Keynote Proceeding Nanocon 014 Pune PDF

Bharati Vidyapeeth
Deemed University Pune (India)

A' Grade University Status by MHRD, GOI
l
'A' Grade
Accredited by NAAC
rd
rd
3 International Conference NANOCON 014

Smart Materials, Composites, Applications and New Inventions
Date: 14th, 15th October, 2014
Keynote Proceeding
In Association with
North Carolina A&T

State University
High Research Activity
The University of Tokushima
rd
3 International Conference on
Smart Materials, Composites, Applications
and New Inventions
th
th
Date: 14 , 15 October, 2014
Keynote Proceeding
Bharati Vidyapeeth,
Pune (India)
Maharashtra has a very old and well nurtured tradition of
private participation in higher education. There are quite a
few, even century old educational institutions, in
Maharashtra which have moulded the generation of
learned notables in the field of politics, industry, arts,
music, sports, literature, social works and the like.
Dr. Patangrao Kadam taking inspiration from the leaders of
earlier generations and realizing that social transformation
can be brought about through the medium of education
established Bharati Vidyapeeth. It was established on 10th
May 1964 with the sole objective of bringing about
intellectual awakening and all round development of the
people of this country through education. Bharati
Vidyapeeth, the parent body of Bharati Vidyapeeth
University has been doing the momentous work of
enhancing the accessibility of higher education and
making it available to different sections of the population
since the last four and a half decades.
Recently Bharati Vidyapeeth has completed its 50 years of
establishment. It has created history by establishing itself
as a leading educational institution in the country with 170
educational units imparting education from Pre Primary to
Doctoral level. The endeavor of Bharati Vidyapeeth has
always been to make available to the students a wide
variety of academic options. Bharati Vidyapeeth has
started Colleges / Institutions imparting education in
almost all conventional as well as emerging disciplines. The
institutions established cater to different disciplines such
as Medicine, Dentistry, Ayurved, Homeopathy, Nursing,
Arts, Science, Commerce, Engineering, Pharmacy,
Management, Social Sciences, Law, Environmental Science,
Architecture, Hotel Management and Catering
Technology, Physical Education, Computer Science, Library
Science, Information Technology, Biotechnology and
Agriculture and Performing Arts. It is also one of the few
private educational institutions in the country which has
started its own research institutes. It has three research

institutes in the areas of Health Sciences, Pharmaceutical
Science and Social Science.
Above educational institutions, which cater to the
educational needs of thousands of students coming from
different parts of India and also abroad, are spread around
India in various cities viz. Pune, Navi Mumbai, Kolhapur,
Solapur, Sang!i, Karad, Panchagani, New Delhi and rural
area such as Jawahar in Thane district. All the institutions
have achieved an acclaimed academic excellence and the
teaching faculty in these institutions includes highly
qualified, experienced, dedicated and student-caring
teachers. The spectacular success achieved by the
institutions and, thus, the Vidyapeeth is mainly a creation
of unusual foresight, exceptionally dynamic leadership and
able guidance of the founder, Hon'ble Dr. Patangrao
Kadam.
The educational institutions of this Vidyapeeth have
become nationally known for their academic expertise.
They have established their academic reputation to such
an extent that they have become the preferred destination
for admissions not only for the students coming from
different parts of India but also from abroad. In recognition
of the academic excellence achieved by these institutions
and the potential for development, which they posses, the
Department of Human Resource Development,
Government of India and the University Grants
Commission of India have accorded the status of "Deemed
University" to the 32 constituent units of Bharati
Vidyapeeth.
Bharati Vidyapeeth is a model for emulation by others who
would like to venture and start self financing institutions of
higher education maintaining high level of academic
excellence.
Organizer
Bharati Vidyapeeth University (BVU)
'A' Grade University Status by MHRD, GOI l
'A' Grade Accredited by NAAC
Dr. Patangraoji Kadam, renowned educationist and
visionary established Bharati Vidyapeeth in 1964 with the
motto "Social Transformation through Dynamic
Education." Now 170 institutions impart education at all
levels. His vision of establishing a university was realized
when on 26th April 1996, the MHRD, New Delhi on the
recommendations of the UGC has conferred the status of
Deemed to be University to a cluster of 12 units of Bharati
Vidyapeeth in appreciation of their academic excellence
and potential for further growth, which led to the
establishment of Bharati Vidyapeeth Deemed University.
Presently, Bharati Vidyapeeth University has within its
ambit 29 constituent Units.
research papers of which 873 are in international journals

and 565 in national journals. Furthermore, 460 of these
research papers are listed in SCOPUS database. The
University has received Rs. 27.56 crore as research grants
from various funding agencies for 147 research projects
undertaken by the faculty. In addition, College of
Pharmacy, Pune has received a funding of Rs. 2.5 Cr. from
the Ministry of Food Processing, Government of India,
especially for establishing a Food Testing Laboratory. One
major initiative taken by the University during last two
years is that of providing substantial seed money to faculty
to undertake minor research projects. The relevance and
applied nature of the research is evident from 44 patents.
Bharati Vidyapeeth University has become, perhaps, the

largest multi-disciplinary, multi-campus, university in
India. In addition, Bharati Vidyapeeth University is the only
university in the country that comprises of research
institutes besides the colleges for professional education.
The University has a vibrant in-house research programme

leading to the Degree of Ph.D in as many as 71 subjects
coming under 12 faculties. Presently, 628 students have
registered under the supervision of 359 faculty of the
University. Till today, 286 students have been awarded
Ph.D Degree. The University has organized a total of 168
conferences / seminars / workshops / symposia at national
and international levels together.
'A' Grade University Status by MHRD, GOI

Reaccredited with A Grade By NAAC
35th Rank by India Today
Academic Programmes
Today, the University is one of the largest multidisciplinary institutions of higher education in India having
29 constituent institutions located in eight sprawling
campuses which together offer 278 plus academic
programmes in 12 disciplines. It offers presently, 44
undergraduate and 104 postgraduate programmes. In
addition, the University offers 37 programmes at Diploma
level. With the academic autonomy it possesses, the
University has introduced quite a few programmes in the
emerging areas and also those of innovative nature; e.g.
postgraduate programme in Geo-Informatics, Hospital
Administration, Nanotechnology etc.
Research
Since its inception, this university has put a great deal of
emphasis on research. It has nurtured research culture on
its campuses and has provided inputs to the research
activities in all the possible ways. One of the distinguished
features of this University is the three specialized research
institutions that it runs with its own funds. These
institutions are Interactive Research School of Health
Affairs (IRSHA), Institute of Research in Pharmaceutical
Science and Applied Chemistry and Yashwantrao Chavan
Institute of Social Science and Research.
In the last academic years, the faculty have published 1438
Elite and Distinguished Achievements and Activities

In October 2012, the Ministry of Human Resource
Development (MHRD), Govt. of India, New Delhi has
placed the University in 'A' Grade status. The academic
excellence of the University is also acknowledged by
National Assessment and Accreditation Council (NAAC) by
awarding 'A' Grade, first in 2004 and recently in 2011. The
UGC has granted 12(B) status to the University, thus
making it eligible for research and travel grants.
The National Board of Accreditation (NBA) has accredited
the undergraduate programmes conducted by our Poona
College of Pharmacy, Pune for 5 years and those
conducted by the College of Engineering for 3 years and
the MBA programmes conducted by Institute of
Management and Research, New Delhi for 3 years.
The College of Engineering, Pune has been selected for a
grant of Rs. 4.00 Cr. under Technical Education Quality
Improvement Programme of MHRD, Government of India,
under the category of self-financing institutions. This
programme is supported by the World Bank. This college is
one of the top 25 colleges in India selected for this grant
out of 236 colleges, which were eligible for the same.
The College of Engineering, Pune, Institute of
Management and Research, New Delhi and Abhijit Kadam
Institute of Management and Social Sciences, Solapur were
awarded ISO certifications.
The University has introduced many examination reforms

including the Choice Based Credit System (CBCS) at the
postgraduate level and it is being extended to other
programmes
The constituent institutions in Engineering, Law,
Management, Pharmacy and Dentistry have been
consistently ranked among the Top Colleges in respective
disciplines in India.
The University caters to the needs of students from rural
and urban areas through distance education.
The University has established a Women's Study Centre
which conducts various self consciousness generating
activities; does counseling to Women's Self Help Groups;
carries out research projects; has brought out nationally
acknowledged publications. It also organizes public
lectures. The University provides substantial financial
assistance to the deserving poor girl students.
Academic and Industry Collaborations:
The University has so far signed 95 MoUs for collaborations
of various kinds with renowned institutions such as NCAT in

the USA, Sussex University in the UK, University of Venice in
Italy and University of Cologne in Germany. The University
has also developed its network with nationally renowned
organizations such as NCL, Bio-Ved and Tata Consultancy.
The above collaborations and networks, which have been
developed by the University, focus on research, faculty
exchange and development, consultancy and faculty and
student training.
Overseas Students
The University rightly boasts of its 1600 faculty, 2000
supporting staff, more than 23,000 degree candidates
hailing from all over India and other nations of the world.
The constituent units of the University have world-class
infrastructure, which caters to the needs of its faculty and
students. This attracts students not only from various parts
of India but also from abroad. At present the University has
1498 students from 47 countries enrolled in various
programmes. To cater to the needs of these students, the
University has established an International Student Cell. In
Organizer
Bharati Vidyapeeth University,
College of Engineering (BVUCOE)
Bharati Vidyapeeth University College of

Engineering, Pune, established in the year 1983, is
one of the oldest colleges having highest intake
capacity in the state of Maharashtra. Over the last 30
years the College has made all round progress and is
now acclaimed as one of the best engineering colleges
in this part of the country.
The college is a constituent unit of Bharati Vidyapeeth
Deemed University, which has got 'A' grade University
status by Ministry of Human Resources Development
(MHRD), Government of India, New Delhi, 'A' Grade
accreditation by National Assessment and
Accreditation Council (NAAC) in 2011 & 2004,'12 B'
certification from University Grants Commission (UGC)
New Delhi.
21st Rank by DATA QUEST-CMR among Technical
School.
Rank 35th level by 'India Today' (June 3,2013 ).
In annual surveys conducted by DATA QUEST-CMR of
technical schools in India, the college has been
consistently ranked among top 50 technical schools in
India. This year, the college has been ranked 21th. It is
also ranked amongst the top 5 technical colleges of
West Zone, and also figures in the top 5 in India for HR
perception (Excluding IITs). This is the 7th consecutive
year that the College has featured in the top 50.
Rank 45th in servey conducted by AICTE-CII for
Industry Institute Interaction
Selected (TEQIP-II) program by (MHRD) New Delhi.
Another feather in the cap of this College is that it has
been selected by Ministry of Human Resource
Development (MHRD) for the funding under the
Technical Education Quality Improvement Program
(TEQIP-II) program that is supported by the World Bank.
Under the scheme, the College has been granted a total
funding of Rs. 4.0 crores for the faculty as well as
infrastructural development.
The College became a constituent unit of BVU from July
2000 onwards. All programmes conducted in the
College are accredited by National Board for
Accreditation (NBA) twice. The College has also been
ranked as 'A' grade Engineering College by the
Government of Maharashtra. In addition, all courses
run by the College are approved by Institution of

Engineers, Kolkata.
Academic Programmes
At present, it offers 10 programme at undergraduate
level in Chemical, Civil, Computer, Electrical, Electronics,
Electronics & Telecommunication, Information
Technology, Mechanical, Production and Bio- Medical
and 8 programmes at postgraduate level in Chemical,
Civil, Computer, Electrical, Electronics, Information
Technology, Mechanical and M.Tech (Nanotechnology),
has been recently been started in collaboration with
JSNN and NCA&T State University, Greensboro, USA.
Under this collaboration five students of M.Tech
(Nanotechnology) gets opportunity to pursue
dissertation research at Joint School of Nanoscience &
Nanotechnology (JSNN) USA with scholarship of
$1000/ per month. The College is a recognized center
for PhD programme.
In addition, the College is an Institution of Engineers'
approved center for conducting workshops and
practicals for students from the AMIE.
Research and Development
The College possesses a strong Research and
Development (R&D) Department with a vision and
mission to pursue and promote Research in Frontier
Technology disciplines. Grant received till date is worth
Rs 4.265 cr.
As the result of constant efforts taken in the research
and development activity, the college has to its credit
many publications in the international peer reviewed
journals and national journals. The faculty members
have also presented a large number of research papers
in the reputed international and national conferences.
The college has total 1155 research papers to its credit,
out of which 635 research papers were published in
international journals, 75 research papers in national
journals and remaining research papers were presented
and published at various national as well as
international conferences.
As an outcome of the research activities conducted, the
institute has got 2 national patients applied for one
international patent in the USA, and 9 national patents
in India. Globally, one of the major thrust areas is in
emerging Nanotechnology Sector; especially on
Bharati Vidyapeeth University,

College of Engineering (BVUCOE)
Manufacturing of nylon 6 nanofibres by electrospinning process
Manufacturing of glass /epoxy nanocomposite with Vacuum Assisted Resin Transfer Molding(VARTM)
Composite Materials. The College has established a

center of composite materials and research is being
carried out in association with North Carolina A& T
State University, USA.
Academic and Industry Collaborations
Being a leading institution, it is extremely important to
be connected with industries and academic institutions
in India and abroad. The college has strong association
with National as well as International companies /
educational institutions. The College has signed
Memorandum of Understanding (MoU's) with North
Carolina A& T State University, U.S.A, University of
Venice, Italy, Actel Corporation, U.S.A., iCarnegie, USA,
Oracle India Ltd, India, Information & Systems
Technology, India, Tata Consultancy Services, India and
SKF India Limited, India. The above collaborations,
which have been developed by the College, focus on
research, faculty exchange and development,
consultancy and student in-plant training.
The college, established in 1983, is one of the oldest and
largest Engineering Colleges in the State of
Maharashtra.
l
Ranked
among top 50T Schools of India DATAQUEST-CMR survey continuously for 7 years.
l
Placement
among Top 20T Schools of India DATAQUEST-CMR survey.
l
Accreditation of the programs by National Board of
Accreditation(NBA),New Delhi.
l
Selected
under Technical Education Quality

Improvement Program, Phase II (TEQIP II) by
Ministry of Human Resources Development
(MHRD), Government of India, supported by World
Bank for the grant of Rs 4 crores.
l
Collaboration
with North Carolina A&T State

University, USA for faculty development and
Research.
Organising
l
biannual International Conference, in

association with North Carolina A&T State
University, Greensboro, USA, Tuskegee University,
Alabama, USA and Center for Materials for
El e ctro n i cs Tech n o l o gy, D e par tm e n t of
Information Technology, Government of India.
l
Opportunity
for students to complete dissertation

at International Universities.
l
Interaction with 396 industries for Inplant Training.
l
The
college has its own spacious, well designed.

building admeasuring 26,286 sq.m located within
the campus. a healthy Student to Book Ratio as
1:22.
l
The
college houses 110 Laboratories,43 Class

Rooms and 21 Tutorial Rooms.
l
Five
storied library with more than 50,000 books,

15,000 volumes 70 National/71 International
Journal subscriptions and Digital library facility.
l
A unique
master programme in Nanotechnology

in association with Joint School of Nano Science
and Nano Technology (JSNN) North Carolina A&T
State University (NCAT), USA.
l
Guidance
to students for Robotics by experts from

iCarnegie Powered by Carnegie Mellon University,
USA.
l
More
than 300 campus placements in 75

companies.
l
Research
grant to the tune of 1.7 Crores in last six
years.
l
State
of Art Laboratories with investment of 75

million INR in last six years.
l
Experienced and qualified faculty members.
l
The training and Placement Section of the Institute
is actively interacting with different Industries for

organising Campus Placements.
l
Training
for students in the areas of Personality
INDEX
Sr. No
Name of Speaker
Topic
Page No.
Dr. Hitoshi Takagi
Keynote 1 -Mechanical performance of green

nanocomposites reinforced with cellulose nanofibers
02
Dr. Barry L.Burks
Keynote 2 - Engaging Private Industry in

University Research
10
Dr. Ajit Kelkar
Keynote 3 -Nanoengineered materials for future

aerospace structures
14
Dr. Li-Chyong Chen
Keynote 4 -Graphene oxide based visible light

photocatalyst for photocatalytic CO2 reduction to
solar fuels
18
Dr. Neil John Coville
Keynote 5 -New directions for spherical carbons
26
Dr. Toshihiro Moriga
Keynote 6-Control of Optical Properties of Oxynitride

Pigments and Phosphors through Stoichiometries
32
Dr. Vijay Jain
Keynote 7-Manufacturing: Vision for future
36
Prof. Ram Mohan
Keynote 8 -Modeling at Nanoscale - Materials and

Mechanics Applications, Potentials, and Challenges
38
Dr. Mikito Yasuzawa
Keynote 9-Immobilization of enzyme using electrodeposition

technique for biosensor application
40
10
Dr. Jitendra Kumar Pandey
Keynote 10-Nano-particles from plants: Opportunities and

Challenges
44
11
Dr. Alva Tontowi
Keynote 11-Experimental Study on NanoBiocomposite of

[nHA/Bioplastic] for Building a Porous Block Scaffold
48
12
Dr. James Ryan
Keynote 12 -Economic Outreach and Engagement through

Academic Research
58
13
Dr. Shaik Jeelani
Keynote 13 -Recent Advances in the Materials Science and

Engineering Research at Tuskegee University Tuskegee,
Alabama
62
14
Dr. Dinesh Amalnerkar
Keynote14 -Innovative biofilm inhibition & anti-microbial

behaviour of molybdenum sulfide nanostructures
generated by microwave-assisted solvothermal route
68
15
Dr. Tae Gyu Kim
Keynote 15 -Conductive CVD Nano Diamond for application

of Cutting Tools
70
16
Dr. Katia Vutova
Keynote 16 -Computational modeling and optimization

approach at material treatment by electron beams
72
17
Dr. Malik Maaza
Keynote 17 -Multi-functionality of VO2 Based

Nanostructures in Photonics & Solar Energy
78
INDEX
Sr. No
Name of Speaker
Topic
Page No.
18
Dr. Nakagaito Antonio Norio
Keynote 18 -Bionanocomposites based on cellulose
82
19
Dr. Yeng Ming Lam
Keynote 19 -Excitonic Solar Cells - Challenges and

Opportunities
86
20
Dr. Ron Naaman
Keynote 20 -The Chirality Induced Spin Selectivity (CISS)

Effect- From Spintronics to Electron Transfer in Biology
90
21
Dr. Daisuke Yonekura
Keynote 21 -Stability of ZnO/self-assembled gold

nanoparticle network film
96
22
Dr. A.Subrahmanyam
Keynote 22 -Plasma Processing of Nano-Matter:

An over view
106
23
Dr. Amanullah Fatehmulla
Keynote 23 -Nanostructured Materials and

Nanocomposites
110
24
Dr. Pankaj Madhukar Koinkar
Keynote 24 -Field Electron Emission investigations of

Polypyrrole film
112
25
Dr. Mahesh V. Hosur
Keynote 25 -Synergistic Effect of Nanoclay and MWCNTs

on the Performance of Epoxy and Carbon/Epoxy
Nanocomposites
118
26
Dr. (Mrs.) Lia Addadi
Keynote 26 -Biogenic Mineralized Nanomaterials:

Ancient Technologiesfor the Future
126
27
Prof. Yun-Hae Kim
Keynote 27 -Processing and Mechanical Properties

of Nanocomposites Based on Halloysite Nanotube and
Unsaturated Polyester Resin
132
28
Dr. Eugenio Coronado
Keynote 28 -Smart molecular materials: From bulk materials

to nanomaterials.
140
29
Dr. Jatinder Yakhmi
Keynote 29 -'NANO' and 'BIO' for movement and life
144
30
Dr. Vivek Polshettiwar
Keynote 30 -Nanocatalysis for Sustainable Energy and

Green Environment
148
31
Dr. Masao Nagase
Keynote 31 -Graphene on SiC substrates fabricated by an

infrared rapid thermal annealer
154
32
Dr. Pawan Khanna
Keynote 32 -Nano-structured Materials- The

Chemical Way Quantum Dots And Metal-polymer
Nanocomposites
160
33
Dr. A. K. Tyagi
Keynote 33 -Nanomaterials, Nanostructures and

Nanocoatings: Synthesis, Characterization and
some Applications
166
3rd International Conference Nanocon 014 Smart Materials, Composites, Applications and New Inventions
Date:14th, 15th October, 2014
SESSION 1A: Thin Films - I
Dr. Hitoshi Takagi

Professor, Department of Mechanical Engineering,
The University of Tokushima, Japan.
Email : takagi@me.tokushmina_u.ac.ip
Research Area
Mechanics of green composite materials, interface/interphase characterization in

natural fiber-reinforced composites, functionality of natural fiber composites, and
fiber surface modification for controlled adhesion
Qualification
Ph.D., Hiroshima University, Japan, Sep. 1993
Awards & Honors
Hatakeyama's Young Scientist Award of Japanese Society of Mechanical Engineers,

Japan,1982
Young Scientists Award of Composites Division
In The Japanese Society of Materials Science, Japan,1999
Best Paper Award of Composites Division
Best Paper Award of Composites Division
Best Poster Presentation
Processing, Malaysia, 2009
Award
of
Asian
Workshop
on
Plastic
Date : 14 October, 2014
Time : 11.20 11.35
Mechanical performance of green nanocomposites reinforced with cellulose nanofibers

Dr. Hitoshi Takagi
Abstract
In this study, a green nanocomposites of polyvinyl alcohol (PVA) reinforced with cellulose nanofibers (CNF) were
developed and their mechanical properties were evaluated. Pre-molding nanocomposite sheets were obtained
by drying a mixture of aqueous solutions of CNF and PVA. CNF-reinforced PVA nanocomposites were fabricated
by laminating a number of pre-molding sheets. However, the surface of the pre-molding sheets would contain
tiny air bubbles. It was considered that the presence of the air bubbles on the surface of the sheets is responsible
for the reduction of mechanical performance of the resulting nanocomposites. Thus, in this study we investigated
the mechanical properties of CNF-reinforced PVA nanocomposites and examined the effects of the presence of
air bubbles generated during the fabrication process of this material on its mechanical properties. The effect of
different parameters such as CNF loading on the mechanical properties was also discussed.
Keywords : Given nano composites, celluosenanofiber, natural fiber biodegradable polymer
1. Introduction
We are now using a wide variety of plastics and plastic-based materials; such as glass fiber reinforced plastics
(GFRP). These plastic-based materials are largely made from fossil resources; such as petroleum and coal. The
total volume of the plastic products has been increasing year by year. Recently increasing attention has been paid
to plastic waste problems as well as resource depletion problems in a global scale [1]. In order to build a
sustainable and prosperous society, we have to change the source of raw materials from exhaustible resource to
reproducible one, and should use bio-based materials. Therefore research and development of natural fiber
reinforced polymer composites have been carried out over a worldwide scale [1]. Several kinds of natural fiberreinforced composites exhibit fully-biodegradable nature, which are often called "green composites", and
therefore they can be easily disposed off after use, and at the same time there is no additional greenhouse gas
emissions even after burning out (so-called carbon neutrality) [2, 3].
Most of initial research works on the development of green composites have been handled macroscopic natural
plant fiber as a reinforcing phase [4-11]. In the case of macroscopic natural fibers, they have often suffered from
various kinds of damage introduced during manufacturing, resulting in lower mechanical performance with wide
scattering in mechanical performances. On the contrary, in the case of nanoscale fiber such as cellulose
nanofibers (CNFs) or cellulose microfibrils, which are extracted from pulp by applying very high shearing force
by using a high pressure homogenization process, it is believed that they have relatively high performance.
Therefore the cellulose nanofibers have attracted a great deal of researchers' attention [12-18].
Yano and Nakahara fabricated starch/microfibrillated pulp composites by a press forming technique, and
evaluated their flexural properties as a function of water retention, which is thought to be one of the most
effective indices for the degree of microfibrillation [16]. They also described that the mechanical properties
depended strongly on the degree of fiber microfibrillation; namely the reinforcing fibers' fineness.
Nakagaito et al. fabricated high-strength micro-fibrillated cellulose fiber-reinforced phenolic composites having
tensile strength of 370 MPa and Young's modulus of 19 GPa [12]. Fully biodegradable cellulose nanofiberreinforced starch-based composites were also developed, and reported that the mechanical properties of the
composites were affected by the processing conditions [13]. Omrani et al. fabricated cellulose nanofiber/epoxy
composites having a maximum fiber content of 5wt%, however they did not carry out tensile tests, but only
dynamic mechanical thermal analysis [14].
Takagi and Asano also made chemically modified starch-based resin/CNF green nanocomposites by hotpressing method, and examined the effect of processing conditions on the flexural properties of resultant green
nanocomposites [13]. They pointed out the importance of uniform dispersion of nanofibers in the resin matrix.
In this study, a green nanocomposite material of polyvinyl alcohol (PVA) reinforced with CNF was developed and
the strength properties were evaluated. Pre-molding sheets (i.e. preform sheets) were obtained by drying a
mixture of aqueous suspensions of CNF and PVA. CNF-reinforced PVA-based green nanocomposites were
fabricated using a hot press by laminating a number of sheets inside a mold. However, the surface of the dry premolding sheets would contain many tiny bubbles. It was considered that the presence of the air bubbles on the
surfaces of the sheets is responsible for the reduction in the mechanical performance of the resulting composites.
Therefore we investigated the mechanical properties of CNF-reinforced PVA and examined the effects of the
presence of bubbles generated during the fabrication process on the composites' mechanical properties. The
effects of different parameters such as filler load on the mechanical properties were also discussed.
2. Material and methods

2.1 Materials
Thin slurry containing 90wt% water and 10wt% CNF (Celish KY-100G, Daicel Cooperation, Japan) (Fig. 1) was
used as the reinforcing material of PVA (RS-2117, Kuraray Co. Ltd., Japan). Figure 2 shows a SEM
photomicrograph of the CNF used in this study. Before preparing the PVA-CNF suspension mixture with a
predetermined CNF loading, a dilute suspension of CNF in water (CNF suspension) and a solution of PVA in water
were made using the following sequences.
Fig. 1 Macroscopic photograph of KY-100G
2.1.1 Preparation of CNF suspension

For the preparation of CNF suspension, 20.0 g of CNF and 450 ml of water were stirred in a beaker using a
magnetic stirrer at 600 rpm for 24 hours at room temperature. During this mixing process, the beaker was
covered with a sheet of thin plastic film to prevent water evaporation.
Fig. 2 SEM photograph of KY-100G
Time : 11.20 11.35
Fig. 3 Process chart for fabrication
2.1.2 Preparation of PVA solution

For PVA solution, 500 ml of water in a beaker was heated to 90C using a mantle heater. When the water
temperature reached 90C, PVA powder was gradually added in the hot water, and was dissolved while stirring
with a glass rod. The final PVA concentration of the CNF suspension was calculated by the ratio of the weights
of PVA powder added and resultant CNF suspension.
2.2 Fabrication of pre-molding sheets
First, CNF suspension and PVA solution were mixed and stirred at 500 rpm for 10 minutes with a magnetic stirrer.
The liquid mixture was poured into a heat-resistant 300 mm by 240 mm plastic tray. Then, the tray containing
the liquid mixture was dried by using a convection-type oven at 70C for 24 hours and finally pre-molding sheets
were peeled off from the plastic tray.
2.3 Vacuum stirrer treatment
During the stirrer mixing treatment described in the section 2.2 many small air bubbles could be seen in the
solution, and therefore the bubbles were also formed on the surface of the resultant pre-molding sheets after
drying. To avoid these small bubbles, a vacuum stirrer treatment was applied to the CNF-PVA mixture. The
process chart is shown in Fig. 3.
2.4 Green nanocomposites fabrication

The dried pre-molding sheets were cut into strips sized 100 mm by 10 mm. These strips were then laminated
and set in a metallic mold. Next the laminated sheets were hot-pressed at 210C, under 10 MPa, for 10 minutes,
and cooled down before specimens were removed from the metallic mold. Then, small burrs at the specimen
edges were removed with sandpaper, and finally paper tabs of 35 mm by 10 mm were attached with adhesive
on both extremities of the specimens.
2.5 Mechanical characterization
Quasi-static tensile tests were performed with an Instron universal testing machine (Model 5567, Instron
Corporation, USA) at a cross-head speed of 1.0 mm/min with a gauge length of 30.0 mm at room temperature
(Fig. 4).
2.6 Surface characterization

The fracture morphology of composites and fibers was examined by an optical microscope (SZH-10, Olympus,
Japan) and scanning electron microscope (SEM: S-4700, Hitachi, Japan). All samples were sputter-coated with
gold/platinum prior to the SEM observation
3. Results and discussion

3.1 Effect of vacuum stirrer treatment
If the pre-molding sheets were produced without the vacuum stirrer treatment, small bubbles were observed on
the surface of the entire sheet as shown in Fig. 5. However when the vacuum stirrer treatment (vacuum
defoaming) was performed, bubbles were not visible at all on the surface of the pre-molding sheets (Fig. 6).
3.2 Mechanical properties
The pre-molding sheets obtained by vacuum stirrer treatment resulted in composites with higher mechanical
properties as shown by the stress-strain curves in Fig. 7. Thus we can see that the presence of air bubbles
generated during stirring and drying processes was one factor that reduced the tensile strength of CNF green
nanocomposites. If the pre-molding sheets contain air bubbles, the surface has irregularities causing adhesion
failure when laminated to make the composites
Time : 11.20 11.35
Fig. 5 Macroscopic photograph of pre-molding sheet without vacuum stirrer treatment
Fig. 6 Macroscopic photograph of pre-molding sheet with vacuum stirrer treatment
Fig. 7 Typical stress-strain curves of CNF/PVA green nanocomposites
In addition, the tensile strength of the CNF composites fabricated from vacuum-stirrer-treated pre-molding
sheets was also affected when the CNF content was varied from 30 to 70wt%. According to Fig. 8, the tensile
strength is highest at 50wt% CNF content, but further increases in CNF content does not lead to higher strength.
Similar dependence was also reported in the CNF-starch green nanocomposite system [15]. Their tensile strength
reached approximately 150 MPa, showing a possibility for engineering applications as structural materials.
Fig. 8 Typical stress-strain curves of CNF/PVA green nanocomposites as a function of CNF loading
Fig. 9 SEM photograph of the fracture surface of green nanocomposite (50wt%CNF, no vacuum-stirred)
Fig. 10 SEM photograph of the fracture surface of green nanocomposite (50wt%CNF, no vacuum-stirred)
3.3 Fracture behavior

The fracture surface of the composite with 50wt% CNF without defoaming treatment is presented in Fig. 9,
showing a laminate cracking. This cracking might lead to reduction both in tensile strength and fracture strain.
In addition, there are many small holes on the fracture surface as shown in Fig. 10. These holes seem to be
formed by agglomeration of much smaller air bubbles dispersed in the PVA solution before drying.
Time : 11.20 11.35
The fracture surface of the composites with vacuum stirrer treatment is presented in Fig. 11, there is no cracking
on the fracture surface.
4. Conclusions
We successfully fabricated CNF-reinforced biodegradable green nanocomposites, and evaluated the mechanical
properties of the CNF-PVA green nanocomposites and examined the effects of the presence of air bubbles
generated during the fabrication process on their mechanical properties. The experimental results showed that
the vacuum stirrer defoaming process is effective to obtain the CNF reinforced green nanocomposites with
better mechanical performance. Their tensile strength reached approximately 150 MPa, showing a possibility for
engineering applications as structural materials.
Acknowledgements
The authors wish to thank Mr. Tomoyuki Ueki and Mr. Satoshi Sugano (The University of Tokushima) for their
technical assistance in SEM observations.
References
[1] A. N. Netravali and S. Chabba, Mater. Today. 6(4), 22 (2003)
[2] H. Takagi, S. Kako, K. Kusano, and A. Ousaka, Adv. Compos. Mater. 16(4), 377 (2007)
[3] P. Wambua, J. Ivens, and I. Verpoest, Compos. Sci. Technol. 63(9), 1259 (2003)
[4] M. Wollerdorfer and H. Bader, Ind. Crops Prod. 8(2), 105 (1998)
[5] S. Luo and A. N. Netravali, J. Mater. Sci. 34(15), 3709 (1999)
[6] S. Luo and A. N. Netravali, Polym. Compos. 20(3), 367 (1999)
[7] P. Lodha and A. N. Netravali, J. Mater. Sci. 37(17), 3657 (2002)
[8] A. K. Mohanty, M. Misra, and G. Hinrichsen, Macromol. Mater. Eng. 276/277(1), 1 (2000)
[9] D. H. Mueller and A. Krobjilowski, J. Ind. Text. 33(2), 111 (2003)
[10] H. Takagi and Y. Ichihara, JSME Int. J. A-Solid. M., 47(4), 551 (2004)
[11] K. Liu, H. Takagi, and Z. Yang, Mater. Design. 32(8-9), 4586 (2011)
[12] A. N. Nakagaito and H. Yano, Appl. Phys. A-Mater. 80(1), 155 (2005)
[13] H. Takagi and A. Asano, Compos. Part A-Appl S. 38(4), 685 (2008)
[14] A. Omrani, L. C. Simonb, and A. A. Rostami, Mat. Sci. Eng. A-Struct., 490(1-2), 131 (2008)
[15] H. Takagi, Key Eng. Mat. 462-463, 576 (2011)
[16] H. Yano and S. Nakahara, J. Mater. Sci. 39(5), 1635 (2004)
[17] J. K. Pandey, H. Takagi, and A. N. Nakagaito, Compos. Part B-Eng. 43(7), 2822 (2012)
[18] J. K. Pandey, A. N. Nakagaito, and H. Takagi, Polym. Eng. Sci. 53(1), 1 (2013)
SESSION 1B : Special Topics - I (Nanostructured materials NT+Grapehene)
Dr. Barry L.Burks

Vice Chancellor
North Carolina Agricultural and Technical State University, USA.
Email. blburks@ncat.edu
Research Area
Nuclear Physics
Qualification
Ph.D., in experimental nuclear physics from the University of North Carolina at Chapel
Hill
Awards & Honors
He has a broad perspective, based on more than 30 years experience conducting

research, developing technology, leading projects and managing programs for the
Department of Energy, Department of Defense, NASA, the commercial nuclear
industry, the automated manufacturing industry, and most recently university-based
applied research.
President of TPG Applied Technology of Knoxville,Tennessee Associate director of the
Charlotte Research Institute at the University of North Carolina Charlotte from 2007
Conference Chair of the American Nuclear Society Third Joint International
Conference on Emergency preparedness & Response and Robotics for Hazardous
Environments, Knoxville,TN,August 7-10,2011
Recipient of the ANS RRSD 2008 /ray Goertz Award, for outstanding contributions to
the field of nuclear applications of Robotics and Remote Systems Technical
Achievement Award, Gunite and and Associated Tanks Project ,September 2000
10
Time : 11.20 11.35
Engaging Private Industry in University Research
Dr. Barry L.Burks
North Carolina Agricultural and Technical State University (NCAT) is a doctoral research university and a
historically black university located in Greensboro, North Carolina, United States of America (USA). The university
serves nearly 11,000 full time students making it the largest historically black college or university (HBCU) in the
USA. The university generates an average of $57 million dollars in sponsored research activities which also ranks
near the top of the list for HBCUs. Although the majority of this research funding comes from federal agencies
several million dollars per year are provided by private companies and other non-governmental organizations.
Connecting students and faculty to private industry is extremely important to the mission of the university. In
addition to the two core missions of teaching and research the university has a responsibility to serve the
community. Broadly speaking service to the community can take many forms including:
Creation of new companies and new jobs based on university generated inventions,
Providing access to specialized equipment for innovation and problem solving,
Providing expertise for planning and problem solving, and
Training the workforce needed for local and national industry.
Collaboration with industry can involve the four areas listed above but it goes beyond those possibilities.
Experiential learning through internships, co-operative assignments, and industry sponsored research enhances
the educational experience tremendously and also gives students a huge advantage when job hunting.
Corporate relationships are obviously beneficial for job placement of graduates but these relationships are also
vital for developing philanthropic gifts, grants, and contracts.
Industry seeks collaboration primarily for access to graduates, faculty expertise, access to specialized equipment
and facilities, and also access to innovative ideas. Collaboration with universities is particularly beneficial for
small companies who can not afford specialized equipment that might be used only occasionally for prototype
development, for example, or infrequent characterization measurements. Unless the skills required to solve a
design or manufacturing problem are core to a company's mission it is much more cost effective to pay
universities to solve these problems than to hire the expertise.
Typical of research universities in the USA NCAT is engaged with private companies in a variety of partnerships
including philanthropy, internships, team teaching, industry sponsored senior design projects, sponsored
research, service for fee and teaming to seek third party funding opportunities. One example of engagement
with industry can be found in the National Science Foundation (NSF) sponsored Engineering Research Center
(ERC) for Revolutionizing Biometallic Materials. NCAT is the only HBCU to be selected to serve as the lead
institution of the prestigious ERC. Industry affiliates partner with the center to gain access to students, faculty,
equipment and ideas. The ERCs are long term programs intended to fund university lead innovation teams from
innovation to commercialization. Funding in the latter years of the programs is dependent on successfully
partnering with industry to ensure translation of ideas from the laboratory bench to commercial product. The
NCAT ERC demonstrated sufficient progress so that funding was extended for an additional 3 years beyond the
original 5 year duration. The ERC focuses primarily on development of medical devices made from magnesium
alloys which both promote healing and because of gradual absorption of the magnesium into the body don't
require subsequent surgeries to remove the devices.
One feature of the North Carolina state university system that is not common elsewhere is that each state
university is permitted to designate a parcel of land as a "Millenial" Campus. By law for activities that are located
at the Millenial Campuses the universities are granted an exclusion from the Umstead Law which precludes
university competition with the private sector. The bottom line of this exception is that the universities can
partner with private industry in more flexible relationships including for example leasing space on these
campuses to private companies. Value of the collaboration to both the university and private companies
increases dramatically from being co-located and sharing access to certain facilities.
11
The main campus of NCAT and the main campus of the University of North Carolina at Greensboro (UNCG) are
located in close proximity to one another. The two universities share a Millenial Campus called the Gateway
University Research Park (GURP) also located in Greensboro. GURP is comprised of two 75 acre tracts that house
a number of research facilities including the Joint School for Nanoscience and Nanoengineering (JSNN). The
JSNN offers graduate degrees only to Nanoscience students enrolled at UNCG and Nanoengineering students
enrolled at NCAT. JSNN was founded to foster collaboration between the two universities and also to serve as
the anchor tenant at GURP to attract private companies interested in collaboration with the universities and
access to the suite of instrumentation located at the JSNN.
In addition to the usual methods of engagement GURP created a Nanomanufacturing Innovation Consortium
(NIC) that offers members access to JSNN equipment, acknowledgement on signage and presentations, access
to meeting and conference facilities, invitation to the NIC annual meeting and JSNN events, input into research
directions and networking with researchers (facilitating hiring and licensing). The NIC members gain maximum
access with minimum investment, minimizes issues with intellectual property, and enables networking among
nanomanufacturers. The NIC has enrolled 27 members as of September 2014.
In addition to the NIC GURP has created an organization called Gateway Materials Test Center (GMTC) as a
mechanism for performing service for a fee using the expertise and facilities at JSNN and additional personnel
hired by the GMTC. The primary purpose of the GMTC is to conduct materials testing associated with
components of aircraft and also other systems that use composite structures though the testing is by no means
limited to composite materials. The GMTC has completed verification testing to demonstrate results equivalent
or improved over results provided at other well established test centers.
During the presentation the speaker will provide several specific examples of successful university-industry
partnership particularly emphasizing partnerships in nanotechnology applications.
12
Time : 11.20 11.35
Nanocon 012
Release of Souvenir of the conference by the chief patron, Dr. Patangrao Kadam, Hon Chancellor, Bharati Vidyapeeth
Deemed University. (Left to Right) Dr. Anand Bhalerao, Prof. Jitendra Yakhmi, Dr. Ajit Kelkar, Dr. Shivajirao Kadam, Dr.
Barry Burks, Dr. Patangrao Kadam, Dr. Ravi Grover, Dr. Shinichi Kikkawa, Dr. Vishwajeet Kadam, Dr. Reshef Tenne and
13
SESSION 1C: Synthesis, Characterization and Applications - I
Dr. Ajit Kelkar

Professor and Chair, Nanoengineering
Associate Director, Center for Advanced Materials and Smart Structures
Joint School of Nanoscience and Nanoengineering Greensboro, USA
E-mail: kelkar@ ncat.edu, ajitkelkar@gmail.com
Research Area
Atomistic Modeling , Nano Engineered Materials, Eletrospinning, Molecular Dynamic

Simulations, Nanotechnology, Multifunctional Materials, Crashworthiness, Low Cost
Composite Manufacturing (VARTM Processing), Mechanical Characterization of
Materials including Metals, Polymeric Composites (Tape and Textile), Ceramics and
Ceramic Composites, Computer Aided Design and Modeling, Finite Element and
Finite Difference Modeling, Numerical Analysis, Fatigue and Impact Modeling and
Testing of Polymeric Composites, Ceramic Composites, Textile Composites,
Micromechanics Modeling and Testing, Single Fiber Modeling and Testing
Qualification
Ph.D., Mechanical Engineering, Old Dominion University, Norfolk, Virginia, 1985

M.S., Mechanical Engineering, South Dakota State University, South Dakota, 1981
B.S., Mechanical Engineering, Poona University, Poona, India, 1975
No. of Patents
No. of Publications
More than 199
Refereed Conference
Prodeeding :
More than 173
Research Proposals
Funded
More than 78
Awards & Honors
Special award from North Carolina A&T State University Division of Research and
Economic Development for the "Founding Member of ADVAERO, Inc.", a first
company that was spun of by A&T in the area of aerospace/composite, NC, April 2008
Recipient of the Best Paper Award-Automotive Division, Ansys Conference, Pittsburg,
April 2006
Recipient of the Best FEA Image Award, CEIVIZ Conference, March 2006
14
Time : 11.20 11.35
NANOENGINEERED MATERIALS FOR FUTURE AEROSPACE STRUCTURES

