless Steel for Chemical Processing ALON Processing
Control of Mechanical Disintegration of Steelmaking Slags During Cooling Charter Steel
High-Strength, Magnetostrictive Composites General Motors
Materials for Heating/Containing Molten Sources in Vapor Coating Processes 3M
New Processing Techniques for Scale Removal via Piekling in Steelmaking Charter Steel
lt is made clear to potential IPs that the primary thrust of their involvement is to be
toward the education of the student team members. If the team makes a significant technical
contribution to the IP, this will be highly regarded by all, but should be considered a "bonus"
by the IP. Team success is judged on the basis of team leaming, not simply on whether the
"problern" was solved to the satisfaction of the PI.
The faculty attempt to provide a selection of topics that would cover known areas of
student acadernic andlor career interest. In addition, 30 to 40% more topics are solicited from
industry than will be needed. The extra topics give individual students selectivity while
rninirnizing the number of awkward communications with potential IPs whose topics were
862
Topic Industria1 Participant
Effect of Pear1ite Stabilizers on the Machinability of Ducti1e Iran Ford Motor Co.
Parging Cracks in Connecting Rads Arnerican Ax1e &
Manufacturing
Piston Crown Oxidation Cumrnins Engine
Reduction in the Coefficient of Friction Between Luge Blades and Iee US Luge Assn and US
Olympic Committee
Distortion in Torque Converters During Brazing Ford Motor Co.
Effects of Zinc in Steelmaking Processes North Star Steel
not popular enough to justify the formation of a student tearn. This system has satisfied
students, faculty and IPs (and potential IPs).
An attempt is made in Table 7 to classify the topic subjects and the type of industry
represented by the IPs during the first three years of MP&D. Clearly, materials processing
has been the dominant subject, comprising about 60% of the total. Materials- plus
phenomena-specific topics, often typical of university research programs, have comprised
only about one-third of the topics
A broad spectrum of material producing and using industries has been represented by
the IPs, as is also shown in Table 7. lt may be noted from Tables 4- 7, though, that the
emphasis from a materials Standpoint has been in metals and alloys. From a prograrnmatic
standpoint, the department would prefer a larger nurober of non-metallic topics. On the other
hand, the industries of the IPs correspond to student interests and to typical career industries
of graduates of the department. These topics are also most suitable for the facilities already
available in the laboratories of the department. In addition, the faculty believe it is the
experience of participating in tearn project activities, not simply the topic, that is important to
the personal and professional development of students.
Table 7. Classification of topics by subject and by industry (information for three years ).
By Subject By Industry
Materials Processing Automobile Manufacturers - 6

Ferrous -1 Melting -1 Steelmaking Companies - 4
Magnetic -2 Recycling - 2 Ferrous Processors/Suppliers - 5
Composites - 1 Coating- 3 Nonferrous Producers/Processors - 3
N onferrous - 1 Steelmaking - 5 Equipment Developers/Suppliers - 5
Rolling/Annealing - 1 Athletic Competition - 1
Design Brazing- 1
Bearings- 1 Forging- 1
Tundish- 1
Phenomena
Oxidation - 1
Friction- 1
Student Responses To MP&D

The faculty have sarnpled student reactions to the course and have, in effect, treated the
students as co-developers of the course throughout the three years MP&D has been offered.
The course has been changed annually in response to the student inputs as well as to faculty
perceptions. Certainly, the course alterations were made to improve the effectiveness of
MP&D in meeting Curriculumgoals (see Table 1) and to enhance the academic value of the
course. We believe also that in the development of such an interactive program student
responses are very meaningful.
863
Table 8 (first five questions) indicates that students have responded favorably to MP&D.
Anecdotal data has indicated that the individual students and tearns were highly motivated to
succeed in the course.
Other data in Table 8 indicate that teamwork efficiency varied significantly from team to
team. We have other data which indicate that the self-evaluations of tearns in terms of
efficiency have correlated very closely with the quality of team oral presentations as
determined by other tearns. Team progress results from efficient teamwork. It is also
noteworthy that students were not enthusiastic about the need for additional faculty -
Supervision of tearns. The faculty would like to interpret this evaluation by the students to
mean that MP&D taught the value of self-sufficiency. This rating also suggests that students
have the ability to learn on their own and realize the importance of such.
Table 8. Student responses to questionnaires at the end of the Fall term.
Average of Student Ratings- ZerotoTen Scale
Fall 1994 Fall 1996
Coursemeeting your expectations? 7.5 7.5

Course a valuable experience? 8.3 9.0
Course consistent with student's academic Ievel? 8.6 8.0
Course is interesting? 8.6 8.3
Course make reasonable time demands? 6.8 7.2
* Should more classroom time be devoted to teamwork? 4.8-9.3
* Does your team function efficiently? 2.0- 8.6
Need more classroom emphasis on teamwork. 6.6
Need more faculty supervision of teams. 4.5
"My team functions efficiently." 6.9
* These Falll994 questions requested ''yes" or "no" answers (zero for "no" and ten for "yes"). Teamscores
were very non-uniform; the ranges of team scores are shown.
Continuing Challenges
The faculty members who have been involved in MP&D as organizers and advisors are
enthusiastic about its positive impact on the preparation of students for productive
professional careers. In fact, some faculty members who were only lukewarm about the
development of such a course have become strong supporters after serving as advisors.
Challenges still remain in the development of MP&D and the improvement of its
effectiveness in meeting curriculum goals.
Several issues relative to the general area of "acadernic curriculum" are bothersome.
Clearly, communication skills are important and we find a wide spectrum of abilities in the
students entering MP&D. Much faculty time is spent throughout the course in instructing
students in oral and written communication skills with varied degrees of success. Significant
faculty effort is focused on commenting on student talks, memoranda and reports, with much
of this work designed to assist tearns in improving their presentations (short-term benefit)
rather than improving the skills of individual students (long-term benefit). Thus, some of the
students entering the course with poor communication skills do not improve significantly in
this regard.
Other curriculum issues include integration of all past courses into the MP&D topics and
the preparation of students for independent studies. Some students are reluctant to use
concepts from prior courses and to apply them to the various facets of their investigations.
These students, rather than regarding past courses as providing understanding to be used in
the future, appear to regard past courses as barriers overcome which will not be encountered
again. Certainly, this situation can be addressed by appropriate faculty-student interactions.
Poor student preparation for independent studies should also be a soluble problern via
treatment in courses prior to MP&D. Students become much too accustomed to laboratoi:y
exercises where they prepare as directed by faculty and carry out processes and operations,
again, as directed by faculty. These exercises are generally designed by faculty to
864
demonstrate principles or provide observations as an adjunct to lecture or recitation
presentations. The critical point is that the design of the exercise, a rnajor intellectual
component, was by the faculty member. In many instances, the students simply follow the
instructions given. This is a far cry from independent sturlies such as those in MP&D where
the students must design the sturlies and experiments; we have found the transition to be very
difficult for some students. More attention to experimental design is needed in prior courses
and students should be instructed in the many differences between demonstration-type
laboratory experiences and engineering inquiries conceming open-ended problerns lacking
definition.
Overall, we have been very pleased with the dedicated and enthusiastic support of the
IPs to the successes of MP&D. On the other hand, in just a few instances, the representative
ofthe IP did not mak:e the necessary commitment to the student team (e.g., Iack of response
to team requests, limited feedback on memoranda and reports, absence from meetings on
campus, etc.). In these instances, team morale and progress were impaired. IP selection by
the faculty is critically important to the success of student teams.
The "academic system" can be an impediment to team progress. We would like to
expand the scope of MP&D to include students from other departments to encourage
inclusion of a broader range of subtopics for consideration of each team. The poor rnatch
between eiepartmental curricula all but eliminates having a non-materials student join a team
for a whole year. We will experiment next year, however, with including mechanical
engineering students in a few teams and will assess this variation in terms of benefits to the
teams and the individual students. It is unfortunate that suitable curriculum matehing does
not appear to exist with other departments. Another systemic problern is the academic
calendar with its interruptions for holidays and term break:s. These discontinuities are a
rnajor detriment to team progress, especially considering the time lost in "getting back up to
speed" after an interruption. We view the probable change in the University's calendar from
quarters (three ten-week terms) to semesters (two fifteen-week terms), i.e., loss of one term
break:, as providing a significant benefit to MP&D.
BENEFITS FROM MP&D

