Green Composites - Properties, Design and Life Cycle Assessment (2010)

CHEMICAL ENGINEERING METHODS AND TECHNOLOGY SERIES
GREEN COMPOSITES:
PROPERTIES, DESIGN AND
LIFE CYCLE ASSESSMENT
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Green Composites: Properties,

Design and Life Cycle Assessment
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2010. ISBN: 978-1-60741-301-1
CHEMICAL ENGINEERING METHODS AND TECHNOLOGY SERIES
GREEN COMPOSITES:
PROPERTIES, DESIGN AND
LIFE CYCLE ASSESSMENT
FRANÇOIS WILLEMS
AND
PIETER MOENS
EDITORS
Nova Science Publishers, Inc.

New York
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Green composites : properties, design, and life cycle assessment / editors, François Willems and
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ISBN 978-1-61324-216-2 (eBook)
1. Composite materials. 2. Green products. 3. Product life cycle. I. Willems, François. II.
Moens, Pieter.
TA418.9.C6G75 2009
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Published by Nova Science Publishers, Inc.  New York

CONTENTS
Preface vii
Chapter 1 Structure and Properties of Green Composites
Based on Wheat Proteins: A Review 1
Yihu Song and Qiang Zheng
Chapter 2 Flax as Potential Fiber for Reinforcement in Composites 31
A. S. Singha and Vijay Kumar Thakur
Chapter 3 Review on Natural Fibers /HDPE Composites:
Effect of Chemical Modification on the
Mechanical and Thermal Properties 53
Daniella R. Mulinari, Maria Odila H. Cioffi
and Herman J. C. Voorwald
Chapter 4 Bamboo, Soybean and Corn as Resources
for Green Composites 79
Kuichuan Sheng, Mehrdad ADL,
Hui Wang, Rui Chang and Kun Fang
Chapter 5 Vegetable Oil-Based Polymers and
Lignocellulosic Derived Composites 99
Mirta I. Aranguren, Norma E. Marcovich
and Mirna A. Mosiewicki
Chapter 6 Chicken Feather Fiber/Poly(Lactic Acid) Green Composites:
Mechanical, Thermal and Biodegradable Properties 119
Hu-Lin Li, Yong-Qing Zhao,
Kin-Tak Lau and Hoi-Yan Cheung
Chapter 7 Mechanical and Moisture Absorption of Corn
and Wheat Flour Composites for Developing Countries 141
Thimothy Thamae, Shanil Vaja, Yiyi Shangguan,
Claire Finoro, Nick Stefano and Caroline Baillie
vi Contents
Chapter 8 Green Composites Based on Biodegradable