Dr. Ajit Kelkar
ABSTRACT
During the past decade use of both carbon and fiberglass composites have increased dramatically for aerospace,
marine and automotive applications. Advances in conventional tape laminates and textile composites provide
aircraft manufacturers important technology, but the industry lacks the confidence to use these composites to
manufacture primary load carrying structures due to low damage tolerance. One of the critical problems is failure
due to delaminations of composite laminates via low velocity impact loadings. To alleviate this problem, several
methods which use applications of nano technology will be discussed. This talk will address various methods and
material systems for processing and integration of the nano material constituents, including: (a) dispersing
alumina nanoparticles using high energy mixing (using ultrasonication, high shear mixing and pulverization) and
(b) electrospinning technique to manufacture nanofibers. This newly developed reinforced polymer
nanocomposites and the processing methodologies have shown a promising means of improving the
interlaminar properties of woven fiber glass composites compared to the traditional methods such as stitching
and Z-pinning to improve interlaminar properties of woven composites.
The electro spinning technology creates nanoscale fibers with improved molecular orientation and the reduction
in concentration of fiber imperfections and crystal defects. Electrospinning process utilizes surface tension effects
created by electrostatic forces acting on liquid droplets, creating numerous nanofibers. These nano fibers are
useful as through the thickness reinforcing agents in woven composites. While the electrospun nanofibers
provide bridging through-the-thickness reinforcement, the use of the nanoparticles influences the thermophysical properties and provides an effective means from commercially available nano level material
configurations to form reinforced polymer nanocomposites. Both these methods and material systems provide
effective means for integrating the nano material constituents into traditional fiber composite systems.
In addition to electrospun nanofibers and alumina nanoparticles, talk will cover development of novel resin
system for multifunctional applications that require thermal and electrical conductivity, self-sensing and selfactuation capabilities without a loss of required mechanical properties. The talk will present fabrication and
characterization efforts that are underway to use single wall boron nitride nano tubes (BNNT) reinforced epoxy
towards the development resin system with improved thermal and radiation shielding properties. Effect of nano
constituents dispersed into the resin as reinforcements on the thermal properties of resin will be addressed. The
talk will cover analytical prediction of mechanical and thermal properties of single-walled boron nitride (BNNT)
nanotubes reinforced epoxy resin (DGEBF) cross-linked with curing agent W (DETDA). The MD models of the
reinforced epoxy were built using the amorphous module of Material Studio (Accelrys Inc.). The COMPASS force
field was used in the simulations. The amorphous structure was achieved by using periodic boundary conditions
and then subjecting to an energy minimization using an ensemble of the constant-volume and temperature
(NVT). The structures were equilibrated for 100 picoseconds (ps) and then followed by MD equilibrations at room
temperature for another 200 ps. Since at room temperature most of the atoms are in static mode, the atoms
were excited using simulation temperatures above the glass transition temperatures.
In an attempt of finding global energy minimum, simulated annealing runs were then carried out starting at
elevated temperatures at atmospheric pressure using the ensembles of the constant number of particles,
constant-pressure and constant temperature (NPT). The molecular structure temperature was then gradually
lowered to a room temperature. Each subsequent simulation was started from the final configuration obtained
at the preceding temperature. Density of the epoxy at each temperature was calculated from the average specific
volume and glass transition temperature (Tg) was estimated based on the discontinuity in the slope of the
density-temperature plot. The amorphous structures obtained at room temperature were analyzed to determine
the fundamental mechanical properties of the BNNT reinforced EPON 862-W. Calculations of fundamental
mechanical material properties of single-walled BNNT were performed using molecular dynamics simulations via
Material Studio. A simple but effective technique of extrapolation was adopted to compensate for the problem
of BNNT distortion because of smaller lattice sizes. Property calculations were performed at each density value
and extrapolated to the actual value of density of BNNT. A similar extrapolation technique was employed to
overcome the issue of achieving exact theoretical mixture densities of BNNT-Epoxy composites in the MD
models.
15
SESSION 1C: Synthesis, Characterization and Applications - I
The proposed new materials will eventually help in the discovery, development and incorporation of improved
nano composite materials with effective manufacturing methodologies for defense and industrial applications.
In addition these materials will allow the full utilization of nanocomposites in not only reinforcing applications
but also in multifunctional applications where sensing and the unique optical, thermal, electrical and magnetic
properties of nanoparticles can be combined with mechanical reinforcement to offer the greatest opportunities
for significant advances in material design and function.
16
Time : 11.20 11.35
Nanocon 012
Honble Chancellor Dr. Patangrao Kadam with International Deligates.
17
SESSION 1D : Nanoelectronics - I
Dr. Li-Chyong Chen

Professor, Distinguished Research fellow & Director,
Center for Condensed Matter Science,
National Taiwan University, Taiwan.
Email : chenlc@ntu.edu.tw
Research Area
Nanomaterials, Plasma-assisted Processes, Chemical and Physical Vapor Deposition

Processes.
Optoelectronics, Energy, Sensing.
Qualification
Ph.D., Applied Physics, Harvard,1989
Awards & Honors
Acharya Vinova International Award in Materials Science and Technology for year
2013, VBRI, India (2013)
Ho Chin-Tui Outstanding Scholar Award, Ho Chin-Tui Foundation (2012)
Outstanding Scholar Award, Foundation for the Advancement of Outstanding
Scholarship (2010-2015)
Outstanding Research Award, National Science Council (2010-2013, and 2007)
Fellow, the Materials Research Society, USA (2010)
Laureate of the Khwarizmi International Award, Iran (2009)
International Federation of Inventors' Association Lady Prize (2009)
Distinguished Visiting Research Fellow, Royal Academy of Engineering, UK (2008)
Outstanding Scholar Research Project, National Science Council (2008-2011)
Honorary Doctor, Linkping University, Sweden (2007)
Fellow, the Physical Society of ROC in Taiwan (2006)
Academia Sinica Young Scholar Research Award (2000)
18
Time : 11.20 11.35
Graphene oxide based visible light photocatalyst for photocatalytic CO2 reduction to solar
fuels
Dr. Li-Chyong Chen
ABSTRACT
Artificial photosynthesis is one of the most anticipated solutions global warming and increasingly energy
demands. Photocatalytic reduction of carbon dioxide with water to yield hydrocarbons (methane, methanol, etc.)
on the surface of semiconductor catalyst has the potential to become a viable and sustainable alternative energy
source to fossil fuel. This work describes a high photocatalytic conversion of CO2 to methanol using graphene
oxides (GOs) as a promising photocatalyst. The modified Hummer's method has been applied to synthesize the
GO based photocatalyst for the enhanced catalytic activity. The photocatalytic CO2 to methanol conversion rate
on modified graphene oxide is 0.172 mol g-cat-1 h-1 under visible light, which is six-fold higher than the pure
TiO2 . Further, Cu and MoS2 nanoparticles were deposited on GO as co-catalysts to enhanced the photocatalytic
-1
reaction. Not only methanol, but also acetaldehyde was detected. Total solar to fuel yield of 6.8 mole g-cat h1
has been achieved, which is 240 times enhancement relative to the commercial P-25 photocatalyst. In all the
above-mentioned hybrids, the photocatalytic performance is always much better than that of constituent
component when used alone.
Keywords: Graphene Oxide, Photocatalyst, CO2 reduction, Solar Fuels, Cu-nanoparticles, MoS2 nanoparticles.
Introduction
In this 21st century, the rising demand of the fossil fuels in our modern society emits vast quantity of carbon
dioxide (CO2). This increasing CO2 concentration is the most threatening environmental concerns associated with
global warming and climate change1. Therefore, to find a solution converting stable CO2 into green energy fuel
is the highly desirable approach for the sustainable energy research. The leading approaches for CO2 reduction
include electrochemical reduction, photochemical reduction and thermal hydrogenation. Despite their individual
technical merit, more fundamental research and physiochemical understanding are still required for each
approach to improve their overall conversion efficiency and product selectivity for practical implementation. The
high kinetic barrier, primarily due to the stability of initial CO2, is one of the critical challenges to reduce CO2 to
another product effectively. Development of energy-efficient technologies for the reduction of CO2 to highenergy density fuels in an eco-friendly manner is also essential. In a broad sense, the biomimetic artificial
photosynthesis method is considered as a potential approach to recycle CO2. Interestingly, in this process, the
hydrocarbons are produced by photoreduction of CO2 coupled with water and solar energy [1, 2]. In 1979, Inoue
et al. first demonstrated the photocatalytic reduction of CO2 to form organic compounds by photosensitive
semiconductor [3]. After this pioneering breakthrough, several wide-bandgap semiconductor materials have
been explored towards the photocatalytic CO2 reduction [4-10]. Among all the semiconductor materials, titanium
dioxide (TiO2) and some TiO2 based heterogeneous photocatalysts have been explored most extensively for the
last three decades due to their low cost, low toxicity and high chemical stability [11, 12]. Besides TiO2, several
non-Ti metal oxides [13], metal sulfides [14] and a few homogeneous organometallic materials [15-18] were
reported to exhibit more effective CO2 reduction under solar light irradiation. In CO2 photoreduction technology,
the major challenge is the low efficiency of the photocatalyst. For instance, the reported methanol conversion
-1
-1
rate for TiO2 in vapor phase, typically, is 0.02 mol g cat h only [19], which is far below the actual requirement.
To overcome this, several strategies have been adopted to enhance the photocatalytic activity of the widebandgap semiconductor materials [20-22]. Among them, the most popular technique is to dope the
semiconductor with noble metal co-catalyst as a charge-carrier trap, which suppresses the recombination of
photo-excited electron-hole pair [23, 24]. However, the prospect of these materials is not satisfactory, due to the
disappointingly low quantum efficiency and lack of fuel-selectivity of the photocatalysts. Thus, it is a great
challenge to develop a potential low-cost photocatalyst for a high CO2 reduction efficiency and simultaneously
producing desired solar fuel under visible light.
Graphene oxide (GO) is a newly emerging material of solution-dispersible polyaromatic, two-dimensional carbon
sheets produced from acid exfoliation of graphite.18 Its like an insulating material with a wide bandgap, through
its electronic structure depends on the stoichiometric carbon-to-oxygen atomic ratio. The basal plane of the GO
19
covalently surrounded by the epoxide and hydroxyl groups, while edges were decorated with carboxyl functional
groups [25]. Due to the presence of several types of oxygen containing functionality, on the basal plane and sheet
edges the aromatic GO can undergo a complex interplay of covalent, noncovalent interactions with different
molecules. GO based hybrids and composite materials with improved properties have been synthesized with a
range of organic and inorganic molecules via covalent, noncovalent and ionic interaction. The oxygenated
2
3
functional groups provide a 2D network of sp and sp bonded atoms in GO, which lead to presence of finite
2
2
3
bandgap depending on isolated sp domains [26]. Tunability of the ratio of the sp and sp fraction by reduction
chemistry can therefore, controllably transform the insulating GO to a semiconductor and to a graphene-like
semi-metal [27].
In 2010, Yeh et al. demonstrated GO as an active photocatalyst for water splitting application [28]. In our previous
study, the result shows that the graphene oxide with the tuning bandgap is a promising photocatalyst for CO2
reduction to methanol under visible light irradiation [29]. We have conducted a systematic investigation of
photocatalytic CO2 reduction on various GO samples synthesized under different conditions. We found that the
modified GO (GO-3), obtained by the modified Hummers method in the presence of excess KMnO4 and excess
H3PO4 to raise the level of oxidation under the protection of GO basal plane, exhibits the highest photocatalytic
efficiency among the studied samples. In Figure 1(a) the observed approximate band gaps of all the GOs,
showing an intrinsic semiconductor like absorption in the blue optical region, are adequately large to overcome
the endothermic energy require for the CO2 reduction (-0.38 V), under solar energy excitation. The photocatalytic
-3
-1
-1
conversion rate of CO2 to methanol on GO is 0.172 mol/ g cat hr under simulated solar-light source for 4 h,
which is six-fold higher than the pure TiO2 as shown in figure 1(c). We have been proposed the possible
photocatalytic mechanism. Figure-1(d) presents the photocatalytic CO2 reduction to hydrocarbon by modified
GO under visible light. Additionally, the isotope tracer analysis confirmed that the methanol was produced
directly from the photocatalytic reduction of CO2 instead of any photo dissociation of the carbon containing
catalyst. The CO2 photoreduction reaction usually suffers from limited solar fuel conversion efficiency of
photocatalyst that is due to the fast recombination and instability of the photo-generated electrons-holes pair.
The bandgap of GO is too large for visible light response, and many methods such as doping with metal ions
preparing solid solutions and combining with various narrow bandgap semiconductors are the vital approaches
to make GO visible light active.
Figure 1. (a) Band gap measurement of synthesized graphene oxides (GO). (b) AFM image of modified GO. (c)
photocatalytic performances of GOs and (d) photocatalytic CO2 reduction mechanism on graphene oxide [29].
In general, CO2 photoreduction reaction suffers from limited solar fuel conversion efficiency of photocatalyst due
to the fast recombination and instability of the photo-generated electron-hole pairs. For GO, though the superior
to TiO2 performance is encouraging, its bandgap is still too large for visible light response, and many methods
such as doping with metal ions, preparing solid solutions and combining with various narrow bandgap
20
Time : 11.20 11.35
semiconductors are the vital approaches to make GO visible light active. In this work, we have developed a series
of GO-based potent photo-catalyst with copper nanoparticles and MoS2 metal sulfide to achieve a substantial
high efficiency under visible light. The choice of metal nanoparticles, metal sulfide as a co-catalyst to improve
the photoreduction efficiency of GO is due to their earth abundance, low cost and moderately large work
function of Cu as compared with GO. However, to the best of our knowledge, it is expected that the Schottky
junction between those co-catalyst and GO in GO-based composite accelerates the separation of
photogenerated electron-hole pairs and consequently, improves the photocatalytic activity. Recently, in the
photocatalytic CO2 reduction to solar fuel generation, selective product formation has been one of the most
important issues.
In this work, a composite photocatalysts were made from wide-bandgap GO and metal nanoparticles and metal
sulfide with narrow size distribution. The redox potential has been tuned using the different composition ratios
of the co-catalyst/GO. We expect to achieve highly selective and efficient production of solar fuels with different
co-catalyst composition in the GO-based composite. Typical one-pot microwave and hydrothermal synthesis
processes for Cu/GO and MoS2/GO hybrid are presented schematically in Figure 2. In the present study, a series
of Cu-NPs decorated GO (Cu/GO) composites with different Cu nanocrystal concentrations were synthesized via
a single pot microwave method. The synthesized Cu-NPs modified GOs are denoted as Cu/GO-1(5 wt% Cu),
Cu/GO-2 (10 wt% Cu) and Cu/GO-3 (15 wt% Cu), with EDX measured Cu loading of 4.12, 9.52 and 15.16 wt %,
respectively. In our experiments, we have synthesized MoS2/GO composites nanostructure by adjusting the
different temperature in the one-pot hydrothermal process. The obtained various MoS2/GO composites denoted
as MoS2/GO-180, MoS2/GO-200 and MoS2/GO-220 according to the reaction temperature 180, 200 and 220 C
respectively.
Figure 2. Synthesis process for Cu/GO and MoS2/GO hybrids.
The phase structures of the Cu/GOs hybrids and MoS2/GO were examined by X-ray diffraction (XRD)
o
o
measurement. Figure 3(a) compares the XRD patterns of pristine GO and Cu/GO hybrids in the range of 5 -70
(2). The observed increase d-spacing of GO sheets is due to the presence of abundant oxygen-moieties on
both sides of the graphene sheet causing an atomic-scale roughness on the graphene surface. As shown in
o
Figure 3(a), the Cu/GO hybrids show peaks at around 42.88 that corresponds to the metallic copper (111)
without any sign of copper oxides signature, indicating that Cu ions were thermally reduced during the
microwave process. In contrast, the Cu/GO hybrids characteristic (002) peak moves to slightly higher diffraction
o
angle at 12.6 , which is mainly attributed to partial modification of pristine GO during microwave treatment.
Additionally, the average crystalline size of Cu NPs in the different Cu/GO sample are 4.21, 4.07 and 4.67 nm for
Cu/GO-1, Cu/GO-2 and Cu/GO-3, respectively (calculation based on the Scherrer formula for the Cu (111) phase).
Figure 3(b) shows the XRD patterns of the as prepared MoS2/GO composites with different temperature in the
o
same initial precursor concentrations. The observed broad and characteristic diffraction peaks at around 34 and
o
58 correspond to the (100) and (110) planes of nano size hexagonal MoS2 (JCPDS# 771716). Additionally, the
prepared all MoS2/GO composites exhibited a characteristic peak at approximately 10.9 , which is
corresponding to the (001) plane of GO reflection in the composites.
21
Figure 3. XRD patterns of (a) Cu/GO composites. Inset Cu(111) peak of the respective Cu/GO hybrids (b) MoS2/GO
composites.
The morphology and microstructure of samples were investigated using transmission electron microscopy (TEM)
as shown in Figure 4(a-c), revealing that the Cu nanoparticles are distributed uniformly on GO, which is facilitated
by the widespread presence of oxygen containing functional groups on it. It was also observed that in all the
images the Cu nanoparticles are formed some small cluster on GO. The TEM images and particle size distribution
histograms (Figure 4 (d-f)) of the Cu/GO show an average size of 5.06 1.3, 4.15 1.3 and 5.36 1.7 nm for
Cu/GO-1, Cu/GO-2 and Cu/GO-3, respectively, which is well consistent with the value obtained via the Scherrer
formula from XRD analysis.
Figure 4. (a-c) TEM images of Cu/GO-1, Cu/GO-2 and Cu/GO-3. Inset HRTEM image of single Cu-NP of the respective
Cu/GO hybrids respectively. (d-f) Cu-NPs size distribution on Cu/GO-1, Cu/GO-2 and Cu/GO-3 respectively. (g)
Representative TEM image of GO.
22
Time : 11.20 11.35
The FE-SEM images of the MoS2/GO composites from the temperature dependent hydrothermal reaction are
shown in Figure 5. It shows that the GO sheets are well decorated with the MoS2 nanoparticles. The MoS2/GO180 synthesized at 180C contains MoS2 nanoparticles without any regular shape. We observed that the MoS2/GO
composites synthesized at 200 and 220 C containing 3D ball like MoS2 microspheres with a diameter of 50-100
nm that are composed of several nanosheets. The detailed local chemical compositions of the synthesized
MoS2/GO composites were further analyzed by energy dispersive X-ray (EDX) mapping. Additionally, the
elemental mapping images show the distinguishing distribution of Mo (blue dot), S (yellow dot) and C (gray dot)
elements, respectively. The aggregation of MoS2 on the GO occurs in MoS2/GO-180 and MoS2/GO-220,
respectively. From all distribution images of Mo and S elements, they show the well dispersion in catalysts. But,
the gradual aggregation of GO is found with the reaction temperature increasing from 180 to 220C. In our
understanding, GO cannot resist the temperature as high as 220 C though MoS2 forms a good structure above
200C, causing the obvious sintering of GO in MoS2/GO-220. Thus, MoS2/GO-200 shows the well dispersion
among the three catalysts.
Figure 5. SEM and elemental mapping images of MoS2/GO nanocomposites.
The photocatalytic activity of the Cu/GO and MoS2/GO hybrids was measured in the gas-phase CO2
photoreduction under visible light irradiation. Methanol and acetaldehyde have been found to be the major
product and hydrogen as a minor product from the photocatalytic reduction of CO2 on Cu/GO, whereas, ethanol
along with the methanol and acetaldehyde were produced as a major products from the photocatalytic reduction
of CO2 on MoS2/GO. The representative CH3OH and CH3CHO formation rate on the synthesized photocatalyst
plotted in Figure 6(a). It is observed that the acetaldehyde formation on Cu/GO hybrid is more favorable
compared with the methanol formation. Interestingly, it shows that the photocatalytic solar fuel yield is increased
with the increasing of Cu loading on GO photocatalyst. However, among all the Cu/GO hybrids it is observed that
the catalytic performance decreased in the presence of Cu over loading (15 wt%) on GO (Cu/GO-3). The highest
methanol and acetaldehyde production rate achieved with the GO having 10 wt% of Cu (Cu/GO-2). The Cu/GO3 with 15 wt% of Cu, shows only acetaldehyde formation. The methanol production rates for the photocatalyst
Cu/GO-1, Cu/GO-2 and Cu/GO-3 were 1.08, 2.94 and 0 mol g cat-1 h-1 after 2 h irradiation. Whereas calculated
acetaldehyde yields are of 1.54, 3.88 and 1.79 mol g cat-1 h-1 for Cu/GO-1, Cu/GO-2 and Cu/GO-3 respectively.
When the Cu-NPs loading at 10 wt% (Cu/GO-2), the solar fuel production rate achieves the highest value of 6.84
mol g cat-1 h-1, which is more than 60 times that of pristine GO, or 300 times that of P-25. Notably, as far as we
know, this is the highest enhancement ever reported in the literature about the photocatalyst for CO2 reduction.
Figure 6(b) shows the maximum production rates of samples, indicating that MoS2/GO-200 has the highest yield
of products among all samples. MoS2/GO-180, MoS2/GO-200 and MoS2/GO-220 show the total yield of 1.1 mole
-1
-1
-1
-1
-1
-1
g-cat h , 1.8 mole g-cat h and 0.65 mole g-cat h , respectively. Thus, the addition of MoS2onto the GO
could further accelerate the production by promoting the adsorption and activation of H2O.
23
Figure 6. Photocatalytic formation of solar fuels on (a) Cu/GO and (b) MoS2/GO using a simulated solar-light source.
Its well accepted that the photocatalytic CO2 reduction mainly involves charge carriers generation, charge carrier
transfer and multi-electron chemical reduction on a particular potential. In an initial step, GO decorated with CuNPs or MoS2 is excited by visible light, photons with higher energy than the band gap of the GO generate
electron-hole pairs on the photocatalyst surface. On the GO photocatalyst surface Cu-NPs acts as an electron
acceptor and suppress the recombination of photo excited electron-hole pair due to enhanced charge
separation at the metal-semiconductor interface. In the MoS2 decorated GO composites MoS2 act as a light
absorber and generate more electronVhole pairs to enhance the photocatalytic activity. Finally, the activation of
CO2 is more effectively performed on the co-catalyst decorated GO surface due to the transfer of an electron
from the metal d orbital to the (C-O) II* orbital. Consequently, the favorable multi electron reduction process
involves breaking of C-O bonds and making of C-H bonds and leads to methanol and acetaldehyde as major
product and hydrogen as minor product. Although the hydrogen evolution reaction may compete with the CO2
reduction reaction but the fact that hydrogen was barely detectable indicates that it is indeed a minor reaction.
Specifically, multi-electron reduction processes are involved in the production of methanol, ethanol and
acetaldehyde in our experiment. The overall photocatalytic CO2 reduction is complex and difficult reaction
process than the water splitting reaction. In the photocatalytic CO2 reduction process, the photogenerated holes
migrate to the surface and cannot be ignored. At the surface of the photocatalyst, the photogenerated holes may
react with adsorbed water to produce oxygen due to the valance band position of the GO based photocatalyst
but its difficult to analyze quantitatively. We assume that the accumulation of holes may be lead to an increase
in surface recombination and decreasing the product formation after certain period of irradiation time. Besides
the photocatalytic activity enhancement of GO hybrids, the variation in the production rate of different products
is an interesting issue. In our GO composites the bulk recombination was reduced by presence of co-catalyst. The
accepting of the charge carrier, however, is strongly related to the metal or metal sulfide nanoparticles size as an
interfacial electronic state that tuned the conduction band position for the favorable reduction potential of
selective product from CO2 reduction. Further study is needed to understand the detailed mechanism of the
productivity change at different cocatalyst content.
Conclusion
In conclusion, a series of Cu-NPs and MoS2 modified GO photocatalysts have been successfully synthesized by
simple microwave and hydrothermal process and demonstrated for enhance photocatalytic activity in solar fuel
-1
-1
production. The Cu/GO-2 (10% Cu) reaches a high solar fuel formation (6.84 mol g cat h ) for the photocatalytic
CO2 reduction under visible light irradiation. This photocatalytic CO2 reduction rate is 60 times higher than that
of the pristine GO under or 240 times than that of commercial P-25 under visible light. MoS2/GO-200 shows the
-1
-1
solar fuel conversion rate can be achieved to 1.8 mol g -cat. hr (methanol (0.8), acetaldehyde (0.25) and
ethanol (0.75)) under 300-Watt halogen lamp irradiation. These conversion rates are much higher than that of
commercial TiO2 (P25). We believe that our finding would be widely applicable to the graphene oxide based
composites with metal or metal sulfide nanoparticles to develop a cost effective technique for simultaneous solar
energy harvesting and CO2 reduction.
24
Time : 11.20 11.35
Acknowledgments
We thank the Ministry of Science and Technology (MOST), Academia Sinica, National Taiwan University and
Ministry of Education (MOE), Taiwan and AOARD of AFOSR for financial support. Technical support from NanoCore, the Core facilities for nanoscience and nanotechnology at Academia Sinica in Taiwan, is acknowledged.
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25

Professor, School of Chemistry, University of the Witwatersrand
Johannesburg
E-mail: neil.coville@wits.ac.za
Research Area
The emphasis on our work is on Solventless organometallic chemistry.

The synthesis of carbon materials for use as catalyst supports, for the fabrication of
hard materials and for various materials programmes.
The synthesis and study of catalysts of industrial interest (Sasol) e.g. in the FischerTropsch synthesis.
Use of carbons in devices (solar cell, sensors, memories, Fuel cells. The above includes
work in the area of carbon nanotubes, and sol-gel synthesis to produce tubular,
spherical etc silica, titania and alumina. Hybrid materials are also made by this
approach.
Qualification
Ph.D.,McGill University, Montreal,1973
No. of Publications
Over 350 including 15 reviews
Awards & Honors
Fellow of Royal Society of South Africa.

Past-President of the South African Chemical Institute.
Member: DST/NRF Centre of Excellence in Strong Materials .
Member: DST/NRF Centre of Excellence in Catalysis.
26
Time : 12.35 12.50
New directions for spherical carbons

The ability of carbon to bond to itself, especially to generate C-C bonds with different bond order, has resulted
in carbon having a wide range of structures and as a consequence carbon containing materials can have a wide
range of properties. The shape and size of these carbon structures can be varied, almost at will, and so many
classical and exotic shapes can be generated as carbon-carbon bonds are formed. One of the most stable
arrangements when making carbon-carbon bonds is to make benzene type rings i.e. to create structures with
C=C bonds. A classical arrangement of C=C double bonds leads to the graphene layer. When the ends of a
graphene layer are formally linked together to form a tube the well known single walled carbon nanotube
structure is formed (Figure 1). The bending of the graphene layer leads to 'tension' within the layer and thus the
reactivity of the benzene rings can be expected to be enhanced. This then will impact on the properties of the
carbon nanotube.
Figure 1: Formation of a single walled carbon nanotube from a graphene layer
What about making spherical shapes with this graphene motif! This is not possible using only benzene rings. A
strategy can be envisaged to overcome this limitation. This is to incorporate cyclic C5 rings into the graphene
layered structure and this leads to the classic C60 fullerene structure. Incorporation of C7 rings can also be added
to a graphene layer, and this will lead to a negative curvature in the graphene layer. In the same way that carbon
tubes can be layered within each other to give multiwalled carbon nanotubes (MWCNTs), so layers of C5/C6 rings
that generate a sphere, can lead, in principle, to multi layered spherical structures. However, no fullerene
structures with a hollow interior and with perfect layers have been made to date.
However the synthesis of small (< 10 nm) spherical structures with a hollow interior and a series of carbon layers,
called onions have been made [1]. Larger spheres with this perfect structure are still not known.
Instead, the large spherical structures are typically seen to comprise of flakes of graphene attached to each other
to generate a solid sphere (Fig 2d) [2]. One suggestion to explain this type of structure has been given by Wang
and Zang [3], as shown in Figure 2. Figure 2(a) and (b) shows the curvature generated in a bowl-like carbon
structure (flake) that forms around a central coil like structure (Fig 2(c)) that generates the final sphere (Fig 2(d)).
It should be noted that spheres can also be built with carbon atoms arranged not only in a concentric manner,
but also with a radial or random distribution of carbon planes [4].
27
Figure 2. Formation of a carbon sphere [2]
Let us take a step back at this stage and look more carefully at these spherical carbon materials [5]. Solid
spherical carbon materials, typically made in an oxidizing environment (e.g. as used in the formation of carbon
blacks) have been know for over a century and have been used in tyres, printer inks, batteries and so on [6]. They
have been given many names that include carbon balls, carbon nanospheres, carbon microbeads, carbon blacks,
onions, mesoporous microbeads, etc. but herein we will refer to them as carbon spheres (CSs) [5]. Thus the
commercial synthesis of spherical carbons is well known.
New directions - synthesis
Many, many studies to make solid carbon spheres have been reported in the literature [5]. The most common
and easy method to make CSs is to use a chemical vapour deposition (CVD) procedure. The CVD process entails
heating a carbon containing material in a quartz tube to high temperatures (700 - 1100oC) and this generates the
CSs in high yield. The diameter and other properties (e.g. surface area/porosity) of the CSs is determined by the
carbon source, flow rate, reactor design etc. Another common method to make CSs is via the use of autoclaves
and this route (typically using a low temperature and autogenous pressure) provides CSs with much higher
surface areas.
But in more recent times new directions have appeared in the synthesis of CSs. Two examples of this include:
i)CSs can now routinely be made with a hollow interior or with egg-yolk (rattle) type morphology (Fig 3). The
hollow carbon spheres (HCSs) are typically made with a removable template. In the synthesis method a spherical
template, usually made of SiO2 (e.g. Stober spheres), is coated with carbon (CVD or autoclave process) and after
silica removal the HCS is formed. The porosity of the carbon can be varied and this leads to the ability to use the
internal part of the HCS as a nanoreactor and for drug release [8, 9].
ii)Another synthesis direction has been to make doped CSs, in particular with N and B atoms. Doping can be
achieved by in-situ procedures, in which the carbon source used to make the doped material contains the dopant
(the C and N sources can also be added simultaneously) or by a post-doping process. In this later procedure the
surface of already synthesized CSs are coated with a dopant. Both the above procedures will apply to all three
types of CSs shown in Fig 3.
Figure 3 Cartoon of (a) hollow, (b) core shell and (c) filled spheres [7].
28
Time : 12.35 12.50
Another area that that has seen growth relates to the functionalization and subsequent chemical reactions of the
new CSs. The CSs have many terminal groups that can be chemically modified and after reaction with polymer
precursors this has led to the generation of new CS-polymer composite materials [10].
New directions - uses
As mentioned above, CSs have traditionally been used in the tyre and printer ink manufacturing business. But
some new uses, taken mainly from our own studies with collaborators, are briefly described below. These relate
to making use of the surface and conductivity properties of the CSs.
i) Hydrostatic pressure sensors [11]. The conductance and capacitance sensitivity of simple hydrostatic pressure
sensors based on carbon sphere (undoped, N-doped and B-doped)-poly(vinyl alcohol) composite films
deposited onto interdigitated electrodes were studied. The doped carbon spheres gave increased sensitivity
variation with respect to pressure when compared to undoped CSs, in a range near to atmospheric pressure. For
higher pressures of ca. 200 kPa, however, the conductance and capacitance sensitivity of sensors based on
undoped carbon spheres was significantly higher, and this was ascribed to a superlinear dependence of both
sensitivities on pressure.
ii) WORM (write once read many times) memory devices [12]. Carbon sphere/
poly (vinylphenol) composites prepared with the addition of hexadecyltrimethylammonium bromide as a
surfactant showed good carbon sphere dispersion, allowing in principle a memory device size reduction relative
to the case when no surfactant was used. Devices constructed with surfactant added carbonsphere/poly(vinylphenol) composites allowed writing the ON state in ca 200 ns; the write operation consumed
5 x10-5 J cm-2 when a pulse with an amplitude of 5 V and a length of 1 ms was used.
iii) Photocatalysis [13] Doped HCS/TiO2 composites were studied for their photocatalytic activities. Enhanced
dispersion due to doping of the NHCSs and BHCSs in TiO2 gave crack free composite films after annealing. All
composite films absorbed more light in the visible range than a pristine TiO2 film. The observed photocurrent
for the NHCS/TiO2 composite showed a more than two fold enhancement over the TiO2 film. The donor
concentration, flat band potential and depletion width calculated from Mott-Schotkky were calculated and were
consistent with addition of NHCSs in TiO2 increasing the flat band potential and depletion width and enhancing
the photocatalytic efficiency.
iv) Catalyst supports [14, 15]. Monodispersed HCSs were made by decomposition of gaseous CH3CN over silica
Stber spheres in a CVD reaction, followed by silica removal. The nitrogen doped HCSs (N = 8.7%) were used as
a support for well dispersed Co3O4 nanoparticles (7-8 nm; 1% and 2% Co). The Co/N-HCS samples were calcined
o
at various temperatures. The materials calcined at 300 C for 3 h were found to oxidize styrene to styrene oxide
(styrene epoxidation) using dry air as oxidant (120oC/DMF) with 99% styrene conversion and 85% selectivity to
styrene oxide; they could also be reused in repeat catalytic reactions. In a similar vein boron-doped hollow
carbon spheres (B-HCSs) were made and studied. These materials, made by the reaction of BCl3 solution (1 M in
heptanes), led to the deposition of carbon and boron on silica spheres as a template. Removal of the silica and
the addition of Pd gave Pd/B-HCSs. The Pd/B-HCS catalyst, was investigated for the solvent free oxidation of
o
alcohols into their corresponding aldehydes under an O2 atmosphere (125 C, atmospheric pressure).
(v) CO2 capture [16] NHCS materials with a high nitrogen loading (14.8 wt%) and a high surface area (767m2 g-1)
have been made. These materials exhibited CO2 capture with a capacity of 2.67 mmol g-1 and a high selectivity
in a mixture gas (N2 or O2).
Conclusion
It is clear that even materials that have been known for decades can be re-studied using the new techniques
available today. This allows for the development of new synthetic strategies and the exploration of new
structure/property relationships.
29
Acknowledgements
I wish to acknowledge financial support from the DST, NRF and the University. I also acknowledge the many postdocs and post grads, colleagues and collaborators who have contributed to my own understanding of this
fascinating material.
References
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Ph. Serp, R. Feurer, Ph. Kalck, Y. Kihn, J.L. Faria, J.L. Figueiredo, Carbon 39 (2001) 621-626.
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A.A, Deshmukh, S.D. Mhlanga and N.J. Coville, Mat. Sci. Eng. R 70 (2010) 1-28
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J-P. Donnet, R.C. Bansal, M-J. Wang (Eds), Carbon Black: Science and Technology, Second Edition (1993)
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10. G. Xingmei, Y. Yongzhen, Z Xuexia, L Xuguang, App. Surf. Sci., 261 (2012) 159- 165.
11. M.A. Mamo, W. S. Machado, N. J. Coville, I.A. Hummelgen, J Mater Sci: Mater Electron 23 (2012) 1332-1337
12. I.A. Hummelgen, N. J. Coville, I. Cruz-Cruza, R. Rodrigues, J. Mater. Chem. C, 2 (2014) 7708-7714
30
13
K. Ranganathan, A. De Morais, I. Nongwe, A. F Nogueira, N. Coville, submitted
14
V. Ravat, R. Meijboom, N.J. Coville, Appl. Catal A: General 466 (2013) 1- 8
15
V. Ravat, I. Nongwe, N. J. Coville, ChemCatChem 4 (2012) 1930 - 1934
16
S. Feng, W. Li, Q. Shi, Y. Li, J. Chen, Yun Ling, A.M. Asirib and D. Zhao Chem. Commun., 2014, 50, 329--331
Time : 12.35 12.50
Nanocon 012
Dr. Patangrao Kadam, Chancelor BVU felicitating Dr. Barry Burks Chancellor NCAT, USA
31
SESSION 2A: Nano-Biotechnology - I

Professor,
Institute of Technology and Science,
The University of Tokushima,
Tokushima 770-8506, Japan
Email : moriga@chem.tokushima-u.ac.jp
Research Area
Inorganic Materials Chemistry such as,

1.Wide-Bandgap Engineering in Oxides and Oxynitrides
2.Research and Development of Oxynitride Phosphors
3.Structural Chemistry in Perovskite-type Oxides for Solid Oxide Fuel Cells
No. of Publications
More than 124
Proceeding of
international Journals
More than 90
Proceeding of
Domestic Journals
More than 164
Awards & Honors
Dr. Sci in Inorganic and Physical Chemistry from Osaka University in 1996
The Teacher of The Year(Faculty of Engineering),Mar.2006
Best teacher in Engineering Education in Global Graduate Course(Graduate school of
Advanced Technology and Science)
Best Poster Award(The Ceramic Society of Japan),Sep.2012
32
Time : 14.30 14.45
Control of Optical Properties of Oxynitride Pigments and Phosphors through

Stoichiometries
ABSTRACT
We have demonstrated that a color of the perovskite-type LaTiO2N oxynitride could be tuned from orange
1,2
through yellow and green to white by proper adjustment of O/N and Ti/La ratios. However, we have not
obtained real red oxynitrides in this system yet. LaTaON2, which contains more nitrogen amount than LaTiO2N,
3+
can be expected as the redder pigment. However, the ionic size of La seems to be so small for accommodating
the ideal perovskite that the crystal structure may be deformed to be monoclinic system. Distortions to bond
3
angle of Ta-(O,N)-Ta were reported to make the bandgap wider. In this study, we prepared solid solutions of
La1-xBaxTa(O,N)3 and the compositional variation of optical properties as well as structural ones were examined.
4
We also studied effects of addition of NaCl flux during nitridation on the color due to particle size distributions.
Perovskite-type La1-xBaxTa(O,N)3 oxynitrides showed slight redshift of absorption edge and deteriorated
reflectivity in the longer wavelength regions after absorption edge with increasing Ba content x due to relaxing
Ta-(O,N)-Ta distortion. Addition of NaCl flux in the oxide precursor of La1-xBaxTa(O,N)3 during the nitridation led
to improvement of the reflectivity after absorption edge without changing the anion ratio.
LaNbON2 should be one of the redder pigments. Substitution of titanium by niobium in LaTiO2N would enhance
covalency in bonding between the cations and anions because electronegativity of niobium is slightly larger than
that of titanium. We also examined anion composition and optical properties of solid-solution of LaTi1-xNbx(O,N)3
and will discuss difference in ways of variation of optical properties against the substitutions mentioned above.
Perovskite-type LaTi1-xNbx(O,N)3 oxynitrides showed redshift of the absorption edge due to enhancement of
covalent character and increased absorption in red region due to anion defects, with increasing Nb content x.
The absorption would possibly affect the gradient of reflectivity curve after the absorption edge
Figs. Diffuse reflectance spectra of (left) La1-xBaxTa(O,N)3 , (center) NaCl-flux assisted La1-xBaxTa(O,N)3 , and (right) LaTi1xNbx(O,N)3 synthesized by nitriding under NH3 flow at 950C for 5h.
2+
Ba3Si6O12N2:Eu exhibited an intense green photoluminescence under near-UV to blue light excitation. We have
shown that Ba3Si6O12N2was stable in a wide range of Si/Ba from 2 to 6, which means Ba3Si6O12N2 would be allowed
to have a considerable barium deficiency.5 We will show advantages in preparing nonstoichiometric Ba3Si6O12N2
phase with Si/Ba=3 in place of the stoichiometric compound. And we also demonstrate significant redshift
appeared in emission by preparing solid-solutions of (Ba,Sr)3Si6O12N2-type oxynitrides phosphors, which can be
applicable for phosphors used in white LEDs .
For Ba3Si6O12N2-type oxynitrides with Si/Ba=3, considerable redshift in emission wavelength was observed when
2+
2+
substituted by Sr and Eu . It was found that reduction of lattice parameters by the substitution redshifted the
33
emission linearly. (Ba0.95-xSrxEu0.05)2Si6O12N2 phosphors showed the redshift in emission wavelengths from 520nm
at x=0 up to almost 550nm at x=0.50, with increasing Sr content. (Ba0.80-xSr0.20Eux)2Si6O12N2 phosphors exhibited
the maximum emission intensity at x=0.15 and kept the higher emission intensity than a commercial YAG:Ce
phosphor, activated by 460nm blue light, even at temperatures as high as 200C.
Fig. Redshift of emission for (Ba0.95-xSrxEu0.05)2Si6O12N2 phosphors by substitution of Ba by Sr.
AKNOWLEDGEMENT
This work was partly supported by a grant-in-aid (Approved No. 09E52007a) from New Energy and Industrial
Technology Development Organization (NEDO).
REFERENCES
34
1.
Moriga et al, Blue-shift of absorption edge in LaTiO2N by controlling the anion nonstoichiometry, phys.stat. sol.
(a) 203 (2006) 2818-2822.
2.
Moriga et al, Influence of Cation Nonstoichiometry on the Optical Properties of the Perovskite-type Oxynitride
LaTiO2N, J. Ceram. Soc. Jpn. 115 (2007) 637-639.
3.
Maegli et al, Perovskite-type SrTi1-xNbx(O,N)3 compounds: Synthesis, crystal structure and optical properties, J.
Solid State Chem., 184 (2011) 929-936.
4.
Moriga et al, Tuning of Optical Properties in La1-xBaxTaON2 Oxynitride through Composition and Particle Size
Controls, J. Nano Res., 24 (2013) 213--218.
5.
Moriga et al, Peak Shift due to a barium deficiency in the Al MAS-NMR spectrum for Eu -activated barium
aluminum silicon oxynitride phosphors, J. Ceram. Process. Res., 12 (2011) S23--S25.
27
2+
Time : 14.30 14.45
Nanocon 012
It is an endeavor of Bharati Vedyapeeth University, Pune, India, to brimg together and provide a platform to the
experts from Academia, Industry and R & D institutes fron India and abroad to interact, deliberate, disseminate and
exchange ideas, share knowledge, and develope a common vission for thr future developements in the field of
Nanotechnology.
35
SESSION 2B : Special Topics - II (Nanomanufacturing and self assembly)
Dr. Vijay Jain

Professor,
Mechanical Engineering Department,
IIT ,Kanpur, India
Email : vkjain@iitk.ac.in
Research Area
Unconventional or Advanced Machining Processes

Machining of Advanced Engineering Materials
Accelerated Cutting
Computer Aided Process Planning (CAPP)
Computer Aided Manufacturing (CAM)
Qualification
Ph.D. in Mechanical Engineering from University of Roorkee ,1980.
No. of Patents
11
No. of Publications
183
Conference
Proceedings Articles
104
No. of Research Funds
23
Awards & Honors
Best paper award (2013) by Global Engineering, Science and Technology (GEST)
conference held at Singapore during 3-4 October, 2013,
Strickland Prize of the Manufacturing Industries Division of The Institution of
Mechanical Engineers (UK)
Vidyabharati felicitation conferred by Hindi Prachaarini Samiti, Kanpur on April 26,
2003 by Honorable Governor of Karnatak, Mr. T. N. Chaturvedi
BEST paper award (1994) by 16th All India Machine Tool Design and Research
(AIMTDR) Conference
Institution Gold Medal (1986-87) by The Institution of Engineers (I)
KHOSLA Research Award: Silver medal and Rs. 500/-(1982) by University of Roorkee
N. K. Ayyanger Memorial Prize (1981)The Institution of Engineers (I)
KHOSLA Research Award: Gold Medal and RS. 1500/-(1981) University of Roorkee
KHOSLA Research Award: Silver Medal and RS. 1000/-(1980) byUniversity of Roorkee
36
Books
Book Chapter
23
Time : 14.30 14.45
MANUFACTURING: VISION FOR FUTURE