Student Benefits
Students have responded enthusiastically to MP&D; the course is the high point of their
final undergraduate year. The association with engineering problems having industrial
origins has bad a very positive influence on their self-confidence and eagemess to ernhark
upon their professional careers. They tak:e justifiable pride in the demonstrated
accomplishments of their teams. The industrial interactions brought about by plant trips,
attendance at professional society meetings and summer employment have contributed in a
major way to their preparation for professional careers.
The extent of skill development in communications, teamwork, program management
and other areas which may be described as "behavioral" has varied substantially from student
to student. In spite of extensive faculty effort aimed at skill development for teams and
individual students, the outcomes have varied widely. However, the importance of these
skills in the practice of engineering is beyond question for all students in MP&D. Thus, even
though some students have not mastered these skills, they know that they must continue their
efforts to become proficient after the conclusion of the course.
Table 9 provieles an example of the student perceptions of the critical skills necessary for
success in MP&D. Even though the table presents a compilation of the advice of the senior-
year students (at the time they were completing the course) to the students Uuniors) who
would be following them, the Iist actually defines the skills that the seniors leamed through
MP&D to be important in engineering. The faculty believe that learning what remains to be
accomplished is the necessary precursor to the ultirnate accomplishment and anticipate that
skill growth has been strongly encouraged via MP&D and will continue as the students
progress in their professional careers.
Students were also asked to define the benefits that they found in the MP&D experience.
The students were to Iist the three benefits which they feit were most appropriate and rate
each on a zero to ten scale. The results, summarized in Table 10, show that the students see
and support the potential benefits which were of paramount importance in the design of
865
Table 9. Advice of seniors finishing the 1994-95 academic year of MP&D to the juniors
who were preparing for the course.
Develop and apply skills in teamwork - cornrnunicate effectively, divide work assignrnents
arnong rnernbers, resolve interpersonal conflicts effectively, focus on irnportant issues and activities, rnake
decisions efficiently, support the suggestions of others, avoid rneetings where there is nothing to discuss,
don't expect that tearn rnernbers will all becorne personal friends, encourage input frorn all rnernbers.
Prepare for report writing and oral presentations - prepare figures and tables as soon as
possible, begin report writing and oral presentation preparation early in each terrn, relax during oral
presentations, be concise and avoid vague Statements, assign individual rnernbers responsibility for specific
sections of reports, use critics in oral presentation rehearsals.
Assess needs for equipment and supplies - identify equiprnent needs as soon as possible, place
orders for supplies before the end of the Fall quarter, rnake certain that equiprnent is suitable to specific needs,
obtain certification to operate equiprnent.
Seek input from many sources - talk to all faculty and staff who are knowledgeable in techniques
and technical aspects relative to a topic, don't rely heavily on a single source.
Plan, replan, maintain plan and don't waste time- get started as soon as possible, keep
experirnents as simple as possible in obtaining needed inforrnation, define problerns clearly, analyze
inforrnation and reach conclusions, be realistic in tearn and rnernber goals, expect goals and rnethods to
change, shift attention to another area when delays occur.
Develop good professional habits - observe proper safety rneasures, be aware of potential hazards,
keep good records of rneetings, telephone conversations, etc., rnaintain a useful notebook.
Determine to succeed - don't get discouraged when experirnents fail or plans change,
anticipate problerns.
MP&D. Table 10 lists 82% of the responses of the students enrolled, "Teamwork" was
indicted by 81%, "oral presentations" by 50%, "real world experience by 38% and "written
communication" by 27%.
Students also benefited from efforts that were clearly "success stories". Certainly, the
teams whose studies were successful were justifiably proud of their accomplishments. On
the other hand, many other teams might easily have found their way into the "winner's circle"
except for unforeseen problems or time restrictions imposed by the length of the course. All
students recognized that meaningful and worthwhile studies do not always end in success in
engineering efforts in academia or industry.
Table 10. Benefits of the MP&D course as evaluated by enrolled students. Survey taken at
the end of the Fall 1996 term; 26 responses (three benefits Iisted on each) were received
from the 28 students enrolled
No. of Responses" Ratingb
Working on a tearn 21 8.7

Preparing oral presentations 13 8.8
Real world problern experience 10 9.4
Written cornrnunication 7 9.3
Practical experimental design 7 8.9
Time rnanagernent 3 8.0
Exposure to industrial processes 3 7.7
a - Nurnber of students selecting that possible benefit.