Polymers and Wood Flour 157
R. Scaffaro, M. Morreale, G. Lo Re,
A. Maio and F. P. La Mantia
Chapter 9 Mechanical Properties and Moisture Absorption
Behaviour of Cellulose-Fibre Reinforced Polymer Composites 175
H. Alamri, A. Alhuthali and I. M. Low
Chapter 10 Densified Wood for Green Composites 197
Andreja Kutnar and Frederick A. Kamke
Index 205
PREFACE
Green composites can be prepared by conventional blending wheat gluten (WG) and
other organic or inorganic components using conventional plastic processing equipments
followed by thermo-molding of the mixture at elevated temperatures to crosslinking the
matrix. In recent years, great attention has been dedicated to the exploitation of natural fibers
as reinforcement for plastics, replacing fibers synthetic materials. This book examines the
methods for surface modification, which can be physical or chemical, according to superficial
modification approach of the fibre. This book also gives a survey about the chemical
composition, various mechanical processes for the separation of flax fiber, mechanical
properties, physical and chemical treatment methods that improve the flax fiber matrix
adhesion, their results and special effects on the various properties of composites. The authors
also investigated the preparation and characterization of Mater-Bi/wood flour green
composites. The investigation was completed by performing biodegradation tests which
allowed assessing the actual biodegradability of the prepared green composites. Other
chapters in this book examine the effects of accelerated exposure to seawater on the flexural
and impact properties of composites. Densified wood, which can be effectively used as raw
material in the production of wood-base green composites, is discussed as well.
Chapter 1 - Green composites can be prepared by conventionally blending wheat gluten
(WG) and other organic or inorganic components using conventional plastic processing
equipment followed by thermo-molding of the mixture at elevated temperatures to crosslink
the matrix. Glycerol as plasticizer might be used to overcome the brittleness and improve
toughness of the composites. Addition of a secondary component in the filler form can
significantly improve the Young‘s modulus and tensile strength of the plasticized composites,
which is accompanied by a decrease in loss factor in the glass transition temperature region of
the gluten-rich phase. Synthetic biodegradable polymers have also been used for preparing
WG blends by incorporation of reactive compatibilizer or by chemical modification of WG
proteins. The mechanical properties, moisture absorption, and molecular relaxation of the
composites could be tailored by adjusting the contents of the secondary component and the
plasticizer as well as the molding temperature and time.
Chapter 2 - Among natural fibers, flax fibers are frequently used as reinforcing materials
due to their characteristics properties such as high mechanical properties, low density,
biodegradability, low cost, high specific strength and modulus, no health risk, easy
availability in nature, renew ability etc. On account of its eco-friendly nature, flax fibers are
considered as a future material for preparing reinforced composites. Over the last few years,
viii François Willems and Pieter Moens
there has been an ever-increasing interest in finding new features for flax - fiber-reinforced
composites. This chapter introduces promising applications and recent developments of flax
fiber and its composites. The physical properties of all natural fibers are mainly determined
by the chemical and physical composition, such as the structure of fibers, cellulose content,
angle of fibrils, the degree of polymerization etc. The physical structure of flax fiber can be
modified by various surface treatments such as grafting, acetylation, silane treatment,
mercerization, peroxide treatment etc. These different treatments modify hydrophilic
character of the natural fibers, so that moisture effects in the composite are reduced. The
application of flax fibers as reinforcements in composite materials requires a strong adhesion
between the fiber and the matrix. This chapter also gives a survey about the chemical
composition, various mechanical processes for the separation of flax fiber, mechanical
properties, physical and chemical treatment methods that improve the flax fiber matrix
adhesion, their results and special effects on the various properties of composites.
Chapter 3 - In the recent years, great attention has been dedicated to the exploitation of
natural fibers as reinforcement for plastics, replacing fibers synthetic materials. Objectives are
not just environmental concerns and consumer pressure but also a unique combination of high
performance, great versatility and processing advantages at low cost. However, certain
drawbacks such as incompatibility with a hydrophobic polymer matrix, the tendency to form
aggregates during processing and poor resistance to moisture reduce greatly the potential of
natural fibers to reinforce polymers. On the other hand, various treatments are being used to
improve fibre-matrix compatibility. This process is considered critical as a development
phase of these materials due to strong interfiber hydrogen bonding, which holds fibers
together. Methods for surface modification can be physical or chemical according to
superficial modification approach of the fibre. In this review, the main results presented in the
literature are summarized, with specific attention on the properties in terms of physical and
chemical structure of natural fibers, thermal and mechanical properties, processing
performance and final properties of natural fibers reinforcing high density polyethylene
matrix. The use of physical and chemical treatments for the improvement of fibers-matrix
interaction was also considered.
Chapter 4 - Bamboo, a well known plant has a broad application in nutrition,
construction, handicrafts as well as furniture and decoration. A huge amount of bamboo
wastes are disposed continuously as a byproduct of its utilization in various purposes
especially in wood and furniture industries. A wide variety of researches and activities have
been performed on utilization of bamboo wastes in manufacturing of green composites and
hence, a wide assortment of substances have been tested to act as the supplementary
components such as Portland cement, petrochemical polymers (e.g. poly-ethylene, poly-vinyl
chloride, poly-propylene, polyester resins), and recently biodegradable polymer matrices such
as poly-lactic acid, plant proteins and poly-butylene-succinate. Scientific efforts have been
studied the different combinations of bamboo wastes with polymer matrices and/or coupling
agents. The most important items in these researches have been the mixing ratios of materials
as composite components, physical and chemical properties of ingredient materials,
production techniques and qualitative properties of composites such as physical
characteristics, mechanical strength, durability, water and moisture resistance, abrasion
resistance and external appearance. Effects of pre-treatment of ingredients have been
extensively investigated by purpose of modification and improvement of composite