Dr. Vijay Jain
ABSTRACT
This lecture with the issues related to futuristic manufacturing in general and Micromanufacturing in particular.
The lecture starts with the definition of 'Micromanufacturing' and 'Micromachining' and then a general
classification of Micromanufacturing processes is discussed. It deals with manufacturing sustainability which has
three dimensions: economic, social and environmental. It cautions about certain Micromanufacturing processes
which are highly energy inefficient which ultimately become non- friendly to environment. The most efficient and
environment friendly process being claimed is Layered Manufacturing / e-Manufacturing.
The second part of the talk starts with the definition of "micromachining", and then divides micromachining
processes in traditional micromachining processes and advanced micromachining processes. It further divides
advanced micromachining processes into mechanical micromachining, thermal micromachining, electrochemical
micromachining, chemical micromachining and biochemical micromachining processes. After discussing the
working principle of various select advanced micromachining processes, it gives interesting specific applications
of different types of micromachining processes, for example, micro filters for textile and food industries, scribing
EXCIMER LASER on human hair, micro-mixer, etc.
The third part of the talk deals with 3-D printing / e-manufacturing /Layered Manufacturing. It enumerates what
is manufacturing without the use of tools, machine tools, employees, assembly lines etc. It is named as
manufacturing without factory. It gives an example of The Vienna University of Technology's 3D-printed race car,
approximately 285 microns long. It was printed in four minutes and many more examples. Further, it enumerates
the challenges being faced by GE engineers in making parts by additive manufacturing to reduce the weight of
the aerospace engine. According to engineers with GE Aviation, the challenges of additive metal manufacturing
are serious as the promises this technology holds. How else can you make an aero plane engine 1,000 pounds
lighter?
The fourth part deals with the specific applications of micro-casting of wires, pillars etc. Micro formed parts such
as micro gears, micro springs, micro fasteners etc. are shown. Certain examples are included which mention
interesting specific applications in thermal and fluid sciences for more efficient heat transfer and applications in
heat pipes. Certain applications in the area of IC engines, specially fuel injector nozzles requiring micro holes for
uniform distribution of fuel in the cylinder. It also shows various kinds of micro sensors used in automobiles.
Micromanufacturing has very high potential of applications in medical sciences, namely, dental surgery, micro
gripper, hearing aids, etc.
The fifth and the last part of the talk deals with nano-finishing. It tells about the working principle of magnetic
as well as non-magnetic nano-finishing processes, namely, CMP, AFM, R-AFF, MRF, MAF, MRAFF, R-MRAFF, etc.
The most important aspects of these nano-finishing processes are their applications in aerospace engineering,
automobile engineering, defense, and biomedical engineering. It has been demonstrated how these processes
can be exploited for low cost, high finishing rate of human implants such as knee joint, hip joint etc.
The talk ends with following remarks:
1.
To cope up the race with the advanced countries, for that matter, any country has to spend
enough money on the innovative R & D activities.
2.
No matter how much you spend on R & D, dedicated team of young, intelligent, honest,
hardworking and sincere researchers is needed in a country.
3.
Micromanufacturing and additive manufacturing (green manufacturing) will have an important place in
the manufacturing industries.
37
SESSION 2C: Synthesis, Characterization and Applications - II
Prof. Ram Mohan

Associate Professor,Nanoengineering
Joint School of Nanoscience and Nanoengineering,
North Carolina A&T State University,
2907 E Lee Street, Greensboro, NC 27401
Email : rvmohan@ncat.edu
Research Area
Computational multi-physics/multi-scale modeling and simulation in engineering

and physical applications
Computational mechanics, nanomechanics, and material sciences
Processing, mechanics, characterization, and computational modeling of composite
and nanoengineered material systems (crystalline, amorphous, cementitious, and bio
material systems and their multi-scale effects)
Computational modeling of bio and nano systems, interfaces and interactions
Transport phenomena; Flow and thermal behavior during composite material
processing and in fibrous porous media
Physics based composite process modeling simulations, process optimization with
experimental investigations by resin transfer molding (RTM), vacuum assisted resin
transfer molding (VARTM) and liquid composite molding (LCM) processes
High-Performance, scalable scientific computing and engineering product
visualization
Engineering education
38
Qualification
Ph.D., Mechanical Engineering, University of Minnesota,1997
No. of Publications
More than 30
No. of Research Funds
04
Time : 14.30 14.45
Modeling at Nanoscale - Materials and Mechanics Applications, Potentials, and Challenges

Prof. Ram Mohan
ABSTRACT
Nanoengineering requires transformational research and technologies in several areas that necessitate
understanding of the nanoscale phenomena and processes using direct measurements and simulations.
Computational modeling in nanoengineering is highly interdisciplinary with a potential to enhance the
nanotechnology field from an empirical science to a quantitative engineering field. Computational modeling in
nanoengineering research thrust area in our group currently focuses on: 1. Multi-scale modeling and mechanics
of nanoengineered material systems, 2. Material interactions in nanoengineered polymer composites, 3.
Deformation behavior at nanoscale, and, 4. Nano and bio systems and interfaces. In complex material systems,
computational modeling provides an enabling computational microscope that images and analyses enhancing
the understanding of their properties and behavior through appropriate computational material models at
different length scales.
In this presentation, an overview of our recent work on the computational modeling at the nanoscale level will
be presented including brief discussions on the molecular/atomistic modeling methods relevant to nanoscale. A
specific application of our recent research work on the understanding of material interactions and property
predictions in the processing and mechanics of polymer composites will be discussed. Hybrid and nano
composites consist of material phases at varying length scales, and include nano material constituents. The
behavior of these composites is influenced by the material interactions during processing, and by the
damages/defects in the associated constituent nano materials. The role of nano scale modeling based on the
molecular material structures to provide an insight into the molecular level interactions that exist, and their
influence on the associated composite properties will be discussed. Other areas of our research focusing on the
deformation and fracture at nanoscale in bi-metallic nanolayers and cementitious molecular material systems will
be briefly highlighted.
Though appropriate computational material models relevant at different length scales are potentially enabling
the understanding of complex multi-scale material systems, processes and features occurring at fundamental
material building blocks influence the engineering level behavior. These require multi-scale paradigms coupling
material science molecular models into engineering design that currently poses significant, yet unresolved
challenges and limitations.
39
SESSION 2D : Nanoelectronics - I I
Dr. Mikito Yasuzawa

Associate Professor,
Department of Chemical Science and Technology,
Tokushima, Japan
Email : mic@chem.tokushima-u.ac.jp
Research Area
Electrochemistry, Biomaterials
Qualification
Ph.D. in Engineering from Osaka City University, 1999
No. of Publications
76
International Conference 55
Domestic conference
69
Activity of
Academic society
The Chemical Society of Japan

Japanese Society for Biomaterials
The Electrochemical Society of Japan
International Society of Electrochemistry
The Electrochemical Society
The Japan Society for Analytical Chemistry
The Polarographic Society of Japan
Books
40
Time : 14.30 14.45
Immobilization of enzyme using electrodeposition technique for biosensor application

Dr. Mikito Yasuzawa
ABSTRACT
Since Clark and Lyons proposed in 1962 the initial concept of enzyme electrode, the development of such
electrochemical devices has made considerable progress [1]. The advantages of these devices are their high
selectivity and the possibility of compact analyzing system production. Electrochemical microdevices are of
growing interest due to their potential application in monitoring and diagnostic tests in clinical fields. One of the
most attractive and effective applications of enzyme electrode is the implantable glucose sensor for continuous
glucose monitoring system (CGMS) for diabetes patients. Management of blood glucose level is of significant
importance to prevent serious diabetes complications and daily self-monitoring of blood glucose (SMBG) is the
essential procedure for blood glucose level recognition and effective treatments. The advantage of CGMS is not
only the reduction of stressful SMBG action but also the provision of blood glucose trend, which will help to
predict the upcoming situation such as hyperglycemia and hypoglycemia. Beside the high utility of CGMS,
sensors currently on the market are not small enough, and minimizations of both sensor diameter and insertion
lengths are essential for the reduction of user physiological and mental load. While several processes are
required for the fabrication of a minimized implantable sensor, the immobilization of enzyme play a big role on
the sensor properties. Conventional methods of enzyme immobilization are covalent attachment, cross-linking,
hydrogel entrapment, electrogenerated polymer entrapment, and the combination of two or more methods.
Among these, electropolymerized film entrapment have advantage on sensor minimization, since the
electrochemical formation of polymer layers of controlled thickness constitutes a reproducible precise
localization on enzyme on small electrode [2-7]. Two groups, Foulds and Lowe [2] and Umana and Waller [3],
who did the pioneering works on this area, described the entrapment of glucose oxidase within the
electrogenerated polypyrroles. On these sensors, sensor response stabilities were not satisfactory for practical
use and varieties of attempts using various pyrrole derivatives were performed to improve the stability of
enzyme-immobilized film [4-7].
Similar to this procedure, Wilson's group reported that layers of enzyme could be formed on the electrode by
applying an oxidation potential in the enzyme solution containing a nonionic surfactant such as Triton X-100 [8,
9]. Since the obtained enzyme layer was not stable and the release of enzyme occurred, the formation of
electrogenerated polyphenol film was performed.
Fig. 1. Diagrams of enzyme-immobilized electrode preparation using (a) electropolymerization procedure, and (b)
electrodeposition/electropolymerization procedure.
Interestingly, polyphenol film functioned not only as an enzyme entrapping film but also as a permselective film,
which reduce the influence of electroactive species excite in the biological fluid. This electrodeposition/
electropolymerization procedure differ with common electropolymerization procedure, since enzyme could be
immobilized in high density and the amount of electrogenerated polymer in enzyme film is low. Thin highdensity enzyme films are favorable to obtain sensors with high sensitivity and fast response. In this study, three
41
SESSION 2D : Nanoelectronics - I I
electropolymerizable monomers, o-phenylenediamine (o-PD), 3-(1-pyrrolyl)propionic acid (PPA) and 1-(6-Dgluconamidohexyl) pyrrole (GHP), were newly applied for enzyme-immobilized electrodes preparation and were
compared with that using phenol. Glucose oxidase (GOx) was employed as the enzyme and the glucose sensor
properties of obtained electrodes were investigated.
Procedure of enzyme-immobilized electrode preparation is as follow. In a phosphate buffer solution of pH 7.0

containing 10 mg/mL GOx and 0.8 mM Triton X-100, Platinum-iridium (Pt 90%-Ir 10%) alloy wire with diameter
of 0.17 mm was poured and a constant potential of 1.3 V (vs Ag/AgCl) was applied to form GOx layer on the
surface. GOx immobilized Pt-Ir wire was then putted into a degassed phosphate buffer solution (pH 7.4)
containing electropolymerizable monomer and applied a certain potential to induce the electropolymerization
reaction. Amperometric responses of the prepared electrodes to glucose were examined in phosphate buffer
solution (pH 7.4) by measuring the electrooxidation current at a potential of 0.65 V (for hydrogen peroxide
detection).
All three electropolymerizable monomers were able to produce enzyme-immobilized electrodes with sufficient
glucose sensor response, while their sensor properties were somewhat different with the others. Electrode
prepared using o-PD provided the highest sensitivity and was more than 50% higher than that using phenol. The
sensitivity of the electrode using GHP was approximately same with that using phenol, while that using PPA was
the lowest. Considering that the electrodeposited enzyme films are prepared at same procedure, the difference
occurred after the electropolymerization process. Since the isoelectric point (pI) of GOx is 4.2, GOx is negatively
charged at neutral media. Therefore, monomers with positively charged substituents can easily diffuse inside the
enzyme film, while monomers with negatively charged substituents will be interferes by electrostatic repulsion.
It is understandable that the use of PPA, which has a carboxylic acid group, provides an electrode with lower
sensitivity compare with the others. The influence of electroactive compounds, such as ascorbic acid, uric acid,
urea, D-(-)-fructose and acetaminophen, to the sensor response were evaluated and was found that the sensor
response of all prepared electrodes were interfered by the existence of uric acid. The electrode prepared using
o-PD and PPA were not interfered by the existence of ascorbic acid, while that using GHP and phenol were not
negligible. The time of the potential application for enzyme electrodeposition also influenced the properties of
the obtained electrode. When phenol, o-PD and GHP were used, the electrode prepared by applying constant
potential for five minutes showed almost twice the sensitivity of that obtained using 60 minutes, while the
interference of uric acid increased on some electrodes with shorter application time. The electrode prepared by
applying 60 minutes may produce thicker highly densed enzyme film compared with the one for five minutes.
Thick high-dense enzyme film obtained by 60 minutes application reduced the diffusion of glucose into the
enzyme film and lowered the diffusion of hydrogen peroxide to the electrode surface. This might be the reason
for lower sensor sensitivity on the electrode on longer application time, which can even have higher amount of
enzyme immobilized on the electrode. On the other hand, thick high-dense enzyme film may also act as a
permselective film and supported to reduce the interference of uric acid. Beside these results, good interference
elimination obtained on the electrode prepared using o-PD with five minutes application, might be due to the
excellent permselective property of electropolymerized o-PD film. However, when the enzyme film was prepared
only by electropolymerization of o-PD, we were not able to the interference of uric acid at same level. This
indicates the advantage of enzyme film prepared by the combination of electrodeposition and
electropolymerization procedure. Moreover, when we introduced outer film of polyurethane on the enzymeimmobilized electrode prepared using o-PD, we were able to obtain an electrode having good sensitivity with
42
Time : 14.30 14.45
negligible influence of electroactive compounds. This electrode showed good sensor response also in biological
fluid such as horse serum.
References
[1] L. C. Clark and J. Lyons, Ann. N.Y. Acad. Sci., 102, 29 (1962)
[2] M. Umana and J. Waller, Anal. Chem., 58, 2979 (1986)
[3] N. C. Foulds and C. R. Lowe, J. Chem. Soc., Faraday Trans. I, 82, 143 (1986)
[4] M. Yasuzawa, N. Matsushita, H. Satake and A. Kunugi, Sensors and Actuators B, 13-14, 665 (1993)
[5] M. Yasuzawa, S. Fujii, A. Kunugi and T. Nakaya, Anal. Sciences, 15, 12, 1175 (1999)
[6] M. Yasuzawa and A. Kunugi, Electrochem. Commun., 1, 459 (1999)
[7] M. Yasuzawa, S. Inoue and S. Imai, Int. J. Modern Physics B, 17, 1217 (2003)
[8] N. Matsumoto, X. Chen, and G. S. Wilson, Anal. Chem, 74, 362 (2002)
[9] X. Chen, N. Matsumoto, Y. Hu and G. S. Wilson, Anal Chem, 74, 368 (2002)
43

Assistant Vice President ( R & D),Research and Development
University of Petroleum and Energy Studies (UPES) Energy Acres, Dehradun
E-mail : jkpandey@ddn.upes.ac.in// jeetu_ncl@yahoo.com // jeetu@snu.ac.kr
Research Area
Energy / value add products from biological wastes,

Bio-inspired polymer nano-composites,
Extraction and application of nano fillers from nature
Biodegradation and Stabilization of Polymers
Qualification
Ph.D. in Chemistry (Polymer Science), in National Chemical Laboratory-Pune by ,

University of Pune, India , 2007
No. of Patents
No. of Publications
34
Conferences
22
Awards & Honors
JSPS (Japan Society for Promotion of Sciences) Fellow , The University of Tokushima,
Tokushima, Japan,2010
Max Planck Research Fellow, Max Planck Institute of Colloid and Interfaces, Potsdam,
Germany,2009
Most cited article award, International Journal of Precision Engineering and
Manufacturing Most Cited Articles Award, 2008 to 2009," Springer, Netherland, May
18, 2010 (IJPEM Vol.9, No. 2, pp. 81-83, 2008).
Brain Korea 21 (BK21) Postdoctoral Fellowship, School of Aerospace and Mechanical
Engineering, Seoul National University, Seoul., South Korea,2007
Senior Research Fellowship was awarded by Council of Scientific & Industrial
Research, Govt. of India,2003
Young Student Award by Society for Polymer Science of India in symposia - MACRO
2002, held at Indian Institute of Technology, Kharagpur, India
Winner, debate competition held at National Chemical Laboratory, Pune, India,2002,
2003, 2004
44
Time : 15.25 15.40
Nano-particles from plants: Opportunities and Challenges

Introduction
Higher mechanical performance of composites at lower filler concentration of nano-particles from plants has
directed a significant amount of research in this area which is primarily focused on the extraction and
compatibilzation with host matrix. One of the most important advantages nano-filler over traditional carbon and
glass fibers is the preservation of eco-friendly nature [1].As explained in the Figure, cellulosic nano-fibers are
complex carbohydrate made up of several thousand glucose molecules linked end to end and working like metal
wires embedded in rubber matrix of pneumatic tires. The peculiar spatial arrangement of different molecules,
there are six different polymorphs with the possibility of conversion from one to another. Cellulose chains are
biosynthesized, deposited in continuous fashion and aggregated to form microfibrils, ultimately forming long
thread like bundles of molecules stabilized laterally by hydrogen bonds between hydroxyl group and oxygen of
adjacent molecules. The extended chain conformation and microfibril morphology result in significant load
carrying capability, whereas the question of whether and how cellulose fibrils are organized in aggregates and
their interaction with other polymers is still a thrust area of research. Depending on their origin, the fibrils
diameter ranges vary from 2-20 nm to several nanometers [2]. Each microfibril is considered as a string of
cellulose crystals joined by amorphous domains, exhibiting modulus around 150 GPa and strength of 10 GPa [3].
Thus, the cellulose microfibrils have no regular surface because they are constituted by crystalline and
amorphous regions. The amorphous regions are randomly oriented in a spaghetti-like arrangement, leading to
a lower density in these non-crystalline regions. Consequently, the amorphous regions are susceptible to acid
attack. The hydronium ions can penetrate the cellulose chains in these amorphous domains promoting the
hydrolytic cleavage of the glycosidic bonds and finally releasing individual crystallites. These crystallites can grow
in size because of the large freedom of motion after hydrolytic cleavage. Therefore, cellulose crystals after acid
treatment may be called microcrystalline cellulose. The term "cellulose crystallites" may be used for rod like
cellulose crystals of nanometer dimensions (2-20 nm wide) extracted after acid hydrolysis and mechanical
treatments [4].
Location and extraction of nano crystalline cellulose (U. S. Department of Energy Programs)
45
2. Opportunities.
Cellulose nanocrystals have been used as geometrically and structurally defined model cellulosic filler with few
practically useful products. Commercial forms of microcrystalline cellulose as a colloidal system are available as
an aqueous suspension at high solid concentration such as Celish, a trade name from Daicel Chemical Industries,
Ltd. (Tokyo, Japan), providing a 10 % slurry of cellulose nano fibers. Solidified liquid crystals have been applied
for optical applications like in security paper. To evaluate the potential application as display substrates, organic
light-emitting diode (OLED) materials were manufactured on the wood cellulose where researchers succeeded in
producing optically transparent wood cellulose nanocomposites with the performances of both low thermal
expansion and low Young's modulus and deposited an electroluminescent layer on these flexible, low-CTE and
transparent wood cellulose nanocomposites [5]. Cellulose whiskers have also been employed for low thickness
polymer electrolytes for lithium batteries at concentrations below 10 % to avoid significant decrease in ionic
conductivity. Films of high Young's modulus and low density for application as loudspeaker membranes have
been obtained from microfibrillated cellulose (may have some amount of cellulose nano whiskers in suspension),
and melamine formaldehyde [6]. An attempt has been made to use electro spun cellulose nanofibers as affinity
membranes. Affinity membranes permits the purification of molecules based on physical/chemical properties or
biological functions rather than molecular weight/size. Rather than operating purely on the sieving mechanism,
affinity membranes separation properties are based on the selectivity of the membrane to 'capture' molecules,
by immobilizing specific ligands onto the membrane surface. Cellulose acetate nonwoven mesh with fiber
diameter ranging from 200 nm to 1 m was prepared by electrospinning technique. Heat treatment of nanofiber
mesh under 208 C for 1 hour improved [7].
3. Challenges
Cellulose nanofibers have to overcome many obstacles against industrial practices due to time consuming
preparation procedure with very low yield, highly hydrophilic surface, commercial unavailability, poor dispersion
because of high agglomeration tendency, low thermal stability and most importantly, in general, comparatively
higher cost through expensive source. In most of the cases, unfortunately, the natural fiber composite does not
reach the same strength level as glass fiber composites mainly because of incompatibility between generally
hydrophobic host polymer matrix and hydrophilic natural fiber, combined with lower thermal resistance of the
cellulosic material. Traditional processing of polymer composites mainly through extrusion and melt
compounding, is not easily possible in case of cellulose nano-composites due to higher possibility of poor
dispersion and degradation of nanofibers. Therefore, issues related to the fabrication of nanofiber-based
products and their application appears to be one of the most important areas in order to enhance their
competitiveness with other nano-particles.
4. Conclusion
Due to the highly crystalline nature, regular shape and high aspect ratio, and added to their low cost, cellulose
nanofibers are the best alternative to improve the material properties of different polymer matrixes ranging from
natural to synthetic origin, with the advantage of biodegradability. It appears that cellulose crystals of different
sizes and shapes may be obtained from any source containing cellulose, even though the major problem seems
to be the use of acids and oxides during the extraction process. The high level of dispersion can be attained for
water soluble polymers due to the outstanding affinity of cellulose nano crystals with water, whereas the
dispersion in other matrixes requires surface modification. The biggest challenge of controlling the dispersion in
host matrix may be solved by changing the surface characteristics. However, it is considered that mixing of nanoparticles may increase the eco-friendly nature of resulting hybrids, quantitative analysis of different parameters
for such behavior needs a clear understanding.
Acknowledgement
Support of Dr. S.J.Chopra, Chancellor of University of Petroleum and Energy Studies, is gratefully acknowledged.
46
Time : 15.25 15.40
References:
1.
Jitendra K.Pandey, H.Takagi, D.R.Saini, A.N.Nakagaito, S.H.Ahn. 2012, Composites Part B,43,2822.
2.
Battista, O.A., Smith, P.A. 1962. Industrial and Engineering Chemistry, 54, 20.
3.
Favier, V., Canova, G.R., Cavaille, J.Y., Chanzy, H., Dufresne, A., Gauthier, C. 1995a. Polymers for Advanced
Technologies, 6, 351.
4.
Favier, V., Chanzy, H., Cavaille, J.Y. 1995b. Macromolecules, 28, 6365.
5.
Pandey, J.K., Ahn, S.H., Lee, C.S., Mohanty, A.K., Misra, M. 2010. Macromolecular Materials and Engineering,
295, 975.
6.
Pandey, J.K., Kim, C.S., Chu, W.S., Lee, C.S., Jang, D.Y., Ahn, S.H. 2009. E-Polymers 52.
7.
Samir, M.A.S.A., Alloin, F., Dufresne, A. 2005. Biomacromolecules, 6, 612.
47
Dr. Alva Tontowi

Professor,
Department of Mechanical and Industrial Engineering
UGM Jl. Grafika 2 Yogyakarta, Indonesia
Email : alvaedytontowi@ugm.ac.id
Research Area
Developing of new materials: Amorphous polymers, Crystalline polymers, Metals, BioCeramics and Composites.
Mechanics of materials relevant to Rapid Prototyping and
applications
Manufacturing
Developing method of Layer Manufacturing: Modeling and Experiment

Product Design and Development
Qualification
Post Doctoral Research Fellow-The Royal Society UK,2002

Ph.D. ,from School of Mechanical Engineering, University of Leeds-UK,2000
No. of patents
No. of Publications
More than 100
Awards & Honors
Member of Masyarakat Standardisasi Indonesia, MASTAN (2007-present)

Member of Indonesian Automotive Engineers Association, IATO (2004-present)
Books
48
Time : 15.25 15.40
Experimental Study on NanoBiocomposite of [nHA/Bioplastic] for Building a Porous Block

Scaffold
Dr. Alva Tontowi
ABSTRACT
This paper presents a biocomposite of nano-bioceramic that applicable for building a porous block of scaffold.
Two main materials, nano hydroxyapatite (nHA) and bioplastic (bP) were used for composing biocomposite.
Others were distilled water and citus acid. Nano HA material was synthesized from white kakap fish scales (Lates
calcarifer Bloch) and the bioplastic was made of starch extracted from cassava. The biocomposite was prepared
by mixing nHA powder with bioplastic in various composition. The composition was set up by rational of nHA
and (nHA+starch): 0, 20, 40, 60 and 80 %w/w of total weight. A porous block was made by freezed drying at o
-1
40 C pressure of 10 Torr. A series test was carried out including diametral tensile strength, scanning electron
microscope and Fourier Transform Infrared Spectroscopy, X-ray diffraction and Transmission Electron
Microscope. Results show that hydroxyapatite powder we used was proven nano hydroxyapatite as shown in
FTIR, XRD and TEM. While in the biocomposite, increasing content of nHA in the bioplastic could improve
diametral tensile strength of the biocomposite. By adding 60%w nHA in the composite the composite performed
the highest diametral tensile strength, but still has porosity that important for growing the life bone. This porous
composite, however, was potential to be applied for bone scaffold since nHA was still exist and bioplastic as a
matrix was fabricated of cassava starch.
Keywords: nHA, bioplastic, starch, biocomposite, porous block, bonegraft.
INTRODUCTION
At least five issues in hard tissue engineering application (bone graft, bone filler, scaffold) that have been
concerned by researchers including kinds of materials, biocompatibility and nontoxycity, porosity, mechanical
strength and geometry. Ideally, this material should mimic the nature of bone such as chemical composition,
biocompatibility and osteoconductivity. Metals in any compositions and bioceramics with Ca/P-based are
commonly material that have been used in tissue engineering as bone substitute material (BSM). However,
bioceramic is more preferable for BSM since it mimics the nature of bone. Hydroxyapatite (HA; Ca10(PO4)6.(OH)2)
is an example of bioceramic that complies the requirements. It can be formed in any particle sizes from nano to
micrometer and it can be derived from natural sources [1] such as bovine bone [2,3], cattle fish [4,5], egg shell
[6-8], seashell [9], fish scale [10], or synthesized from coral [11], gypsum [12-15], calcite [16,17], etc. HA is
biocompatible material and its chemical composition similar to that of natural bone [18,19]. HA material also has
important characteristic for synthetic bone like bioactive, osteoconductive and osteoingrative that stimulate and
could generate conducive environment allowing the live bone grows in it. In using nano size of HA can provide
large interfaces, giving high catalic activity and great adsorption capability in the catalysis and separation fields
[20] , Growing would be intensive when there are any pores within the block as scaffold. Typically, the ideal size
of the pores for live bone to grow was in 300-400m [21]. Pore size and its distribution within the block could
be controlled by setting the pre-freezing temperature prior to freezed drying and crystal size of the ice during
the pre-freezing. In term of forming pure HA, some of recent studies, however, indicate that at room
temperature, a pure HA in the form of powder is difficult to shape into a certain geometry as block or bulk since
this material is brittle and hard [22]. It was only possible to shape by sintering at high temperature of typically
o
within 1200-1350 C.
Applying these ranges temperature, its mechanical strength was still low and even ease of breaking. At sintering
o
temperature higher than 1300 C, some of HA component will change its phase into -tricalcium phosphate (TCP) that easier to degrade [23-24]. In order to be formed into a certain shape at room temperature, another
material should be added to the HA powder which acts as a binder in indirect sintering process or as a matrix of
a composite for 2 bonding of enhancement material. Other methods in forming of HA into a particular shape
with pore inside is freeze-drying and additive manufacturing or layer manufacturing. Freeze drying works based
on sublimation condition. In this condition, ice water content within the sample is sublimed and drying it up.
Whilst additive manufacturing works based on manufacturing of layer by layer material, stacking the layers into
49
a 3-dimensional forming an object [25]. This method enables us to form a very complex hollow shape with
various ranges of materials [25]. Among the additive manufacturing technologies that available commercially, 3D
printing technology was the one that applicable [26]. Concerning matrix and binder materials that enabling pure
HA to be formed, several materials such as PVA [27,28], PLA [29], PMMA [30], gelatin [31], chitosan [32] have
been used extensively. Scientifically, all matrices or binders mentioned in these composites have been accepted
as additional materials in hard tissue applications. Those materials were biocompatible and biodegradable that
matchs to the important factors needed in tissue engineering applications. Currently, biodegradable material is
becoming favorable material for medical application such as bonegraft and resorbable implants. Attention has
been paid to the use of various natural sources for making biodegradable materials such as corn, potato, cassava
and many others [33]. These materials could be source of starch for making bidegradable polymer [34]. Since
these materials actually are food materials, therefore these are eatable and non-toxic. In this current work,
cassava starch [35] would be used as matrix of the biocomposite and nano hydroxyapatite was used as a
reinforcement of the biocomposite.
MATERIALS AND METHOD

Materials
Two main materials have been used in the experiment i.e. nano hydroxyapatite (nHA) and cassava starch. The
pure nHA powder was supplied by PAIR-BATAN Jakarta that synthesized from fish scales of Indonesias white
Kakap fish (Lates calcarifer Bloch), while cassava starch was commercial starch that obtained from the local shop.
Other materials were citric acid and distilled water.
Methods
Biocomposite samples were prepared by mixing of reinforcement (nHA) and matrix (bioplastic). The
reinforcement was prepared by dispersing nHA in 10% citric acid solution to form 20% (w/v) nHA suspension. It
was then centrifuged at 3000 rpm room temperature to obtain 54.6% nHA concentration in the form of paste.
Whilst the matrix of bioplastic was made by dispersing cassava starch powder in distilled water in the baker to
form 20% (w/v) cassava starch solution. To prepare biocomposite, cassava solution was mixed with nHA paste to
get various final composition of 0% w/w (code:NHAB-0), 20% w/w (code:NHAB-1), 40% w/w (code:NHAB-2), 60%
w/w (code:NHAB-3) and 80% w/w (code:NHAB-4), respectively.
Table 1 shows detail percentages of composition.
Each composition of the mixed solution was stirred at 200 rpm at room temperature for 1h or up to the solution
o
was homogenous. While it was still manually stirred, it was heated up at 70 C and hold for 10 minutes and the
composite paste was ready to cast in three mold with the same size and shape. The same procedure was applied
to other compositions. The next process was carried out by putting the casted composite into the refrigerator at
o
o
-44 C for 24h prior to freeze drying. Condition of freeze drying was set up at temperature -40 C and pressure 101 Torr for 48h. Now, samples were ready to be tested. A series tests for samples were performed by diametral
tensile strength (DTS), scanning electron microscope (SEM) and Fourier Transform Infra-Red (FTIR). Whilst X-Ray
Diffraction (XRD) and Transmission Electron Microscope (TEM) were only performed to observe nHA particles.
50
Time : 15.25 15.40
RESULTS AND DISCUSSION

Five varying biocomposite samples composed by nHA and bioplastic have been developed successfully and
series of tests employing UTS, scanning electron microscope, FTIR and TEM have been carried out. In this work,
there was no further biocompatible test for the materials for both nHA and bioplastic since nHA with Ca/P ratio
of 1.67 is biocompatible material; and the bioplastic was prepared using cassava starch that material was nontoxic. Test of XRD, FTIR and TEM for the reinforcement powder shown in Figure 1 (a) XRD, (b) FTIR and TEM in
Figure 2. These figures indicated that the hydroxyapatite used in this work that was synthesized from white kakap
fish scale (Lates calcarifer Bloch) was really nano hydroxyapatite.
Figure 1. (a) X-ray diffraction of nHA and (b) Fourier Transform IR of nHA
Figure 2. Transmission electron micrograph of particle nano hydroxyapatite
51
For biocomposite of [nHA/Bioplastic], results of the series tests carried out in FTIR, UTS and SEM were exhibited
in Figure 3 and 4. As shown in Figure 3, FTIR spectra of biocomposites represented the combination of FTIR
spectra of bioplastic and hydroxyapatite. The IR spectra of pure bioplastic was characterized by broad and strong
-1
-1
peak of O-H stretching band at 3417 cm , sharp peak of O-H bending vibration at 1635 cm , broad peak of C-1
O-C stretching in the glucopyranose ring at 1042 cm , and C-H asymmetric vibration at 2932 cm-1. While IR
-1
spectra of nHA was was characterized by broad and strong peak of O-H stretching band at 3479 cm- , sharp
-1
-3
-1
-3
peak of O-H bending vibration at 1612 cm , dual PO4 stretching band at 1065 and 987 cm , and triple PO4
-1
-1
bending band at 601, 570 and 524 cm . Additional peaks was also observed in 1566 and 1543 cm due to C=O
stretching vibration of ester groups from citric acid that used to suspensed nHA powder. Intensity of any peak
seems increased by the increase concentration of sourced material in the biocomposite. But it is interesting that
the peak of O-H bending vibration from hydroxyapatite was observed to merging with peak from bioplastic. This
condition may indicate the interaction of bioplastic with nHA through hydrogen bond between hydroxyl groups
from bioplastic with hydroxyl group from apatite crystal of nHA.
Figure 3. FTIR spectra of bioplastic, nHA and biocomposite at varied composition.
Biocomposite underwent densification rather than showed final fracture during the compressive test which is in
accordance to Sundaram and Durance [36]. Considering nHA is a brittle material, it seems flexible nature of
bioplastic matrix play roles in absorbing and dissipating applied stress. Reinforcement of bioplastic matrix by
nHA led to increase in diametral tensile strength at nHA concentration more than 60% (w/w). At that
concentration, nHA seem to form skeleton with interconnective grain in biocomposite that bear mechanical load.
But at nHA concentration of 20 % and 40%, the mechanical strength was lower than pure bioplastic matrix. This
result is in accordance to Sundaram et al. [37] and Zhang et al. [38] that mention the trend of increasing diametral
52
Time : 15.25 15.40
tensile strength of biocomposite does not follow a straight-line relationship with filler concentration. The filler
content affects the interparticle distance and the stress state of matrix polymer surrounding the voids [39,40]. At
low filler concentration, the particle distance is long so the interparticle matrix ligament lies in plane strain state
which is hard to yield so that the mechanical strength cannot be improved. But if filler concentration is increased
so that the interparticle distance reach the suitable range, the interparticle matrix ligament lies in plane press
state which can be plastic yield easily and the mechanical strength can be improved [38]. It was clear that as
shown in the micrograph that increasing content of nHA improved its diametral tensile strength. However, this
strength achieved maximum value for sample with 60% of nHA, then going down due to the limited binder
bonding the particle.
Figure 4. DTS (Diametral Tensile Strength) and micrograph of biocomposite for various compositions
ACKNOWLEDGEMENTS
This study was part of the research that funded by research grant of the Department of Mechanical and Industrial
Engineering Gadjah Mada University. For this, the authors would like to thank for.
53
CONCLUSIONS
Biocomposite of nHA/Bioplastic with various compositions has been developed successfully. This biocomposite
has potential to be used in hard tissue engineering application since nHA was biocompatible and bioactive,
whilst bioplastic was non-toxic and biodegradable. By adding nHA particle within the bioplastic could improve
its diametral tensile strength with the micro pores were still exist. Among those compositions, sample with
composition of 60% nHA gained the highest diametral tensile strength (2.70.2 MPa). This strength and the
pores have fulfilled with the requirement of scaffold application.
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56
Time : 15.25 15.40
Nanocon 012
From Left - Dr. Barry Burks felicitated Dr. Anand Bhalerao for success of Nanocon 012.
57
SESSION 3A : Special Topics - III (Nanofluids and applications)
Dr. James Ryan

Founding Dean
Joint School of Nanoscience and Nanoengineering
North Carolina A&T State University and the University of North Carolina at Greensboro,
Greensboro, North Carolina
USA
Research Area
Thin film deposition

Interconnect technology
Semiconductor manufacturing technology
Radiation hardened nanoelectronics.
Qualification
Ph.d., in chemistry from Rensselaer Polytechnic Institute,1988
No. of Patents
57
Awards & Honors
First Invention Achievement Award 9/83, Seventeenth Invention Achievement Award

12/04
IBM's Top Inventor ,1992
IBM Master Inventor
IBM Patent Portfolio Award for U. S. Patent 5,401,675, P.-I. Lee, T. Licata, T. McDevitt,
P. Parries, S. Pennington,
Outstanding Technical Achievement Award for "Damascene Wiring Technology
Innovation and Implementation," (6/98)
Outstanding Technical Achievement Award for "Contributions to Copper Technology
Development," (6/99).
Corporate Headquarters Excellence Award for Recruiting (12/99)
Matsuda, "PECVD Method of Depositing Fluorine Doped Oxide Using a Fluorine
Precursor Containing a Glass Forming Element." (5/04)
The SRC 1999 Mahboob Khan Mentor Award for Contributions to Student Mentoring
Named as one of "The Triad's Most Influential People (2009)" by The Business Journal.
58
Time : 16.50 17.05
Economic Outreach and Engagement through Academic Research

Dr. James Ryan
The Joint School of Nanoscience and Nanoengineering (JSNN) is a collaboration of North Carolina A&T State
University (NC A&T SU) and The University of North Carolina at Greensboro (UNCG). NC A&T SU is an Historically
Black University with strong programs in engineering. UNCG, the former Woman's College of the UNC system,
has built considerable capabilities in the basic sciences. NC A&T SU and UNCG have come together to create this
new joint school. The core values of JSNN include collaboration, innovation and cooperative, technology-driven
problem solving. JSNN has four degree programs, a Professional Science Master's (PSM) in Nanoscience, a Ph.D
in Nanoscience, an M.S. in Nanoengineering and a Ph.D. in Nanoengineering and is one of only two schools in
the U.S. to have both nanoscience and nanoengineering degree programs. The Nanoscience degrees are
awarded by UNCG and the Nanoengineering degrees are awarded by NC A&T SU. The curricula are "aggressively
interdisciplinary" and enable students to take classes from both universities. JSNN's PSM degree program
features courses in nanoscience as well as business and is intended to produce future nanomanufacturing
professionals for the high tech industries in the region.
JSNN's $56.3 Million facility contains an array of leading-edge equipment and facilities that include
nanoelectronic and biocleanrooms, a nanofabrication facility, a modeling and visualization suite, extensive
analytical, microscopy and bioscience laboratories, as well as classrooms and office spaces. The unique
environment of the JSNN enables the pursuit of corporate collaborative relationships that serve as a "reactor" for
emerging technologies and fosters an environment conducive to discovery.
JSNN is devoted to graduate nanotechnology education and research, but is also responsible to assist the
Greensboro community with economic development. JSNN focuses on engagement with industry through its
program of research as well as through access to its facility using a shared infrastructure model.
JSNN's faculty was selected due not only to their prowess in teaching and research but also because their
research field "mapped" into the industries of North Carolina. Their expertise helps promote relationships with
the industrial base of the state as well as introduces their students to the areas where their research is applied
(and they might seek employment).
JSNN's equipment and infrastructure is heavily used for research but extra capacity exists on key equipment.
Enabling access to the equipment also helps build relationships and promotes job creation/economic
development in the region. JSNN created the Nanomanufacturing Innovation Consortium in order to formalize
the relationships and assure that all partners have equal opportunity for access. To date, we have 27 industrial
partners in our consortium and it is expected to continue to grow.
At JSNN, our focus on nanomanufacturing was chosen as a unifying theme where innovative, fundamental
research on nanoparticles, nanofibers, thin films and new devices leads to new applications and innovative
manufacturing technologies. Nanomanufacturing brings together our research and education mission with the
needs of local industrial entities and is viewed as a critical enabler for national priorities. In order to build a
program that strives for nanomanufacturing leadership, an integrated approach has been developed featuring
workforce training, nanomanufacturing research, and improving commercialization through public-private
partnering models.
Nanomanufacturing focus areas in nanoscience include nanoparticle manufacturing methods, nanopore
fabrication and nanobiomanufacturing. Nanoparticles are a broad group of materials includes fullerenes,
nanotubes, self-assembled structures and thin films that are used in products from cosmetics to computers.
Nanomanufacturing topics in nanoengineering include nanocomposite fabrication, nanobioelectronics and
computational nanotechnology. Nanocomposites are used in structural and energy applications.
Nanobioelectronics combines semiconductor processing technology with biotechnology in order to create new
diagnostic or medical devices. New protocols for combined Nano and Bio manufacturing must be developed
(JSNN has a cleanroom capable of both nano and bio technologies). Computational Nanotechnology develops
new predictive models for "nanobio" as well as other complex problems where nanomaterials and bulk materials
are combined to create a useful system.
The combination of leading-edge research, state-of-the art equipment and facilities and a business-friendly
approach to collaboration and commercialization offers significant leverage to nanomanufacturing entities. From
59
SESSION 3A : Special Topics - III (Nanofluids and applications)
a business perspective, three key attributes of the Consortium model have enabled its growth. First, members
receive equipment access with minimum investment. Second, our membership agreement minimizes issues with
intellectual property. Third, access to JSNN's seminars, conferences and other technical presentations enables
networking among nanomanufacturers and faculty.
Although there may be concerns on each side about issues such as confidentiality (from the industrial entities)
and about collaboration causing a lack focus on educational and fundamental research priorities (University),
these concerns are quickly set aside because, for the most part, the industrial personnel and university personnel
function in a "parallel play" mode where they only interact in mutually beneficial circumstances.
Industrial entities and the Universities gain a variety of benefits from the model. For industrial entities, they find
leasing expensive equipment better than owning for the "bottom line" and they work with highly capable
resource that they don't need to directly employ. The Universities learn from working with industry about the
current, leading-edge problem set, as well have the potential to receive guidance and even sponsored research
funding through their relationships. An additional benefit is that industry becomes more aware of university
technologies and may choose to obtain licenses for them.
60
Time : 16.50 17.05
Nanocon 012
Felicatation of Dr. J.v. Yakhmi BARC (India) by Dr. Shivajirao Kadam, Vice Chancellor, BVU
61
SESSION 3B : Nanocomposites - I
Dr. Shaik Jeelani

Vice President, Research and Sponsored Programs,
Director, Center for Advanced Materials
Director, Ph.D. Program in Materials Science and Engineering
Tuskegee University, USA
E-mail: jeelanis@tuskegee.edu
Research Area
Processing (hand layup, vacuum bag, autoclave, compression molding), Process