b- Rating score; average rating ofthe students selecting the benefit (zero toten scale).
866
It is noteworthy that national recognition has been given to two teams for their
accomplishments. The team studying the toxicity of commercial ferrosilicon in 1994-95 (see
Table 4) was able to show that the US Department of Transportation ruling that "ferrosilicon
was hazardous when wet" (thus resulting in shipping restrictions and increased costs for
steelmakers and foundries) was not applicable. The paper describing the students' work was
presented at the Electric Are Fumace Conference of the Iron and Steel Society and was
awarded the Charles W. Briggs Award for "best paper". Waivers of the USDOT ruling on
ferrosilicon have been made.
The team studying oxide scale removal from steel rods in 1995-96 (see Table 5) was
presented with the Bar Award of the American lron and Steel Institute. The process
improvements developed by the team for an effective and environmentally-sound technique
for scale removal are currently undergoing steel mill trials at the facilities of the lndustrial
Participant.
Benefits To Faculty Members And The Department

Faculty members have benefited from MP&D through the increased interaction with
industry and the exposure to industrial engineering problems. The increased professional
contacts have brought more engineering examples into classroom presentations and have
resulted in increased faculty involvement with these industrial organizations. Additionally,
the nature of MP&D promotes more faculty-student interaction, especially informal
interaction, than would result from a lecture-type course. We believe this to be distinctly
beneficial to the department's overall academic program.
MP&D has also provided the basis for research support at the graduate level. The
success of the ferrosilicon activities in MP&D in 1994-95 has resulted in a three-year
research effort in the graduate program and is supported by Elkem and the Norwegian
Ferroalloy Association. The research is aimed at the fundamental aspects of phosphide phase
forrnation during ferrosilicon solidification and the relationships between microstructure and
toxic gas evolution.
ACKNOWLEDGMENTS
The authors acknowledge the support of their colleagues, Professors T. H. Courtney,
S. A. Hackney, L. A. Heldt, M. Krishnamurthy, K. B. Rundman and D. W. Smith, who
have contributed significantly to MP&D as instructors and team advisors. The efforts and
program support of the Industrial Participants (and their representatives) listed in Tables 4, 5
and 6 are gratefully appreciated. The Ferrous Metallurgy Grant of the lron and Steel Society
to one of the authors (CLN) is also greatly appreciated and provided support to teams
addressing topics associated with steelmaking.
REFERENCES
1. R. W. Heckel, J. Pilling and M. R. Plichta, A senior-year materials processing and design course, in:
ASEE Annual Conference Proceedings, American Society of Engineering Education, Washington, DC (1995)
pp. 982-988. (Presented at the 1995 ASEE Annual Meeting, Anaheim, CA, June 1995.)
2. R. W. Heckel, J. Pilling and M. R. Plichta, A senior-year materials processing and design course, Journal
of Materials Education, accepted for publication. (Presented at the Workshop on Materials Education,
"Changing the Paradigm in Materials Education", at the Materials Research Society, 1995 Fall Meeting,
Boston, MA, November 1995.)
867
ECONOMIC OPPORTUNITIES IN NATURAL FIBER-
THERMOPLASTIC COMPOSITES
Roger M. Rowell
USDA Forest Service, Forest Products Laboratory, One Gifford Pinchot Drive,
Madison, WI 53705-2366 and Department of Biological Systems Engineering,
University of Wisconsin, Madison, WI 63706
INTRODUCTION
Combining agro-fibers (lignocellulosics) with other resources provides a strategy for

producing advanced composite materials that take advantage of the properlies of both types
of resources. It allows the scientist to design materials based on end-use requirements
within a framework of cost, availability, recyclability, energy use, and environmental
considerations. Lignocellulosic resources have low densities, are low in cost, renewable,
non-abrasive, have excellent specific mechanical properlies, and are potentially outstanding
reinforcing fillers in thermoplastic composites. The specific tensile and flexural moduli, for
example, of a 50% by volume of kenaf-PP composite compares favorably with a 40% by
weight of glass fiber-PP injection molded composite. These new composite materials are
finding new applications and new markets never before envisioned by the agro-based
industry.
Properlies of natural fiber-thermoplastic composite materials are given in another
paper in this book called "Lignocellulosic fiber reinforced thermoplastic composite materials"
by R.M. Rowell, A.R. Sanadi, D.F. Caulfield, and R.E. Jacobson (also see Sanadi et al.
1994 andIn Press). The reader is asked to refer to these papers for the technology on how
these materials are made and their mechanical properlies.
This paper will deal with the economics of producing these composite materials.
PLASTIC INDUSTRY
In 1994, the world plastic production was 110 million metric tons. Global plastic
consumption is expected to rise 3.8 percent per year to over 135 million metric tons by the
year 2000 (Modem Plastics Encyclopedia, 1996). Table 1 shows the breakdown of the
world plastics production for 1994.
While many plastics can be used in natural fiber-thermoplastic composite, the plastic
we have concentrated on is polypropylene. As seen in Table 1, polypropylene represents
about 14 percent of the total plastics production in 1994 and markets for this plastic are
expected to grow 5 to 10 percent per year over the next few years (Chemical and Engineering
News July 15, 1996). The rapid growth in polypropylene markets is due to its versatility.
Uses of polypropylene include Substitutions of traditional paper packaging, containers,
roofing membranes, irrigation canal Iiners, apparel, films, autornative interior components
and carpeting. Table 2 shows world polypropylene production in 1994 by region and the
expected production by the year 2000. The largest markets are now and projected to be in
North America with Western Europe close behind. The fastest growing segment of the
market is Asia followed by Africa and the Middle East.

Table 1. World plastics production in 1995.
Plastic Metric tons Percent of market
Polyethylene 34.1 31
Polyvinyl chloride 18.7 17
Thennosets 16.5 15
Polypropylene 15.4 14
Other thennoplastics 15.4 14
Polystyrene 9.9 9
Total 110 100
Table 2. World production of polypropylene by region
Region 1995 2000 Percent change

million of lb. million of lb. 1995-2000
North America 10,928 13,693 4.6

South America 1,708 2,293 6.1
Western Europe 10,845 13,109 3.9
Eastem Europe 1,218 1,422 3.2
Africa/Middle East 650 926 7.3
Japan 5,127 6,395 4.5
Other Asia 7,507 10,981 7.9
Total 37,983 48,819 5.1
Table 3. Distribution of polypropylenein the United States in 1995