Sensing, low-cost manufacturing using RTM, VARIM processes, static and dynamic
(low-velocity, high strain rate, ballistic impact) of Fiber Reinforced Composites,
Sandwich Composites, Fatigue and Fracture, Microstructural characterization (SEM,
Optical Microscopy, Thermo-gravimetric Analysis), Structural Analysis, Non
Destructive Evaluation
Qualification
Ph. D. from North Carolina State University, Raleigh, North Carolina,1974
No. of Publications
177
Papers Presented at
Technical Meetings
323
Technical Reports
36
No of Funded Grant
81
Awards & Honors
Global Messenger Award presented by Southeastern Consortium for Minorities in

Engineering (SECME), 2001
Outstanding Contribution Award by the National Association of Minority Program
Administrators (NAMEP A), 1996
Exxon Foundation Faculty Development Award for Outstanding Research, 1984.
Outstanding Teacher from ME Department, 1978-1979
Outstanding Teacher from School of Engineering, 1977-1978
Faculty Achievement Award, 1977
Outstanding Teacher from School of Engineering, 1977
UNCF Professor of the Year, 1976
Tuskegee Teacher of the Year, 1976
62
Time : 16.50 17.05
Recent Advances in the Materials Science and Engineering Research at Tuskegee University
Tuskegee, Alabama, 36088
Dr. Shaik Jeelani
ABSTRACT
The Department of Materials Science and Engineering, formerly known as the Center for Advanced Materials (TCAM), has been contributing to basic and applied research in Materials Science and Engineering and is acclaimed
nationally and internationally for over three decades for its enormous success in research, education and
outreach in the science and engineering of advanced materials. The department offers Master's and Ph.D.
degrees in Materials Science and Engineering. The faculty and students associated with the department are
involved in basic applied research on materials related to current and future needs of the society. Major research
activities that are currently in progress are:
"
Multifunctional Fiber Extrusion
"
Polymer Modification for Multi-functionality
"
Polymer Nanocomposites for Structural Applications
"
Sandwich Composites
"
Synthesis of Nano-Fillers: CNTs, Metals and Metal Oxides
"
Nanomaterials for Healthcare applications
"
Biodegradable Composites.
Earlier focus of research at the T-CAM was on the development of multifunctional, affordable and
environmentally safe polymeric materials, particularly composites. In this regard, researchers associated with the
center have developed innovative syntheses, processing, modeling and simulation, and characterization
techniques that are still being used. T-CAM has been directed toward producing a variety of nanomaterials
including metal and metal oxides, single and multi-walled carbon nanotubes, and their hybrid nanoparticles and
using these materials as reinforcement to enhance mechanical, electrical, and thermal performance of materials
for a variety of applications. Specific products and processes that have been developed using nanofillers include
sandwich composites, extruded multi-functional thermoplastic fibers; filament wound composite laminates,
nanoparticles for drug delivery and biocomposites.
Agencies that have been funding research and education in Materials Science and Engineering at Tuskegee
University include Air Force Research Laboratory, Army Research Laboratory, Army Research Office, U. S. Army
Construction Engineering Research Laboratory, National Aeronautics and Space Administration, National Science
Foundation, Office of Naval Research, State of Alabama, the U. S. Army Cold Regions Laboratory and industry.
In 2011, Tuskegee University established the Department of Materials Science and Engineering (MSE) that houses
the two graduate programs in MSE and the Center for Advanced Materials.
Figure 1 shows current active grants in the Department of MSE.
63
Fig 1. Active grants at Tuskegee University's Department of Materials Science and Engineering.
Through this presentation, the authors would like to highlight only a few research activities in the area of
nanomaterials that distinguish Tuskegee University as a highly competitive research and educational institution
in the field of Materials Science and Engineering.
Multifunctional Fiber Extrusions
The department has the capability to extrude fibers of various materials with nanofillers including carbon
nanotubes to enhance the properties of the fibers for a variety of applications. Figure 2 shows enhancement in
strength and stiffness of nylon-6 as the result of infusion of 1% by weight of carbon nanofibers, carbon
nanotubes and SiO2 nanoparticles.
Figure 2. Stress-Strain behavior of Nylon 6 fiber reinforced with nanofillers
64
Time : 16.50 17.05
Nano Particles for Health Care

Nanoparticles are widely used in healthcare because of their unique tunable properties and applications.
Biocompatible magnetic and nonmagnetic particles ranging in size from nano meter to micrometer scale are
increasingly being used in biomedical and drug delivery applications. At Tuskegee University the nanoparticlebased drug delivery systems are being developed to control the release of drug in the body to protect the drug
from enzymatic or chemical degradation, and to attain organ or tissue-targeted delivery. For example the egg
shell based calcium carbonate (CaCO3) nanoparticles are highly porous, biocompatible, biodegradable, and have
pH-sensitive properties. These properties make CaCO3 nanoparticles one of the best candidates for a drug
delivery system, especially for toxic cancer drugs. The important properties of these biobased nanomaterials are
non-toxicity, biocompatibility, injectability, and high-level accumulation in the target tissue or organ.
Near infrared (NIR) Photothermal Nano-Therapy (PNT) is a minimally invasive local therapy that utilizes gold
nanorods (AuNRs) as a thermal-contrast agent to provide a site-specific thermal response in combination with
otherwise harmless NIR laser irradiation. The NIR laser emits light in a spectral range that is transparent to
normal tissue and overlaps with the plasmon resonance absorption of the gold nanoparticles. The AuNRs
absorb NIR light energy, convert rapid electron oscillations into thermal energy, and cause the death of tumor
cells. AuNR injections followed by NIR laser irradiation of tumors, PNT, demonstrate the potential of NIR
photothermal therapy as a viable localized treatment approach for primary and early stage tumors by avoiding
nanoparticle uptake by the reticuloendothelial system (Fig. 3). PNT resulted in approximately 100% tumor
regression in ~90% of treated tumors which was statistically significant in comparison to the average of all
control groups across all time points (p<0.01).
Figure 3. Schematic representation of Photothermal-Nano-Therapy treatment platform: (a) biocompatible gold nanorods,
transmission electron microscope images and 785 nm peak absorption spectra shown, were used in multiple radial
intratumoral injections followed by (b) a single 10-minute near infrared laser irradiation of tumor and resulting in (c)
tumor discoloration and eventual tumor regression.
Biodegradable Composites
Advanced composite materials are finding a wide variety of structural applications in aerospace, marine, mass
rapid transportation, automotive etc. However, they suffer from a major drawback that they are not
biodegradable. At the end of their service life, most of them end up in landfill thereby causing adverse
environmental impact. Hence, in order to address this crucial issue, researchers at Tuskegee along with their
partners across several universities are working toward developing composite materials derived from natural and
waste resources which offer comparative performance and yet at the same time are biodegradable. In a recent
study, flax fibers were treated with alkali with 2.5, 5, and 7% solutions of sodium hydroxide at room temperature
for an hour. Morphological studies were carried out through scanning electron microscopy (SEM) and X-ray
diffraction (XRD). Based on the results obtained, samples treated with 2.5% solution of sodium hydroxide were
further evaluated at elevated temperatures of 34 and 45 C. Thermal, morphological and mechanical
characterization showed that a temperature of 35 C was appropriate. In the next step, fiber mats were prepared
by immersing fibers in water which were then dried in an oven at 80 C for 24 hours. Flax fiber reinforced
polyester composites were prepared by compression molding. Mechanical and thermal test results indicated that
65
alkali treated composites show increase in flexural properties and storage modulus and reduced moisture
uptake. In a recent study, Cellulose was extracted from non-wood cellulosic biomass by formic acid, peroxy
formic acid treatment and hydrogen peroxide bleaching. The extracted celluloses were then subjected to acid
hydrolysis or ball milling to isolate cellulose nano-fibers (CNFs). Cellulose nano-fibers (CNFs) were incorporated
in an epoxy resin system at 1 wt. %, 2 wt. % and 3 wt. % to fabricate nano-composites. Addition of CNFs in epoxy
shown significant improvement in storage modulus (figure 4), thermal and mechanical properties compared to
those of control ones. Best results were obtained for 2 wt. % addition of CNFs in epoxy. Flexural strength for 2
wt. % nanoparticle modified polymers depicted about 30% improvement compared to control ones. An increase
of about 20 C in decomposition temperature was also observed. Therefore, an enhancement of mechanical,
thermal and thermo-mechanical properties was achieved by incorporating CNFs to polymers.
Figure 4. Storage modulus versus temperature of neat and CNF reinforced composites.
66
Time : 16.50 17.05
Nanocon 012
Dr Patangrao Kadam, Chancellor BVU Addressing NANOCON012
67
SESSION 3C : Sensors

Executive Director,
C-MET,
Panchawati, Off Pashan Road, Pune
Email : amalnerkar@cmet.gov.in
Research Area
Thick Film Materials

Photoconducting Materials
Nanomaterials/Q-Semiconductors
Conducting Polymers
Qualification
Ph.D. in Physical Chemistry from University of Pune , 1982.
No. of Indian Patents
20
US Patents
No. of Publications
More than 160
Conference
75
Awards & Honors
He is recipient of the Materials Research Society of India's prestigious Medal Award

for the year 2008 for his significant contributions in Materials Science and
Engineering.
He is a Fellow of Maharashtra Academy of Sciences
68
Time : 16.50 17.05
Innovative biofilm inhibition & anti-microbial behaviour of molybdenum sulfide

nanostructures generated by microwave-assisted solvothermal route
ABSTRACT
The incessant use of antibiotics against infectious diseases has translated into a vicious circle of developing new
antibiotic drug and its resistant strains in short period of time due to inherent nature of micro-organisms to alter
their genes. Many researchers have been trying to formulate inorganic nanoparticles-based antiseptics that may
be linked to broad-spectrum activity and far lower propensity to induce microbial resistance than antibiotics. The
way-out approaches in this direction are nanomaterials based (i) bactericidal and (ii) bacteriostatic activities. We,
herein, present hitherto unreported observations on microbial abatement using non-cytotoxic molybdenum
disulfide nanostructures (MSNs) which are synthesized using microwave assisted solvothermal route. Inhibition
of biofilm formation using MSNs is a unique feature of our study. Furthermore, this study evinces antimicrobial
mechanism of MSNs by reactive oxygen species (ROS) dependent generation of superoxide anion radical via
disruption of cellular functions.
69
SESSION 3D: Synthesis, Characterization and Applications - III
Dr. Tae Gyu Kim

Professor,
Department of Nanomechatronics Engineering
Pusan National University,
Gyungnam, 627-706, Korea.
Email : kream0401@gmail.com
Research Area
Characterization of Diamond Films: Structure and Properties, Boron doped nanodiamond

Characterization of DLC Films : Structure and Properties
Modification of DLC Films by Third Element Addition or Nano-scale Structural
Manipulation
Tribological Behavior of DLC Films : Environmental Dependence & Mechanism
Functionalization of DLC films for biological applications
Nanoscale structural manipulation of carbon films
Field Emission from Carbon Materials
Synthesis of Carbon Nanotube (CNT) and SiC films
70
Qualification
Ph.D ., Department of Mechanical Engineering, Yeungnam University, 1994
No. of Publications
35
Time : 16.50 17.05
Conductive CVD Nano Diamond for application of Cutting Tools
Dr. Tae Gyu Kim
ABSTRACT
In Diamond-coated cutting tools are used primarily for machining non-ferrous and non-metallic materials such
as aluminium-silicon alloys, copper alloys, carbon fiber reinforced plasticity, green ceramics and graphite.
Because the tool life of cemented carbide cutting tool is greatly improved by diamond coating, and typically
more than 10 times the tool life is obtained. However research of boron-doped diamond coating tool has not
been done a lot.
Keywords: CVD Nano-diamond, WC-Co Cutting Tool, Boron Doped Diamond(BDD)
In this study, we have succeeded to make boron doped nanocrystalline diamond coated on cutting tool to
compare with existing diamond-coated tools. Boron doped nanocrystalline diamond (BDD) thin film is deposited
on Co-cemented tungsten carbide insert and end mill cutting tool by using Micro Wave Chemical Vapor
Deposition (MPCVD) method. Scanning electron microscope and Raman spectroscopy are used to characterize
the as-deposited diamond films. The Nano-indentation test shows that boron doping could effectively improve
the adhesive strength on substrate of as deposited thin diamond films.
[1] K.Kanda, etc., Application of diamond-coated cutting tools, Vol 73, Surface and Coationgs Technology, 1995.
[2] Xuelin, etc., Effect of Boron-Doped Diamond Interlayer on Cutting Performance of Diamond Coated Mircro
Drills for Graphite Machining, Advances in Surface Coatings, 2013
71
Dr. Katia Vutova

Head of the Laboratory of Physical Problems of Electron Beam Technologies,Institute of Electronics, Bulgarian
Academy of Sciences (IE-BAS)
72 Tzarigradsko shosse, 1784 Sofia, Bulgaria
E-mail: vutova@ie.bas.bg ; katia@van-computers.com
Research Area
Electron beam technologies, nanolithography, mathematical modeling, mathematics

applications in physics and technical sciences, mathematical modeling of physical
processes at materials treatment by electron and ion beams, new materials
Qualification
D.Sci., Institute of Electronics BAS, 2007

Ph.D., Institute of Electronics BAS, 1991
M.Sci., Sofia University, 1985
No. of Publications
136
Awards & Honors
Award "Academician E.Djakov" of the IE-BAS for the best scientific publication in the
field of radio physics, physical and quantum electronic, nanotechnologies and
nanoelectronics, 2004 and 2008;
Nominated for the award "Young Professor" of the Ministry of education and science
given to professors of 55 and younger, Bulgaria, 2007;
Nominated for the award "Pitagor" of the Ministry of education and science in the
category "Award for the most successful woman-scientist", Bulgaria, 2009.
Invited and plenary talks and lectures in Japan, Germany, India, Romania, Ukraine.
Co-Chair of the Tenth Anniversary International Conference on Electron Beam
Technologies EBT'2012, Varna, Bulgaria, June 1-4, 2012 and Eleventh International
Conference on Electron Beam Technologies EBT'2014, Varna, Bulgaria, 8-12 June,
2014.
Books Chapters
72
Time : 17.35 - 17.50
Computational modeling and optimization approach at material treatment by electron

beams
Dr. Katia Vutova
ABSTRACT
Computational modeling yields a possibility for better understanding and investigating the heat transfer
mechanisms and can be used for optimizing the electron beam melting process in view of obtaining new
materials with improved characteristics that have many applications in the power industry, medicine, electronics,
instrument engineering, transport, etc. We developed a physical model and a software tool for modeling the heat
transfer processes, and simulating and optimizing the electron beam melting and refining (EBMR) of metals. The
accumulated knowledge on computational modeling of the thermal distributions in the cast ingot and the
thermal flows through the wall of water cooled crucible as well as the calculation of the refining constants at
various mechanisms of molten metal refining are described. The analysis of the refining processes includes the
thermodynamic condition determination and description of the refining kinetics of various nonmetal and
metallic components and inclusions in the purified metal. Mechanisms of impurity removal at EBMR are
investigated. A discussion of obtained results, chemical composition, other peculiarities and optimization criteria
and procedures of the fabrication of metals by EBMR connected with practical aspects of the EBMR applications
are done.
Introduction
Despite the rapid development in the field of electron beam melting and refining (EBMR), many unsolved
problems still remain. The study of mechanisms and relationships of macroscopic heat and mass transfer during
heating a free liquid surface by an intensive energy flux is a fundamental problem. Improving the energy
efficiency is crucial in optimizing the technologies and reducing the price of the pure metals obtained. This
requires detailed studies of the thermal processes taking place in the zone of beam-material interaction,
thorough knowledge of the processes and factors limiting the geometry of the molten pool, and precise
evaluation of the temperature distribution and behavior of the metals and their compounds in the refining
process. The successful application and optimization of EBMR of metals and alloys depend also on the adequate
physical models, computational modeling and optimization approaches of the processes involved; this will assist
one in studying the influence of the large number of technological parameters and the various limiting factors.
Results and discussion

The thermal transfer processes are important in the production of metal ingots with good quality (structure,
surface and composition). The optimization of the EBMR technology and the quality and price of the new
materials obtained requires a detailed study of the heat processes and an adequate modeling. A time-dependent
3D axis-symmetrical heat model was
proposed and applied for computational modelling of the thermal transfer during EBMR of metals and alloys,
that is a continuation and extension of our quasi-steady-state heat model [1,2,3]. The temperature distribution
along the cast ingot was described by the non-stationary heat equation in cylindrical coordinates:
73
at heating time t at points with height z and polar distance r; k(T)= (T) (T); is the density of the metal; is the
heat capacity and is the thermal conductivity. The last term in the left-hand side of equation (1) describes the
casting process, i.e., the heat added by the molten metal poured (from the raw material being melted) into the
crucible, which is given by the heat energy transfer from the material moving with velocity V along the z-axis. By
assuming three mechanisms of heat transfer through the different boundaries, i.e., three types of thermal contact
interfaces, namely, areas with ideal thermal contact; areas with Newtons type of heat transfer and areas where
the radiation losses predominate, the corresponding boundary conditions (Eqs. 3-6) were formulated taking into
account the radiative and vaporization losses:
A corresponding numerical method (modified Pismen-Rekford method) and a computer program were
developed [4,5]. The numerical scheme is absolutely stable and implicit in terms of the heating time. The implicit
nature of the scheme was overcome by applying the Thomas method for solving three-diagonal linear systems.
The heat model was validated by conducting numerical experiments for wide ranges of regime conditions
variation (e-beam power, beam diameter, casting velocity, heating time, ingot dimensions, etc.) and for different
metals (tantalum, hafnium, copper, etc.). A good correspondence between the simulation and the experimental
data was demonstrated. The model allows simulation of the thermal processes in the metal ingots solidified in
the water-cooled crucible, as well as in the feeding rod [6]. The temperature dependencies of the thermal
conductivity f and the specific heat capacity Cp for each metal investigated were estimated using experimental
data [4,6].
Application software for simulation of the heat processes during electron beam melting of metals is also
developed. It is based on a non-stationary heat model proposed by us and uses a modified numerical scheme
of Pismen-Rekford type. The input data are the EBMR technological parameters (the power and radius of the
electron beam, heating time, casting velocity, etc.), the thermo-physical parameters of the material, the
dimensions of the cylindrical metal ingot, etc. These data are imported via the developed graphical user interface
(GUI). The application software simulates the variation of the temperature fields in the metal ingot during the
heating and, at the same time, systemizes the data on the variation of important parameters such as: the heat
streams through the different ingot boundaries, the geometry of the liquid pool in the cast block, etc. At the end
of the numerical experiment performed, data about the variation of important main parameters characterizing
the EBM process are systemized. The results obtained give a possibility of studying and recommending suitable
EBMR regimes for process optimization and production of pure metals.
In order to optimize the technological regimes, different criteria were proposed for improving the quality
74
Time : 17.35 - 17.50
(structure and composition) of the new materials produced by EBMR. Analytical problems of the mathematical
optimization were formulated, discretized and solved via heuristic methods [4,7,8,9]. Different criteria for
1
2
minimization of L , L norms of the radial derivative of the temperature field were used to investigate appropriate
technological regimes. Criteria were proposed for minimization of the curvature of the liquid/solid contour, which
is directly connected with the quality of the structure of the metal produced. The flat molten pool shape permits
the formation of a vertical dendrite structure and a uniform impurities' displacement toward the ingot top
surface. At a fixed moment of heating tf , the liquid/solid contour can be defined mathematically as a curve
r(tf)={(r, z) |T ( r,z,tf) =Tmelt}, where Tmelt is the melting temperature of the investigated metal. For example, the
following optimization criteria for minimization of the curvature of the crystallization front r(t)were defined:
where is a fixed heating time interval, is a weight function, s is a natural parameter for r (t) and tf is a fixed
moment of heating. The temperature field T is the solution of equation (1) subject to the initial condition (2) and
boundary conditions (3-6) for metal samples with height H and diameter D = 2R, for electron beam radius rb and
heating time F. After discretization of the model and implementation of the developed method for calculation of
the criterion, a discrete optimization problem was solved [4,7,8]. Heuristic methods can be applied for solving
the discrete optimization problem obtained, because the dependence of the criteria on the control variables is
implicit [4]. The proposed optimization technique does not need experimental data for chemical analysis of the
impurities' concentrations like the statistical approach in [10], which is an important advantage of this
optimization method.
The proposed important tool developed for studying, modeling, simulating and optimizing the process of EBMR
of metals can be summarized as follows:
1. Theoretical modeling of the heating processes during EBMR of metals and alloys, including the equations
system of the physical model (heat equation, corresponding initial and boundary conditions);
2. Construction of a modified Pismen-Rekford numerical scheme of the model;
3. Development of software for model simulation via the numerical scheme;
4. Verification of the model;
5. Development of analytical criteria for optimizating the quality of the new materials obtained by achieving
flatness of the crystallization front shape;
6. Discretization of the criteria synchronically with the numerical discretization of the model and computer
implementation;
7. Choice of heuristic optimization techniques and synchronization of all computer programs developed;
8. Tests using different combinations of criteria, control variables and optimization techniques.
A locally one-dimensional, economic and conservative numerical scheme was also proposed [9] for discretization
and numerical simulation of the non-stationary heat model for EBMR. It takes into account the discontinuous and
complicated nature of the thermo-physical parameters of metals more precisely and can be easily built on in the
case of 3D model. The axis-symmetric problem was decomposed into two locally one-dimensional problems. For
the two problems, implicit and absolutely stable schemes were built for which the decomposition method gives
rate of convergence of order one for both the space and time variables. The obtained discrete problems lead to
linear systems of equations with three-diagonal matrixes which were solved via Thomas method. Proposition for
the stability and realization of Thomas method was proved for one of the two one-dimensional problems.
Criteria, related to the geometry of the crystallization front, for improvement of the quality of the obtained
material after EBMR were discussed [9]. Approaches for discretization of the criteria over the numerical solution
of the model were proposed. Comparisons between experimental and simulation results were made and good
correspondence was observed.
75
Based on the studies of the EBMR refining kinetics, metal samples were analyzed together with our Indian
colleagues from the Centre for Materials for Electronics Technology (C-MET), Hyderabad, India. The research is
being pursued in the framework of a joint project under the Bulgarian-Indian inter-governmental program of
cooperation in science and technology. Data was obtained and analyzed about the concentration of metal
impurities (ICP MS), oxygen and nitrogen in the initial (raw) materials and in the new materials produced after
EBMR of hafnium and titanium under the technological conditions examined. The values were estimated of the
coefficients of relative volatility of metal impurities in hafnium and of the free energy for possible chemical
reactions during EBMR of Hf scrap [11]. The factors controlling the refining processes were investigated and
criteria concerning the possibility for refining were selected [8]. A technological scheme for EBMR of hafnium
scrap was proposed for concrete electron beam equipment.
Conclusions
On the basis of the experimental and theoretical studies performed, data and dependencies of practical
importance were obtained about the heat fluxes through the boundaries, the geometry of the molten pool, the
temperature distributions in vertical and/or horizontal cross-sections of the cylindrical metal samples at different
combination of criteria, technological control parameters and optimization techniques, and recommendations
were given concerning the choice of proper regime conditions in order to optimize the EBMR process. The results
are important and useful in view of studying, controlling and optimizing the quality and purity of the new
materials obtained by EBMR. The proposed optimization approach can be applied for optimizing other expensive
advance micro- and nano-technologies.
The software tool developed and the results obtained are important and open a possibility for better
understanding and exploring the heat transfer mechanisms, for controlling the quality of the new material
produced by this expensive modern technology and for optimizing the process parameters, as well as for more
efficient collaboration between the laboratory team, scientific organizations and companies. Studying the
processes involved in EBMR and developing better technologies and equipment for obtaining new materials by
recycling waste products of refractory, reactive and other metals and alloys using EBMR form a good basis for
technological transfer and for specialized industrial applications of the research results obtained.
Acknowledgments
This research was funded by the Bulgarian Science Fund at the Ministry of Education and Science of Republic of
Bulgaria under contract DO 02-127 (BIn- 5/2009).
References
[1] Vutova K, Vassileva V and Mladenov G 1997 Vacuum 48/2 143-8
[2] Vutova K, Koleva E and Mladenov G 2011 IREME Special Issue on Heat Transfer 5 257-65
[3] Vutova K, Donchev V, Vasileva V and Mladenov G 2012 Supplemental Proceedings: Materials Processing and
Interfaces (TMS Wiley USA) 1 125-32
[4] Vutova K and Donchev V 2013 Materials 6 4626
[5]
Vutova K, V.Donchev, V.Vassileva, E.Koleva, G.Mladenov 2012 Proc. of the International Conference on HighPower Electron Beam Technology ebeam 2012, Reno, Nevada, USA, Oct.2012, 35-41
[6] Vutova K., Donchev V., Vassileva V., Amalnerkar D., Munirathnam N., Prakash T. 2013 Proc. EPD Congress 2013
volume, TMS2013, Wiley, USA, 253-260
[7] Donchev V.,Vutova K. 2013 Journal of Physics: Conference Series, Proc. of the 2nd International Conference on
Mathematical Modeling in Physical Sciences, Prague, Czech Republic, Sept. 2013, v.490, 012211,
doi:10.1088/1742-6596/490/1/012211
[8]
76
Donchev V., Vutova K., Vassileva V. 2014 Journal of Physics: Conference Series, 18th International Summer
School on Vacuum, Electron and Ion Technologies, v.514, 012047, doi:10.1088/1742-6596/514/1/012047
Time : 17.35 - 17.50
[9] Donchev V, K. Vutova, T. Chernogorova 2014 J. Electronics and Electrical Engineering, Vol.49, N 5-6, 132-137
[10] Vutova K, V.Vassileva, E.Koleva, E. Georgieva, G.Mladenov, D.Mollov, M.Kardjiev 2010 Journal of Materials
Processing Technology, 210, 1089-1094
[11] Vutova K, V.Vassileva, G.Mladenov, E.Koleva, T.Prakash, N.Munirathnam 2011 Supplemental Proceedings: v.3:
General Paper Selections TMS2011, Wiley, USA, 725-732
77
SESSION 4A : Nanoelectronics - III
Dr. Malik Maaza

Professor & Chairman, NANOAFNET,
Nanosciences Laboratories,
Materials Research Department,
iThemba LABS-National Research Foundation of South Africa UNESCO
Email : mazza@labs.ac.za
Research Area
Nanosciences, nanotechnology & advanced materials

Renewable energy & smart devices for solar energy applications
Photonics & laser based technologies
Neutron research reactors, neutron, X-rays scattering and nuclear based techniques
Vacuum technologies & thin film coatings synthesis techniques
Modeling of surface & interface phenomena
E-learning and ICT based education,
Communication, marketing and S&T public awareness
Science policy, South African Science, Technology and Innovation landscape
Fundraising.
Qualification
Ph.D in neutron sciences,Paris VI and Commissariat a l'Energie Atomique,SaclayFrance.
No. of Patents
No. of Publication
154
Awards & Honors
UNESCO Africa chair, Paris-France, 2012

National Research Foundation-iThemba LABS excellence award, Cape Town-South
Africa, 2011
Fellow of the Islamic Academy of Sciences (IAS), Amman-Jordan, 2010
Fellow of the African Academy of Sciences (AAS), Nairobi-Kenya, 2010
National Research Foundation-iThemba LABS excellence award, Cape Town-South
Africa, 2009
Cambridge award, Outstanding scientists of the 21st century in "Nanophotonics",
London-UK, 2007
American International Scientist of the Year award, Philadelphia-USA, 2007
Global School for Advanced Studies-Global Nanotechnology Network Award, TaipeiTaiwan, 2007
Mellon Foundation Award "with A. N. Mpela", Johannesburg-South Africa, 2000
Khambule Award "with P.M. Kibasomba", Johannesburg-South Africa,1999
Friedel Sellschop Award|Johannesburg-South Africa, 1998
Honeywell International Prize "with I. Stegic", Johannesburg-USA, 1998.
78
Time : 9.30 - 9.45
Multi-functionality of VO2 Based Nanostructures in Photonics & Solar Energy

Dr. Malik Maaza
ABSTRACT
While it took nearly a half-century since the pioneering works of Morin and Sir Neville Mott to measure the
duration of the singular 1st order metal-insulator transition (MIT) of Vanadium Dioxide (VO ) which was found to
be in the femtosecond regime by Cavalleri et al, VO2 is gaining an exponential interest within the R&D
community. Indeed, VO2 which belongs to the correlated electrons systems, holds a great promise for future
high-speed optical switches and other optoelectronic devices. Being a smart oxide, transiting reversibly at a
o
temperature close to room temperature Tc~ 341K (~68 C), stoichiometric VO undergoes a unique 1st order
metal-insulator electronic transition, which is accompanied by a sharp structural crystallographic transition from
a low-temperature monoclinic phase to a high-temperature rutile phase. The latter result causes a sharp change
in the electronic resistivity over several orders of magnitude induced by the band gap closing. From photonics
point of view, this reversible MIT is accompanied by a large and reversible variation of the refractive index under
an external stimulus such as temperature, pressure, and electromagnetic excitations. Hence, VO based nanocoatings have been attracting considerable interest both from fundamental & technological grounds. The sound
technological potentialities include applications such as (i) smart windows for solar heat modulation and air
conditioning, (ii) active coating for heat management in satellites, (iii) ultralight compact bolometry, (iv) ultrafast
optical limiting and (v) femtosecond tunable nanoplasmonics as well as ultrafast tunable single nano-crystals
based optoelectronics, and even H2 gas sensing.
2
In the late 50s up to the 70s, it was established through a variety of more advanced characterization techniques
that above Tc, VO2 crystallizes in a tetragonal rutile-type with lattice constants of a~ 0.455 nm and c~ 0.285 nm.
A second, at a lower value than Tc, is monoclinic VO2 with a~ 0.5753 nm, b~ 0.4526 nm and c~ 0.5383 nm. This
monoclinic VO2 can inversely and reversibly transit to the tetragonal rutile VO2 phase. A third monoclinic VO2
structure does exist too, but with a~ 1.209 nm, b~ 0.3702 nm and c~ 0.6433 nm. However, this later VO2 phase
does not show the so attractive Mott reversible transition characteristics. The 3 phases mentioned above are
known as VO2(T) for the tetragonal type, VO2(M1) for the monoclinic type with the Mott phase transition, and
VO2(M2) for the non-transiting monoclinic type. More precisely, above the transition temperature Tc, VO2(T)
adopts the tetragonal rutile (P42 /mnm) structure with chains of edgeshared VO6 octahedral along the c-axis; the
V.V distances along the chain are 0.2851 nm. Below TC , i.e. in the monoclinic (P21/c) crystal structure of VO2(M1),
the dimerized vanadium atoms have alternate V.V distances of 0.2619 and 0.312 nm. It is widely accepted that
the formation of an electron pair in the monoclinic crystalline structure results in the insulator phase while the
tetragonal is metallic. The possible mechanism in relation to the phase transition may be due to changes in the
3d band structure associated with the crystal structure changes. More precisely, the upper d||.an unoccupied in
conduction band of semiconductor phase is within the broad *-band which is empty, but more strongly
hybridized with oxygen 2p-orbitals and lies above the Fermi level EF. In the metallic phase, however, all 3 d-bands
are close to the Fermi-level. Upon the laser excitation, the main transitions related to ultrafast light-induced
phase transition are from occupied d||-valence band to unoccupied d||.* mixed conduction band followed by
resonant transitions to unoccupied excited states of the metallic phase. As a result the screening of the charge
transfer by conduction electrons in metallic phase takes place by ultrafast laser excitation. The additional
complementary recent work of Lysenko et al. indicated that upon a laser excitation, an instantaneous response
in the transient reflectivity and transmission was observed followed by a relatively longer relaxation process. The
observed phase transition has been then associated with the optical interband transition in VO2.
In 2004, having demonstrated the ability to generate and use sliced x-rays in an energy range that cannot be
reached with any other x-ray source, Cavalleri et al have resolved a 5 decades solid state problem about the true
nature of the phase transition in VO2 and its duration. Ultrafast spectroscopy has been used to establish the timedomain hierarchy between structural and electronic effects in the strongly correlated electron VO2 system. The
formation of the metallic phase by prompt hole photo-doping into the valence band of the low-T insulator was
observed. The insulator-to-metal transition is, delayed with respect to hole injection, exhibiting a bottleneck time
scale, associated with the phonon connecting the two crystallographic phases. This structural bottleneck is
observed despite faster depletion of the d bands and is indicative of important bandlike character.
79
SESSION 4A : Nanoelectronics - III
In 2005, in addition to the first demonstration of tunable nanoplasmonics by Maaza et al, Haverkort et al
reported the first experimental measurements and simulation of the polarization-dependent Xray absorption
spectra of VO2 in both phases at the V L2,3 edges (2p 3d, hv . 510-530 eV). A dramatic switching of orbital
occupation across the transition was observed; from almost isotropic in the metallic R phase to almost
completely 3dp-polarized in the insulating M1 phase, indicating the crucial role of the orbitals and lattice in the
correlated electrons f motion. This crucial study has shown that the VO2 phase transition is an orbital-assisted
`collaborative' Mott-Peierls transition.
In 2006, Uhd-Jepsen et al, have observed the MIT in VO2 thin films with Terahertz spectroscopy at the vicinity of
the MIT. Phase-sensitive broadband spectroscopy in the frequency region below the phonon bands of VO2 gives
insight into the conductive properties of the film during the phase transition. The simultaneous measurement of
both transmission and phase shift allowed to show that Maxwell-Garnett effective-medium theory, coupled with
the Drude conductivity model, can account for the observed behavior, whereas the widely used Bruggeman
effective-medium theory has been found not consistent with the experimental findings. In addition, the results
showed that even at temperatures significantly above the transition temperature the formation of a uniform
metallic phase is not complete.
In 2007, Baum and Nobel Prize Laureate Zewail have onducted the first 4-D electron diffraction visualization
within which VO2 was considered as the ideal system. They measured femtosecond-tonanosecond changes in
intensity of various electron-diffraction spots across the photoinduced transition in single-crystal VO2, using 120fs infrared (800nm) laser pulses to initiate the transition and time-delayed electron packets to probe the
structural dynamics via Bragg diffraction. They have observed two distinct timescales femtosecond and
picosecond corresponding to the temporal evolution of diffraction intensity of different Bragg spots, which
indicate stepwise atomic motions along different directions. It was concluded that (i) the initial femtosecond
motion occurs along the monoclinic a-axis, which is the direction of the V-V bond, and that (ii) the picosecond
structural transformation projects along the c and b axes because if the femtosecond motion had large
components along b or c, it would show up in the dynamics of all investigated spots, contrary to the
observations. More accurately, it was proposed a stepwise transformation path for the VO2 transition on the
atomic scale, as follows: the initiating excitation at 1.55 eV (800 nm) primarily involves the 3d// band, which arises
from bonding of the vanadium pairs. From a chemical perspective, the excitation is to an antibonding state, which
instantly results in a repulsive force on the atoms, and they separate along the bond direction (initial fs-scale VV dilatation). In sequence and on a slower timescale, the unit cell transforms toward the configuration of the
rutile phase. Therefore, the observed stepwise atomic motions show that the phase transition proceeds by a
nondirect pathway on the multidimensional potential energy surface and not by a direct structural conversion.
The coincidence of the thermal and photoinduced transition thresholds at different temperatures suggests the
common pathway mechanism for the transition.
In 2009, the first measurement of the spectrogram of a supercontinuum light pulse was demonstrated by
Cielento et al using specifically the ultrafast MIT of VO2 as a medium. More precisely, the possibility to determine
the temporal and spectral structure (spectrogram) of a complex light pulse exploiting the ultrafast switching
character of a non-thermal photoinduced phase transition was demonstrated. The abrupt variation in the VO2
film optical properties, over a broad infrared/visible frequency range, is exploited to determine, in situ and in a
simple way, the spectrogram of a supercontinuum pulse produced by a photonic crystal fiber. The determination
of the structure of the pulse is mandatory to develop pump-probe experiments with frequency resolution over
a broad spectral range (700-1100 nm).
In 2012, Liu et al reported the first observation of MIT transition by a Terahertz electric field using VO2 as a testbed material. More precisely, this was achieved using metamaterial-enhanced picosecond, high-field Terahertz
pulses to reduce the Coulomb-induced potential barrier for carrier transport. A nonlinear metamaterial response
is observed through the phase transition of VO2 thin film demonstrating that high-field terahertz pulses provide
alternative pathways to induce collective electronic and structural rearrangements. The metamaterial serves to
amplify the local terahertz field, as well as to detect macroscopic changes in VO2. Through direct, time-resolved
observations, the authors established a detailed microscopic picture of the structural and electronic changes
underlying the MIT transition.
In view of the re-birth of the R&D global interest in the femtosecond governed optical and electronical singular
properties of VO2 coupled to the remarkable advances in ultrafast optical spectroscopy, this contribution reports
on the multifunctionality of nano-scaled VO2 in optoelectronics & photonics.
80
Time : 9.30 - 9.45
Nanocon 012
Dr Anand Bhalerao, Chairman Nanocon012 felecitating Dr Jaume Veciana, Director, Molecural Nanocience and
Organic Material Institute Barcelona, Spain
81
SESSION 4B : Thin Films- II

Department of Mechanical Engineering,
Tokushima, Japan
Email : norio@me.tokushima-u.ac.jp
Qualification
Ph.D.,from Kyoto University,2005
No. of Publications
26
International Conference 70
Domestic Conference
40
Awards & Honors
JSMS Shikoku Branch Award for Best Presentation (JSMS Shikoku Branch) Aug. 2013
JSMS Shikoku Branch Award for Best Presentation (JSMS Shikoku Branch) Apr. 2014
Book Editor
82
12
Time : 09.30 09.45
Bionanocomposites based on cellulose

Abstract
The excellent mechanical properties of cellulose nanofibers make them promising substitutes for conventional
high-performance reinforcing materials like glass or aramid. Besides, cellulose is biodegradable and derived from
renewable resources. However, there are some serious difficulties and challenges to be overcome, and this article
describes some efforts being made to exploit the cellulose's mechanical properties to the most of its potential.
Keywords: cellulose; nanofiber; nanocomposite; nanofibrillation
1. Introduction
Cellulose nanofibers are mostly found in the cell wall of plant fibers, acting as the framework of a biocomposite
made of matrix substances lignin and hemicelluloses. Such natural nanofibers have diameters of a few
nanometers and are made up of a bundle of cellulose molecular chains arranged parallel to the longitudinal
direction of the nanofibers. The crystalline portions possess a Young's modulus of 138 MPa [1], with the
theoretical tensile strength predicted to be about 10 GPa [2]. Besides, the molecules are aligned along the axial
direction of the nanofibers even in the amorphous regions, so the real strength of nanofibers is estimated to be
over 2 GPa. The mechanical properties of cellulose nanofibers are comparable to those of aramid fibers, making
these naturally occurring nanofibers a renewable and sustainable alternative to high-strength synthetic fibers.
Berglund [3] states that the first attempt to exploit cellulose nanofibers in composites was probably made by
Boldizar et al. in 1987 [4]. Prehydrolyzed pulp fibers were mechanically treated by a beater or a high-pressure
homogenizer to extract the nanofibers, and subsequently compounded with thermoplastic polymers and
injection molded. Even though the modulus of the composites increased significantly in relation to the neat
matrixes, the tensile strength did not change or even decreased. This was probably due to agglomerations of the
hydrophilic cellulose nanofibers, which are extremely difficult to disperse in the hydrophobic molten polymer.
Later in 1995, researchers in France extracted cellulose whiskers by acid hydrolysis from natural cellulosic sources
and composed with elastomers to study the reinforcement mechanism. Favier et al. [5, 6] mixed copolymerized
styrene and butyl acrylate latex with an aqueous suspension of cellulose whiskers, and casted films by water
evaporation. As the cellulose whiskers and resin were suspended in water medium during processing, the
whiskers were homogeneously dispersed in the composite film, and a 6wt% whisker content composite resulted
in a shear modulus in the rubbery state of over two orders of magnitude increase over the neat elastomer. And
differently from the modulus of the matrix, which decreased with temperature, the modulus of the composite
levelled off up to the temperature of cellulose decomposition. The remarkable reinforcing effect and the
unchanged modulus regardless of temperature increase, led the authors to assume that the whiskers formed a
percolated network due to hydrogen bonds joining the exposed hydroxyl groups of cellulose. Percolated systems
are formed by an unbroken cluster of interconnected reinforcing elements spanning the whole material. It is
similar to a single stiff framework supporting the matrix resin instead of a multitude of individual reinforcing
elements. In later studies, it was found that the bonds in percolated systems of cellulose nanofibers delivered
better reinforcement than whiskers, when compared with the same matrix material [7-9]. The reasoning was that
besides hydrogen bonds, cellulose nanofibers were interconnected by physical entanglements, due to the
enhanced flexibility compared to whiskers. Cellulose nanofibers, although not as strong as crystalline cellulose
whiskers, are also suited to be used as reinforcement in composites.
2. Nanocomposites based on cellulose nanofibers