Use Percent of market
Fibers 33
Consumer products 13
Rigid packaging 13
Film 10
Transportation 9
Appliances 3
Other 19
Table 3 shows the uses of polypropylenein the United States in 1995. The largest
single use is for fibers. The "other" category includes blending and compounding resins and
uses such as pipe fittings, battery cases, drinking straws, foams, wire and cable insulation
and medical tubing.
Polypropylene ha been called the "poor man's engineering resin" since its price is
lower than the price of traditional engineering resins while offering engineering resin
properties. Commodity grades of polypropylene sell for about $0.45 per pound which is
weH below the $1.00 per pound cost for typical engineering resins.
Polypropylene can also compete with lower price commodity polyethylene.
Polypropylene, with a density of 0.9 g/cc is the lightest of all commodity plastics. It is 5
percent lighter than high-density polyethylene, 14 percent lighter than polystyrene and ABS
and 33 percent lighter than PVC. Polypropylene has a high melting point (165-170 C)
which enables it to be used up to temperatures of 120 C before it softens. lt has good
chemical resistance to hydrocarbons, alcohols and non-oxidizing agents. lt is supplied in a
wide range of melt-flow rates and is suitable for virtually all types of processing equipment,
injection molding, blow molding, extrusion, blown and cast film and thennofonning.
In tenns of end use consumption in the United States (1994), polypropylene is used
for injection molding the most (31%), followed by fiber fonns (29%), followed closely by
compounded or filled applications (24%). Other uses include films (10%), sheets (2%),
blow molding (2%), and all other (2%).
870
Fillers have been used in the plastics industry for almost 90 years. Wood flour was
first used to extend and improve the processability of thermosetting resins in 1907. The total
amount of all fillers used in 1993 in the plastics industry was estimated to be 700 million
pounds. The reason manufacturers use filled plastic is to replace part of the high cost
polypropylene with a low cost filler such as wood flour or talc or calcium carbonate. Plastic
pellets are produced from mixtures of polypropylene and filler which is used in high volume,
low cost markets such as interior autornative panels, garbage pails, crates, and lawn and
garden equipment. Current fillers for polypropylene include wood flour, talc, and calcium
carbonate. Filled plastic usually improves the characteristics of the polypropylene. Tale and
calcium carbonate provide some increase in strength to the plastic, but also add weight and
decrease the life of the molds and extruder due to abrasion by the filler. Fiberglass and
nylon add considerable strength to the product, but at a substantial cost.
There are several economic advantages of using a natural fiber as a filler in
polypropylene. Processing temperatures are reduced which decreases energy costs, cycle
time may be reduced up to 25 percent which means more parts tumed out per unit time, less
material is used per unit volume of pellets due to lower specific gravity of the natural fiber,
shipping costs are reduced due to lower weight, and molds last Ionger due to less wear and
tear on them due to the less abrasive nature of the natural fiber. In addition, the product
allows a more "green" marketing strategy tobe developed based on the recycling possibilities
of the product (Jacobson et al. 1995).
DETERMINATION OF PRODUCT COSTS
Using a very simple formula, it is possible to estimate the cost of different blends of
natural fiber-polypropylene pellets.
$/lb = [P(X) + F(Y) + Cl

E
Where: $/lb is the product cost in dollars per pound,

P is the percent of plastic in composite,
X is the estimated cost of the plastic in cents per pound,
Fis the percent of agro-based fiber in the composite pellet,
Y is the estimated cost of the agro-based fiber filler in cents per pound,
C is the cost of compounding in cents per pound, and
E is the efficiency of operation
If P = 70%; X= 0.50; F = 30%; Y = 0.03; C = 0.20, and E = 1

Then $/lb is $0.559
If P = 60%; X= 0.50; F = 40%; Y = 0.03; C = 0.20, and E = 1

Then $/lb is $0.512
If P =50%; X= 0.50; F =50%; Y = 0.03; C = 0.20, and E = 1

Then $/lb is $0.465
If P = 40%; X= 0.50; F = 60%; Y = 0.03; C = 0.20, and E = 1

Then $/lb is $0.418
It is obvious that the more natural fiber at three cents a pound that can be put into the
pellet, the lower the cost. The compounded pellets are cheeper than pure polypropylene
when the mixture has a natural fiber content of about 50 percent. Compounded mixtures
have been made with up to 65 percent natural fiber in them and experiments are presently
underway to extend the fiber content to 70 to 75 percent. This makes the economics of using
natural fibers as reinforcing fillers in polypropylene very attractive.
871
REFERENCES
Jacobson, R.E., Rowell, R., Caulfield, D., and Sanadi, A.R., (1995). United States based
agricultural "waste products" as fillers in a polypropylene homopolymer.
Proceedings, Second Biomass Conference of the Americas: Energy, Environment,
Agriculture, and Industry. August, 1995, Portland, OR, NREUCP-200-8098,
DE95009230, 1219.
Sanadi, A.R., Caulfield, D.F., and Rowell, R.M., (1994). Reinforcing polypropylene with
natural fibers. Plastic Engineering, Vol L(4): Z7.
Sanadi, A.R., Caulfield, D.F., Jacobson, R.E., and Rowell, R. M., (In Press). Renewable
Agricultural Fibers as Reinforcing Fillers in Plastics: Mechanical properlies of Kenaf
Fiber-Polypropylene composites. lndust. Eng. Chem. Research.
872
SILICONE SURFACE SCIENCE OPPORTUNITIES
F. W. Gordon Fearon and Michael J. Owen

Dow Coming Corporation
Midland, Michigan 48686-0994, USA
INTRODUCTION
In some circles it has become fashionable to argue that the great days of scientific
discovery are over and what science now knows is more or less what it will ever know.
An example of this genre is "The End of Science, Facing the Iimits of Knowledge in the
Twilight of the Scientific Age" by John Horgan 1 . For a senior interpreter of science to
believe not only that the most exciting discoveries have already been made but also that
the remaining mysteries may weil stay unsolved is a marked example of the currently
popular disillusion with science and technology. Technophobia can arise in unexpected
places but there is little room for it in the expanding field of synthetic silicon-based
materials.
Figure 1 shows the number of papers published on this topic in recognized
scientific joumals for five-year periods starting in 19302 . This figure also shows the
number of worldwide patents which have been granted during the same time period. A
constant search protocol has been employed so although the absolute numbers can be
challenged, the trends are indisputable. Publications are tracked through the Chemical
Abstracts Service of the American Chemical Society and patents through the databases of
Derwent Information Ltd. The publications clearly show a continuing expansion of
scientific knowledge in this field. Patents give some measure of conversion of this
science to useful technology and here we may have a cause for concem. During the last
five-year period growth of patents has slowed, in fact it peaked at circa 8,000 in 1993.
This implies that the problern we may be facing in the silicon materials field is not Iack
of discoveries but a reduction in society's ability to convert this new scientific knowledge
to goods and services at historic rates. This slowdown might be due to what Natalie
Angier3 calls sociopolitical irritants: dwindling financial resources, vicious competition,
strident antipathy of animal rights activists, religious fundamentalists, technophobes, and
the like. To this Iist we would add the decreasing number of students continuing in
scientific fields in some parts of the world, particularly North America, and the rise of
special interest groups seeking td profit from the possible impact chemieals might have
on the environment and health of the population.

873
60
50
40
.
"D
c
11 30
6
~
20
10
o4---.-~~~~-4-==+--~--~--~--+---~~~~--~
1930 1935 1940 1945 1950 1955 1960 1965 1970 1975 1980 1985 1990 1995
5-Year Totals
Figure 1. Papers published and patents granted on the subject of synthetic silicon-
based materials.
CHARACTERISTICS OF POLYDIMETHYLSILOXANE
Notwithstanding these naysayers, business based on silicon science and tech-

nology is also growing with many thousands of products sold into most market segments
in all geographical areas. Worldwide sales of silicon-based materials exceeded $6 billion
in 1995. Many of these materials areintermediates or additives incorporated into other
products so the ultimate business supported is very much !arger. From a commercial
standpoint, polydimethylsiloxane (PDMS) is by far the most important silicon-based
material. Table 1 is a quantitative Iist of some key properties of PDMS that account for
its historic importance and potential future growth.
Space limitations preclude a detailed review of all the points in Table 1 but we
must enlarge a little on the final two items as impact on environment and health and
safety are probably the most critical issues facing the future of silicon science and
technology today. To prove that something is totally safe is impossible, we can only
show that different materials are relatively more or less safe and have relatively more or
less impact in specific applications compared with accepted materials which can be used
as standards. By these criteria all current evidence suggests that PDMS is one of the most
acceptable polymeric materials known from the standpoint of health and environmental
impact.
Despite court verdicts that largely ignore the rules of science, all documented
scientific investigations 4 including several of recent vintage from weil recognized
investigators continue to show that there is no association between silicone and either
typical and atypical connective tissue disease or breast cancer. Moreover, although stable
874
Table 1: Qualitative Attributes OfPDMS Polymer
Low surface tension

High water repellency
No surface viscosity
Large free volume
Low g1ass transition temperature
Liquid nature at high molecu1ar weight
Small temperature variation of physical constants
High compressibility
High dielectric strength
High gas permeability
Low fire hazard
High thermal and oxidative resistance
Essentially non-toxic
Environmentally benign
in their intended applications, polydimethylsiloxanes do not bioaccumulate and are

degraded in the environment. High MW PDMS is adsorbed onto soil or particulate matter
where it is biotically degraded to short-chain, water-soluble silanols. These materials
further photodegrade to carbon dioxide, water and polysilicic acid. Polysilicic acid is a
naturally occurring material present in all groundwater and is the primary building block
for incorporation of silicon into diatoms, plants and other life forms. Low MW PDMS
quickly volatilizes into the atmosphere and undergoes rapid oxidative chemical
degradation to silica, carbon dioxide and water, all naturally occurring in the
environment.
The Iist of desirable attributes given in Table 1 that account for the growth so far
of polydimethylsiloxane-based materials are the consequence of four other more
fundamental properties, namely:
Low intermolecular forces between methyl groups

High chain flexibility of siloxane backhone
High siloxane bond energy
Partially ionic backhone
Quantitative data on these properties are given in Table 2. The first two account
for much of the physical behavior of PDMS in various environments whereas the latter
two account for the chemical consequences of the PDMS structure. Table 2 contains data
Table 2: Fundamental Polymer Properties
PDMS PIB PTFE
Liquid surface tension (mN/m) 21.3 35.6 25.6

Critical surface tension ofwetting (mN/m) 24 27 18.3
Glass transition temperature ("K) 146 200 390
Bond energy (kJ/mol) 445(Si-O) 376(CH3-CH3) 413(CF3-CF3)
306 (Si-C) 456 (C-F)
Polar nature ofbackbone (%) 41 0 0
875
for polyisobutylene (Pffi) [= poly(1,1 dimethylethylene)], an "all-carbon" analog of
PDMS, for comparative purposes as the terms high and low in the preceding lists are
meant to be in relation to organic hydrocarbon-based polymers. The table also contains
data on the most common fluoropolymer, polytetrafluoroethylene (PTFE), as only
fluoroaliphatic groups have lower intermolecular forces than methyl groups.
Much of today' s business for silicones arises from the surface activity of PDMS.
Adhesion, release, foam stabilization, antifoaming, surface protection, etc. all depend in
one way or another on the properties of silicone interfaces. Because of the extreme
localization of the fields of force in covalently bonded groups, the pendent methyl groups
on PDMS behave as an array of close-packed methyl groups with little direct effect from
the siloxane backhone despite its considerable polarity. The backhone has a major effect
on the ease with which the pendent groups can be arranged in the surface. The more
flexible the backhone the more readily will the lowest surface energy configuration be
adopted. In this simple view PDMS is seen as a particularly favored case of a very low
intermolecular force group arranged along the most flexible backbone, thus enabling the
methyl groups to be presented to their best effect and accounting for the multitude of
PDMS surface applications.
To say that PDMS is a low surface energy polymer because the intermolecular
forces between methyl groups are low is true but strikes some as tantamount to stating
the same fact twice. There is non-surface evidence for low intermolecular forces such as
the lower boiling points of organosilicon compounds of similar molecular weight, but
perhaps the most convincing demonstration is provided by the Shih and Flory equation of
state5 :
p* = Ty[(3 + 4aT)/3(1 + aT)] 2 (equation 1)
The characteristic pressure p* is a measure of the mean intermolecular energy per

unit volume corrected for the density of packing in the liquid. Some data is given in
Table 3. The values for PDMS and hexamethyldisiloxane are similar and lower than for
organic liquids, comparable values are only found for fluorocarbons. Note also the
expected reasonable correlation between p* and liquid surface tension.
Table 3: Characteristic Pressure(p*) And Surface Tension(er)
Fluid p* (J/cm 3) cr (mN/m)
Polydimethylsiloxane (PDMS) 341 21.3