The cellulose nanofibers described in this article are produced commercially by Daicel Corporation (KY-100G).
Among the different processes available for nanofiber production, this one is obtained from pulp fibers
subjected to mechanical treatments by a disk refiner and a high-pressure homogenizer, as first described by
Turbak et al. [10]. The pulp fibers are converted into nanofibers by a process called nanofibrillation. Pulp fibers
are obtained from wood fibers after removal of matrix substances like lignin, and serve as raw material to make
paper. Pulp fibers are micro-sized tubular cells made of a complex arrangement of nanofibers. These microfibers
are subjected to shear forces to separate the nanofibers from the cell wall.
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SESSION 4B : Thin Films- II
Dispersing hydrophilic cellulose nanofibers in mostly hydrophobic polymer resins by melt compounding is quite
difficult as the cellulosic elements tend to agglomerate by the formation of hydrogen bonds between their
surface hydroxyl groups. Instead, a process to take advantage of this phenomenon was conceived [11] by first
preparing paper-like sheets of cellulose nanofibers by suspending in water and subsequent filtration. Once they
are dried, a percolated framework is formed, and this reinforcing phase is impregnated by a matrix resin. These
nanofiber sheets were dipped into a solution of phenolic resin, dried, stacked in layers and compression molded
at high pressures up to 100 MPa. If compared to microcomposites made from the original pulp fibers, the
Young's modulus was unchanged at around 18~19 GPa, but as the nanocomposites have much higher strains at
fracture, the flexural strength was increased from about 250 MPa of microcomposites to 370 MPa. Fig. 1 shows
the stress-strain curves of such nanocomposites compared with magnesium alloy and polycarbonate. The highly
expanded surface area of the nanofibers results in a much denser hydrogen bond formation, producing smaller
fracture sites distributed in the material volume that delay failure and increases strength.
Fig. 1. Flexural stress-strain curves comparing cellulose nanofiber/phenolic resin composites with a typical metal alloy and
engineering plastic
The degree of fibrillation, or the extent of separation into nanofibers, plays an important role in terms of strength
of the resulting composites. It was found that fibrillation restricted to the microfibers surface does not result in
any gains in strength, this only happens when the fibers cell wall is completely broken and the thick nanofiber
bundles are separated into sub-micron-sized bundles [12]. Even when nanofibers of different grades are used,
thick nanofiber bundles in coarser morphologies acts as defects that reduce the ultimate strength of composites
[13].
Another attractive characteristic of cellulose nanofibers, is the possibility of further increase their composites'
toughness by a simple and inexpensive alkali treatment. The nanofiber sheets are dipped into a strong sodium
hydroxide solution at 20wt% concentration, washed and dried before phenolic resin impregnation. The
composite Young's modulus is reduced as the cellulose crystalline structure is converted from cellulose I with a
modulus of 138 GPa [1] to cellulose II with a reduced modulus of 88 GPa [1]. Nevertheless, the strength is
maintained as a consequence of gain in strain at fracture, resulting in enhanced toughness [14].
There are some other ways to produce nanocomposites based on the formation of the percolated framework of
nanofibers. Instead of impregnating with a diluted resin, thermoplastic polymers in the form of fibers can be
incorporated to the compounds by just suspending in water together with the nanofibers. The aqueous
suspension is then filtered and the polymer fibers are entrapped in the cellulose nanofibers interconnected by
hydrogen bonds. These sheets can be compression molded at temperatures above the melting point of the
matrix resin. Polylactic acid derived from corn starch was composed with cellulose nanofibers to produce
completely biodegradable nancomposites via this process [15]. An alternative process is to use resins in the form
of emulsions. As micrometer-sized polymer particles are waterborne in water medium, they can be easily mixed
with aqueous suspensions of cellulose nanofibers. Sheets are obtained as usual by filtration and drying and
nanocomposites fabricated by compression molding.
Proper dispersion of cellulose nanofibers in the matrix is one of the big challenges in research. The highly
hydrophilic cellulose elements cannot be easily dispersed especially in molten polymers, making difficult to make
composites by melt compounding and injection molding. But another major limiting factor is the highly costly
84
Time : 09.30 09.45
nanofiber extraction processes. The usual methods are highly energy consuming, with low production yields and
require specialized equipment. This limits the access to the nanofibers by potential researchers, confining the
study and development of new materials to few groups in the world. If a lower cost and simpler process of
nanofiber extraction were developed, the research for new applications of cellulose nanofibers would accelerate
and eventually commodity products would soon become a reality.
Acknowledgements
The authors are deeply grateful to the researchers making contributions to the development of cellulose
nanofibers and their applications.
References
[1] T. Nishino, K. Takano and K. Nakamae, J. Polym. - Polym. Phys. 33, 11 (1995)
[2] W. Helbert, J. Y. Cavaille and A. Dufresne, Polym. Compos. 17, 4 (1996)
[3] L. A. Berglund in Natural Fibers, Biopolymers, and Biocomposites, Edited A. K. Mohanty, M. Misra and L. T. Drzal,
CRC Press, Boca Raton, FL, USA (2005), pp. 807-832.
[4] A. Boldizar, C. Klason, J. Kubat, P. Naslund and P. Saha, Int. J. Polym. Mater. 11, 4 (1987)
[5] V. Favier, G. R. Canova, J. Y. Cavaille, H. Chanzy, A. Dufresne and C. Gauthier, Polym. Advan. Tech. 6, 5 (1995)
[6] V. Favier, H. Chanzy and J. Y. Cavaille, Macromolecules 28, 18 (1995)
[7] M. N. Angles and A. Dufresne, Macromolecules, 34, 9 (2001)
[8] M. N. Angles and A. Dufresne, Macromolecules, 33, 22 (2000)
[9] M. A. S. A. Samir, F. Alloin, M. Paillet and A. Dufresne, Macromolecules, 37, 11 (2004)
[10] A. F. Turbak, F. W. Snyder and K. R. Sandberg, J. Poly. Sc. 37 (1983)
[11] A. N. Nakagaito and H. Yano, Appl. Phys. A -Mater. Sci. 80, 1 (2005)
[12] A. N. Nakagaito and H. Yano, Appl. Phys. A -Mater. Sci. 78, 4 (2004)
[13] H. Takagi, Key Eng. Mat. 462-463 (2011)
[14] A. N. Nakagaito and H. Yano, Cellulose 15, 2 (2008)
[15] A. N. Nakagaito, A. Fujimura, T. Sakai, Y. Hama and H. Yano, Compos. Sci. Technol. 69, 7-8 (2009)
85
SESSION 4C : Quantam Dots
Dr. Yeng Ming Lam

Associate Professor, School of Materials Science and Engineering
Nanyang Technological University, Singapore
Senior Scientist, RWTH Aachen, Germany
E-Mail: ymlam@ntu.edu.sg/lam@iwe.rwth-aachen.de
86
Research Area
Understanding and the application of self-organization of peptides and polymer
Qualification
Ph.D .,at Department of Materials Science and Metallurgy, University of Cambridge,

UK,2001
Bachelor of Applied Science (Materials Engineering),
B.A.Sc (Hons, Cl 1), 1996
No. of Patents
No. of Publications
73
Research Funds
Singaporean-German S&T Cooperation-1N-Programme:

"Towards Hybrid devices for Energy Conversion"-Euro 47,218
NRF Competitive Research Funding: "Nanonets: New Materials, Devices for
Integrated Energy Harnessing & Storage"- $10 million
Central Strategic Initiative for Inter-disciplinary Competitive Fund: "Synthesis of new
donor acceptor materials for organic photovoltaic cells"-S$200,000
A*STAR ThematicFund: "Roll-to-Roll Manufacturing of Printed Pho tovoltovoltaic"S$711,225
Awards & Honors
Nanyang Award for Excellence in Teaching,2006

L'Oral Unesco For Women in Science National Fellowship 2009
Nanyang Outstanding Young Alumni Award ,2009
Research Outcome Award and Recognition (ROAR),2006
Tan Chin Tuan Fellowship in Engineering,2005
Book Chapters
Time : 09.30 09.45
Excitonic Solar Cells - Challenges and Opportunitie

Dr. Yeng Ming Lam
Introduction:
Excitonic solar cells, such as organic and hybrid cells, have emerged as an increasingly attractive class of
photovoltaic technology in recent years. Their solution-processability feature offers a promising approach
for cost-efficient processing. The central theme in the pursuit of increasing power conversion efficiency of
excitonic solar cells is the control of the nanoscale morphology in the active layer. This is related to the
incompatibility between the absorption behaviour and the exciton lifetime of these materials. On top of
this, good transport pathways have to be maintained for good charge extraction. Interaction strengths
between solvents, interface chemistry and the polymers can be made use of to achieve optimal phase
separation. There are several ways to control the interaction energies between the various components:
control their chemical structures through controlled synthesis, intelligent selection of interface chemistry
and rational selection of solvents. These methods will give rise to supramolecular self-assembled
nanostructures with controllable interfaces and sufficient connectivity for exciton dissociation and charge
transport.
Results & Discussion:
1-3
Despite numerous examples of the successful application of the solvent concept for BHJ OPVs , the selection
rule for appropriate solvents has yet to be fully established. In this work, we will discuss about what are the
rational considerations in the selection of solvent additives for optimum nanomorphology. The phase separation
phenomenon can be correlated with both the boiling point of the solvent additive and degree of interaction of
the additive with PCBM, which is further supported by characterization techniques using grazing incidence X-ray
diffraction (GIXRD) and scanning transmission X-ray microscopy (STXM) (Figure 1). For the first part of the
discussion, we will focus our discussion on binary poly(3-hexylthiophene):[6,6]-phenyl-C61-butyric methyl ester
(P3HT:PCBM) blends and also ternary polymers-fullerene derivative blend system involving the use of iridium
complex to encourage more triplet excitons in the system. Power conversion efficiency (PCE) as high as 3.1% for
thiophene-based system and some improvement can be achieved in the optimally phase-separated ternary
blend if morphology can be stabilized prior to the addition of the third component. This improvement is due to
the improved exciton dissociation and reduced charge recombination. Extension of the solvent induced
nanomorphological control to nanofiber systems (Figure 2) for photovoltaic applications so that we can avoid
thermal annealing will also be shown.
The importance in morphological control extends to hybrid solar cells systems. In the case of the hybrid
systems, the interface chemistry of the inorganic nanocrystals played a crucial role in the determining both
the dispersion stability and also the distribution in of the donor and acceptor phases in the active layer. We
explored a variety of surface ligands ranging from amines based ligands to acid based ligands and
comparing them to the commonly discussed pyridine ligand. Through time resolved spectroscopy studies
and electrical analysis of the devices, it was found that a combination ligands may be useful in optimizing
morphologies in 5,6,7
hybrid cells and also rather than being charge transfer limited, they are more electron
transport limited. As a result of this understanding, there should be a rethink in the ideal architecture of
such cells and the materials properties required to make such cells feasible.
The understanding of the rationale behind this versatile technique offers the possibility of novel
architectures, controlled morphology and thermal-annealing free processes for excitonic cells.
87
SESSION 4C : Quantam Dots
Figure 1. STXM of P3HT-PCBM blends treated with different solvent additives. (a) Hexanedithiol, (b) Nonanedithiol.
Figure 2. P3HT nanofibers formed by controlling interaction energies between marginal solvent and polymer.
References:
88
1.
J. K. Lee, N. E. Coates, S. Cho, N. S. Cho, D. Moses, G. C. Bazan, K. Lee and A. J. Heeger, Appl. Phys. Lett.,
2008, 92, 243308.
2.
Y. Liang, Z. Xu, J. Xia, S.-T. Tsai, Y. Wu, G. Li, C. Ray and L. Yu, Adv. Mater., 2010, 22, E135.
3.
R. Qin, W. Li, C. Li, C. Du, C. Veit, H.-F. Schleiermacher, M. Andersson, Z. Bo, Z. Liu, O. Ingans, U. Wuerfel
and F. Zhang, J. Am. Chem. Soc., 2009, 131, 14612.
4.
T. Salim, L. H. Wong, B. Bruer, R. Kukreja, Y. L. Foo, Z. Bao, Y. M. Lam, J. Mat. Chem., 2011, 21, 242.
5.
J.Y. Lek, L. Xi, B.E. Kardynal, L.H. Wong, Y.M. Lam, ACS Appl. Mat. Inter., 2011, 3, 287.
6.
D. G. Cooke, P. Uhd Jepsen, J.Y. Lek, Y.M. Lam, F. Sy and M. M. Dignam, Phys. Rev. B, 2013, 88, 241307.
7.
J.Y. Lek, G. Xing, T.C. Sum, Y.M. Lam, ACS Appl. Mat. Inter., 2014, 6, 894.
Time : 09.30 09.45
Nanocon 012
Indian culture fest at NANOCON012
89
SESSION 4D : Synthesis, Characterization and Applications - IV
Dr. Ron Naaman

Professor,
Chemical Physics Department,
Weizmann Institute of Science,

Rehovot Israel
Email : ron.naaman@weizmann.ac.il
Research Area
He investigates the interaction of electrons with self-assembled monolayers and the

electronic interactions within these hybrid structures.
His group discovered the Chiral Induced Spin Selectivity (CISS) effect and is utilizing
this effect for a new type of electronics which is spin dependent.
He and his group produce molecular-scale electrical devices and investigate their
properties as the basis for a new generation of nanoelectronics and their immediate
practical applications as fast, accurate, andhighly sensitive sensors.
Qualification
PhD., from the Weizmann Institute of Science, 1978
Awards & Honors
Fellow, American Physical Society, 2007

Lectureship Award Winner of the Division of Colloid and Surface Chemistry of the
Chemical Society of Japan.
Member of the advisory board of the Journal of Physical Chemistry, From 2008 to
2011,
Erasmus Mundus research scholarship at the Technical University Dresden,2011.
Israel Vacuum Society Research Excellence Prize.
Member of the editorial board of the Beilstein Journal of Nanotechnology and the
advisory editorial board for the journal Physical Chemistry Chemical Physics.
90
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The Chirality Induced Spin Selectivity (CISS) Effect- From Spintronics to Electron Transfer
in Biology
Dr. Ron Naaman
ABSTRACT
The advent of quantum mechanics and the discovery of electron spin in the 1920's transformed our
understanding of matter and electronic materials. Over the twentieth century the ideas associated with quantum
mechanics (quantization, wavefunctions and probability density, ..) and the symmetry constraints associated with
spin and the Pauli principle have been well integrated into a comprehensive description of matter. The "electronspin concept" is particularly important for understanding molecules with unpaired electrons, materials with high
spin-orbit coupling, and the multiplet structure of spectra (energy splitting generally). However, it is considered
of little importance when dealing with closed shell systems, especially when hydrocarbons are involved, where
the spin orbit coupling is small and no ferromagnetism exists at room temperature. Moreover, spin constraints
are rarely considered when studying electron transfer in organic molecules or in bio-related systems.
In the late 1980's the concept of spintronics emerged, in which the electrons' spins are used for transferring
information and for computation (1,2).Because hydrocarbons display small spin-orbit energy level splittings,
spintronics is associated primarily with inorganic materials, such as metals, oxides, or semiconductors. If organic
molecules could be used for spintronics applications however, they would be of great advantage because they
offer desirable properties like flexibility, ease of production, compatibility with biological systems, and are
inexpensive (3). Some work in this direction is underway; organic molecules have been introduced into spinvalves (4,5), and spin dependent tunneling has been demonstrated for organic molecules adsorbed on magnetic
substrates. In these applications, however, the spin selectivity is determined by the magnetic properties of the
substrate and its interaction with the adsorbed molecule (6). Thus the magnetoresistance observed in these
organic materials (7,8) originates from the magnetic properties of the inorganic electrodes, rather than any spin
selectivity arising from the organic molecules (9).
In my talk I describe recent findings on the unusually large electron spin polarization of photoelectrons and
electron tunneling currents that arise for chiral molecules and/or molecular layers; an effect referred to as Chiral
Induced Spin Selectivity (CISS). The term chirality (hand) has been attributed to Lord Kelvin who in 1894 used this
term to describe a molecule or material's lack of parity symmetry, namely it has no inversion symmetry and a
mirror symmetry operation transforms one enantiomer into the other (10). Because many biomolecules are chiral
and many biochemical reactions involve chiral molecules, much effort has been placed on understanding
enantioselectivity in chemical transformations (11,12,13) and the physicochemical properties of chiral molecules
(14). Although the special spectroscopic properties of chiral molecules have been appreciated since the
beginning of the 19th century, the influence of chiral symmetry on molecules' electrical properties has not been
well studied.
The discovery of the CISS effect provides a new strategy for using organic materials to manipulate electron spins
(see Figure 1) (15). In particular, it was found that the electron transport through chiral molecules is spin selective
and the consequent spin polarization is very large as compared to inorganic spin filters. This phenomenon is
unanticipated, as organic molecules are known for their small spin-orbit coupling (SOC) and the molecules used
are not magnetic. Hence the experimental observations provide a challenge to theory, as conventional chemical
physics approaches for describing the experimental effectsrequire SOC magnitudes that are much larger than
those derived from spectroscopy experiments.
91
Figure 1: Schematic representation of the CISS effect. When electrons are moving within a left or right handed chiral
potential, their spin is aligned parallel or anti-parallel to their velocity, respectively. Taken from reference 15.
A number of works have investigated the CISS effect from a theoretical perspective (16-28) and the approaches
used can be divided into three categories. In one category, tight binding models are used to describe electron
transmission through large helical molecules, like DNA and oligopeptides (21-23). In another category, a spindependent scattering theory is used to obtain spin dependent electron transmission (20). In the third category,
models that include a large spin-orbit coupling from the metal substrate give rise to spin selectivity via angular
momentum selection (25).
While these theoretical treatments provide an explanation for the spin selectivity, several major questions remain
unexplained. Of particular importance, is the need to understand the size of the spin-orbit coupling that has to
be invoked for a quantitative description of the spin polarization. All of these treatments rely on using a spinorbit coupling (SOC) value that exceeds that of a free carbon atom, ~3.6 meV, and certainly exceeds that for
hydrocarbons, which are smaller by one to three orders of magnitude. The origin of the unusually large effective
SOC, claimed to be up to1 eV in DNA (29), is a major feature that must be provided by a quantitative theory.
Another open question, which is of major interest, is the relation between the molecular structure and a
molecule's CISS effect; namely, how the secondary structure affects the spin selectivity and how the molecular
dipole moment influences it. So far, the main experimental studies have been performed on chiral molecules
having a helical structure, and it is found that in some peptides and proteins denaturation reduces the spin
selectivity, however no detailed model exists that relates those results with spin polarization.
It is possible to motivate the magnitude of the SOC by considering a simplified model of a helical molecule. As
was discussed before (~30), the spin-orbit interaction in systems that lack inversion symmetry leads to
topological spin phase effects. As stated in ref. 20, "even in the absence of an external magnetic field the electron
spin in low dimensional structures is influenced by the momentum-dependent effective magnetic field because
the electron's Hamiltonian includes a term linear in momentum". Namely, if one considers an electron to
propagate through a helical potential and parallel to its symmetry axis, the electron wavefunction acquires a
contribution to its phase from the geometry of the system(or Berry phase), as is well established in Berry's theory
(31,32,33) This phase can be related to an "effective magnetic field". This picture is consistent with a recent report
for the spin-orbit coupling in strained graphene, which is reported to be on the order of 30 meV (34).
The magnitude of this magnetic field can be estimated by considering that the force it generates must be large
enough to confine the electron within the helical system; namely the magnetic field keeps the electron within
the radius of the helical molecule, like in cyclotron motion (35). Using the model of cyclotron motion, the
effective magnetic field is given by:
(1)
in which m, v, and q are the electron's mass, velocity, and charge, respectively; and r is the radius of the helical
92
Time : 09.30 09.45
-19
path of the electron. If we take q=1.6x10 C, assume that the mass is the rest mass of a free electron,
-31
5
m=me=9x10 kg, take the velocity to be v=6x10 m/sec (assumes a 1 eV kinetic energy or the Fermi velocity in
graphene), and use a radius r of 0.5 nm, we find that the spin-orbit coupling is given by
(2)
and henceHSOC 390 meV; the splitting between the two spin states is of course twice this value. Thus, this
simplified picture yields an HSOC that is large enough to explain the CISS effect.
This value of HSOC is very large and exceeds the spin-orbit splitting reported for hydrocarbons by several orders
of magnitude. It results directly from the symmetry breaking that arises from the chirality of the system, which
introduces lower order terms in the SOC expression than those found in systems having inversion symmetry
(atoms, achiral molecules) and when the electron path is a closed path. The detailed expression for the SOC term
is given in ref. . It is shown there that the SOC effect in the case of electron transmission through a chiral system
is not relativistic and is similar to the Zeeman splitting. Therefore, in the expression relating the electric field in
the system and the effective magnetic field, a factor related to the speed of light does not appear.
The CISS effect can be found in Biology, as observed recently in our wok on the Photosystem I ( 37 ) and it
introduces chiral molecules as a new material for spintronicsapplications ( 38 ).
References
1
Baibich MN, Broto JM, Fert A, Nguyen Van Dau, FN, Petroff F, Etienne P, Creuzet G, Friederich A, Chazelas J.
1988 Phys. Rev. Lett. 61: 2472-2475.
Binasch G, Grnberg P, Saurenbach F, Zinn W. 1989 Phys. Rev. B 39: 4828.
Szulczewski G, Sanvito S, Coey M. 2009 Nat. Mater.,8: 693-695.
Xiong ZH, Wu D, Vardeny ZV, Shi J.2004 Nature 427: 821-824.
Sun DL, Yin LF, Sun CJ, Guo HG, Gai Z, Zhang XG, Ward TZ, Cheng ZH, Shen J. 2010 Phys. Rev. Lett.,104:
236602.
Atodiresei N, Brede J, Lazic P, Caciuc V, Hoffmann G, Wiesendanger R, Blugel S. 2010 Phys. Rev. Lett., 105:
066601.
Francis TL, Mermer O, Veeraraghavan G, Wohlgenannt M. 2004. New J. Phys.,6: 185.
Majumdar S, Laiho R, Laukkanen P, Vayrynen IJ, Majumdar HS, Osterbacka R. 2006 Appl. Phys. Lett.,89: 122114.
Romeike C, Wegewijs MR, Ruben M, Wenzel W, Schoeller H. 2007 Phys. Rev. B,75: 064404.
10
Bentley R. 1995 Perspectives in Biology and Medicine 38: 188-229.
11. Jacobsen EN, Pfaltz A, Yamamoto H, eds. 1999. Comprehensive Asymmetric Catalysis. Springer, Berlin,.
12
Ojima I, eds. 2000. Catalytic Asymmetric Synthesis, 2nd ed. Wiley, New York,
13
see also: Yoon TP, Jacobsen EN. 2003. Science, 299: 1691-1693.
14
Barron LD, 2000. Nature, 405: 895-896.
15
Naaman R, Waldeck DH, 2012. J. Phys Chem. Lett, 3:2178-2187.
16
Eremko AA, Loktev VM, 2013. Phys. Rev. B 88: 165409.
17
Krstic V, Rikken GLJA, 2002. Chem. Phys. Lett. 364: 51-56.
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18
Koretsune T,Arita R, Aoki H, 2012Phys. Rev. B 86: 125207.
19
Yeganeh S, Ratner MA, Medina E, Mujica V, 2009, J. Chem. Phys. 131, 014707.
20
Medina E, Lopez F,. Ratner MA, Mujica V, 2012 EPL99, 17006.
21
Gutierrez R, Daz E, Naaman R, Cuniberti G, 2012, Phys. Rev. B 85: 081404.
22
Gutierrez R, Daz E, Gaul C, Brumme T, Domnguez-Adame F, Cuniberti G, 2013, J. Phys. Chem. C117; 2227622284.
23
a) GuoAM,.Sun QF, 2012Phys. Rev. Lett.108; 218102. b) Guo AM, Sun QF, 2012, Phys. Rev. B 86, 115441 Phys.
Rev. B 86;115441.
24
Rai D, Galperin M,2013, J. Phys. Chem. C117; 13730-13737.
25
Gersten J, Kaasbjerg K, Nitzan A, 2013, J. Chem. Phys. 139; 114111.
26
Vager D, Vager Z, 2012, Phys. Lett. A, 376; 1895-1897.
27
Kuzmin SL, Duley WW,2014Phys. Lett. A, 378:1674-1650.
28
Eremko AA, Loktev VM, 2013, Physical Review B 88; 165409.
29
Xie Z, Markus TZ, Cohen SR, Vager Z, Gutierrez R, Naaman R, 2011. Nano Letters, 11: 4652-4655.
30
Aronov AG, Lyanda-Geller YB, 1993.Phys. Rev. Lett. 70; 343-346 and references cited therein.
31
Berry MV, 1984, Proceedings of the Royal Society A 392; 45-57.
32
See for example: Alexeyev CN, Yavorsky MA, 2006. J. Opt. A: Pure Appl. Opt. 8: 752-758.
33
Castro Neto AH, Guinea F, Peres NMR, Novoselov KS, Geim AK, 2009.
Rev. Mod. Phys. 81: 109-162.
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34
Levy N, Burke SA, Meaker KL, Panlasigui M, Zettl A, Guinea F, Castro Neto AH, Crommie MF, 2010.
Science329:544-547.
35
Fuchs JN, Pichon F, Goerbig MO, Montambaux G. 2010. Eur. Phys. J. B 77: 351-362.
36
Michaeli K, Naaman R, in preparation.
37
CarmeliI, KumarKS, HiefleroO,CarmeliC., NaamanR, 2014.Angew.Chemie53: 8953 -8958.
38
KumarKS, Kantor-UrielN, MathewSP, GuliamovR, NaamanR, 2013. Phys. Chem. Chem. Phys., 15: 18357-18362.
Time : 09.30 09.45
Nanocon 010
From Left Honble Dr. Patangrao Kadam, Shri. Prithviraj Chavan, Minister of Science and Technology, Goi, Dr. James
Ryan, NCAT, USA, Dr. Anand Bhalerao, BVUCOE & Dr. Dinesh Amalnerkar, CMET
95
SESSION 5A : Thin Films - III

Department of Mechanical Engineering.
E-mail : yonekura@tokushima-u.ac.jp
Research Area
1. Surface modification of metals.

2. Thin film deposition.
3. Fatigue properties of hard thin film deposited on metals by PVD Method.
4. Tribological properties of surface treated materials.
5. Optical and electrical properties of thin films.
Qualification
Ph.D., from Keio University,2002

Degree of Master of Engineering from Keio University
No. of Publications
48
Proceeding of
51
International Conference
Proceeding of Domestic 47
Conference
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Time : 11.40 11.55
Stability of ZnO/self-assembled gold nanoparticle network film

Abstract
In this paper, self-assembled gold nanoparticle network films were formed on a glass substrate/silicon substrates.
Zinc oxide films were deposited on the network film by dc magnetron sputtering method to examine the effect
of the thickness of zinc oxide film on the optical properties and electrical stability of the ZnO/self-assembled gold
nanoparticle network film double layer films. As a result, the initial electrical resistivity of all double layer films
having 15 and 30 nm thick ZnO top layer was less than 10-3 cm and the resistivity was maintained after 100 days.
The electrical resistivity and stability improved with decreasing the thickness of the ZnO top layer. In contrast, the
optical transmittance and the reflectance slightly improved with increasing the thickness of ZnO top layer. In
addition, the intensity of the peak related to surface plasmon resonance increased with increasing the thickness
of ZnO top layer. Thus, although the double layer with thin ZnO top layer shows slightly lower optical properties,
the deposition of thin ZnO top layer is effective in preventing a break in the nano-wires due to age deterioration
and in keeping the high electrical conductivity.
Keywords: Self-assembly; gold nanoparticle; ZnO; age deterioration; opticaltransmittance; conductivity
1. Introduction
Transparent conductive oxides (TCO) films can be used as electrodes for touch screens, flat panel displays and
solar cells [1-4]. Zinc oxide (ZnO) film is one of the TCO film which is low-cost, abundant amount, non-toxic [5,
6], and has high stability in a hydrogen plasma [7, 8]. ZnO has been widely studied as an alternative material for
indium-tin-oxide (ITO) [9] which is widely used for TCO film [10, 11], because indium used in ITO is a rare metal.
Optical transmittance of higher than 80% is generally required for TCO materials. Moreover, a sheet resistance of
400700 O/sq is required for touch screen electrodes, and sheet resistance below 10 O/sq is required for
electrodes in large area flat panel displays and thin film solar cells [12]. ZnO shows high transmittance in the
visible light region, while simultaneously having low electrical conductivity. Therefore, multilayer films with a thin
metal layer, such as ZnO/metal/ZnO and ZnO/metal, have been studied. It has been reported that the structures
of these multilayer materials show the good electrical conductivity as well as high transmittance. The metal
intermediate layer, such as Ag, Au and Cu used for the multilayer structure, are generally made by a magnetron
sputtering method [13, 14].
Self-assembling technique is a very attractive method to control the nanostructure of the metal film made from
metal nanoparticles. Self-assembly method offers to generate one-, two-, or three-dimensional nanostructures
made from nanoparticles [15, 16]. Self-assembled metal thin films will be also effective to improve the electrical
conductivity of ZnO/metal multilayer film. In particular, self-assembled gold nanoparticles (GNPs) network film
has a potential to improve the electrical and optical properties because the good conductivity is achieved by the
continuous structure and the good optical properties will be obtained by light trapping by enhanced forward
scattering from metal nanoparticles [17]. However, the self-assembled GNPs film has one problem when the film
is used as a single layer; the nano-wires in the network structure are easily broken in air at room temperature as
shown in Fig. 1 and the electrical conductivity rapidly decreases[18]. To prevent the age deterioration of the
electrical conductivity, covering the self-assembled GNPs film with other TCO film will be effective because the
top layer will hinder the gold atom mobility and will prevent the age deterioration.
97
Fig. 1 SEM images of self-assembled gold nanoparticle films formed at 20 C; (a) 0 day after fabrication and (b) 40 days
after fabrication.
In this study, we focused on the double layer of ZnO film and self-assembled GNPs film with network structure.
The self-assembled gold nanoparticle network films were formed on a glass substrate and silicon substrates and
zinc oxide films were deposited on the network film by dc magnetron sputtering method and the effect of the
thickness of zinc oxide film on the optical properties and the stability of the electrical resistivity of the ZnO/selfassembled gold nanoparticle network double layer film was examined.
2. Material and methods

2.1. Fabrication of gold nanoparticles solutions
In this study, GNPs solution was prepared under a condition which was determined by our previous study [18].
The GNPs solution was obtained by boiling the solution of 1.0ml of HAuCl4 (1wt%) and 70 ml of distilled water.
Then, 3.0 ml (1wt%) of sodium citrate was added into the boiling solution and kept to boil for 6 minutes until the
color of the solution changed to wine red. A transmission electron microscope (TEM, JEM-2100F, Jeol Ltd.) image
of obtained GNPs is shown in Fig. 2 (a). The mean diameter of GNPs was approximately 16 nm. Figure 2 (b) shows
the optical absorbance spectrum of the GNPs solution. A clear peak was observed near the wavelength of 520
nm. The absorbance peak agrees with the wave length of local surface plasmon resonance of GNPs [16].
Fig. 2 (a) TEM image of gold nanoparticles; (b) absorbance spectrum of gold nanoparticles solution.
2.2. Fabrication of gold nanoparticles self-assembled films.

The GNPs solution was poured into Petri dishes with a diameter of 9 cm in room controlled at 20 C. Pentanol
of 1.5 ml and ethanol of 0.5 ml were dropped gently into the GNPs solution surface and the solution was left for
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Time : 11.40 11.55
3 hours. Then a self-assembled gold nanoparticles (SA-GNPs) film was formed at the interface between the GNPs
solution and the alcohols. The fabricated SA-GNP film was transferred onto a glass substrate to evaluate the
optical properties, the electrical resistivity and the morphology. The SA-GNPs film was also transferred onto a
silicon plates to measure the optical reflectance. The substrates were cleaned carefully using an ultrasonic bath
in acetone prior to transfer. TEM image of SA-GNPs film transferred on a Cu grid is shown in Fig. 3(a). After the
self-assembling process, the GNPs linked together and made a network structure. In the network, the GNPs kept
the spherical shape and the boundary of the particles were clearly distinguished. Figure 3 (b) shows a AFM image
of SA-GNPs film deposited on the glass substrate. The thickness of the nano-wire, which consists of linked GNPs,
was about 20 nm.
Fig.3 TEM and AFM mages of self-assembled gold nanoparticles; (a) TEM image and (b) AFM image.
2.3. Fabrication of ZnO/self-assembled gold nanoparticle network double layer film

Double layer films of ZnO a nd SA-GNPs films were prepared by deposition of ZnO film on the SA-GNPs film
transferred on the glass and the silicon substrate. The substrates with GNPs films were placed on a holder in a
-3
vacuum chamber. After the chamber was evacuated to 3.010 Pa, process gases were introduced into the
chamber through mass flow controllers. To deposit ZnO top layer, a gas mixture of argon (>99.999%) and oxygen
gas (>99.999%) was used as the process gas. A pre-sputtering treatment was carried out in argon atmosphere
for 1 minute to remove surface contamination and any oxidation layer of the target. The ZnO film was then
deposited onto one side of the substrate using a zinc plate target (99.9%). Details of the conditions used are
shown in Table 1. The processing time was adjusted to produce a film about 15, 30 and 45 nm thick in this study.
Table 1 Deposition conditions of ZnO top layer.
2.4. Characterization of films

The optical transmittance and absorbance spectra were measured using a UV-vis-NIR spectrometer (JASCO,
V570) in the wavelength range of 300 - 800 nm. The electrical conductivity was measured using a Hall Effect
measurement system (EDK, HEM-2000) by Van der Pauw method. The morphologic properties of gold
nanoparticles self-assembled films were observed using a field emission-scanning electron microscope (FE-SEM,
Hitachi S-4700) and a atomic force microscope (AFM: SPA300, Seiko Instruments).
3. Results and discussions

3.1. Surface morphology of double layer films
Figure 4 shows AFM images of ZnO/SA-GNPs double layers with different thickness of ZnO top layer. In the case
99
of 15nm thick ZnO top layer, fine grains of ZnO crystals were observed on the surface. Several hollows, indicated
as arrows in Fig. 4 (a), were also observed in the observation area. When a top layer is deposited on a bottom
layer with hollows such as a network structure, the surface morphology of the top layer reflects the morphology
of the bottom layer and then, the hollows are observed on the surface. Therefore, these hollows observed in Fig.
4 (a) are attributed the influence of the nano-sized gaps of the GNPs network. The hollows were also observed
for 30 nm thick ZnO top layer, however, the size of ZnO grain became large compared with 15 nm thick sample.
In contrast, the hollows were not observed for the sample of 45 nm thick ZnO top layer and the ZnO grains
became larger than the case of 30 nm thick ZnO.
Fig.4 AFM images of double layer surfaces with various top layer thickness; (a) ZnO 15nm thick, (b) ZnO 30nm thick and
(c) ZnO 45 nm thick.
The relationship between the ZnO thickness and the root mean square (RMS) roughness calculated from the
AFM measurements are shown in Fig. 5. The RMS roughness of SA-GNPs single layer was 3.32 nm. The RMS
roughness slightly decreased by the deposition of 15 nm thick ZnO top layer which was RMS = 1.56 nm. The
decrease of the surface roughness is attributed to the smoothing of the surface by covering the nano-sized gap
of the GNPs network structure. However, the surface roughness increased with increasing the thickness of the
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Time : 11.40 11.55
ZnO top layer and the roughness of 30 nm and 45 nm thick ZnO top layers were clearly higher than that of single
layer. For these thick top layers, the influence of the grain size of ZnO on the surface roughness will higher than
that of the roughness of SA-GNPs bottom layer because the ZnO grain size increases with increasing the
deposition time. Thus, when the thickness of the ZnO top layer exceeds the thickness of the SA-GNPs bottom
layer, the surface roughness of the double layer is mainly influenced on the roughness of the ZnO top layer.
Fig.5 Relationship between the thickness of ZnO top layer and the root mean square roughness.
3.2. Optical properties of double layer films

Figure 6 shows the transmittance spectra of ZnO single layer, SA-GNPs single layer and ZnO/SA-GNPs double
layer deposited on glass substrates. ZnO single layer showed a good transmittance, in particular, the
transmittance of the ZnO single layer of 15 nm thick was more than 80 % in all wavelength range. The
transmittance of ZnO single layer decreased with increasing the thickness, but the transmittance for ZnO single
layer of 45 nm thick ,which was the most thick sample in this study, was kept more than 80% in the range of 500
- 800 nm. The results mean the influence of the ZnO thickness on the optical transmittance was small. In contrast,
the transmittance was obviously degraded by the SA-GNPs single layer and the transmittance of the SA-GNPs
single layer on the glass substrate was less than 75%. This low transparency is caused by the agglomeration of
the GNPs and the dense parts of the network structure. In the SA-GNPs film, the network structure consists of
nano-wires which are made from linked GNPs. However, several GNPs are agglomerates and make large clusters
in the network observed as dark parts (represented as black arrows in Fig. 3). Since incident light cannot
penetrate these large GNPs clusters and the light is scattered, the low transmittance was measured for SA-GNPs
single layer. In addition, film-like dense parts without nano-sized gaps were also observed in Fig. 3 (represented
as white arrows). Since these dense parts also act as obstructions to penetrate the incident light, the dense part
is another factor to degrade the optical transmittance. Thus, the transmittance of the SA-GNPs film depends on
the nano-sized structure. The transmittance of ZnO/self-assembled double layer was slightly lower than that of
SA-GNPs single layer. In particular, the difference was quite small for 15 nm thick ZnO top layer. The small
difference of the transmittance will be caused by the decrease of the surface roughness described in previous
section because the smooth surface reduces a scattering of the light. In addition, the transmittance in the long
wavelength range increased with increasing the thickness of the ZnO top layer, however, the reason is unclear in
this study.
Figure 7 shows the absorbance spectra of ZnO single layer, SA-GNPs single layer and ZnO/SA-GNPs double layer
deposited on glass substrates. A weak absorption peak can be observed for both SA-GNPs single layer and
ZnO/SA-GNPs double layers in the wavelength range of 520-600 nm. In particular, relatively clear peak was
observed for the double layer samples compared with SA-GNPs single layer. In contrast, no peaks were identified
for the ZnO single layers. It indicates that the peaks observed for GNPs single layer and ZnO/GNPs double layers
are related to surface plasmon resonance in the self-assemble GNPs film. The peak heights of double layers were
similar for 15nm and 30 nm thick ZnO top layers as shown in Fig.7 (d), however the peak for 45 nm thick ZnO
top layer was slightly lower than that for thin top layer. In addition, the absorbance of the double layer samples
decreased with increasing the ZnO thickness in long wavelength range (?> 600 nm). These results are attributed
to the anti-reflection effect of ZnO in the long wavelength range which increases with increasing the ZnO
thickness.
101
Fig. 6 Transmittance spectra of substrate, single layers and double layers with different ZnO thickness.
Fig. 7 Absorbance spectra of single layers and double layers with different ZnO thickness.
Figure 8 shows the reflectance spectra of silicon substrate, ZnO single layer, SA-GNPs single layer and ZnO/SAGNPs double layer deposited on silicon substrates. In the case of SA-GNPs single layer, the reflectance decreased
in the shorter wavelength range of about ? < 500nm and increased in the longer wavelength range of about ? >
500nm. The decrease of the reflectance by surface plasmon resonance was not observed in the wavelength range
of 520-600 nm. In the case of double layer and ZnO single layer samples, the reflectance obviously decreased by
deposition of ZnO layer and the reflectance decreased with increasing the thickness of the ZnO layer. The spectra
of ZnO/GNPs double layer were similar to the spectra of the ZnO single layer. However, the decrease of the
reflectance by surface plasmon resonance was also not observed. These results suggest that the influence of the
antireflection by ZnO layer is stronger than that of the light absorption by surface plasmon resonance.
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Time : 11.40 11.55
Fig. 8 Reflectance spectra of single layers and double layers with different ZnO thickness.
3.3. Electrical properties.

To examine the stability of ZnO/GNPs double layer, the resistivity was measured after 0, 40, 70 and 100 days after
ZnO deposition. For this measurement, the samples were left to stand in air at room temperature. Figure 9 shows
the resistivity of SA-GNPs film and ZnO/ SA-GNPs films having deferent ZnO thickness. The initial resistivity of
all samples before ZnO sputtering are less than 3.010-4 ?cm. After ZnO deposition as the top layer, the resistivity
increased for all ZnO thickness. The resistivity obviously depended on the ZnO thickness and the sample having
-3
thick ZnO layer indicated high resistivity more than 1.010 ?cm. The resistivity also increased with increasing
the standing time, but the change of resistivity was small for the sample having 15 nm and 30 nm thick ZnO layer.
It indicates that the deposition of ZnO top layer is effective to prevent the degradation of SA-GNPs network film
such as wire breaking. However, when the 45 nm thick ZnO layer was deposited on the SA-GNPs film, the
prevention effect decreased and the resistivity was clearly increased with increasing the standing time. In this
-3
case, the resistivity after 100 days was more than 1.5 10 ?cm which was approximately 4 times higher than
that of 15 nm thick sample. The acceleration of the degradation is attributed to residual stress in ZnO layer which
increases with increasing the film thickness. The high residual stress in thick ZnO layer will lead to break the GNPs
wire during long standing time
Fig. 9 Aging deterioration behavior of double layers with different ZnO thickness.
In conclusion, it is found that good transparency, absorbance, reflectance and resistivity with good stability are
obtained by deposition of ZnO top layer with appropriate thickness.
4. Conclusions
In this study, self-assembled gold nanoparticle network films were formed on a glass substrate/silicon substrates
and zinc oxide films were deposited on the network film by dc magnetron sputtering method and the effect of
the thickness of zinc oxide film on the optical properties and the stability of the electrical resistivity of the
ZnO/self-assembled gold nanoparticle network double layer film was discussed. The following conclusions were
103
reached.
(1) When the thickness of the ZnO top layer exceeds the thickness of the self-assembled GNPs bottom layer, the
surface roughness of the double layer is mainly influenced on the roughness of the ZnO top layer.
(2) The transmittance of ZnO/self-assembled double layer was slightly lower than that of self-assembled GNPs
single layer. In particular, the difference was quite small for 15 nm thick ZnO top layer.
(3) The relatively clear absorbance peak was observed for the double layer samples with thicker ZnO top layer.
(4) The double layer samples having 15 nm and 30 nm thick ZnO top layer showed good electrical stability.
References
[1] A. J. Morfa, K. L. Rowlen, Appl. Phys. Lett. 92, 013504 (2008)
[2] S. Pillai, K. R. Catchpole, T. Trupke, M. A. Green, J. Appl. Phys. 101, 093105 (2007)
[3] N. Fang, H. Lee, C. Sun, X. Zhang, Science 308, 534 (2005)
[4] D. K. Gifford, D. G. Hall, Appl. Phys. Lett, 81, 23 (2002)
[5] I. L. Hsiao, Y. J. Huang, Science of the Total Environment 409, 1219 (2011)
[6] X. Peng, S. Palma, N. S. Fisher, S. S. Wong, Aquatic Toxicology 102, 186 (2011)
[7] N.H. Al-Hardan, M.J. Abdullah, A. A. Aziz, International Journal of hydrogen energy 35, 4428 (2010)
[8] Z. Zhou, K. Kato, T. Komaki, M. Yoshino, H. Yukawa, M. Morinaga, International Journal of hydrogen energy 29,
323 (2004)
[9] T. Mouet, T. Devers, A. Telia, Z. Messai, V. Harel, K. Konstantinov, I. Kante, M. T. Ta, Applied Surface Science, 256,
4114 (2010).
[10] C. Guillen, J. Herrero, Optics Communications, 282, 574 (2009)
[11] G. Leftheriotis, P. Yianoulis, D. Patrikios, Thin Solid Films, 306, 92 (1997)
[12] C. Guillen, J. Herrero, Thin Solid Films 520, 1 (2011)
[13] D. Zhang, P. Wang, R. Murakami, X. Song, Appl. Phys. Lett. 96, 233114 (2010)
[14] D. Zhang, H. Yabe, E. Akita, P. Wang, R. Murakami, X. Song, J. Appl. Phys. 109, 104318 (2011)
[15] R. Zhang, M. Hummelgard, H. Olin, Physica B 405, 4517 (2010)
[16] X. Ji, X. Song, J. Li, Y. Bai, W. Yang, X. Peng, J. Am. Chem. Soc. 129, 13939 (2007)
[17] P. Spinelli, V. E. Ferry, J. van de Groep, M. van Lare, M. A. Verschuuren, R. E. I. Schropp, H. A. Atwater, A. Polman,
J. Opt. 14, 024002 (2012)
[18] D. Yonekura, H. Ushita, Y. Sakaguchi, R. Murakami, "Influence of Self-assembly Conditions on Film Formation,
Optical and Electrical Properties of Gold Nanoparticle Network Film", Journal of the Society of Materials
Science , Japan 63, (2014) in press
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Time : 11.40 11.55
Nanocon 010
Honble Dr. Patangrao Kadam Presenting Conference Memento to shri. Prithviraj Chavan, Miniser of Science and
Technology, Goi.
105
Session 5B: Nanoelectronics - IV
Dr. A. Subrahmanyam
Professor, Department of Physics
Indian Institute of Technology, Madras
Chennai, India
Email : manu@iitm.ac.in
Research Area
Functional Metal Oxide and metal nitride Thin Films
No. of Publications
More than 120
Awards & Honors
Alexander von Humboldt Fellowship, 1989-91

BOYSCAST Fellowship, 1988-89.
He has been the first Saint Gobain Chair Professor at Ecole Polytechnique, Paris,
France during 2008 and an Invited DAAD Professor at Technical University
(during 2008-09) Dresden, Germany.
106
Time : 11.40 11.55
Plasma Processing of Nano-Matter: An over view

Dr. A.Subrahmanyam
ABSTRACT
Nano matter has exotic physical and chemical properties and several applications. While preparing the nano
matter the fundamental question is the control of size. Plasma is a versatile tool being used routinely in
semiconductor industry both for nano material preparation and for surface engineering. Present talk summarizes
the plasma production and control of plasma parameters and the material preparation using well known and
conventional techniques like sputtering and chemical vapour deposition. One of the emerging techniques is
plasma in liquids: a most versatile and powerful technique to prepare nano matter and to control the size and
shape of nano matter
The fundamental strength of nano-technology is in the basic principle that the decreasing size scales of solid
clusters can result in dramatic changes in the physical properties. This, in turn, requires control, often at the
atomic level, of the nanostructures, nano-chemistry, and cluster nano-organization. The bond coordination in the
nano cluster should always be preserved, as in the case of bulk materials. When the cluster sizes reaches the
nano-meter scales (of the order of the spatial extent of electron wave-functions), the quantum mechanical effects
take over (sometimes referred to as size effects).
Nano materials have extremely small size which having at least one dimension 100 nm or less. Nano materials
can be nano-scale in one dimension (eg. surface of films), two dimensions (eg. strands or fibres), or three
dimensions (eg. particles). They can exist in single, fused, aggregated or agglomerated forms with spherical,
tubular, and irregular shapes. Common types of nanomaterials include nanotubes, dendrimers, quantum dots
and fullerenes.
Techniques for creation of nanomatter starting from atomic species are also Bottom-Up techniques. However,
it is also possible to create nanomatter by Top -Down techniques such as etching , ball milling , mechanically
thinning of a bulk material, controlled template growth , etc. In layered structures such as graphite,MoS2, mica,
nanomatter can be created by cleaving the bulk material . Graphene is the best known example . Nanometric
coatings can also be prepared from the micro to nano size powder paste of a material . Such Top-Down
techniques are called Thick Film techniques to differentiate from the Bottom-Up Thin-Film deposition
techniques . It is important to keep in mind that nanomatter created from the same starting material by TopDown and Bottom-Up techniques have vastly different properties due to the dominance of structural properties
resulting from nucleation and growth processes
The formation of the nano-clusters, either in the form of nano sized powders or in nano sized grains in a thin
film, basically is controlled by the energy supplied to the atoms forming these clusters and on the nucleation
kinetics (how the atoms and molecules come together to form clusters). The fundamental question to be
addressed is: how much energy is required to form a nano sized clusters in two dimensions to achieve the
desired physical properties and how to impart this energy to the nucleation centre. Since the answer to this
question is not easy, the approach followed is to experiment on how to give energy in a controlled fashion to
the atoms to form the clusters of desired size. One of the approaches, rather an easy approach, is to process the
clusters through controlled plasma energy. This is how the plasma processing gains high technological
importance in nano-technology.
Plasma is a powerful tool for synthesis of nano matter and surface preparation and surface etching of patterns
at nano scales. Low Temperature Plasmas (LTP) is a versatile tool for the production of nanoparticles and
quantum dots of materials that are hard to produce in other media. The intriguing question is what makes low
density Plasma so versatile a tool in material preparation and surface engineering? The answer lies in the fact
that the low density plasma possesses such a high energy that even most complex chemical and physical
reactions take place which facilitates controlled formation of matter. Also, the ease and cost effectiveness with
which the low density plasma created and sustained makes it most versatile tool.
Another very important question to be addressed is: how to control the size of the matter using plasma?
The plasma assisted material growth is well known. Physical vapour deposition (PVD) techniques like sputtering
and Chemical techniques like Chemical vapour deposition (CVD) are now an industry standard. One of the
107
Session 5B: Nanoelectronics - IV
emerging technique in nano matter preparation is Plasma in Liquids.

Plasmas generated in liquids (see figure) is a recent development in preparing nano-matter. Plasma-liquid
systems can produce strongly non-equilibrium environments. Plasma-liquid interactions represent a great
opportunity for developing novel chemistries and related technologies.
An electric discharge between two electrodes consisting of a medium gives raise to plasma. If the medium is
water or any liquid, in principle, plasma can be generated. Liquids, particularly water has a high dielectric
constant and dielectric strength than gas phase, thus it is being used as an insulating media for high voltage
pulse lines in pulsed power systems. The conduction or insulation is determined by the Maxwellian relaxation
time. Long electric pulses results in electrolysis of water; short pulses produce stress in the medium and it
sustains till breakdown occurs.
Electrical discharges formed directly in liquid water include three general cases where (a) streamer-like plasma
channels form in, but do not span, the electrode gap, (b) spark discharges produce transient plasma channels
that span the electrode gap, and (c) arc discharges form plasma channels with relatively longer life times.
It is shown that discharges in, and in contact with, liquids generate intense UV radiation, shockwaves and active
radicals (OH, atomic oxygen, hydrogen peroxide, etc) which make these discharges particularly suitable for
decontamination and sterilization purposes also.
In the present talk, the details of glow discharge plasma and plasma in liquids will be described for preparing the
nano matter.
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Nanocon 010
Felicitation of Dr. JamescRyan, NCAT, USA, by Dr. Shivajirao Kadam
109
SESSION 5C : Super Capacitor

Department of Physics & Astronomy,
College of Science, King Saud University,
Riyadh -11451, Saudi Arabia
E-mail: aman@ksu.edu.sa
Research Area
Thin film technology, solar cells, TCO (Gas sensors),Metal induced crystallization (MIC)
of amorphous silicon, renewable energy and environment, micro and nanostructured
materials and nanoparticles
Qualification
Ph.D., Physics Osmania University,Hyderabad (A.P),India
No. of Publictions
More than 50
Scientific Talk
Solar Energy
Nanotechnlogy
Professional Affiliations Member, International Solar Energy Society (ISES)

Member, Indian Association of Physics Teachers.
Member, Instrument Society of India
Member, National Semiconductor Society, India
Member, Society for the advancement of solid state Sciences (SAAS), Hyderabad,
India.
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Nanostructured Materials and Nanocomposites

ABSTRACT
Materials exhibiting optical band gap tuning ability assume importance in several potential applications in
photovoltaics, photodiodes, optoelectronics etc. CdO is considered to be one among these promising materials
due to its high optical transmittance and high electrical conductivity. Using a cost effective sol-gel spin coating
technique, nanostructured Cu doped CdO films were synthesized. Results of Surface morphology and band gap
engineering will be presented.
ZnO is another unique wide band gap material which has received much attention due to its novel exciting
properties. Ni doped ZnO films have been prepared by low cost spin coating method with its unique nano
structures. Investigations of the influence of Ni concentration on the structural, photoluminescence and optical
properties will be highlighted.
Among the device side, Ag/n-CdO/p-Si MIS structure has been prepared by sol-gel method. The frequency
dependent electrical properties of this device have been explored using capacitance - voltage (C-V) and
conductance -voltage (G/w-V) characteristics. A brief overview of some nanocomposites will also be discussed.
111
Session 5D : Synthesis, Characterization and Applications - V

Assistant Professor
The Center for International Cooperation Engineering Education (CICEE),
Tokushima, Japan
Email : koinkar@tokushima-u.ac.jp
Research Area
1D nanostructure (carbon related materials and oxides), Conducting Polymer, Field

Emission Microscopy and Engineering Education.
Qualification
Ph.D. in Physics (Materials Science) from North Maharashtra University, India, 2005
No. of Publications
More than 32
Awards & Honors
He is recipient of the Research Fellowship through Chief Minister fund from North
Maharashtra University, Jalgaon, India. Senior Research Fellowship as well as Research
Associate from CSIR, New Delhi, India.
He has been working as a reviewer for more than 30 SCI journals from
Elsevier(Holland)
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Field Electron Emission investigations of Polypyrrole film

ABSTRACT
Electrochemical synthesis of Polypyrrole (PPy) thin films on Sn substrates has been carried out under cyclic
voltammetry (CV) mode. Furthermore, field emission (FE) characteristics of the PPy thin film emitter were carried
out at base pressure of ~ 110-8 mbar. The simplicity of the synthesis route coupled with the capability to deliver
very high emission current density at relatively lower applied field make the PPy thin field emitter as a potential
candidate for practical applications in field emission based devices.
Keywords: Conducting polymers, Polypyrrole, Electrochemical synthesis, Field Emission
Summary
Conducting polymers, owing to their exotic physico-chemical properties, such as, tunable electrical conductivity,
good mechanical and environmental stability, electrochemical reversibility, lighter and flexible, easy and
inexpensive synthesis etc., are recognized as promising candidates for various applications, including
electrochemical supercapacitor, solar cells, battery electrodes, corrosion inhibition, chemical and biological
sensors microelectronics, light emitting diodes, catalysis, and so on. [1-5] Amongst the different conducting
polymers Polypyrrole (PPy) has been one of the important conducting polymers, because of ease of synthesis
and better control of physical and chemical properties.
Synthesis of PPy in thin film or powder form has been achieved employing various routes like chemical,
electrochemical, seeding polymerization, electrospinning, template assisted synthesis etc [2-6]. Recently, the
conducting polymer nanostructures are considered as promising field emitter, following the first report on field
emission (FE) studies of poly(3-octylthiophene) (P3OT) pellets reported by Musa et al. [7] Thereafter, FE studies
of other CPs like, Polyaniline, poly(3,4-ethylenedioxythiophene) and their composites with the other polymers,
metals, semi-conductors, and graphene have been carried out by various researchers. [8-15] In the context of
PPy, H. Yan et al. have reported the FE behavior of amorphous PPy nanowires. FE studies of nanofibrils of
copolymer comprising of pyrrole and aniline have been has been reported. [16] Recently our group has reported
the FE investigations of chloride doped PPy films synthesized by interfacial polymerization. [17].
In the present study, we report the electrochemical synthesis of PPy films on Sn substrate and their structural,
chemical and field emission investigations. The significant result of the present studies is that the PPy film
emitter exhibits capability to deliver very high emission current density. The PPy thin film was synthesized on Sn
substrate at room temperature employing cyclic voltammetry (CV) mode of electrochemical deposition.. At least
three samples were prepared under identical experimental conditions to check and ensure the reproducibility of
the PPy film.
The CVs recorded during the electrochemical synthesis of PPy film on Sn substrate at room temperature are
depicted in figure 1(a). The CVs clearly indicate deposition of PPy film on the Sn substrate under prevailing
experimental conditions.
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Figure 1(a) Cyclic voltammetry curves recorded during the synthesis of the PPy film on Sn substrate by
sweeping the
applied potential between -0.6 to 1.2V at the scan rate of 0.01 V/s. (b) SEM image of the as-synthesized PPy film. The
inset shows a magnified image of a single PPy gain.
The SEM image of the as-synthesized PPy film on Sn substrate shown in figure 1(b) indicates uniform deposition
of the PPy on entire substrate surface. The surface morphology of the PPy film is observed to be granular. The
surface 'roughness' offered by the cauliflower grains is beneficial in FE behaviour, as it assist in enhancing the
local electric field.
A typical UV-visible spectrum (figure 2(a)) exhibits presence of the characteristic peaks of conducting state of PPy
and is identical to the earlier reports [18-20]. The FTIR spectrum of the PPY film is depicted in figure 2(b), which
is in good agreement with the earlier reports [21-22]. It exhibits appearance of various characteristic peaks due
to PPy. The strong peaks at~ 799, and 945 cm-1are attributed to ring bending vibrations. The peaks at ~1053
-1
-1
and ~ 1223 cm are attributed to C-H deformation vibrations, and the peak at ~ 1331 cm is due to C-N
-1
stretching vibrations. The absorption peaks located at ~ 1574 and ~ 1485 cm are due to the symmetric and
anti-symmetric ring stretching modes, respectively.
Field emission (FE) investigations of PPy film were performed in a planar diode configuration at base pressure ~
110-8 torr. Figure 3(a) depicts the current density versus applied electric field (J-E) plots of the emitter
corresponding to different separations between anode and cathode, viz, 2, 3, and 4 mm. Initially, the emission
current is observed to increase slowly at lower applied voltages followed by rapid increase, for the same
increment in the applied voltage. The exponential nature of J-E plot confirms that the electron emission is due
to quantum mechanical tunnelling of electrons as per the Fowler-Nordheim (F-N) theory. Interestingly, very high
2
emission current desnity of 12.87 mA/cm has been drawn at an applied 2.8 V/m. This is the highest emission
current density drawn from the PPy emitter till date.
Figure 2: (a) UV-visible spectrum and (b) FTIR spectrum of the as-synthesized PPy film.
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Figure 3: (a) Field emission current density (J) versus applied field (E) plots of the PPy film emitter
recorded at different
cathode-anode separations of 2, 3, and 4 mm. (b) Folwer-Nordheim (F-N) plots derived from the observed J-E
characteristics.
The graph of ln(J/E2) versus 1/E known as the Fowler-Nordheim (F-N) plot, is depicted in figure 3(b). The nonlinear behaviour of the F-N plot is indicative of semiconducting nature of the emitter.
In the present case, the emission stability has been investigated over duration of more than 3 h at various preset
values of ~ 1, 10 and 100 A/cm2. The 'spike' like fluctuations are attributed to the adsorption-desorption of the
residual gas species on the emitter surface. The field emission images recorded at the onset of emission current
stability (1 and 100 A) are shown as the inset of figure 4. The bright field emission images comprised of large
number of tiny spots suggests that the emission is from the PPY grains.
Figure 4: Field emission current (I) versus time (t) plots of the PPy film emitter recorded at different preset values of 1, 10
and 100 A. The inset shows the field emission images recorded at the onset of emission current stability (1 and 100 A)
ACKNOWLEDGEMENT
Dr. S. S. Patil would like to acknowledge BARC for financial assistance. The field emission work is carried out as
part of CNQS programme of Department of Physics, Savitribai University of Pune, Pune.
References
[1] Lin-Xia Wang, Xin-Gui Li, Yu-Liang Yang, Reactive & Functional Polymers 47, (2001), 125-139.
[2] J.Molina, A. del Rio, J. Bonastre, F.Cases, Eur.polym. J. 44, (2008), 2087 - 2098.
115
[3] J.I. Lee, S.H. Cho, S.M. Park, J.K. Kim, J.W. Yu, Y.C. Kim, T.P. Russel, Nano Lett. 8, (2008), 2315-2320.
[4] K. Fukami, F.A. Harraz, T. Yamauchi, T. Saka, Y.H. Ogata, Electrochem. Commun. 10, (2008), 56-60.
[5]
Tongjie Yao, Xiao Li , Quan Lin , Wu Jie, Zhiyu Ren , Chuanxi Wang , Junhu Zhang, Kui Yu, Bai Yang, 50, (2009),
3938-3942.
[6] T V Vernitskaya, O N Efimov, Russian Chemical Reviews, 66, 5, (1997), 443.

[7] I. Musa, D. A. I. Munindrasdasa, G. A. J. Amaratunga, W. Eccleston, Nature, 395, (1998), 362.
[8] H. Yan, L. Zhang, J. Shen, Z. Chen, G. Shi, B. Zhang, Nanotechnology (2006), 17, 3446.
[9] X. H. Li, W. M. Liu, C. W. Wang, H. L. Li, J. Mater. Sci. Lett. 2003, 22,1519.
[10] S.S. Patil, S.P. Koiry, D. K. Aswal, P.M. Koinkar, Ri-ichi, Murakami and Mahendra A. More, J. Electrochem. Soc.,
158 (6),(2011), E63-E66.
[11] Nan Chen, Xuemin Qian Haowei Lin, Huibiao Liu and Yuliang Li, J. Mater. Chem, 22, (2012), 11068.
[12] I. Sameera, Ravi Bhatia, Jianyong Ouyang, V. Prasad, R. Menon, Appl Phy Lett., 102, (2013), 033102.
[13] Sandip S Patil, Shankar P Koiry, DK Aswal, Mahendra A More, (PEFM-2010), AIP publishing, 297, (2010).
[14] R. B. Rakhi, K. Sethupathi, S. Ramaprabhu, Appl. Surf. Sci. 2008, 254, 6770.
[15] R. Nair, B. Premlal, A. Das, A. K. Sood, Solid State Commun. 2009, 149, 150.
[16] X. H. Li, W. M. Liu, C. W. Wang, H. L. Li, J. Mater. Sci. Lett. 2003, 22, 1519.
[17] Sandip S. Patil, Purushottam Jha, D.K. Aswal, S.K. Gupta, J.V. Yakhmi, Dilip S. Joag Mahendra A. More, Polym.
Adv. Technol. 23, (2012), 215-219.
[18 ]T. Inoue, T. Yoneyama, Bull, Chem. Soc. Jpn. 56, (1983), 985.
[19] J. Arjomandi, R. Holze, J. Solid State Electrochem. 11, (2007), 1093.
[20] D.K. Kim, J.Y. Lee, D.K. Moon, C.Y. Kim, Synth. Met. 69, (1995), 471.
[21] J. Arjomandi, Anwar-ul-Haq A. Shah, S. Bilal, H. Hoang, R. Holze, Spectrochimica Acta, Part A, 78, (2011),
1-6.
[22] N. Velhal, N. Patil, S. Jamdade, V. Puri, Appl. Surface Science, 10.1016/j.apsusc.2014.03.180.
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Nanocon 010
Dr. Daniel Davis, University of Huston, USA, Addressing the Valedictory Function
117
Session 6A : Nanoelectronics V
Dr. Mahesh V. Hosur

Professor, Materials Science and Engineering
Tuskegee University, Tuskegee
E-mail: hosur@mytu.tuskegee.edu, mhosur@gmail.com
Research Area
Advanced fiber reinforced composites,

Sandwich composites,
Nanophased composites,
Advanced green composites
Qualification
Ph.D., Aerospace Engineering,Indian Institute of Science, Bangalore, India, 1996
No. of Publications
92
Research Funds
Funding as PI: $22,107,196, as Co-PI: ($31,316,480)

Other Funding:$908,250
Awards & Honors
Selected as Fellow of American Society for Mechanical Engineers, April 2013

Faculty Achievement Award at Tuskegee University, 2011-2012 .
Faculty Performance Award for Research in the College of Engineering, Architecture
and Physical Sciences,2009-2010.
ASME Materials Division recognition for organizing symposia on Design and
Manufacturing of Composites, 2003-2009
ASME Region XI recognition for serving as the Chair of Chattahoochee Section,
2003-2005
Named in the 2003/2004 America's Registry of Outstanding Professionals
Best paper award at the 14th World Conference on NDT, New Delhi, India, 8th-13th
December 1996
Fellowship, Indian Institute of Science, Bangalore, India, for Ph. D Program
Fellowship, Indian Institute of Technology Bombay, for M. Tech Program
National merit Scholarship, from 11th till completion of Bachelor of Engineering
Program
Books
Book Chapter
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Synergistic Effect of Nanoclay and MWCNTs on the Performance of Epoxy and

Carbon/Epoxy Nanocomposites
Dr. Mahesh V. Hosur
ABSTRACT
In this study, 0.3 wt. % of COOH-MWCNT, 2 wt. % of MMT and 0.1 wt. % COOH-MWCNT/2 wt. % MMT binary
nanoparticles by weight of epoxy were incorporated to modify SC-15 epoxy resin system. The nanocomposites
were subjected to flexure test, dynamic mechanical and thermomechanical analyses. Morphological study was
conducted with scanning electron microscope. In addition, laminated composites were fabricated using satin
weave carbon fabrics using these resin combinations and all the characterizations were carried out as for the
matrix samples. Further, low velocity impact tests were also carried out. Resulting damage was analyzed through
thermography NDE technique. Addition of each of the nanoparticles in epoxy showed significant improvement
in mechanical and viscoelastic properties compared to those of control ones. But, best results were obtained for
addition of 0.1% MWCNT/2% MMT binary nanoparticles in epoxy. The increase in properties was attributed to
synergistic effect of MWCNTs and nanoclay in chemically interacting with each other and epoxy resin as well as
in arresting and delaying the crack growth once initiated.
Keywords: Composites, Carbon Nanotubes, Nanoclay, Flexure, Viscoelastic properties, Low-Velocity Impact.
1. INTRODUCTION
Fiber reinforced polymers (FRPs) are popular alternatives to conventional metallic materials in aviation, naval and
automotive industries due to their low density, higher specific strength and higher specific stiffness, higher
corrosion resistance and improved fatigue performance. Researchers have been investigating FRPs to enhance
the mechanical properties, thermal stability and resistance against environmental degradation of FRPs. Different
filler materials are incorporated with FRPs to enhance mechanical, thermal, viscoelastic properties of FRPs.
Generally, filler materials are infused with matrix materials to enhance the properties. Various micro and
nanosized particles are added with FRPs as filler materials. Hence it is important to study the effect of fillers on
the performance of polymers used as matrix materials in FRP composites. Addition of carboxyl functionalized
MWCNTs can successfully initiate curing of thermoset polymers at lower temperature and reduce activation
temperature [1]. Diversified application and high prospect of carbon nanotubes come with a price; CNTs may be
hazardous to animal and plant life [2]. This potential hazardous effect of CNTs has lead researchers to use organic
nanoparticles like nanoclays. Clay particles are plate like structures with a thickness only up to 3nm while in lateral
directions ranging from 200 to 600 nm. Thermal and mechanical behavior of clay-epoxy composites are
investigated by numerous researchers and obtained best properties for 2 wt. % of nanoclay reinforcement [3, 4].
Nowadays researchers are exploring a new era of nanoparticles, the synergistic effect of nanoparticles. When two
nanoparticles are grown together and used as reinforcement then the combination of nanoparticles are called
hybrid nanoparticles. Sometimes two nanoparticles are used together without being grown together to reinforce
composite system. These nanoparticles may react with polymers differently and result in better properties than
single nanoparticle reinforcement. These combined nanoparticles are called binary nanoparticles. In a recent
study Hazarika and Maji reported significant improvement in DMA, tensile and flexural properties were achieved
by 3 phr nanoclays and 1.5 phr MWCNTs treatment of wood polymer nanocomposite [5]. In current research
work, epoxy SC-15 resin was reinforced with 0.3 wt. % MWCNTs, 2 wt. % of nanoclays and binary nanoparticles.
0.1 wt. % of MWCNT and 2 wt. % nanoclays of epoxy resin were mixed to form binary nanoparticles and reinforce
epoxy composites and fiber reinforced composites. Mechanical, thermal and viscoelastic properties of
nanocomposites were obtained and compared with control epoxy resins and fiber reinforced composites.
Further, low-velocity impact response of the nanophased woven carbon composites was also investigated.
2. EXPERIMENTATION
2.1 Materials
In this study, carbon fiber reinforced epoxy composites serve as control samples. The resin used was SC-15 epoxy
resin supplied by Applied Poleramic Inc which is a toughened, low viscosity resin. It consists of two parts, part A:
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diglycidyl ether of bisphenol A, and part B: cyclo aliphatic amine hardener with a stoichiometric ratio of A:B=10:3.
The fabric used for laminate fabrication was 8-harness satin weave carbon fiber. The carbon fabric has a tow size
3k and thickness of 0.4572mm and was supplied by US composites. Average fiber volume fraction was 58-62%
and void content were 3-5%. The COOH functionalized multi-walled carbon nanotubes having a diameter of 1020nm and length of 10-30 micrometer were purchased from Nanostructured and Amorphous Materials Inc.
Montmorillonite nanoclay Nanomer I-30E which is surface modified and contains 25-30 wt. % octadecylamine
was purchased from Sigma-Aldrich.
2.2 Dispersion of nanoparticles
A multi-step procedure was used for proper dispersion of the nanoparticles in epoxy matrix. As primary
dispersion method for breaking the agglomeration of nanoparticles, ultra-sonication was used at 40% amplitude
and 30 second on /30 second off pulse cycle. MWCNTs were mixed with epoxy through sonication for 15
minutes. Then nanoclays were added and the mixture was sonicated for an additional 25 minutes at the same
o
condition stated previously. Throughout the process the temperature was maintained at 40 C to reduce the
viscosity of the resin as nanoparticle addition tends to increases the viscosity and dispersion becomes difficult.To
ensure further uniformity of dispersion, the mixture was stirred magnetically at 800 rpm for around 12 hours.
During this step the beaker containing the mixture was placed on top of a hot plate and the temperature was
o
maintained at 40 C to ensure reduced viscosity of the resin. Finally, three-roll shear mixer was used to ensure
consistent and uniform dispersion of binary nanoparticles in the epoxy resin
2.3 Laminate fabrication
After dispersion, nanoparticle incorporated epoxy SC-15 part A was mixed with part B at a ratio 10:3. High speed
mechanical mixing was applied for 10 minutes to obtain a stoichiometric mixture that is utilized as the matrix of
the laminates. For control samples, Part A and part B were mixed at a stoichiometric ratio and used as the matrix.
Carbon fiber-epoxy nanocomposites were fabricated by a combination of hand lay-up process and compression
molding technique. At first, sheets of same size were cut from the roll of carbon fabric. Eight layers were
impregnated with resin using a rolling pin and were stacked together. The orientation of fiber sheets was aligned
in the same direction. The stacked layers were then placed in a hot press for 4 hours, where a pressure of 130
KN was applied and the temperature was maintained at 120oC to obtain completely cured carbon-epoxy
composites. The thickness of the laminates obtained was about 2.42 mm.
2.4 Testing Procedure
Nanoparticles reinforced nanocomposites were subjected to various tests to obtain the mechanical, thermal and
viscoelastic properties. Properties obtained from composites were compared with the properties obtained from
control ones. Moreover microscopic and morphological analyses were performed on fracture surface of the
samples.
2.4.1 Flexure test
In our research, flexure test was conducted according to ASTM D790-02. The test was conducted in three-point
bending configuration using Zwick-Reoll Z 2.5 machine. The test was performed under displacement control
mode at a rate 1.2mm/minute. Sample size was maintained according to the ASTM, where span length to
thickness ratio is 16:1. For nanocomposites, the sample size was 72 mm12.5mm4.5mm.
2.4.2 Dynamic mechanical analysis (DMA)
Viscoelastic properties of nanocomposites were obtained from dynamic mechanical analysis. DMA tests were
conducted according to ASTM D4065-12 using TA instrument DMA Q 800. The tests were performed in three
point bending mode at a frequency 1 Hz and amplitude 15 m. The temperature ramp was 10 C/minute within
the range 30 C and 180 C. The sample size was 60mm13mm3mm for the test. Storage modulus, loss
modulus and tan-delta as a function of temperature were obtained from dynamic mechanical analysis. Glass
transition temperature was considered as the temperature corresponding to the peak of tan-delta curve.
2.4.3 Scanning electron microscopy
Scanning electron microscopic analyses were performed to analyze the fracture mode at higher magnification.
Analysis of fracture surfaces was carried out using a JEOL JSM-6400 scanning electron microscope (SEM) at 15
kV accelerating voltage. Specimen surfaces were coated with a thin gold film for SEM observation. One sample
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from each set was observed under scanning electron microscope to understand failure behavior at various
magnifications.
2.4.4 Low Velocity Impact Testing
Low velocity impact tests were conducted using DYNATUP 8210 drop weight impact testing machine. During the
test, sample was held with a round edged pneumatically operated clamp fixture. The specimen was placed at the
bottom of the drop tower and held with clamp which provided a clamped circular support span of 75mm in
diameter. The weight of crosshead was maintained at 6.62 kg and it was guided through two smooth guide
columns. The height and weight of impactor was changed to strike the samples at energy levels of 30J and 40J.
Peak load, time to attain the peak load and deflection of samples at peak load were observed from the data
acquired and compared for different samples. Other related parameters like absorbed energy were calculated
from area under the load versus deflection curve.
2.4.5 Thermography analysis
A cutting edge thermal imaging instrument was used to qualify and the ensuing damages in the samples. The
system consists of a bright flashlight which flashes for a fraction of a second and as a result enables the sample
under observation to absorb heat energy. The heat is conducted through and radiated from the surface of the
sample. An infrared camera catches up the radiated heat signature of the specimen. The heat conducted or
radiated depends on the quality of the sample. This directly provides information on the defects or damages
present in any sample. In our work, the thermal signal was captured for 15 seconds at 30 fps. Then the output
signature was differentiated twice to get a noise free signal. The colored image was converted to a black and
white image which clearly differentiates the damaged and undamaged portions. Finally, damage area was
calculated using MATLAB coding from this image by taking percentage of black portion of the image as function
of the total area.
3. RESULT AND DISCUSSION

3.1 Epoxy Studies
3.1.1 Flexure test
Characterization of flexural properties of nanocomposites was conducted by subjecting MWCNTs, nanoclays and
binary nanoparticles reinforced samples as well as control resin samples under three point bending load. All
nanoparticles incorporated samples exhibited significant improvement of flexural strength and modulus with a
maximum increase of 29% and 44%, respectively in binary nanoparticles reinforced samples compared to control
samples. After initiation of crack due to loading, the propagation of crack can be arrested by the presence of
nanoparticles. As the crack faces nanoparticles in the propagating direction, it has to change the direction. Thus,
presence of nanoparticles ensured the change in the direction of crack propagation, the fracture surface of
nanocomposites was rougher than that of the control samples. Among the nanocomposites, binary nanoparticles
reinforced ones exhibit most rough fracture surface. This direction change requires more energy, which enables
the nanocomposite samples to carry higher load.
3.1.2 Dynamic mechanical analysis
Dynamic mechanical analysis provides the viscoelastic properties of composite samples as a function of
temperature. Unmodified carbon fiber/epoxy composites as well as MWCNT, nanoclays and binary nanoparticles
modified composites were subjected to dynamic mechanical analysis to observe the effect of nanoparticles on
stiffness of composites. Storage modulus increased due to the addition of nanoparticles in almost all
temperature regions. In the glassy region that is before the glass transition temperature, significant increase in
storage modulus was observed, whereas after glass transition temperature at rubbery region storage modulus
increased slightly. Thus at room temperature, the storage modulus exhibited by MWCNTs, nanoclays and binary
nanoparticles reinforced nanocomposites is 13%, 14% and 27% higher than the storage modulus exhibited by
control ones. For all composite samples, loss modulus increases with temperature up to glass transition
temperature, then decreases with further increase of temperature. Temperature associated with the peak of loss
modulus represents the glass transition temperature indicating change of glassy state to rubbery state. In case
of loss modulus, binary reinforcements provide best result. Glass transition temperature for binary nanoparticles
reinforced composites increases by about 25% compared to control samples. Nanoparticles in nanocomposites
restrict the molecular motion of polymer chains when the temperature increases. Thus, the polymer chains in
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resin- nanoparticles network starts to move only at a higher temperature than the polymer chains of the control
resin samples, resulting in high glass transition temperature.
3.2 Carbon/Epoxy Composites Studies
3.2.1 Flexure test
Carbon fiber reinforced composites modified with nanoparticles were subjected to three point bending load to
compare the flexural properties of nanoparticles modified samples to control. Flexural strength and modulus of
all the samples increased with addition of nanoparticles. The maximum enhancement was observed for binary
nanoparticles modified CFRPs with an increase of 31% and 30% of flexural strength and modulus.In fiber
reinforced composites, carbon fibers are the primary load carrying agents. Nanoparticles undergo chemical
reactions with polymers as well as the functional groups present on the surface of fibers thereby form a very
strong chemical bond at the fiber-matrix interface as well as between the layers. In bending load, the composite
structure is loaded in thickness direction, in which direction the composite structures are most vulnerable.
Individual plies in the composite structure are prone to separation due to shear stress on the laminate. Hence
nanoparticles come into play acting as crack arrestors or bridges between the plies whenever there is an initial
of crack which tries to propagate. Thus, when loaded these bridge structures between plies must be severed
before delamination, which required more energy to break the specimen. Therefore, nanoparticles are more
effective when used as a reinforcement of CFRPs as they reinforce the resin as well as act as bridge structure
between individual plies. These were confirmed through SEM studies which are outlined in a later section.
3.2.2 Dynamic Mechanical Analysis
Nanophased and control carbon fiber/epoxy composites were subjected to dynamic mechanical analysis to
obtain viscoelastic properties. Transient data obtained from this experiment were accumulated and storage
moduli, loss moduli and tan-delta as a function of temperature were plotted. It was evident that binary
nanoparticles reinforced carbon fiber/epoxy composites possess much higher storage modulus and glass
transition temperature than control composites. Moreover, nanoclays reinforced composites had higher storage
modulus, yet lower glass transition temperature. On the contrary, MWCNTs reinforced composites exhibited
lower storage modulus, yet high glass transition temperature. Therefore, in binary nanoparticles reinforced
composites, MWCNTs tend to increase the glass transition temperature along with nanoclays reinforcing the
resin mechanically. Loss modulus for nanoparticles reinforced carbon fiber/epoxy composites is much higher
than the control composites. Binary nanoparticles possess highest loss modulus, thus highest amount of energy
is dissipated while three point bending load is applied. When the load is applied, the nanoparticles try to hold
the laminae in place, so more amount of energy is required to deform the samples. Thus, nanoparticles
reinforced composites required higher load and loss modulus increased for nanophased composites. Damping
properties of nanophased composites are much higher than control composites. Binary nanoparticles increase
damping properties of carbon fiber/epoxy composites by about 29%. Also glass transition temperature obtained
from tan-delta plot exhibits similar behavior as nanocomposites. Nanoclays, MWCNTs and binary nanoparticles
increase the glass transition temperature by about 12%, 8% and 19% respectively.
Fig 1: Thermography images of different samples before and after conditioning at 30J and 40J energy levels
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3.2.3 Low Velocity Impact Testing

Low velocity impact test was conducted for control and modified samples at dry condition and after 6 months
of sea water conditioning. The tests were conducted at 30J and 40J energy levels. For each energy level three
samples of each kind of composites were tested and average of the three measurements is reported. Load vs
displacement curves were plotted for all types of samples before and after degradation tested at different energy
levels. It was found that before conditioning, the modified samples exhibited better performance than control
samples at both energy levels. At 30J energy level the load-displacement profile was very smooth for both
samples except for a small drop in load and change of the slope in load-displacement curve indicating no
catastrophic failure. On the contrary, tests conducted at 40J energy levels shows sudden drop of the profile for
both control and modified samples. The sudden drop in load indicates partial or full penetration of the sample.
After 6 months of conditioning, at 30J energy level binary nanoparticle modified samples still retained a similar
profile as that of the unconditioned sample. However, control samples exhibited substantial drop of load after
reaching the peak. This sudden drop signifies that control samples were degraded by absorption of moisture
after submerging in marine environmental conditions. Tests conducted at 40J energy level also confirm this
observation by displaying reduced peak load and lower time for maximum load. Modified samples also showed
slight degradation due to moisture absorption. However, the degradation for nanoparticle modified samples was
considerably lower compared to control samples signifying increased durability. Octa-decylamine
functionalization of MMT may have bonded with COOH functionalization of MWCNTs. As a result more energy
was required to break this bond and damage the modified simples which give the binary nanoparticle modified
samples significant advantage over control samples.Thermal images of the samples after low velocity impact
tests were taken and the damage area was measured. Significant reduction of damage area for binary
nanoparticles modified samples was observed before and after conditioning, results of some of which are shown
in Figure 1. Moreover, this reduction was found to increase after conditioning which indicates increased durability
of the modified carbon/epoxy samples. The reduction of damage area is more significant at 30J energy level.
CONCLUSION
This research provides detailed analyses on mechanical, thermal and thermo-mechanical analysis of MWCNTs,
nanoclays and binary nanoparticles reinforced nanocomposites. The results obtained from tests conducted on
these nanocomposites are compared with the properties of control resin samples. Flexural stress and strain of all
nanocomposites are higher than epoxy resin samples. Dynamic mechanical analysis revealed almost similar
trends.Scanning electron microscopy showed rougher fracture surface for nanocomposites compared to the
surface of the control resin ones.Carbon fiber reinforced epoxy composites modified with MMT/MWCNTs binary
nanoparticles displayed better mechanical, viscoelastic and impact resistance than control samples. Moisture
uptake by modified samples was lower compared to control samples. Although both kinds of samples exhibited
degradation due to moisture absorption, modified samples retained properties significantly. This retention of
properties signifies that modification with MMT nanoclays along with MWCNTs slowed marine environmental
degradation of carbon/epoxy composites and increased durability. The improvement is more pronounced at
lower impact energy level. The improved impact resistance and reduced degradation of modified composites will
help to address some of the major issues with using composite materials in naval vessels and offshore structures
without sacrificing the advantages of composite structures. However, further study is required to find out the
optimum composition of binary nanoparticles by varying the percentages of nanoclay and MWCNTs used in the
investigation.
ACKNOWLEDGEMENTS
Author would like to acknowledge NASA-EPSCoR (NNX10AN26A), NSF-EPSCoR (EPS-1158862), DoD
(W911NF1210053), UNCF-SP-NSTI grants for their financial support in this research.
123
REFERENCES
1.
N. Jahan, A. Narteh, M. Hosur, M. Rahman, and S. Jeelani, "Effect of Carboxyl Functionalized MWCNTs on the
Cure Behavior of Epoxy Resin," vol. 2013, no. April, pp. 40-47, 2013.
2.
J. Du, S. Wang, H. You, and X. Zhao, "Understanding the toxicity of carbon nanotubes in the environment is
crucial to the control of nanomaterials in producing and processing and the assessment of health risk for
human: A review.," Environ. Toxicol. Pharmacol., vol. 36, no. 2, pp. 451-462, May 2013.
3.
F. H. Chowdhury, M. V. Hosur, and S. Jeelani, "Studies on the flexural and thermomechanical properties of
woven carbon/nanoclay-epoxy laminates," Mater. Sci. Eng. A, vol. 421, no. 1-2, pp. 298-306, Apr. 2006.
4.
Y. Zhou, F. Pervin, V. K. Rangari, and S. Jeelani, "Influence of montmorillonite clay on the thermal and
mechanical properties of conventional carbon fiber reinforced composites," J. Mater. Process. Technol., vol. 191,
no. 1-3, pp. 347-351, Aug. 2007.
5.
A. Hazarika and T. K. Maji, "Strain sensing behavior and dynamic mechanical properties of carbon
nanotubes/nanoclay reinforced wood polymer nanocomposite," Chem. Eng. J., vol. 247, pp. 33-41, Jul. 2014.
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Nanocon 010
Dr. Venkatesan Renugopalakrishnan/ Professor, Harvard University, Boston, USA Addressing conference
125
Session 6B : Nano-Biotechnology - II

Department of Structural Biology,
Weizmann Institute of Science,
Rehovot, Israel.
E-mail: lia.addadi@weizmann.ac.il
Research Area
Nanomaterials
Qualification
Ph.D.,Structural Chemistry, Weizmann Institute of Science, Rehovot, Israel,1979

B.Sc., M.Sc.,Organic Chemistry, Universita' degli Studi di Padova, Italy.
Invited Lectures
54
Awards & Honors
J.F. Kennedy Memorial Prize for Ph.D. students,1978

G.M.J. Schmidt prize for Ph.D. thesis, 1981
Chaim Weizmann Fellowship for postdoctoral studies, 1981-1982
Incumbent of the Helena Rubinstein Career Development Chair, 1982-1984
Incumbent of the Charles Revson Career Development Chair, 1985-1988
Ernst Bergmann prize in Chemistry, 1986
Annual Award of the Israel Chemical Society for young scientists, 1989
Incumbent of the Dorothy and Patrick Gorman Professorial Chair, 1991
NIDR prize for basic research in biological mineralization, 1996
Prelog medal in Stereochemistry of the ETH, Zurich, 1998
Shell Distinguished lecture, Northwestern niversity,200
37th Burgenstock Conference on Stereochemistry, President, 2002
Rosalind Franklin lecturer, Cambridge, UK, 2005
Dorothy Hodgkin lecturer, University of Zurich, Switzerland, 2006
Dauben lecturer, University of Seattle, US, 2006
Kolthoff prize of the Technion, Haifa, Israel , 2006
Spiers Medal of the Royal Society of Chemistry, Faraday Division, 2007
"Sigillo della citt di Padova" for illustrious citizens living abroad, 2007
Order of merit of the Republic of Italy "Cavaliere della Repubblica", 2009
Israel Chemical Society prize of excellence, 2009
Gordon Conference on Biomineralization, Chair, 2010
Gregori Aminoff Prize in Crystallography of the Royal Swedish Academy of Sciences,
2011
Included in Gordon Research Conference Hall of Fame , 2011
Gerhard Schmidt Memorial Lecture, Weizmann Institute of Science, 2013
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Biogenic Mineralized Nanomaterials: Ancient Technologies for the Future