Polyethylene 485 34.3
Polyisobutylene (Pffi) 448 35.6
Natural ruhher 519 31(JKR)
Polystyrene 547 40.7
Polyoxyethylene 670 45.0
Hexamethyldisiloxane 358 15.6

Cyclohexane 432 24.7
n-perfluorohexane 362 11.9
876
Table 4: Surface Innovations At Silicon(e) Interfaces
NEW TECHNIQUES
* Microscopy:
Environmental SEM, AFM, Brewster angle microscopy
* UHV Surface Analysis:
Imaging XPS, SSIMS (SNMS)
* Surface Forces:
Israelachvili apparatus, JKR technique (yVJ
* Surfactant/Polymer Microstructure:
Cryo-TEM, Freeze-fracture TEM, SAXS, SANS (neutron reflectivity)
NEW MATERIALS
* 2D/3D Nanocomposites:
Self-assembled monolayers, polymer "brushes", ceramers, dendrimers
* Block Polymers:
Surface modification, "tethering" concept, "switchable" properties
* Novel Surfactants:
Ionic hydrophiles, new hydrophobes, vesicles, microemulsions
* Fluorosilicones:
High F content, low surface tension (PMNFHS not PMTFPS)
* Photoluminescent Porous Silicon
* Biomaterial Surfaces:
Antifouling, antithrombogenic, contact lenses, implants
NEW INSIGHTS
"' Polymer Physics:
Influence of de Gennes, centrat role of PDMS;
Spreading, wetting ("superwetting"), adhesion, Langmuir film behavior
* Polymer Dynamics:
Surface restructuring, hydrophobic recovery (plasma), surface viscoelasticity
* Direct Process Catalysis Studies
* Fundamentals Of Adhesion And Friction:
Nanoscale information, proof of IPN and Si-0-M bonding concepts
NEW SILICONE SURFACE DEVELOPMENTS
A comprehensive review of new directions in silicone surface science has become

an increasingly difficult challenge as the field continues to expand in many new and
diverse ways. Wehave recently published our view6 of some of the more important of
these developments, shown in summary in Table 4. Many groups, both academic and
industrial, in all parts of the world are constantly providing new insights into the
structure and properties of organosilicon molecular interfaces. This work is often led by,
or drives, the discovery and development of new analytical techniques, both static and
dynamic, to characterize these interfaces. Based on this improved understanding, new
families of silicon-based materials are being developed with specifically tailored
structure and performance characteristics.
Paramount among these new insights are the studies inspired by the ideas of de Gennes7,
877
whose theories of polymer wetting and adhesion have encouraged many to explore his
provocative themes. These explorations focused attention on the need for a polymeric
material that is well characterized, liquid over a wide MW range, with controlled MW
distribution and crosstinkable in a controlled fashion. PDMS provided the best available
candidate and has become centrat to a revolution in polymer surface physics. Likewise,
organochlorosilanes have proven to be one of the most versatile classes of self-
assembling monolayers for fundamental study.
Much polymer surface chemistry assumes equilibrium behaviors but many
important applications for surface active materials such as foaming, defoaming,
emulsification, de-emulsification, release antifouling etc. are dynamic in nature and
require new theories and techniques to study phenomena like surface restructuring and
the viscoelastic behavior of monolayers. Careful examination of the release of adhesives
from silicone and other release coatings has revealed that the process is strongly
influenced by rheological as well as surface forces which explains why silicone release
coatings are often superior to fluorocarbon materials, even though they have higher
surface energy. Likewise, fundamental study of reactions at silicon surfaces has sparked
new understanding of adsorption and desorption of reactive intermediates, and shed new
light on the catalytic mechanism ofthe "Direct Process", the most important reaction for
the industrial production of methylsilicon intermediates where methyl chloride is reacted
with a copper silicon alloy.
Intertwined with these new insights are new developments in microscopy, UHV
surface analysis, techniques to measure surface forces and to characterize
surfactant/polymer microstructure. All this work has led to the discovery of families of
new surface active materials, nanocomposites, block copolymers, novel surfactants,
fluorosilicones with very low surface tensions as weil as providing the understanding for
new applications ofwell established materials. A fertile field indeed!
TUEFUTURE
The growth of surface related opportunities for PDMS will continue as a direct
consequence of its remarkable polymer architecture. Two applications in particular where
considerable growth is expected are in silicone surfactants and surface modification of
organic polymers. There are some important surfaces in the 20-30 mN/m range such as
skin, plant surfaces, and low surface energy plastics such as polypropylene which are
poorly wet by organic surfactants. The utility of siloxane surfactant "superwetters" on
such substrates has been amply demonstrated. This situation, and the fact that PDMS is
of lower surface energy than all common polymers with the exception of those based on
aliphatic fluorocarbons, will ensure growth in these areas.
Many of today' s applications are concentrated on air/liquid and air/solid
interfaces (for example, antifoams and polyurethane foam stabilizers). This state of
affairs occurs because silicone benefits can be readily conferred on such surfaces owing
to the thermodynamically favorable drive to accumulate there. Silicone can be very
beneficial at condensed interfaces (for example, release coatings) but interfacial
energetics are not usually so favorable for PDMS as surface energetics. Consequently,
reactive, cross-linkable systems which stay in place once positioned will become
increasingly important, particularly energy-efficient, environmentally-benign variants
such as UV initiated eure systems and those with neutral or no byproducts. So too will
carefully tailored block copolymers, possibly including organosilicon-natural product
hybrids.
878
We do not anticipate the commercial exploitation of an alternative inorganic
polymer backhone to siloxanes that will be more flexible. Its nearest rival currently is the
polyphosphazenes, the dimethyl version of which has a 60"K higher glass transition
temperature. Lower intermolecular force pendent groups than methyl are already
exploited in fluoropolymers. For this reason the growing availability of more highly
fluorinated fluorosilicones, such as polymethylnonafluorohexylsiloxane, with surface
energies significantly lower than PDMS will produce new market opportunities. Just as
PDMS-based additives and treatments have produced new applications for organic
polymers, so too will fluorosilicones aid in the growth of conventional silicones. The use
of fluorosilicone release coatings with PDMS-based pressure-sensitive adhesives is one
example of this future. Other applications such as antisoiling and antifouling treatments,
lubrication and wear control, and other protection and release opportunities will surely
follow the considerable patent activity currently in these areas.
The environmental benefits of using silicone materials are becoming appreciated
and accepted. We are optimistic that the samewill happen in the health and safety area
and provide growth opportunities once our society' s current concems with Iitigation
based on fear and greed is better balanced with the scientific realities. Should this not
occur it would be a Iimitation not only on the growth of silicones but also on alt synthetic
materials. Finally, we have focused on siloxanes but there arealso many indications that
the broader field of silicon-containing materials, particularly silicon inorganic materials,
is still in its infancy. Silicon is the most abundant solid element in the earth's ernst.
Simplistically, if we follow nature, silicon should be a major, not minor, part of our
material science and technology and when all is said and done, nature's models generally
prevail!
HEFERENCES
I. J. Horgan, "The End of Science. Facing the Limits ofKnowledge in the Twilight of
the Scientific Age", Addison-Wesley Publishing Co., (1996).
2. F. W. G. Fearon, "SI- Some Interpretations", in press, Proceedings ofMunich
Silicon Days '96.
3. N. Angier, "The Job is Finished", New York Times Book Review, p. 11, June 30,
1996.
4. M. Angell, "Shattuck Lecture- Evaluating the Health Risks of Breast Implants: The
Interplay of Medical Science, The Law, and Public Opinion", New England J.
Med, 334:1513 (1996).
5. H. Shih and P. J. Flory, "Equation-of-State Parameters for Poly(dimethylsiloxane)",
Macromolecules, 5:758 (1972).
6. M. J. Owen, "New Directions in Organosilicon Surface Science" in "Frontiers of
Polymersand Advanced Materials", P. N. Prasad, ed., Plenum Press, New York,
(1994).
7. P. G. de Gennes, "Wetting: Statics and Dynamics", Rev. Mod Phys., 57:827 (1985).
879
INDEX
ABSresin,117 Corona discharge, 535