Biomineralization refers to the processes by which living organisms produce minerals, often to harden or stiffen
their soft tissues, but also for many other functions, such as protection, mastication, navigation or light
manipulation (Lowenstam and Weiner 1989). Organisms have been building materials for at least 550 million
years, during which time nature had the advantage of optimizing, discarding or preserving not only the specific
materials, but also the fundamental mechanisms and strategies developed. The level of sophistication in the
design and construction of the materials at all hierarchical levels, from ngstroms to millimeters, is unparalleled
by any man-made material. Much can therefore be learnt about nano-technology from studying biominerals,
because the biological processes, the strategies used and the solutions evolved by organisms are often
completely unexpected. Biomineralization is a potentially endless source of unconventional ideas for building
composite materials with control at the nanometer level.
Fig 1: Cross section of the shell of the pteropod Diacria quadridentata
A look at the hard materials produced by a group of barely studied organisms, the pteropods (Fig. 1), shows just
how amazingly complex and elegant such structures can be. The pteropods are planktonic mollusk snails that
live their entire lives in the open ocean, and because of the way they "fly" through the water, they are called "sea
butterflies" (Lalli 1989). Pteropods build their shells out of complex curved or blocky structures at the nano-meter
level (Fig 1). These structures, made of aragonite crystal bundles twisted in three-dimensional arrangements that
are not yet well-understood, provide the animal with shells that are light-weight, strong and flexibile at a level
superior to those of the best composite nano-materials.
Another striking example of biomineralization is the photonic multilayer crystals composed of guanine crystal
platelets alternating with cellular matter (Fig 2). The regularity of these stacks provides copepods (planktonic
crustaceans) with narrow band structural colors ranging from orange to deep blue (Chae and Nishida 1994).
Wouldn't we love to be able to produce such crystalline nano-ultrastructures!
We shall focus on one discovery from the 1960s (Towe and Lowenstam 1967), that has gained enormous
importance in the field of biomineralization, especially during the last 15 years or so. We refer to the importance
of amorphous phases and in particular transient amorphous precursor phases as a strategy evolved by organisms
for shaping crystals into fantastic shapes (Weiner and Addadi 2011).
One of the most striking observations in the area of biomineralization, that has baffled scientists for many years,
is that many organisms, such as brittle stars, sponges and sea urchins, build skeletal parts with incredibly
convoluted shapes, out of single crystals of the mineral calcite (calcium carbonate). How can this be, and are
these are really single crystals? These questions have been intensively debated in the biomineralization field from
the 1960's until this day (Addadi and Weiner 1992).
127
Fig 2: Cross section of the cuticle of the copepod Sapphirina metallina, showing the structure of the photonic crystal layer
composed of hexagonal guanine crystal platelets separated by cellular material.
Sea urchin larvae have an endoskeleton formed of 2 spicules, each of which behaves under polarized light and
diffracts X-rays as a single crystal of calcite (Fig 3). A partial answer to the apparent paradox of the formation of
such single crystals with reproducible, convoluted shapes came in the late 1990's, when Beniash et al discovered
that the spicule is formed in its initial phases mostly of amorphous calcium carbonate (ACC)(Beniash, Aizenberg
et al. 1997), in the form of nanospheres with a typical size of 20-30nm. The spicule deposition strategy appears
to involve first molding the object out of an isotropic material into the desired shape, and then transforming it
in a controlled manner into a crystalline material.
Information about the 'structure' of the transient ACC and the mechanism of transformation was obtained mainly
from spectroscopic techniques, such as XAS and X-PEEM, providing information on the disordered phases at a
resolution of up to 20nm (Politi, Levi-Kalisman et al. 2006; Politi, Metzler et al. 2008). The conclusion was that
there are two distinct phases of ACC: one is disordered at the ngstrom level and contains water, whereas in the
other the calcium coordination sphere is already that of calcite, but the relative packing of the coordination
spheres is disordered in the medium and long range. The crystallization would involve the transformation from
ACC to calcite occurring by nucleation from one particle to the next in a complex network.
Fig 3: Light microscope image of an embryo of the sea urchin Paracentrotus lividus. The two spicules have been artificially
highlighted in different shades of blue. Inset: High magnification micrograph of the spicule showing the nano-sphere
morphology at the nanometer level.
We recently discovered that the initial disordered phase is deposited inside the embryo cells. These cells are full
of vesicles containing calcified granular nanoparticles of the same sizes as those composing the spicule.
Interestingly, the vesicles filled with amorphous deposits are observed not only in the spicule forming cells, but
also in the epithelial cells. The embryo seems thus to commission the whole organism to concentrate and deposit
calcium carbonate during the spicule production period (Vidavsky, Addadi et al. 2014).
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Fig 4: Cystolith extracted from a leaf of Ficus microcarpa. Inset: High magnification micrograph of the spicule showing the
nano-sphere morphology at the nanometer level.
Additional information on the mechanism of transformation of ACC to calcite in the sea urchin spicules came
from a completely different direction, namely while we were studying plant cystoliths. Cystoliths (Fig 4) are
calcified objects formed in the leaves of certain plants. Cystoliths are composed of stable ACC, with the typical
nano-sphere morphology of around 20 nm in size. Cystoliths function as light scatterers distributing the sunlight
flux more evenly inside the leaf. Light penetration from the light saturated upper layer to the light deprived inner
layer of the leaf is facilitated by the cystoliths, increasing the photosynthetic yield in the leaves (Gal, Brumfeld et
al. 2012). The cystoliths are known to crystallize easily when exposed to humidity. Surprisingly, when bathed in a
limited volume of water, the crystallization yields faceted crystals of calcite with morphology, at the nanometer
level, consisting of nano-spheres (Gal, Habraken et al. 2013).
It appears that the nano-spheres crystallize, preserving their morphology as a memory of the ACC that originated
them. This is a chemically extraordinary process of non-conventional crystallization from relatively large particles,
and thus is of interest for the study of crystallization in general. The crystallization process involves a competition
between the growth of the crystal from ions and the growth from nanoparticles: the nano-spheres detach from
their location in the cystoliths and migrate as such to the crystal, where they crystallize by secondary nucleation.
The macroscopic morphology results from deposition from solution of dissolved ions on the crystal faces.
We also showed in a totally in vitro experiment using ACC precipitated in gels made from pectin, agarose, and
gelatin, or ACC precipitated in the presence of phosphate, that the transformation in small volumes of water
results in crystals of calcite built of nanospheres (Gal, Kahil et al. 2014). Most important, when we precipitated
ACC in the presence of macromolecules extracted from sea urchin spicules, the same effect of single calcite
crystals built of 20-30nm sized nano-particles was also observed, reminiscent of the biological material in nanomorphology and single crystalline properties.
It seems that we have identified a very fundamental mechanism that has not only a physiological relevance, but
also has relevance to the building single crystalline materials of any desired shape and of any desired size with
control at the nanometer scale.
References
[1] Addadi, L. and S. Weiner (1992). "Control and design principles in biological mineralization." Angew. Chem. Int.
Ed. Engl. 31: 153-169.
[2] Beniash, E., J. Aizenberg, et al. (1997). "Amorphous calcium carbonate transforms into calcite during sea-urchin
larval spicule growth." Proc. R. Soc. London B Ser. 264: 461-465.
[3] Chae, J. and S. Nishida (1994). "Integumental ultrastructure and color patterns in the iridescent copepods of
the family Sapphirinidae (Copepoda: Poecilostomatoida)." Marine Biol 119: 205-210.
[4] Gal, A., V. Brumfeld, et al. (2012). "Biominerals in leaves scatter light to enhance photosynthetic efficiency." Adv.
Mater. 24: OP77-OP83.
129
[5 ]Gal, A., W. Habraken, et al. (2013). "Calcite Crystal Growth via a Solid State Transformation of Stabilized
Amorphous Calcium Carbonate Nanospheres in a Hydrogel." Angew. Chem. Int. Ed. 52: 4867 -4870
[6] Gal, A., K. Kahil, et al. (2014). "Particle Accretion Mechanism Underlies Biological Crystal Growth from an
Amorphous Precursor Phase." Adv. Funct. Mat.
[7] Lalli, C. M., Gilmer, R.W. (1989). Pelagic Snails: The biology of Holoplanktonic Gastropod Molluscs. Palo Alto,
Stanford Press
[8] Lowenstam, H. A. and S. Weiner (1989). On Biomineralization. New York, Oxford University Press.
[9] Politi, Y., Y. Levi-Kalisman, et al. (2006). "Strucutural characterization of the transient calcium carbonate
amorphous precursor phase in sea urchin embryos." Adv. Funct. Mater. 16: 1289-1298.
[10] Politi, Y., R. A. Metzler, et al. (2008). "Transformation mechanism of amorphous calcium carbonate into calcite
in the sea urchin larval spicule." Proc. Natl. Acad. Sci. (USA) 105: 17362-17366.
[11] Towe, K. M. and H. A. Lowenstam (1967). "Ultrastructure and development of iron mineralization in the radular
teeth of Cryptochiton stelleri (Mollusca)." J. Ultrastructure Res. 17: 1-13.
[12] Vidavsky, N., S. Addadi, et al. (2014). "Initial stages of calcium uptake and mineral deposition in sea urchin
embryos." Proc. Nat. Acad. Sci. USA 111 (1): 39-44.
[13] Weiner, S. and L. Addadi (2011). "Crystallization Pathways in Biomineralization." Annu. Rev. Mater.
Res. 41: 21-40.
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Nanocon 010
Dr. Shaik Jeelani delivering keynote address.
131
Session 6C : Nanocomposites-II
Prof. Yun-Hae Kim

Professor,
Korea Maritime & Ocean University,
Vice President, The Korean Society for Engineering Education,
Chairman, ACEE2013 and AMDP2014,
Editor in Chiefs, Nano Hybrids, Advanced Engineering Forum,
IJOSE, The Korean Society of Ocean Engineers, Korea
E-mail:yunheak@hhu.ac.kr
Research Area
Development of Environment-friendly Technology

Development of New Fabrication Method in Composite Structure
Application of Composite to Marine Equipment
Awards & Honors
Busan Mayor Prize from Busan Metropolitan City,

Prize of The University of Tokushima, Japan,
Best Paper Prize, Korean Society of Marine Engineers, Jang, Young-Sil Prize,
Best Ministry Award in Korea, Nominated in Marquis Who's who, 2008-2013,
Nominated in IBC, UK, Appointed as the 100 Scientist in 2008, IBC, UK,
Innovation Award for Engineering Education, Ministry of Education in 2011.
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Processing and Mechanical Properties of Nanocomposites Based on Halloysite Nanotube

and Unsaturated Polyester Resin
Prof. Yun-Hae Kim
ABSTRACT
Halloysite nanotube, which has been used in the polymer, has been spotlighted as a useful functional materials
in the improvement of mechanical properties such as impact modified, excellent strength and heat resistance. In
the current study, we are going to establish the optimal nanoparticle dispersion and to analyze the mechanical
characteristics and behavior of composites reinforced by halloysite nanotubes (HNT) have been synthesized by
dispersing HNTs to the polyester resin of bisphenol (base material matrix) and their mechanical characteristics,
especially the tensile strength, inter laminar sheer strength have been analyzed. Additionally, the reinforcement
effect and its variation according to the amount of HNT was also studied.
Keywords: Halloysite Nanotubes, Nanocomposites, Unsaturated Polyester Resin, Mechanical Property, Fiber
Reinforced Plastic, Vacuum assisted Resin Transfer Molding
1. Introduction
Polymer composite, used as additives/reinforcement compounds, is one of the demanding materials in
nanotechnology [1]. Such composites are a heterogeneous mixture of two or more materials with different
properties, especially strength and reinforcement added to the base material. Furthermore, these composites
can have high specific strength yet low stiffness, which can be controlled depending upon the final application
[2].
Composites using nanoparticles as a reinforcing material to the polymer matrix are referred to as nano
composites [3, 4], which can be further tailored to exhibit the desired mechanical and chemical properties. Nano
composites can be synthesized by dispersing nano-sized ceramic and/or metal particles in a polymeric resin [5].
Nano-reinforcement composites have been spotlighted as a new class of materials that possess several improved
features, such as mechanical, thermal and electrical characteristics. These improved functionalities arises mainly
due to the large surface area, imparted by the nanoparticles, in comparison to the conventional reinforcement
composite materials. According to S. Y. Jeong et al [6], clay minerals, with a layered structure, are dispersed in
the polymer resin first. And then, it is peeled as the nanoscale and used. The polymer nano composites can
remarkably increase the strength ithout causing any loss in the impact resistance, toughness and transparency
of the pure matrix. The nano composites are also capable of improving the transmission inhibiting ability of gases
and liquids, high temperature stability, and wear resistance. Therefore, nano composites, consisting of nanosized materials can overcome the limitations of a single material's properties [7].
Recently natural halloysite nanotubes (HNTs) have attracted significant attention due to their useful properties.
HNTs can be used as a substitute to carbon nanotubes and various studies have been made using the unique
tubular crystalline HNT. HNTs consist of Si-O tetrahedral plate, the basic structure of kaolin mineral, coupled with
Al-OH (O) octahedral plate in 1:1 ratio to form a layer.. Depending on the laminated structure, halloysite displays
polymorphism, including HNTs [9, 10].
The components of the composite materials include fiber, particle, layer, and sand. Furthermore, depending on
the structure of the reinforcement, the composite materials can be divided into two groups, viz. fiber-reinforced
composite materials and particle-reinforced composite materials. The particle-reinforced composite materials
are lighter in weight than the conventional steel materials and also have excellent corrosion resistance, wear
resistance and strength and low variation on the external load[11]. Moreover, the properties of these materials
can be controlled through their synthetic procedures and also make relatively subsequent processing easy.
However, two major concerns related to these particle-reinforced composite materials are delamination process
between the particles and the matrix, and aggregation of the particles, which lead to variable physical properties.
The current study analyzes the mechanical characteristics and nanoparticle's behavior in the glass fiber-
133
reinforced unsaturated polyester resin composite materials by dispersing HNTs in the base material. Additionally,
we are trying to make sure the reinforcement effect and its potent according to the amount of HNTs added to
base matrix(Unsaturated polyester resin).
Experimental work
Materials. The reinforcement material is glass fiber which is plain woven yarn cloth of E-glass fiber with weight
190g/m2 and thickness 0.2mm. The matrix is LSP-8020, a thermosetting resin of CCP COMPOSITES's. It is a low
viscous unsaturated polyester resin of bisphenol A type for molding machine. HNTs, the reinforcement material,
product of DOORICHEM's, has a white, odorless, particle and has chemical formula of H4 Al2 O9 Si2?2H2O.Sample Preparation. The glass-fiber reinforced composite material was synthesized by first mixing HNTs to the
unsaturated polyester resin at different proportions of 0, 0.5, 1, 1.5, 3 and 5 wt%, followed by a two-hour
ultrasonic homogenization. According to a previous study [12], the mechanical property and the multifunctionality of nano composites is primarily decided by the amount of nanoparticles distributed inside the resin.
In this regard, to achieve a uniform, optimal distribution of the nanoparticles that are of solid type to liquid resin,
mechanical agitation is generally performed using ultrasonic wave.
o
In the current work, the resin with dispersed HNTs attained a temperature of about 100 C due to the heat
o
generated from the ultrasonication, which was then cooled to -20 C for an hour and finally warmed up to the
o
room temperature of 22~23 C for fabrication. Using the vacuum assisted resin transfer molding (VARTM)
technique, a specimen is a fabrication of 17 sheets of glass fiber and unsaturated polyester resin/HNT composite
o
produced for evaluation. The specimen was hardened in the lab at 22 C for a day. VARTM originally involved
insertion of a resin within the layers of a carbon fiber. In the VARTM, the resin viscosity is a critical parameter
when it comes to resin flow. In the present work, seven samples were formed with various proportions of HNTs
to evaluate their mechanical properties.
Fig.1 Configuration of tensile(left-up) and interlaminar shear strength (left-bottom) of a test sample and picture of the
machine
The Agitation Process. To achieve an optimum dispersion of the HNTs, both mechanical and ultrasonic
agitations were employed. Such agitations break the clusters of nanoparticles and help the particles to uniformly
disperse in the resin matrix. Otherwise, any clustering of the nanoparticles reduces the features of polymer. Such
agitations, especially the ultrasonic one, are the most common way to disperse CNTs, which are, otherwise,
difficult to disperse effectively [13]. Currently, dispersion studies of the HNTs in the composite materials are fairly
insufficient. As a part of the current work, therefore, attempts have been made to optimize the dispersion
process through the proven effective ultrasonic agitation method. Furthermore, the level of dispersion of the
particles was analyzed through a microscope.
Evaluating the Mechanical Property. To evaluate the mechanical properties of the nano composites, a tension
test and a three-point bending test were performed (Fig.1), using instruments- ASTM D 638 and ASTM D 2344
respectively by Universal Test Machine of Kyung-do corporation (KDMT-156). Both these tests were done at
5.00mm/min at room temperature. Tensile strength represents maximum tensile load divided by specimen's
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cross-sectional area and is the basic tension criteria of a material. The three-point bending test is a more simple
and effective way to test a composite's quality than other mechanical tests, and thus, was performed to estimate
the interlaminar shear strength (ILSS), which is the maximum value of interlaminar shear stress that can cause
delamination between fibers. It is also applied to find out the mechanical interfacial properties of composites
and calculated through formula (1). The measured strength value is presented with error bars along with the
mean value of results obtained from seven test observations.
Other parameters related to strength are the fiber content and the specific strength depending on the content
of HNTs. To evaluate the fiber contents, several specimens of same volume were heated inside an electric furnace
o
at 625 C . The initial mass and the mass of the container that contains residues after combustion were recorded.
Density of each specimen was calculated and the tensile strength of the concerned specimen was divided by
specific weight to obtain specific strength using formula (2). To distinguish between a weak and strong material,
the values of specific strength is used for comparison. Among the currently used structural materials, composites
such as high-tensile steel, titanium alloys and reinforced plastics have a high specific strength.
Results and Discussions

Optimization of the Agitation Process. In the dispersion of the HNTs in the resin matrix, both mechanical and
ultrasonic dispersion processes are prone to reaggregation of the HNTs with time. This reaggregation is possibly
due to spatial balance of the molecules. Observation through a microscope revealed that, for the mechanical
dispersion, a large number of bubbles were generated and the aggregation of the nanoparticles was also high.
By contrast, the clustering of the nanoparticles and also the formation of bubbles were much lower during the
ultrasonic dispersion. This can be explained considering mechanical dispersion to be simply a mechanical
movement in the polymer(Fig. 2). In Fig.2-(a), HNTs dispersed ultrasonic is mixed evenly with UPR. In the case of
(b), it can be seen that the aggregated HNTs. Furthermore, center of aggregated HNTs was not impregnated with
UPR. This part is likely to be stress concentration when preparing composites.
In the ultrasonic process, bubbles were first created and the ultrasonic wave was transmitted into the resin,
containing the nanoparticles. The bubbles burst due to a pressure difference, forming a very fast jet locally, which
breaks any interconnection between the nanoparticles, thereby preventing aggregation. It has been reported
that the spreading speed of the aligned polymers decreases and its viscosity increases as the molecular
structures are more branched. Therefore, the current study used ultrasonic method for the dispersion of the
HNTs. Furthermore, the resin, on interaction with the ultrasonic wave was mechanically agitated and prevented
the spatial equilibrium of the molecules.
Fig. 2 Optical micrographs of HNTs dispersed in UPR(200x magnification)
135
Characterization of the Microstructure.

Fig. 3 shows the optical microscopic images of the cross-section of a synthesized nano composite specimen.
Each specimen was proceeded polishing depending on the weight ratio of the HNT to resin and their quality was
monitored at 100x magnification. First, glass fiber reinforced composite, synthesized from pure unsaturated
polyester resin without any HNT was rarely found to contain any pore. However, a small number of pores were
identified in the specimen that contained HNT, and the number and size of the pores increased with the HNT
content. The reason for this behavior is possibly because the dispersed HNTs within the resin matrix, increased
the viscosity of the resin and thereby, altered the fiber combination of the resin.
Fig. 3 Optical micrographs of nano composites based on the ratio of HNTs/UPR
Study of the Mechanical Property. The mechanical behavior of the nano composites based on unsaturated
polyester/HNT is shown at Fig. 4. The tensile strength curve shows that, all HNT containing samples have larger
tensile strength than the pure composite (267.14 MPa), with no HNT. Specifically, nano composites reinforced
with 1 % HNT showed an enhanced strength by more than 12.4 % than the pure composite. This demonstrated
that HNT has reinforcement effect through the proportionally-increasing curve. Unlike the tensile strength curve,
the interlaminar shear strength curve showed a negligible improvement in the property than the pure composite
and showed partly reinforcing effect only for samples with 0.5% and 1% HNT loading. In particular, interlaminar
shear strength became weaker than the pure composite as the HNT content increased to 3 % and more. This
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implied that addition of HNT weakens the bonding between the glass fiber and the unsaturated polyester resin
matrix. According to an earlier report, a load applied to the nano composites was transmitted to the
nanoparticles through the matrix. The nanoparticles resisted the transmitted force and eventually suppressed
any deformation of the nano composites [14]. Therefore, the nanoparticles curbed cracked transmission of matrix
and cross-linking at the same time. Similarly, the HNT provided reinforcement effect to the nano composites
reinforced with 1% loading, but a higher amount of loading can deteriorate the mechanical property. To account
for the above observations, some possible reasons can be assumed. First, the main cause of reduction in strength
is the addition of nanoparticles by mechanical agitation. If the nanoparticles are not distributed evenly, the HNTs
aggregate and forms lumps within the matrix. The lumps of HNTs form certain empty spaces inside the resin or
defect inside the material, and any external pressure can cause stress concentration. Second, the VaRTM process
directly injected resin between the fiber layers, which was affected by the viscosity of the resin. If the resin flow
is affected by viscosity, an increasing resin viscosity would reduce the fiber integration rate and increase the rate
of pore generation. In the current work, when nanoparticles were added to the resin matrix, it was critical to
overcome any phase separation inside the matrix, any coherence, poor distribution and poor adhesion.
Therefore, it can be considered that viscosity increased naturally and this caused pores and re-clumping of the
nanoparticles, since appropriate conditions to overcome the above-mentioned factors were not set up
sufficiently during the experiments, except the ultrasonic and mechanical agitations during loading of the HNTs.
Fig. 4 Mechanical property related to strength of nano composites based on UPR/HNTs
All specimens had fiber contents of more than 60 %. Especially, nano composites reinforced with 1 % and 8 %
HNT were measured with fiber contents of 63 % or more (Table 1). The specific strength of all the nano
composites was found to deteriorate significantly, as compared to the pure composites (Fig.5). In particular, nano
composites reinforced with 1 % HNT experienced a reduction in strength by 6.14 % or more. It is estimated that
high fiber content in nano composites reinforced with 1 % HNT increased the weight for the same volume, when
compared with the other specimens. The density also increased to a large extent, similar to the tensile strength.
Therefore, a rise in specific weight led to the reduction in the specific strength.
137
Fig. 5 Specific strength rate of the UPR/HNTs nano composites
Conclusions
The current study examined the mechanical property of nano composites based on unsaturated polyester/HNT.
The main conclusions are-(1) An optimum dispersion processing for the nanoparticles was employedmechanical dispersion after ultrasonic dispersion. This is to prevent any deterioration of the mechanical
properties due to clustering of the nanoparticles. Moreover, in order to stop the re-aggregation phenomenon
after the ultrasonic dispersion, mechanical dispersion was also carried out.
(2) Samples containing HNT was found to contain more pores than the pure composite sample. Moreover, the
pore size increased with an increase in the HNT content. Viscosity also increased when HNT was distributed
within the resin and the increased viscosity resulted in developing a large number of pores due to certain
disadvantages of the VARTM process.
(3) HNT containing nano composites showed a high strength compared to the pure composite, implying the
contribution of HNT in improving the composites' strength.
(4) The tensile strength and the interlaminar shear strength increased depending on HNT content and the
change in strength was negligible after saturation level, beyond which the interlaminar shear strength started to
decrease. This was probably because the nanoparticles were not evenly distributed during the mechanical
agitation of HNT, causing the nanoparticles to cluster again inside the resin. Such chunks of nanoparticles inside
the matrix weakened the bonding between the fiber and the matrix.
References
[1] J. W. Lee, W. H. Jo, W. N. Lee and J. H. Byun: The Korean Society for Composites Materials Vol. 24(2011),
[2] M. T. Ku, J. H. Kim, H. Y. Kang and G. W. Lee: Trans. Korean Soc. Mech. Eng. A Vol. 37(2013), p.657-664
[3] T. G. Kim, J. C. Goak, N. S. Lee, J. W. Lee and J. H. Park: Trans. Korean Soc. Mech. Eng. A Vol. 28(2004),
p.1534-1540
[4] A. G. Sorina, G. Adi, C. Floriana and I, Horia: Polymer-Plastics Technology and Engineering Vol. 50(2011),
p.1096-1102
[5] B. S. Lee, J. H. Lee, I. T. Kim, M. H. Lee and C. W. N: Trans. Korean Soc. Mech. Eng. A(2002), Vol. 26, p.262426303
[6] S. Y. Jeong and E. I. Jeong: Journal of Korean Powder Metallurgy Institute Vol. 12(2005), p.122-130
[7] Y. J. Moon, J. Y. Choi, B. A. Kim and C. K. Moon: Journal of the Korea Society for Power System Engineering
Vol. 14(2010), p.68-75
[8] Y. I. Tae, Y. S. Yun and O. H. Kwon; Jornal of the KIIS Vol. 17(2002)
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Time : 13.40 13.55
[9] G. Y. Jeong: The Mineralogical Society of Korea Vol. 24(2011), p.111-118

[10] N. C. Larissa, S. D. Tales, V. S. Gabriel, S. C. Janaina and S. M. Raquel: Applied Clay Science Vol. 87(2014),
p.311-319
[11] S. R. Ha and K. Y. Rhee: Korean Society for Precision Engineering (2006), p.507-508
[12] J. H. Park and J. Y. Kim: International Journal of Aeronautical and Space Sciences Vol. 30(2002), p.88-93
[13] M. Y. Ku, J. H. Kim, H. Y. Kang and G. W. Lee: Trans. Korean Soc. Mech. Eng. A Vol. 37(2013), p.657-664
[14] J. H. Kim and D. H. Kim: Journal of Academia-industrial Technology Vol. 14(2013), p.2544-2549
139
Session 6D : Synthesis, Characterization and Applications - VI

Scientific Director,
Institute de Sciencia Molecular Universidad ,
Valencia, Spain
Research Area
His research career has been devoted to the design and synthesis of new molecular
materials with magnetic, electrical and optical properties.
Qualification
Ph.D., Aerospace Engineering,Indian Institute of science, Bangalore, India, 1996
No. of Publications
550
Awards & Honors
European Research Council awards Prof. Eugenio Coronado's scientific excellence

with the advanced grant
(Eugenio Coronado will receive for the development of this Project an amount of
approximately two million Euros. Around 1.500 European researchers applied to this
call,and only less than one hundred have obtained an Advanced Grant )
Coronado is the first Spanish chemist to be granted with this funding, coming from
program IDEAS of 7FP
His research career has merited several prizes and distinctions, such as:
Premio Nacional de Investigacin Cientfico-Tcnica Rey Juan Carlos I,1997
Ctedra Van Arkel de la Universidad de Leiden,2003
Premio Rey Jaime I de Nuevas Tecnologas,2003
Fellow de la Royal Society of Chemistry,2004
Premio Nacional de Investigacin, rea de Ciencias Fsicas, Materiales y de la Tierra,
otorgados por el,2009
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Time : 13.40 13.55
Smart molecular materials: From bulk materials to nanomaterials.

Responsive materials for which physical or chemical properties can be tuned by applying an external stimulus
are attracting considerable interest in materials science. This kind of materials may be viewed as a new
generation of multifunctional materials in which two (or more) functional properties are not simply co-existing
in the same material but strongly coupled to guaranty its response to the external stimulus.
A molecular-based building block approach has provided appealing examples of such systems, in particular at
the single-molecule level, as is the case of bistable catenane and rotaxane molecules. These interlocked
molecules are able to perform controlled mechanical motions in solution and therefore they have been proposed
to be an ideal platform for the design of molecular nanodevices displaying mechanical, electronic, information
or sensing functions. However, these applications in molecular electronics are strongly limited by the need to
interface these functional molecules with the macroscopic world. Thus, an active focus of research in this area
involves the organization of these molecules on surfaces, interfaces or solid matrices.
Another source of stimuli-driven molecular materials results from the construction of hybrid solids formed by
inserting a responsive molecule into a functional network. In this last case the structural or electronic changes
induced in the responsive molecule by the applied stimulus can result in a change in the structure and properties
of the functional network.
Here we will illustrate how this molecular approach can be used to design a new generation of smart materials
in which their magnetic properties can be tuned by applying an external stimulus. We will present the effects on
the magnetic properties of physisorption of molecules as chemical stimulus, and light, or temperature as physical
stimuli. These examples will be taken from our own research and will cover from bulk materials to nanomaterials.
Molecule-based magnetic materials responding to a chemical stimulus.
Coordination chemistry has allowed the engineering of materials having novel topologies and remarkable
properties. An appealing example is provided by the porous coordination polymers, also known as metal-organic
frameworks (MOFs). These materials contain pores that can be filled by molecules and therefore can accept /
release molecules. These processes can induce structural changes in the coordination framework. The result will
be a dynamic material undergoing reversible structural changes to respond to the applied stimulus [1]. Taking
advantage of this feature we have prepared a series of spin-crossover MOFs able to adsorb gas molecules. These
compounds are based on flexible organic ligands containing two tetrazole units linked by an organic bridge to
coordinate Fe(II) centers. In octahedral environments and weak crystal fields this metal ion can change its ground
spin state from the low-spin configuration, S = 0, to the high-spin one, S = 2, under the influence of diverse
external physical stimuli (temperature, light or pressure). In the present case the crystalline material shows a
chain structure that contain void pockets of nanometric size, which can be filled by CO2. Interestingly, the
presence of this molecule in the pores produces a change in the spin transition temperature, which is shifted by
8K. That is due to the interaction of the adsorbed CO2 molecule with a nitrogen atom of the tetrazole ligand,
which is sufficient to affect the crystal field around the Fe(II) thus affecting the spin crossover temperature.
Hence, we have shown here that a chemical stimulus (sorption of a molecule) is able to affect the magnetic
properties of the material, thus making these magnetic MOFs suitable for sensing of gases [2].
Photo-responsive magnets: Hybrid magnetic materials formed by inorganic layers and photochromic
molecules.
Layered double hydroxides (LDHs) are formed by positively charged sheets built up from the interconnection of
octahedrally coordinated metal ions via 2-hydroxide bridges. Rational choice of these transition metal ions
permits producing magnetic layers with behaviors ranging from ferro- to ferrimagnetic. The overall positive
charge of the [M1-xIIMxIII(OH)2]+x sheets is balanced by anions occupying the interlamellar space that can be
exchanged under mild conditions. This enables chemical design of a broad range of hybrid functional materials
by deliberate choice of the guest whose physical properties can be then combined with the intrinsic magnetism
of the host leading to a superstructure in which both properties coexist and can even interact.
141
Session 6D : Synthesis, Characterization and Applications - VI
In this context, the introduction of anionic photo-switchable molecules in the interlamellar space of the LDH host
can produce a photoresponsive material whose magnetism can be reversibly tuned with light through the
switching of the guest molecule [3]. As photo-switchable molecules we have chosen azobenzenes as these
molecules undergo photo-induced trans-cis isomerization in solution upon UV light irradiation. Concretely, we
have intercalated trans-azobenzene-4,4'-dicarboxylic acid molecules in a ferromagnetic CoAl-LDH. We have
observed that the magnetism of the host is substantially modified upon light irradiation as result of the partial
photo-isomerization of the guest to the corresponding cis isomer. Thus, exposure to UV light triggers a
compression of the layered structure of the hybrid as result of the guest's isomerization, causing a drop of the
magnetization close to 27% at 2K and an increase in the TM of ca. 1K. This photo-induced change can be reverted
by exposure of the solid to water, thus enabling reversible switching of the magnetism of the solid.
Electrically-driven spin-crossover at the nanoscale
As we have already pointed out above, SCO materials constitute an extensive class of molecule-based responsive
materials in which their ground spin state can be switched from low-spin to high-spin near room-temperature.
Despite the fact that the SCO phenomenon is purely molecular, most of the works devoted to these materials
were focused on their bulk properties. Still, it can be of interest to take advantage of this switching phenomenon
at the nanoscale to prepare electronic devices. Very recently we succeeded in electrically addressing this kind of
SCO materials at the nanoscopic level [4]. This was achieved in nanoparticles of down to 10 nm in size based on
the polymeric one-dimensional (1D) family ([Fe(Htrz)2(trz)](BF4)), (Htrz = 1,2,4-triazole), which is one of the most
promising SCO systems for designing electronic devices working at room temperature. In these singlenanoparticle devices we observed a change in the electrical conductance by a factor of 4 when the spin changes
from low spin to high spin. Interestingly this change is accompanied by a thermal magnetic hysteresis near room
temperature. We also observed that not only the temperature can be used to switch the spin state. Keeping the
temperature constant, an electric field is also able to trigger this spin change, opening the possibility of using
these SCOs nanomaterials in spintronics.
References
[1] E. Coronado, G. Minguez Espallargas. Chem. Soc. Rev. 45, 1525-1539 (2013)
[2] E. Coronado, M. Gimenez-Marques, G. Minguez Espallargas, F. Rey, I. J. Vitorica-Yrezabal J. Am. Chem. Soc.135,
15986-15989 (2013)
[3] G. Abelln, E. Coronado, C. Mart-Gastaldo, A. Ribera, J. L. Jord, H. Garca Adv. Mat. 26, 4156-4162 (2014).
[4] F. Prins, M. Monrabal-Capilla, E.A. Osorio, E. Coronado, H.S.J. van der Zant, Adv. Mater. 23, 11545 - 1549 (2011).
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Nanocon 012
Dr. Christopher Kepley delivering the keynote address.
143
Dr. Jatinder Yakhmi

Former Associate Director, Physics Group,
Bhabha Atomic Research Centre (BARC),
Trombay, Mumbai
Email : yakhmi@barc.gov.in
Research Area
Molecular Magnets
Self-assembly
Polymers
Nano-phase materials
Surfactants
Liquid Crystals
Qualification
Ph.D. in condensed matter physics from Bombay University
No. of Publications
400
Invited Lectures
Over 350
Awards & Honors
He serves as Member of several Expert Advisory Committees of Govt. funding

agencies like DST, DBT and DRDO.
He is a Fellow of National Academy of Sciences and an elected Member of Asia Pacific
Academy of Materials.
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'NANO' and 'BIO' for movement and life

Dr. Jatinder Yakhmi
ABSTRACT
In the 21st century, the quest for new functional materials is moving increasingly from conventional hightechnology materials like steel and plastics towards the study of the large variety of remarkably robust and
hierarchical materials used by Nature in the living world. The living world invariably means spontaneous,
autonomous movement. To impart movement, we humans have a long-held obsession with wheels, pulleys,
gears, etc., whereas Nature does not use wheels! How does Nature manage this?
Bio-materials with diverse characteristics are produced by Nature by adopting different arrangements and
combinations of the same universal motifs. These materials mostly belong to the category of soft condensed
matter built from nano-scale building blocks. The basic unit of life - a cell manufactures its internal structure to
grow, and cells can reproduce by mitosis, cells maintain a resting electrical potential difference between their
interiors and the outside world, ells can sense internal/environmental conditions, and then do proper feedback.
Most of all, the cells can move by crawling/swimming. With the increasing availability of new tools to investigate
the structure of all forms of matter at the smallest levels (sub-nano scale), there are attempts, obviously, to
examine if one could design autonomous active matter, with capability of self-propulsion, using nature's
principles of self-assembly and self-organization. For this, one has to first understand that living organisms
survive due to homeostatic abilities (control of their body T, BP, pH and sugar levels), achieved via interconversions of chemical and mechanical energy, and self-regulating feedback loops. But with limited unidirectional chemo-mechanical or mechano-chemical modes, synthetic materials cannot perform selfmonitoring/self-regulating behaviour due to their limitation to do chemo-mechano-chemical conversion of
energy. Can we create self-regulating, homeostatic materials which provide precise chemo-mechano-chemical
feedback loops at nano/micro scale? Perhaps yes. Using bilayers with hydrogel-supported, catalyst-bearing
microstructures, Aizenberg's group at Harvard University have evolved a strategy to create self-regulating, selfpowered, homeostatic materials capable of precisely tailored chemo-mechano-chemical feedback loops on the
nano- or micro-scale [1].
Very recently, there have been encouraging reports on successful efforts to create life (a living organ) or the
equivalent of a carrier of movement in the biological world. For instance, for the first time, an entire complex
living organ, which is organized and functional has been grown from lab-created cells at University of Edinburgh
[2] - a thymus, an organ next to the heart that produces immune cells, called T cells, which guard against disease,
grown from cells that were created outside of the body by reprogramming. Similarly, scientists at the Kiel
University [3] have constructed molecules that wiggle, to imitate cilia, the tiny, hair-like structures, which move
bacteria along. To make these molecular cilia up and running, they were fixed on a surface. Making of artificial
cilia epithelium raises possibilities of the creation of autonomously moving artificial organelles.
With many applications in diverse areas, the field of robotics, is throwing up a spate of developments in the manmade movement. Development of artificial flexible electromechanical actuators is possible using conducting
polymers [4]. Therefore, an obvious question comes - can one design multi-tasking autonomous robots with
flexible actuators? A controlled flight of a biologically inspired, insect-scale robot has been recently
demonstrated [5], raising the vision for achieving artificial insect-like flight. Building blocks of bio-materials
combine "protein-toughness" + the "mineral-stiffness". This has recently brought into emergence a new field
called Materiomics, bordering on materials science/engineering and biology, which essentially aims at
developing new materials a la Nature, using the principles of self-assembly, self-repair and self-organization to
develop hierarchical structures from colloids, polymers or amphiphilic materials. One can also draw on the vast
repertoire of Nature to fabricate or design new materials, such as the use of DNA as a template [6]. Can the
hierarchically assembled materials become Active Matter, exhibiting spontaneous motion? This points essentially
to a materials problem, which can be split into parts sequentially: (i) to produce materials which can resist fracture
by arresting the propagation of cracks, and can self-repair and regenerate themselves; (ii) to design materials
which combine the toughness of proteins and stiffness of minerals; and finally (iii) to create self-regulating,
homeostatic materials which finally lead to movement and life. Progress at different levels has been made on all
145
these fronts as discussed below.