Acrylonitrite, 117 Cosmetics, 494
Aminosilica coatings, 840 Courses, 859
Antenna, 521 Cross-linking, 806
Antimicrobial activity, 495 Cross-ply Iaminates, 42
Aqueous slcohol solutions, 805 Crystallinity, 807
Aqueous ethanol solution, 805
Atmospheric pressure, 598 Decay, 718
Azeotropic mixture, 805 Decay-time, 186
Degradation, 573, 718
Bioartificial polymeric materials, 449 Degree of swelling, 806
Biodegradable fiber, 609 Dendrimeric molecules, 521
Biodegradable plastic, 464 Dendrimers, 521
Biomaterials, 449 Depolymerization, 597
Bipolarons, 366 Design, 859
Blends, 450 Dielectric mirrar, 189
Blowing agent, 118 Diffusivity, 810
Butadiene, 117 Dimensions! stability, 723
Diphenylacetylene, 523
Capillary electrochromatography, 835 Dynamic light scattering, 497
Caprolactam, 2
Capstone, 859 Economics, 871
Cathode, 650 Education, 860
Cationic polymer, 493 Electro-opticsl properties, 186
Cell adhesion, 544 Encapsulated electroactive unit, 233
Cellulose, 494, 609 Energy funnel, 522
Chargeahle functionsl groups, 536 Energy transfer, 521
Chemicsl derivatization, 589 Engineering, 860
Chemicsl modfication, 719 Environmental protection, 603
Chemicsl recycle, 607 Ethanol-permselective membranes, 805
Chemicsl resistance, 117 Ethynyl perylene, 525
Chemoenzymatic synthisis, 479 Evapomeation, 805
Chitosan, 493, 805 Exciton hopping, 522
Chitosan membrane, 805
Cho1esteral acetate, 186 Fatigue tests, 46
Cholesteric focal conic texture, 188 Fire, 718
Cholesteric liquid crystals, 185 Fluorescence, 497
Cholesteric twisting power, 186 FTIR-spectrometry, 587
Communications, 859
Composite, 717 Gelatin, 450
Composites, 869 Glass transition temperatures, 808
Concentration, 805 Glutaraldehyde, 805
Conjugated polymers, 365 Glutaraldehyde cross-linked chitosan (GAC)
Contact angle, 812 membrane, 806
881
Gradient surfaces, 536 Oligopeptide, 513
Graft copolymer membranes, 808 Optical coatings, 637
Optical disk, 4, 329
Heparin affinity chromatograpy, 514 Optical memory, 5
Heparin, 513 Optical memories, 329
Holographie recording, 329 Oral drug delivery, 513
Holographie multiplexing, 330 Ozone layer depletion, 118
Homogeneaus solution, 186
Hydrophilie groups, 807 Particle-like LC grains, 186
Hydroxypropyl chitosan, 494 Permeation rate, 806
Permselectivity, 805
Industry, 861 Pervaporation, 805
Information bearing units (!BUs), 231 Perylene, 525
Information technologies, 2 PET, 597
Intensity reflected light, 191 PET bottles, 604
Intermolecular hydrogen bonds, 807 Phase transfer catalyzed alkaline, 600
Irradiated light, power of, 191 Phase-change type optical disk, 4
ITO-coated glass plates, 186 PHA, 464
P(3HB), 463
JISEDAI project, 5 Photochemical hole buming (PHB), 6
Photochemistry, 1
Laser darnage threshold, 646 Photon, 5
Light, 1 Photooxidation, 590
Light absorber, 189 Photoreactive materials, 5
Light emitting diodes, 365 Photosensitive polymers, 4
Light scattering, tremendous, 185 Photosensitive polymide, 4
Lignocellulosic, 717 Photosynthesis, 2
Liquid crystal + polymer complexes, 185 Photosynthesis protein, 6
Localized excitations, 372 Photosystem ll, 6
Localized states, 522 Photo technologies, 5
Phycobilisome protein system, 6
Materials, 859 Phycocyanin, 7
Maxwell's model, 809 Plastics, 603
MC-15, 186 Polarons, 366
Membrane separation techniques, 805 Polyblend, 574
Methyl methacrylate, 808 Polydomain focal conic texture, 185
MicroFTIR analysis, 587 Po1ydomain texture reformation, 186
Microholograms, 329 Polyethylene, 536, 573
Microphase-separated structures, 808 Poly (3-hydroxybutyrate), 464
Microphase separation, 809 Polymer, 488
Modelization, 368 Polymer-disperse liquid crystals, 185
Molecular design, 8 Polymerized by irradiating
Multiplexing techniques, 331 uv light, 186
Polymer recycle, 603
Nanoscale information storage, 231 Polymer surface reforming agent, 810
Nanostar, 527 Polymerwall effect, 186
Natural fiber, 718, 871 Polyparaphenylene, 366
New chemistry, 8 Polyphenylene-vinylene, 369
Non-polarizer usage, 185 Polypropylene, 587, 869
Nylon 46, 597 Polyquat, 493
Nylon 66, 597 Polyquaternium 10, 494
Polysaccharides, 505
Oligodimethylsiloxane macromonomer, 808 Poly [1-(trimethylsilyl)-1-propyne], 809
Oligomers, 365 Poly (vinyl alcoho1), 449, 489
882
Processing, 863, 871 Supermolecules, 522
Projects, 859 Supertrap, 527
Properties, 718 Surface modified, 813
Protease, 480 Synthetic fiber, 603
Protein engineering, 8
Teamwork, 859
Quatemary immonium salts, 493 Thermal recycle, 608
Quinoid, 370 Thermochromism, 658
Thermoplastic, 869
Raman Scattering, 365 Thin films, 649
Reading light, 189 Thin polymer films, 185
Recombinant bacteria, 463 Threshold-voltage, 185
Refrigerator, 117 Transmission electron micrographs, 808
Resistance of the photo-conductive Transverse cracking, 35
plate, 189 Trap, 529
Response time, 185 Turbidity, 186
Selectivity, 810
Ultravialet degradation, 718
Separation, 805
Sexiphenyl, 366
Smectic C focal conic texture, 188 Valence force field, 368
Sol-gel, 637 Vanadium oxides, 649
Sol-gel-derived phases, 837 Voltage-transmittance curve, 188
Sol-gel process, 649
Sol gel technology, 837 Wall effects, 186
Solid state NMR, 365 Waste water treatment, 3
Solubility, 810 Water soluble polymer, 488
Starch, 573 Water-permselective membranes, 805
Static tests, 35 Water-permselectivity, 806
Stiffness reduction, 49 Weathering, 728
Stress and strain distributions, 46 Writing light, 189
Students, 860
Styrene, 117 X-ray diffraction, 807
Sugar branch, 478 X-ray photoelectron spectrometry (XPS), 813
883