Synthetic self-propelled colloids have been prepared recently using Janus particles. These are propelled by
chemical reactions on their surfaces, for instance Janus polystyrene spheres half coated with platinum are motile
in an aqueous solution of H2O2. In order to study active and collective phenomena like self-organization, a
suspension of synthetic photoactivated colloidal particles were prepared where rapid control of particle selfpropulsion as a nonequilibrium activity can be distinguished from thermal Brownian motion. And the result was
2-D "living crystals," which form, break, explode, and re-form elsewhere [7]. Active materials, like water-in-oil
emulsion droplets, have been shown to exhibit spontaneous autonomous motility and self-sustained flows when
partially compressed between chamber surfaces, in the absence of external forces - a hallmark of living systems,
[8] because they get liberated from equilibrium constraints, and attain tunable properties of far-from-equilibrium
materials. A self-organized rotating bacterial spiral coils built from bacterial swarms showed motility [9]. A selfpropelled synthetic (bio-hybrid) swimmer has been fabricated from polydimethylsiloxane (PDMS) filament and
cardiomyocytes [10], which swims at 5-10 ms-1. The construction of in vitro assemblies exhibiting properties of
living matter is also useful to shed light on the dynamic reorganization that continuously occurs inside cells.
There have been successful attempts to imitate the heart movement in the lab using external forces, but not in
an autonomous manner [11]. This is unlike the Self-regulated Intelligent Systems (SIS) which exhibit autonomous,
reversible and periodical variations without any external stimuli, such as in heartbeat, brain waves, pulsatile
secretion of hormones, and biorhythms. The self-regulated state is sustained over a long period of time outside
the thermodynamic equilibrium. Self-oscillating smart polymers and gels have recently been developed utilizing
chemical oscillators based on the Belousov-Zhabotinsky (BZ) reaction [12-15].
An autonomous amphiphilic assembly has been reported which is driven by a pH-oscillator exhibiting
vesicle/micelle transition [16]. A synthetic DNA walker has also been fabricated that transports nanoparticles
one-dimensionally along SWCNT tracks, coated with RNA molecules [17]. Finally, Schindler et al [18] have
fabricated 3-headed and 4-headed myosins which show processive motion at speeds 10m s-1, higher than
natural 2-headed myosin motors can do.
REFERENCES
[1]. He, Aizenberg, Kuksenok, Zarzar, Shastri, Balazs and Aizenberg, Nature 487 (2012)
214-218
[2]. Bredenkamp, Ulyanchenko, O'Neill, Manley, Vaidya and Blackburn, Nature Cell
Biology, 16 (2014) 902-908.
[3]. Tellkamp, Shen, Okamoto and Herges, Europ. Jl. of Org Chem., Issue 25 (Sept.
2014) 5456-5461
[4]. Sutar, Aswal, Gupta and Yakhmi Jl. of Pure and Appl. Phys 45 (2007) 354
[5]. Ma, Chirarattananon, Fuller and Wood, Science, 340 (2013) 603-607.
[6]. Bagkar, Choudhury, Bhattacharya and Yakhmi, J. Phys. Chem. B 112 (2008) 6467-6472
[7]. Palacci, Sacanna, Steinberg, Pine and Chaikin, Science, 339 (2013) 936-940
[8]. Sanchez, Chen, DeCamp, Heymann and Dogic, Nature, 491 (2012) 431-434
[9]. Lin, Lo and Lo, Soft Matter, 10 (2014) 760-766
[10].Williams, Anand, Rajagopalan and Saif, Nature Commun., 5:3081 (published 17 Jan 2014) DOI:
10.1038/ncomms4081
[11]. Yusuf, Balakrishnan and Yakhmi, US Patent US/2012/0323318A1, filed on: 03-03-2010. Published on Dec 12,
2012 International Publication No. WO2011/107996A1, dated 09-09-2011
[12]. Zhou, Ding, Zheng and Peng, Soft Matter, 9 (2013) 4956-4968
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Time : 14.35 14.50
[13]. Zhou, Liang, Ding, Zheng and Peng, Chem. Comm., 48 (2012) 10553-10555;
[14]. Suzuki, Kobayashi, Yoshida and Hirai, Soft Matter 8 (2012) 11447-11449.
[15]. Yoshida and Ueki, NPG Asia Mater. (2014) 6, e107, doi:10.1038/am.2014.32
[16]. Lagzi, Wang, Kowalczyk, and Grzybowski, Langmuir 26 (2010) 13770-13772
[17]. Cha, Pan, Chen, Salgado, Li, Mao and Choi, Nature Nanotechnol., 9 (2014) 39-43
[18]. Schindler, Chen, Lebel, Nakamura and Bryant, Nature Nanotechnol. 9 (2014) 33-38
147
Session 7A : Synthesis, Characterization and Applications - VII

Principal Investigator,
Nanocatalysis Laboratories,
Reader, Division of Chemical Sciences,
Tata Institute of Fundamental Research (TIFR), Mumbai.
Email: vivekpol@tifr.res.in
Research Area
Advanced nano-materials.
Nanocatalysis.
Green chemistry.
Qualification
Ph.D. from Jiwaji University, Gwalior, 2005
No. of Publications
75
Awards & Honors
Asian Rising Stars Award at 15th ACC, Singapore, from Nobel Laureate Professor
Ei-ichi Negishi,2013
Top-25 Cited Author in 2011 by Tetrahedron.2011
Young Scientist Award at DSL-2012.
Marie Curie Fellowship (not accepted due to my prior commitment to KAUST),2009
Scientific & Technology Achievement Award (special mention in green chemistry, by
US-EPA).2009
ORISE Research Fellowship (for the development of independent scientist by ORISE
& US-EPA).2007-2010
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Time : 16.30 16.45
Nanocatalysis for Sustainable Energy and Green Environment

Catalysis is becoming a strategic field of science since it represents a new way to meet the challenges of energy
and sustainability. These challenges are becoming the main concerns of the global vision of the societal
challenges and world economy. The societal pressure has been at the origin of the concept of sustainable
chemistry which is becoming a leitmotiv in any important project dealing with this strategic domain of science.
Catalysts are chemical substances that enable the transformation of fine chemicals into value-added chemical
products or synthetic materials. Catalysts are traditionally divided into two major groups based on the type of
phase of the catalyst is in relative to the catalytic reaction mixtures, i.e., homogeneous or heterogeneous
catalysts. Homogeneous catalysts are those that exist in in the same phase as the reactants. They are generally
soluble organic or organometallic complexes and often give chemo-, regio- and stereo-selective products.
However, they are relatively difficult to separate from reaction mixtures for reuse at the end of reactions. On the
other hand, there are solid or insoluble catalysts, also called heterogeneous catalysts. In many instances, the solid
catalysts contain homogeneous catalysts supported on neutral or catalytic-active solid support materials such as
porous silica or alumina. These types of catalysts are easily separable and reusable at the end of reactions;
however, they often give relatively poor reaction yields, compared to many of their homogeneous counterparts.
Thus, the catalyst which can bridge homogeneous and heterogeneous system is needed (Figure 1).
(Figure 1)
The fields of nanotechnology have been unquestionably thriving over the last few decades. One of the most
stimulating features of nanotechnology is its potential use in almost any field. The discovery of nanoparticles
with varied size, shape and composition has stretched the limits of technology in ways that scientists would never
5
have dreamt of a century ago. Nature makes and chemistry re-shapes; huge varieties of nanoparticles have
emerged in our daily life, in every field from drugs and electronics to paints and beauty care, and they are now
emerging in the field of catalysis, nanocatalysis.
Nanocatalysis can thus be simply defined as the use of nanoscale materials in catalysis. Nanocatalysts are highly
active (like homogeneous system) and also easy to recover/reuse (like heterogeneous system). In other words,
nanocatalysts exhibit quasi-homogeneous or quasi-heterogeneous catalytic properties, and thus allow for rapid
and selective chemical transformations, with excellent product yield and ease of catalyst separation and recovery.
It has also made the greening of chemistry possible. In addition to the size, nanocatalysts are extremely shape
sensitive and their catalytic efficiency and selectivity dramatically depend on their shape and morphology (Figure
2). The concept of nano-catalysis, which makes the catalysis science even more creative, has become integral part
1-4
of sustainability.
149
(Figure 2)
Accessibility of surface area plays the major role in nano-catalysis, and generally this surface area is due to pores
and not easily accessible. Silica's like SBA-15 or MCM-41 are generally used as a support and the effectiveness
of these materials as catalyst supports is mainly due to their microstructures, which allow active catalytic sites to
disperse on the large internal surfaces and pores, which in turn improve the activity of the catalyst system.
However, high surface areas of these materials are due to the pores, which are not always accessible and can also
get blocked during catalysts preparation (Figure 3). Poor accessibility to the active sites inside these pores
sometimes limits their applications for which significant mass transport is essential. Therefore, to design better
nanocatalysts, with higher accessibly and thus higher activity, we need a new support material which could have
high surface area and also which could preserveitsaccessible surface area even after coating or functionalization
during catalyst preparations.
(Figure 3)
In this regard, recently we discovered new high-surface-area silica (KCC-1) made of nano-spheres with
unprecedented fibrous morphologies.6Its high surface area is due to dendritic silica fibers and their respective
channels and not due to the pores. It is clear from their SEM and TEM images (Figure 4), that these fibers are
easily accessible from all the side and hence any active sites on them will also be accessible. Notably, this material
exhibits excellent physical properties, including a high surface area, a fibrous surface morphology, a good
thermal and hydrothermal stabilities and a high mechanical stability.
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Time : 16.30 16.45
(Figure 4)
KCC-1 can be very useful as catalysts support, wherein accessibility of active sites can be increased significantly.
In order to prove this, KCC-1 has been tested as support in a variety of catalytic systems, particularly TaH/KCC1,7 Pd/KCC-1,8 and Ru/KCC-1.9 In all these systems we did observed that use of KCC-1 support is advantageous
in terms of activity and stability of catalysts, as compared to SBA-15 or MCM-41 support. However, none of these
clearly prove the advantage of fibrous nature of KCC-1, as in all these catalysts system, in addition to role of
surface area, other reaction components such as shape and size of active metal nanoparticles or use of hydrogen
gas (in TaH system) also played the role. Thus, there was a need to prove this concept by conducting the reaction
which fully depends on surface area accessibility only.
We developed novel solid base by ammonolysis of KCC-1 and showed the advantages of its fibrous morphology
and highly accessible surface area. Ammoniated KCC-1 was found to be very active and robust base, for
Knoevenagel condensation of challenging substrates, which is not possible using most of the the nitridated
bases. It even showed multifold better activity than recently reported active base, Me-NSBA. This enhancement
in activity was explained on the basis of accessibility of amines, which is excellent in KCC-1 due to its open and
flexible fibrous structure (unlike MCM-41 or SBA-15) which helps substrates to easily penetrate and interact with
basic amine sites, which in turn accelerate the overall reaction.10
These materials were also evaluated for the first time as sorbents for CO2 capture. They exhibit the following
advantages over conventional amine-grafted silica: 1) good CO2 capture capacity; 2) faster kinetics; 3) easy
regeneration and efficient reuse of sorbents; 4) excellent mechanical strength; 5) high thermal stability in inert
and oxidative environment and 6) clean and green material synthesis and less expensive production costs, which
allows the overall process to be sustainable.11
References:
1.
"Nanocatalysis: Synthesis and Applications", Eds Vivek Polshettiwar and Teddy Asefa; 2013, ISBN: 978-1-11814886-0, by WILEY. http://eu.wiley.com/WileyCDA/WileyTitle/productCd-111814886X.html
2.
Magnetically Recoverable Nano-Catalysts. Vivek Polshettiwar,* R. Luque, A. Fihri, H. Zhu, J. M. Basset, Chem.
Rev.2011, 111, 3036- 3075
3.
Green Chemistry by Nano-catalysis. Vivek Polshettiwar* and R. S. Varma, Green Chem. 2010, 12, 743-754
4.
Nano-Catalysis for Suzuki Coupling Reaction. A. Fihri, M. Bouhrara, B. Nekoueishahraki, J. M. Basset, Vivek
Polshettiwar,*Chem. Soc. Rev. 2011, 40, 5181-5203.
5.
Self-assembly of metal oxides into 3D nano-structures: Synthesis and nano-catalysis. Vivek Polshettiwar,*
Babita Baruwati, and R. S. Varma, ACS Nano 2009, 3, 728-736.
6.
High Surface Area Silica Nanospheres (KCC-1) with Fibrous Morphology. Vivek Polshettiwar,* D. Cha, X. Zhang
and J. M. Basset, Angew. Chem. Int. Ed. 2010, 49, 9652-9656.
151
7.
"Hydro-metathesis" of Olefins: A Catalytic Reaction using a Bifunctional Single-Site Tantalum Hydride Catalyst
Supported on Fibrous Silica (KCC-1) Nanospheres. Vivek Polshettiwar,* Jean Thivolle-Cazat, M. Taoufik, F.
Stoffelbach, S. Norsic, J. M. Basset, Angew. Chem. Int. Ed. 2011, 50, 2747-2751.
8.
Fibrous Nano-Silica (KCC-1) Supported Palladium Catalyst: Suzuki Coupling Reactions under Sustainable
Conditions. A. Fihri, M. Bouhrara, D. Cha, Vivek Polshettiwar,*ChemSusChem, 2012, 5, 85-89.
9.
Fibrous Nano-Silica Supported Ruthenium (KCC-1/Ru): A Sustainable Catalyst for the Hydrogenolysis of
Alkanes with Good Catalytic Activity and Lifetime. A. Fihri, M. Bouhrara, D. Cha, Y. Saih, U. Patil, Vivek
Polshettiwar,* ACS Catalysis 2012, 2, 1425-1431.
10.
Nitridated Fibrous Silica (KCC-1) as a Sustainable Solid Base Nanocatalyst. M. Bouhrara, C. Ranga, A. Fihri, R.
Shaikh, P. Sarawade, A. Emwas, M. N. Hedhili, Vivek Polshettiwar*,
ACS Sustainable Chemistry and
Engineering, 2013,, 1, 1192.
11. Silicon Oxynitrides of KCC-1, SBA-15 and MCM-41: Unprecedented Materials for CO2 Capture with Excellent
Stability and Regenerability. U. Patil, A. Fihri, A. Emwas, Vivek Polshettiwar,*Chemical Science, 2012, 3, 22242229
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Nanocon 010
Dr. Anand Bhalerao discussing future of NANOTECHNOLGY with Dr. Dan Davis.
153
Session 7B : Nanocomposites-III
Dr. Masao Nagase

Professor,
Department of Electronic Engineering,
2-1, Minami-josanjima-cho, Tokushima,
770-8506 JAPAN
Email : nagase@ee.tokushima-u.ac.jp
Research Area
Semiconductor device,
Nanostructure,
Silicon,
Graphene,
Nanometrology
Qualification
Ph.D., in nanometrology for nano devices from Waseda University, TOKYO, 1997
No. of Publications
More than 135
International
Conference
26
Domestic Conference
39
Awards & Honors
Member of the Japan Society of Applied Physics (JSAP)

MNC 2006 Paper Award (Most Impressive Presentation) (20nd International
Microprocesses and Nanotechnology Conference), Nov. 2007,
MNC 2008 Award for Outstanding Paper (22nd International Microprocesses and
Nanotechnology Conference), Nov. 2009,
Books
154
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Graphene on SiC substrates fabricated by an infrared rapid thermal annealer

Dr. Masao Nagase
ABSTRACT
Large-scale single-crystal graphene is necessary for the future of graphene-based electronics. Epitaxial graphene
on silicon carbide (SiC) substrates is one of the most promising candidates for wafer-scale graphene. Large area
graphene with minimal roughness was successfully fabricated using infrared rapid thermal annealing. A surface
structure control technique was established to create a uniform single-crystal monolayer of graphene on a SiC
substrate. A 10 mm x 10 mm monolayer graphene sample was fabricated. Electrical contact properties of
graphene layers were investigated using stacked structures of two graphene samples. The graphene-graphene
contact conductance was varied by changing the contact area of the stacked layers. Contact properties between
graphene and a metal electrode were also investigated using scanning probe microscopy (SPM). It was found
that contact conductance was drastically altered by the scanning probe at the edge of the atomic step on the
5
SiC substrate. A conductance on/off ratio induced by the step structure was approximately 10 . This "atomic layer
switching" phenomena may be useful to realize graphene nano-electro-mechanical switch systems.
Keywords: graphene; SiC; single-crsytal; contact conductance;
1. Introduction
Graphene has is being widely researched because it exhibits many useful properties. It has the potential for
extremely high carrier mobilities that can be 100 times higher than those of silicon. For future post-silicon
technology, wafer-scale single-crystal graphene is desired. Epitaxially grown graphene on a SiC substrate is the
only candidate for large-area single crystals. In this paper, we discuss the fabrication of graphene on SiC using
an infrared rapid thermal annealer (IR-RTA).
2. Graphene on SiC
Fabrication of epitaxial graphene on a SiC substrate is simple. Single crystal SiC is subjected to high temperature
annealing in an inert atmosphere (Ar). Thermal decomposition of SiC at high temperatures causes desorption of
silicon atoms from the SiC surface, and the carbon atoms that remain on the surface form the graphite network.
Single-crystal graphene is epitaxially grown on the Si-face of the SiC substrate, such as 6H-SiC(0001) and 4HSiC(0001). The Si-face 4H-SiC is preferred for controlling the surface morphology during the annealing process.
In this work, we used an infrared rapid thermal annealer to fabricate the graphene samples to achieve precise
control of the temperature profiles. Figure 1 shows a photograph and schematic of the IR-RTA system. The heat
source is a 2-kW infrared lamp on one focus of the spheroidic gold mirror, and the sample is placed on the other
focus of the mirror. The maximum temperature of this system is 2000oC. The maximum rate of temperature rise
is approximately 10oC/sec around 1600oC. The annealing atmosphere was controlled using a vacuum pump and
gas flow system. Typical annealing temperature profiles are shown in Fig. 2. The maximum sample size is limited
by the size of the fused silica tube. Typically, a 10 mmx10mm sample cut by a laser dicer is used. Figure 3 shows
the annealed sample whose surface is covered with single-crystal monolayer graphene.
Figure 3 shows scanning probe microscopy (SPM) images of monolayer graphene. Well-aligned step-terrace
structures originating from the crystallographic nature of the SiC substrate are observed in the topographic SPM
image (Fig. 4(a)). No bi-layer graphene signature is observed in the phase image (Fig. 4(b)). Microscopic Raman
mapping of full width at half maximum (FWHM) of the 2D graphene peak (Fig. 5) indicates that the sample
surface is covered with a homogeneous monolayer of graphene. The key for obtaining uniform monolayer
epitaxial graphene on SiC is step height control. The height of the step structures must be less than 1 nm for
elimination of bi-layer graphene regions.
155
Figure 1
Figure 1. Infra-red rapid thermal annealer from Thermo-Riko. (a) Photograph; (b) Schematic.
Figure 2
Figure 2. Temperature profiles of annealing for graphene growth.
Figure 3
Figure 3. 100mm2 single-crystal graphene on SiC substrate
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Time : 16.30 16.45
Figure 4
Figure 4. Scanning probe microscopy images of uniform monolayer graphene. (a) Topography, (b) Phase image.
Figure 5
Figure 5. Microscopic Raman mapping results of 2D peak full-width at half maximum of monolayer graphene on SiC.
3. Electrical contact properties of graphene on SiC

The electrical contact properties of graphene for conductive materials are important for device applications. The
contact resistance between graphene and metals is very high compared to that between silicon and metals.
Therefore, graphene-graphene and graphene-metal contact properties are investigated.
The electrical characteristics of a graphene-graphene junction are measured using stacked graphene layers. Two
graphene samples are placed in contact with each other with a rotation angle of 45o, as shown in Fig. 6(a). The
stacked samples are attached face-to-face, and four contact probes are placed on the sample surface. Since the
samples are slightly distorted by the contact probes, the contact area is limited to the center of the samples. As
shown in Fig. 6(b), the characteristics of graphene-graphene junction are ohmic. By changing the contact force
between two stacked samples, the contact resistance can be controlled, as shown in Fig. 6(b). The graphene on
SiC is naturally electron doping via substrate effects. From this view point, a graphene n-n junction device is
successfully fabricated using the direct bonding technique. If a p-type sample is used for one side of the stacked
samples, a graphene p-n junction would be realized.
Characteristics of graphene-metal nanojunctions are measured using conductive SPM. An interesting
phenomena referred to an "atomic layer switching" is found. The contact resistance between graphene and the
metal probe is changed when the probe passes the step-edge of the graphene on the SiC. Figure 7(a) shows an
SPM current image taken using a Rh coated conductive probe. The conductance of the region on the left side is
low (dark), while that on the right side is high (bright). As shown in the topographic image (Fig. 7(b)), the
electrical conductance boundary corresponds to the step edge. The current switching phenomena at the step
edge occurs for all scan lines in the conductance image. A buckled graphene structure is induced using a metal
157
probe scanning in a downward motion across the step structure, as illustrated in Fig. 7(c). This formation of
buckled nanostructure is caused by compressive stress in epitaxial graphene may be a possible explanation for
the "atomic layer switching" behavior. The on/off ratio of the switch is stable and reaches value on the order of
5
10 . Graphene nano-electro-mechanical system (NEMS) switches with a high on/off ratio can be realized by using
simple structures comprising graphene on SiC and metal nanoelectrodes.
Figure 6
Figure 6. (a) Four-probe measurement configuration of stacked graphene device. (b) Current vs. voltage characteristics of
the device. The contact area of the stacked graphene was controlled by applying force on the center of the sample.
Figure 7
Figure 7. (a) Contact conductance (current) image of graphene on SiC taken using a Rh coated conductive probe. (b)
Topographic image of the same area of conductance. (c) Schematic of "atomic layer switch".
4. Summary
We have successfully grown large area (100mm2) monolayer single-crystal graphene on a SiC substrate. Step
height control using IR-RTA is the key for eliminating bi-layer graphene regions. The electrical contact
characteristics of the graphene-graphene system and graphene-metal system are discussed. Ohmic contact is
observed for stacked structures consisting of two graphene samples. The contact conductance between
graphene and nanoprobe exhibits a bi-stability near step edges.
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Time : 16.30 16.45
Nanocon 012
Dr. Anand Bhalerao felicitating Dr. Yeshayahu (Ishi) Talmon.
159
Session 7C : Nanoelectronics-VI
Dr. Pawan Khanna

Dean, Academics
Defense Institute of Advance Technology,
( Deemed University) Girinangar,Pune
E-mail:khannap@diat.ac.in
Research Area
New Chemical strategies for developing nanomaterials/quantum dots via direct and
molecular precursor route. Nanotechnology via solution chemistry targeting particles
dimension of <10 nm.
Synthesis of quantum dots of semiconductor and their applications in energy devices,
photonics and bio-nanotechnology, development of hydrophilic and magnetic
quantum dots
Applied research on Organometallic chemistry of selenium and tellurium
R&D in Nano-chemistry via Inorganic and Organometallic chemistry
R&D on Nano-particles of metals and their chalcogenides
R&D on inorganic/polymer Nano-composites e.g. QDs/metal/polymer
Synthesis of Nano-particles by use of biomolecules
Sol-Gel Chemistry (mostly for Nano-oxides)
Metal Nano-particles for petroleum energy
Green chemistry for Nanotechnology
No. of Patents
10
No. of Publications
105
26
Domestic Conference
39
Awards & Honors
Best Entrepreneur Award, British Council, India, 2008-09

Materials Research Society of India (MRSI) Medal-2010
Editorial Board Member of International Journal on Green Nanotechnology: Physics
and Chemistry (Taylor and Francis, USA)
Guest Editor of Special issue of 'Journals Synthesis and Reactivity in Inorganic, MetalOrganic and Nano-Metal Chem.' (Taylor & Francis, USA) vol. 37(1/2), 2007.
Expert group member of Department of Biotechnology (DBT) Govt. of India, core
committee on Nanobiotechnology (2006-2011)
Expert group member of Department of Biotechnology (DBT) Govt. of India, core
committee for setting up of Nanobiotechnology center at IIT Guwahati (2008-2013)
Member, Academic Board of Viswakarma Inst.Tech.(VIT), Pune
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Time : 16.30 16.45
NANO-STRUCTURED MATERIALS- THE CHEMICAL WAY

Quantum Dots and Metal-Polymer Nanocomposites
Dr. Pawan Khanna
The nanotechnology has taken over the lime light in applied science and technology. Today, there are large
number of researchers across the globe practicing nanotechnology by various methods and in many directions.
Nanotechnology considered as a broad area that includes nanochemistry, nanophysics and nanodevices thus
bringing in scope for different subjects to come together e.g. chemists to designe and produce nanomateirals,
physicists to study their properties and engineers to fabricate devices that can be used in different areas of
science and technology including medical field. Chemists have been smartly altering the design and properties
of nano-particles of range of types and characterisitics e.g. surface capping to alter their behaviour, core elements
to alter their physics and combining the tiny particles with other reagents and materials to build new types thus
the chemists have played crucial role to be able to provide what it needs to develop the field of nanotechnology.
The present article and presentation from it will focus on the chemical methods for desigining and producing a
range of nano structured materials such as semiconductor nano-particles called as quantum dots and magic-size
clusters from them, oxide nano-particles, metal nano-particles and their polymer nano-composites.
Quantum dots (QDs) are inorganic nanocrystals composed of elements from various groups from the periodic
table thus generating compound semiconductors of type II-VI, IIIV, and IV-VI with sizes of approxima 2-20 nm. As a result of these sizes, QDs show size-tunable optical properties
1-3
based on their absorption and emission behaviours due toquantum confinement effect. Quantum dots have
5,6
potential application in various fields viz; photovoltaics e.g. solar cell4, light emitting diodes , quantum
computation, flat panel displays, memory elements, photo detectors, and lasers. Additionally, great applications
are expected in the areas such as in catalysis, coatings, textiles, energy storage, biotechnology, health care,
7,8,9
11,16
biomedical and pharmaceutical industries including bio-sensors and bio-imaging
. Uses of quantum dots
with the help of quantum physics and neuroscience, to control brain cells could one day offer a non-invasive
10
treatment for disease similar to Alzheimer's, depression and epilepsy . Mainly application areas of QDs
technology have been categorized in to healthcare, semiconductor, optoelectronics, quantum optics, sustainable
energy, security and surveillance. Hybrid inorganic-organic composite materials find numerous applications in
biodiagnostics. Usually, organic dyes are employed as fluorophores for bioimaging but since they are
photodegradable and not sostable in normal environment, there is requirement for analternative. Dyes are also
not good for multi-colour imaging because of their broad emission spectrum, thus restricting their wide use in
imaging technology. Highly dispersible and narrowly distributred, QDs have potential benefits over dyes in their
property e.g. QDs show continuous absorption, narrow emission spectra, and are stable under insensitive
environmental circumstances. Due to these properties, colloidal semiconductors QDs have created a revolution
in nanotechnology for application in biological sciences. Therefore, it is highly desirous that new synthetic
approaches be developed using universal solvent like water. Another type of semicinductor nano-particles from
within the quantum dots are greatly important magic sized nanoclusters (MSNCs). In case of CdSe, these clusters
with defined molecular structures in the size range between 1 and 2 nm. Typically, they contain no more than
11-12
one unit cell of the bulk crystal and possess close shell structures
. Magic sized nanoclusters appear always at
fixed and discrete sizes. Experimentally, magic sized nanoclusters of semiconductors can be detected by the
appearance of sharp absorption peaks at persistent and isolated positions. Among them, colloidal CdSe NCs are
undoubtedly the most widely studied because of their tunable photoluminescence (PL) band in the visible range.
Recently, CdSe MSNCs with defined molecular structures in the size range between 1 and 2 nm have attracted
attention in fundamental studies and technical applications due to their unique properties. Because of the closeshell configuration, these nanoclusters are thermodynamically more stable than the clusters which are either a
little smaller or a little bigger but without a close-shell structure. Defence application can be expected in the form
of solar cells, detection of heavy metal ions in drinking water, development of LEDs and quantum dot dust for
tracking warfare and devices. Over the past few years, researchers in chemistry have focused their extended
interest in synthesis of semiconductors nano-particles of various shapes, size and morphology e.g. nano-wires,
nanorods, nanotubes. Thus researchers have developed many methods for for prepration of Quantum dots.
These therefore, can be conveniently synthesized by i) Organometallic method, ii) Sol-Gel method iii) Chemical
vapors deposition, iv) Hydrothermal method and infact there are many more which either are combination or fall
within the same type with individually desined modification. Typically quantum dots of II-VI semiconductor
compounds or the magic-sized nanocrystals derived from them can be classified into following three type
161
Amphiphilic quantum dots

Hydrophobic
Hydrophilic and
There are various chemical methods for synthesis these quantum dots of amphiphilic, hydrophobic, and
hydrophilic nature. For generating amphiphilic surfaces around the quantum dots, reagents that have miscibility
with water loving as well as water repelling solvents either directly by virtue of their functional groups or via utility
of a catalyst where they can be transferred from one type of medium to another type with ease and can be
utilized for the purpose. There are host of biomolecules that posses such properties along side organic molecules
and specific polymers are also employed for preparation of such type of quantum dots. They find applications
in biology and coatings and several defence applications can be anticipated for such materials. An amphiphilic
polymer such as octylamine-modified polyacrilic acid could be effective for generating water friendly QDs.
Core-shell semiconductor quantum dots are another high end research target in nanotechnology including solar
cell and light emitting diode applications. In silicon solar cell show theoretical efficiency of 29%, as against
conversion efficiency achieved so far of ~ 20%. Dye sensitized solar cell (DSSC) have shown maximum conversion
efficiency of about 11% as against theoretical efficiency of 33%. These gaps and difficulties in conversion of solar
light to electrical energy can be filled by use of using quantum dots sensitized solar cell (QDSSC). QDSSC can
offer 44% of theoretical conversion efficiency which is much higher than DSSC. QDSSC with 7% has been
reported recently and more efforts in this direction will surely bring their practical application to public.
In addition to semiconductor quantum dots there are range of other nano-particles that needs to be chemically
tailored before their practical application as interesting applications from the nano-particles have emerged in
electronics due to flexible printing devices and for such application, nano-ink is one of the major requirement.
We have undertaken various activities in this area and in thhis lecture we will cover a bit of those as well. Nanoinks of various materials have attracted wide attention due to its environmentally friendly, low-cost, large-area
processing. Different nanoparticles can easily be formulated to prepare the desired nano-ink using suitable
solvents and/or stabilizers. The smaller sized nanoparticles (less than 20 nm) can be converted easily in to nanoink using only organic solvent but in case of bigger nanoparticles, stabilizer along with solvent is needed for
stable dispersions. Nano-ink preparation involves many important key facts such as viscosity, conductivity and
surface properties which will be discussed along with the general requirements for direct printing methods. The
synthesised nanoparticles can be characterised by using various tools like UVVis spectroscopy; XRD, SEM etc and
used for the preparation of nano-ink.
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Time : 16.30 16.45
Another useful application of nano-particles are in the form of their composites with polymer thereby making
them useful as a coating materials or as substrate or protective sheilding to make use of them in desired areas.
As electromagnetic radiation specially that a high frequency range of few KHz to GHz such as radio wave
emerging from cellular phone tend to interface with electronics (e.g. computers and communication systems),
EMI shielding of both electronics radiation source is needed and is increasing required by government around
the world. The electromagnetic wave can be divided into reflection absorption and transmission. Electromagnetic
interference shielding is the process of reducing the electromagnetic field in a space by blocking the field with
barriers made of conductive or magnetic materials. The EMI shielding measurement performed on a R & S ZVA
40 vector network analyzer using complex scattering S-parameter averaging frequency range 8-18 GHz (X & Ku
band). As the metals have exceptional electrical, mechanical & thermal properties, many researchers working on
nano-composites using metal nanoparticles as filler material. Pt-PPy nano-composite exhibit improve physical
and chemical properties over their single-component counterparts and are potentially useful in a broad range of
applications. It is well known that the smaller amount of Pt nanoparticles will enhance the electrical properties
of PPy. For this purpose, Pt/PPy nano-composite can be loaded with desired wt% concentration of metal nanoparticles to prepare thin films by solution casting method. EMI shielding study in the range of 8-18 GHz (X and
Ku bands) frequency region can yiled maximum shielding effectiveness (SE).
Polypyrrole (PPy)/metal nano-composites have front line applications and several of their compositions have
been successfully synthesized by chemical methods whereby either polypyrrole is used as matrix or metal nanoparticles are loaded in pre-synthesized polypyrrole. There are others who have reported polymerization of
pyrrole by external oxidizing agents and subsequent reaction of metal salt with the so-formed polypyrrole. Of
late, researchers have opted for direct use of metal salts to react with pyrrole monomer under different
conditions e.g. thermal reaction, UV, sonochemical and microwave irradiation for synthesis of metal nanoparticles
via reduction of metal salt and subsequently so-generated metal nanoparticles act as catalysts for polymerization
of pyrrole to polypyrrole. Thus silver nanoparticles have been generated by reduction of silver nitrate by pyrrole
via thermal reaction, under microwave irradiation and ultrasound assisted technique. The reaction progress can
be monitored using UV-visible spectroscopy and characteristic peaks for polypyrrole can be understood. In-situ
reduction of metal salts by pyrrole monomer is caused by the amine group which is known to be reducing centre
in organic molecules. So-synthesised M/PPy composite was characterized by UV-Visible and FTIR spectroscopy,
powder XRD measurement and SEM/TEM/EDAX for study of morphology and particles size and TGA for thermal
decomposition of the composites. The formation of PPy was identified by absorption spectroscopy showing
bands at 430nm and ~464 nm. In case of Ag/PPy composite, XRD measurement confirmed characteristic peaks
o
for fcc silver and presence of PPy at two theta ~23 . Transmission electron microscopy (TEM) images showed
non-aggregated spherical Ag nano-particles of about 20 nm. The metal nano-composites have wide range of
sensing for gases and vapours. These were found to be excellent for NH3 and Liquefied Petroleum Gas (LPG)
sensing. e.g. Ag/PPy and Pt/PPy. Their synthesis and application as sensor is discussed in this lecture.
163
Similarly, polymer composites can be generated from Zinc-oxide nanoparticles (ZnO) which can be re-dispersed
in suitable solvent systems and mixed with polycarbonate (PC) to form PC-ZnO nano-composite films.
Transparent thin films can be prepared by blade coating technique by pouring the mixed nano-composite
solution on glass substrates. For the thin films, antimicrobial properties with various ZnO loading percentages
showed inhibition in the growth of food-borne microorganism such as E-coli and S-aureus. Similarly, TiO2-PC
films can be effectively utilized for such purpose as they too show good antibacterials propertiesagainst such
pathogens. ZnO-PC nano-composite thin films showed good EMI shielding ability in the X-band (8-12 GHz).
Thus, due to UV-blocking properties, high mechanical strength, anti-bacterial properties and EMI shielding
ability, the as-prepared ZnOPC thin films and sheets can be useful in many applications like flame retardant
materials, optical lenses, windows, bullet and shatter resistance, electronic gadgets and electrical packaging.
Another interesting and most widely targetted application which has found its way in to commercial sector, is
utility of nano-fluids derived from the nano-particles and these can not be effectively generated without
experimenting wonderful nano-chemistry. Nanofluids are dilute liquid suspensions of nanoparticles with at least
one of their principal dimensions smaller than 100 nm. They are engineered colloid formed with stable
suspensions of solid nano-particles in traditional base liquids. Nanofluids have been reported to show enhanced
thermo physical properties such as thermal conductivity, thermal diffusivity, viscosity and convective heat transfer
coefficients compared to those of base fluids like oil or water. Nanofluids clearly exhibit enhanced thermal
conductivity, which goes up with increasing volumetric fraction of nanoparticles. The effects of several important
factors such as particle size and shapes, clustering of particles, temperature of the fluid, and dissociation of
surfactant on the effective thermal conductivity of Nanofluids have not been studied adequately and there is a
vast scope to carry our range of studies in this field.Use of metal or oxide nanoparticlein their application as
nanofluids arise fronm thefact that they offer following major advantages,
Ability to enhance thermal conductivity.
Being Nano in size so they can not clog the tiny channels of the devices.
Rapid settling of nano-particles in fluids.
Nanoparticles stay suspended much longer than micro-particles.
The surface area per unit volume of nanoparticles is much larger (million times) than that of micro
164
Time : 16.30 16.45
particles.
These properties can be utilized to develop stable suspensions with enhanced flow, heat-transfer, and
other characteristics.
In conslusion
It can be said that chemically transformed and tuned nano-particles of semicondcutoirs or metals can be made
suitable for a range of applications. Th electure will mainly be dedicated to chemical methods for such useful
nano-structured materials.
Author and presentor of this lecture is thankful to all his present and past students and staff.
References
1.
Efros, A. L.; Efros, A. L. Sov. Phys. Semicond. 16, 772-775, 1982,
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Ekimov, A. I.; Onushchenko, A. A.; Tsekhomskii, V. A. Sov. J. Glass Phys. Ch. 6, 511-512. 1980.
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Rossetti, R.; Ellison, J. L.; Gibson, J. M.; Brus, L. E., J. Chem. Phys. 80, 4464-4469, 1984.
4.
Huynth, W. U.; Dittmer, J. J.; Libby, W. C.; Whiting, G. L.; and Alivisatos, A. P., Adv. Func. Mater. 13, 73, 2003.
5.
Schlamp, M. C.; Peng, X. G. Alivasatos, A. P. , J. Appl. Phy. 82(11), 5837, 1997.
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Seth Coe.; Woo, W. K.; Bawendi, M. G.; Bulovic, V., Nature, 420, 800, 2002.
7.
Geissler, D.; Charbonniere, L. J.; Ziessel, R. F,; Butlin, N. G.; Hildebrandt, N. Angew. Chem., Int. Ed. 49, 1396-1401, 2010.
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Zrazhevskiy, P.; Sena, M.; Gao, X. H. , Chem. Soc. Rev. 39, 4326-4354, 2010.
9.
Gao, X.; Cui, Y. Y.; Richard, M. L.; Leland, W. K. C.; Nie, S. M., Nature Biotechnol. 22, 969-976, 2004.
10. Katherine, L.; Xiaoyu, M.; Fred Rieke.; Lih,.Y. L., Opt. Express. 3(3), 447-454, 2012.
11. Z. Adam Peng and Xiaogang Peng, J. Am. Chem. Soc. 124, 3343-3353, 2002.
12. V. N. Soloviev, A. Eichhofer, D. Fenske, U. J. Banin, J. Am. Chem. Soc. 122, 2673, 2000.
13. S. Bhanoth, Priyesh V. More, Aditi Jadhav and Pawan K. Khanna, RSC Advances, 4 (34), 17526 - 17532, 2014
14. N. Gaikwad, S.Bhanoth, P. More and Pawan K Khanna, Nanoscale, 6 (5), 2746 2751, 2014
15. P. K. Khanna, K. S. Rao, K. R. Patil, B. R. Mehta, V. N. Singh, J. Nanoparticle Res., 12(1), 101-109, 2010,
16. Pawan K. Khanna, Jin-Ook Baeg, M. S. Lee, J Nanotechnology, (Springer), 1131-7(9-12) 38, 2010
17. P. K. Khanna, N. Singh, J. Luminescence, 174, 474-82, 2007
18. P.K.Khanna, P. More, B.G. Bharate and A.K.Viswanath, J.Luminescence, 130, 18-23, 2010.
19. P. K. Khanna, Priyesh More, Rahul Shewate, R.K. Beri, A. K. Viswanath, V.N. Singh and B. R. Mehta, Chemistry Letters,
38(7), 676-77, 2009
165
Session 7D : Nano-Biotechnology - III
Dr. A. K. Tyagi
Head surface and nanoscience division,
Materials Science group,
Indira Gandhi centre for Atomic research,
Kalpakkam
Email : akt@igcar.gov.in
Research Area
Thin films, surface analysis and surface engineering,ion implantation, amorphous

metallic alloys, thin films, helium in metals, high temperature oxidation, thermal and
radiation enhanced diffusion, temperature programmed thermal decomposition,
laser surface modification, plasma material processing, nanomechanical
characterization of thin films and coatings, scanning electron microscopy, scanning
probe microscopy techniques and secondary ion mass spectrometry.
Qualification
Ph.D. in Physics from I IT Delhi ,1985.
No. of Publications
325
Awards & Honors
Materials Research Society of India Medal, 2008,

Excellence in Nanoscience award by Sathyabama University in year 2011
Eminent Mass Spectroscopist award by Indian Society of Mass spectrometry (ISMAS)
in year 2013.
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Nanomaterials, Nanostructures and Nanocoatings: Synthesis, Characterization and some

Applications
Dr. A. K. Tyagi
ABSTRACT
A vibrant program on synthesis of nanocrystalline powders, nanostructures and nanostructured coatings is
being pursued at IGCAR. A large number of nanomaterials like Al2O3, CeO2, ThO2, CaO, Cr2O3, TiO2, ZrO2, CrN and
SnO2 have been synthesized. Oxides have been prepared by temperature programmed decomposition of metal
nitrates, carbonates, oxalates and hydroxides as well as by soft chemistry routes. Using TGA-EGA-MS system,
each decomposition stage of precursors were monitored by subjecting them to linear heating. For synthesis of
nitrides like CrN, we used direct gas phase nitridation of corresponding nano oxides in reactive atmosphere
(NH3).Various nanostructures of GaN like nanowires, nanorods, nanotubes and belts are produced by vapourliquid-solid CVD technique. TiO2 nanorod arrays were synthesized by anodization of Ti. Nanocrystalline coatings
of oxides like alumina, zirconia and titania were obtained by combustion CVD, plasma CVD, laser pyrolysis, spray
pyrolysis, pulsed laser deposition and electron beam PVD. Multilayers are obtained through magnetron
sputtering as well as PLD and constructed out of alternate nanometric layers like TiN/TiAlN. XRD, XPS, FT-IR, LRS,
PL,TEM, SEM, AFM and SIMS are used for characterization. Nanomechanical characterization through
nanoindentation and scratch testing is performed for evaluation of hard coatings. Tribology studies are
performed to engineer low friction surfaces using nanotechnology recepeis.Oxide and nitride nanostructures are
explored for gas sensing applinations. The present talk will give an overview of our activity highlighting synthesis,
characterization and possible applications of these nano powders, nanostructures and nanostructured coatings.
167
Nanocon 012
Chairman Dr. Anand Bhalerao addressing Nancon 012.
The college is a constituent unit of Bharati Vidyapeeth Deemed University, which has got 'A' grade
University status by Ministry of Human Resources Development(MHRD), Government of India,
New Delhi,'A'Grade accreditation by National Assessment and Accreditation Council (NAAC) in
2011 & 2004,'12 B' certification from University Grants Commission(UGC) New Delhi and ranked
to 35th level by 'India Today' (June 3,2013 )
The college, established in 1983, is one of the oldest and largest Engineering Colleges in the State
of Maharashtra.
Ranked among top 50T Schools of India - DATAQUEST-CMR survey continuously for 7 years.
21st Rank by DATA QUEST-CMR among Technical School.
Rank 35th level by 'India Today' (June 3,2013 ).
Rank 45th in servey conducted by AICTE-CII for Industry Institute Interaction.
Accreditation of the programmes by National Board of Accreditation(NBA),New Delhi
Selected under Technical Education Quality Improvement Program, Phase II (TEQIP II) by Ministry
of Human Resources Development (MHRD), Government of India, supported by World Bank for
the grant of Rs 4 crores.
Collaboration with North Carolina A&T State University, USA for faculty development and
Research.
Organising biannual International Conference, in association with North Carolina A&T State
University,Greensboro,USA, Tuskegee University,Alabama,USA and Centre for Materials for
Electronics Technology,Department of Information Technology,Government of India
Opportunity for students to complete dissertation at International Universities.
Interaction with 396 industries for Inplant Training
The college has its own spacious, well designed building admeasuring 26,286 sq.m located within
the campus. a healthy Student to Book Ratio as 1:22
The college houses 110 Laboratories,43 Class Rooms and 21 Tutorial Rooms
Five storied library with more than 50,000 books, 15,000 volumes 70 National /71 International
Journal subscriptions and Digital library facility.
A unique master programme in Nanotechnology in association with Joint School of Nano Science
and Nano Technology( JSNN) North Carolina A&T State University (NCAT),USA
Guidance to students for Robotics by experts from iCarnegie Powered by Carnegie Mellon
University, USA
More than 300 campus placements in 75 companies.
Research grant to the tune of 1.7 Crores in last six years .
State of Art Laboratories with investment of 75 million INR in last six years.
Experienced and qualified faculty members.
The training and Placement Section of the Institute is actively interacting with different Industries
for organising Campus Placements.
Training for students in the areas of Personality Development, Aptitude Test, Group Discussions
and Personal Interviews is a regular event.
The college has total 1155 research papers to its credit, out of which 635 research papers were
published in international journals, 75 research papers in national journals and remaining research
papers were presented and published at various national as well as international conferences.

Keynote Proceeding Nanocon 014 Pune PDF

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Keynote Proceeding Nanocon 014 Pune PDF

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Bharati Vidyapeeth

Deemed University Pune (India)

3 International Conference NANOCON 014

North Carolina A&T

The University of Tokushima

Date: 14 , 15 October, 2014

started its own research institutes. It has three research

research papers of which 873 are in international journals

Bharati Vidyapeeth University has become, perhaps, the

The University has a vibrant in-house research programme

'A' Grade University Status by MHRD, GOI

Elite and Distinguished Achievements and Activities

The University has introduced many examination reforms

of various kinds with renowned institutions such as NCAT in

Bharati Vidyapeeth University College of

run by the College are approved by Institution of

Bharati Vidyapeeth University,

Manufacturing of nylon 6 nanofibres by electrospinning process

Composite Materials. The College has established a

among Top 20T Schools of India DATAQUEST-CMR survey.

under Technical Education Quality

with North Carolina A&T State

biannual International Conference, in

for students to complete dissertation

college has its own spacious, well designed.

college houses 110 Laboratories,43 Class

storied library with more than 50,000 books,

master programme in Nanotechnology

to students for Robotics by experts from

than 300 campus placements in 75

grant to the tune of 1.7 Crores in last six

of Art Laboratories with investment of 75

is actively interacting with different Industries for

for students in the areas of Personality

Dr. Hitoshi Takagi

Keynote 1 -Mechanical performance of green

Dr. Barry L.Burks

Keynote 2 - Engaging Private Industry in

Dr. Ajit Kelkar

Keynote 3 -Nanoengineered materials for future

Dr. Li-Chyong Chen

Keynote 4 -Graphene oxide based visible light

Dr. Neil John Coville

Keynote 5 -New directions for spherical carbons

Dr. Toshihiro Moriga

Keynote 6-Control of Optical Properties of Oxynitride

Dr. Vijay Jain

Keynote 7-Manufacturing: Vision for future

Prof. Ram Mohan

Keynote 8 -Modeling at Nanoscale - Materials and

Dr. Mikito Yasuzawa

Keynote 9-Immobilization of enzyme using electrodeposition

Dr. Jitendra Kumar Pandey

Keynote 10-Nano-particles from plants: Opportunities and

Dr. Alva Tontowi

Keynote 11-Experimental Study on NanoBiocomposite of

Dr. James Ryan

Keynote 12 -Economic Outreach and Engagement through

Dr. Shaik Jeelani

Keynote 13 -Recent Advances in the Materials Science and

Dr. Dinesh Amalnerkar

Keynote14 -Innovative biofilm inhibition & anti-microbial

Dr. Tae Gyu Kim