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Science and Technology of

Polymers and Advanced Materials

Springer Science+Business Media, LLC

International Chairperson National Chairperson

Professor P. N. Prasad Professor H. A. Aziz Moursy

Professor J. E. Mark Professor F. E. Karasz Professor Sherif Kandil

Dato' Dr. Ahmad Tajuddin Ali Prof V. Kouzminov

i>r. M. I. Al-Qurtas Dr. F. Marruffo

Professor Dr. M. A. El-Sayed (Chairman) Professor I. L. Kamel

Professor Nabil Y. Abou-Zeid (Chairman) Chemist Abdel Moez Okeil

Dr. lbrahim M. Hussein Mr. Al Motaz Bellah Abdel-Maksoud

National Organizing Committee

Professor Badran M Badran (Chairman) Professor Abdel Rahman Moussa

Professor Alaa Eldin A. Bahgat Dr. AshrafMansour

Dr. Mohamed Resharn EI-Sherif Professor Mohamed Abdella El Gamal

Professor Mahmoud Rashirn Abdel-Kader

To promote the development of scientific ilifrastructure in this field among the

To create a basisforfuture long-term scientific exchanges between the USA and

To prevent environmental contamination in the region through enhancing production

P. N. Prasad J. E. Mark SherifKandil Zakya Kafafi

GENERAL PLENARY SESSION

Light and the New Chemistry-Expectation for Photo Technologies ................... 1

COMPOSITES AND BLENDS

Reactive Extrusion Compatibilization of Poly (Vinyl Alcohol)

Miscibility and Properties of Liquid Crystalline P-Acetoxy Benzoic Acid

Analysis of Fracture Processes in Cross-Ply Laminates ............................... 35

Thermoplastic Polymer Blends Containing Conductive Polyaniline .................. 51

In-Situ Composite Processes from PEI/TLCP Blends .................................. 61

Electrical and Mechanical Characterization of PEO-LiN(CF3 S~h

ffiGH PERFORMANCE MATERIALS

Improved Elastomers through Control of Network Chain-Length Distributions ... 85

Surface Properties of Silicone High Voltage Insulators ................................ 99

Recent Development of Chemical Resistant Styrenic Polymers for the

Simulations on Thermoplastic Elastomers From Polypropylene ..................... 125

Study of Energy Gap and Electronic Transitions in Model Polymer Systems:

Template Polymerization of Dimethylaminoethyl Methacrylate in the Presence of

Acid Corrosion Inhibition of Nickel by Some Organic/Macrocyclic

MATERIALS FOR ELECTRONICS AND PHOTONICS

Advanced Spatial Light Modulator by Using Polymer Cell-Wall Type Liquid

Novel Organic Composites Based on N-Substituted Quinacridone Derivatives for

Photorefractivity and Optical Wave Mixing Effects in Nematic Liquid Crystals

Cluster Size Effects as a Bridge to Molecular Electronics ............................ 241

Electric Field Effect on Frenkel-Wannier-Mott Exciton States in Organic-

Chirality Effects in Second-Order Nonlinear Opties ................................... 259

Solution Properties of Conducting Polymers ........................................... 299

High-Speed Photonies Polymer-Transmission and Display ........................... 309

High Density Disc Storage by Multiplexed Microholograms ........................ 329

Polymersand Organie-Inorganic Hybrids for Second-Order Nonlinear

Recent Progress in Nonlinear Photonie Deviees and Phenomena Basedon Organic

Advanced Organie Materials for Optoelectronic Integrated Devices,

Nanoscale Synthesis and Processing of Multifunctional Polymers and

Interface Control of Polymer-Based Light-Emitting Devices ........................ 403

Electrical Transport and Magnetoconductivity in Doped Polypyrrole .............. 411

Electrical Properties of Pure PVC ....................................................... 421

Emission Characteristics of a New Class of Strongly Fluorescent Phenanthrene

BIOMATERIAL AND BIOTECHNOWGY

Gelatin-Poly (Vinyl Alcohol) Blends as Bioartificial Polymerie Materials ......... 449

Production of Poly (3-Hydroxybutyrate) by Recombinant Bacteria ................. 463

Chemoenzymatic Synthesis of Water-Soluble Sugar-Branched

Preparation and Potential for Application of Cationic Polysaccharides in

Interaction of Oligopeptides with Heparin .............................................. 513

Dendrimeric Antenna Supermolecules with Multistep Directed Energy

Composite Hydrogels as Intervertebral Disc Prostheses .............................. 547