characteristics. Extractable proteins from soybean and corn have also been studied as polymer
Preface ix
matrix for making green composites. Zein, a plant protein found in corn that is widely
applicable as coating agent or adhesive, is an example that has fulfilled experiments for
making particle boards. Further similar experiences have been carried out on making
composites from wood or bamboo sawdust or fibers with soybean proteins. The more
common objectives through the above mentioned researches have been to find the best
mixing ratios, the most effective coupling agents and/or modifiers, the optimum operational
parameters in manufacturing processes, the qualitative measures such as tensile strength,
bending strength, internal bond, modulus of elasticity, water absorption, thickness swelling,
density and porosity. This chapter reviews technical and scientific attempts on making
composites from bamboo wastes and various matrices and coupling agents especially those
which have been performed in Zhejiang University and academic organizations cooperating
with.
Chapter 5 - The growing environmental concerns together with the reduction of
petroleum resources have been a motor for revitalizing the interest in using raw materials
from renewable resources. Among those, vegetable oils constitute a valuable renewable
source. Their chemical modification is a promising alternative to substitute (at least partially)
petrochemical materials used in polymer formulations. In this chapter, the focus will be on
the use of castor and tung oils to synthesize polyols for the polyurethane industry. The
polymers derived from these polyalcohols present different properties depending on the
vegetable sources, synthesis path for the polyol, additives, etc., and thus, polyurethanes can
be produced to fit the requirements for different applications. The addition of lignocellulosic
reinforcements like wood flour or plant fibers noticeably affect the properties of the
polyurethanes due to the strong interaction that these fillers/reinforcements develop with the
polar polyurethane matrix. The biocomposites prepared from the bio-based polymers and
biofillers/biofibers can be a useful alternative to substitute synthetic composites (from solid
composites to filled foams) reducing the environmental impact usually associated to
traditional polymers. The physical, thermal and mechanical properties of the neat
polyurethanes and derived composites are presented and analyzed in this chapter.
Chapter 6 - To reinforce poly(lactic acid) (PLA) and take full advantage of chicken
feather, the first time chicken feather fiber (CFF) was used as reinforcement for PLA, and
prepared completely biodegradable PLA/CFF biocomposites by using melting compound
method. By means of tensile test, dynamic mechanical analysis (DMA), differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis (TMA),
enzymatic degradation test and scanning electron microscopy (SEM), the effect of CFF on the
structural, thermal and mechanical properties and enzymatic degradation behavior of PLA
matrix was investigated. As CFF was incorporated into PLA matrix, the tensile modulus of
the PLA matrix was slightly increased, and the storage modulus (bending mode) could be
remarkably enhanced at glass and rubbery regions of PLA. DMA results showed the motion
of PLA chain segments could be effectively restricted when 10 wt% of CFF was added into
the PLA matrix. On the other hand, the thermal stability and dimension stability of the PLA
matrix became poorer with the addition of CFF. Moreover, the presence of CFF also
significantly enhanced the enzymatic degradation ability and crystallization ability of the
PLA matrix. The content of this chapter is believed to assist the development of
environmentally-friendly composites from biodegradable polymers, especially for converting
agricultural waste – chicken feather into useful products.
x François Willems and Pieter Moens
Chapter 7 - Low cost processing methods for natural fibre composites could be suitable
for developing countries context. The challenge is to make composites with properties that
are not overly compromised by the use of low technogly. Composites were made using
corn/wheat stalk flour and waste high density polyethylene and were tested for moisture
absorption, impact, tensile and flexural properties. The composites made from outer ring corn
stalk flour absorbed more water than those made from whole corn stalk flour. When wheat
stalk flour composites were extruded before being moulded, they absorbed about 15% less
water at equilibrium than when they were just layered, shredded and moulded. The above
mentioned parameters in both corn and wheat stalk composites did not make significant
differences on impact properties of the composites. Sealing the wheat straw composites had
the unexpected effect of absorbing about 5% more water at equilibrium than the unsealed
wheat straw composites. Neither silane nor sodium hydroxide treatments improved the tensile
or flexural properties of the corn stalk composites, likely due to poor mixing governed by the
selected processing methods. By careful selection of the processing techniques and materials,
it is possible to make composites that may be affordable without overly sacrificing their
properties.
Chapter 8 - The use of natural-organic fillers for polymer composites is mainly due to
environmental and economical reasons. In fact, natural-organic fillers are usually cheap and
easily available (often coming from wastes), are less abrasive to processing equipments, give
less hazard concerns regarding health of production workers, provide a fundamental help in
reducing the use of non-renewable sources throughout the life-cycle of the material. On the
other hand, in order to achieve fully environmental-friendly products, a complete
biodegradability is required. This can be obtained only by using polymer matrices which are
biodegradable as well. One of the most widely known is the Mater-Bi® family.
In this work, the preparation and characterization of Mater-Bi®/wood flour green
composites were investigated. Since the actual composition of the Mater-Bi® grade used was
proprietary, statistical analysis was carried out in order to individuate the most influential
processing variables and their optimal values. Mechanical, rheological and morphological
tests were carried out as well. Based on these results, another Mater-Bi® grade with the most
suitable amount of wood flour was tested, and the analysis was focused mainly on the
determination of the best processing technique. The investigation was completed by
performing biodegradation tests which allowed assessing the actual biodegradability of the
prepared green composites.
Chapter 9 - Epoxy and vinyl polyester matrix composites reinforced with cellulose fibre
were fabricated and characterized with respect to their flexural, fracture and impact
properties. Reinforcement of the polymer by cellulose fibres resulted in a significant increase
in the strain at failure, fracture toughness and impact toughness but only a moderate increase
in flexural strength and flexural modulus. Moisture absorption of the composites in water was
analysed. The kinetics of sorption-diffusion process was investigated and typical kinetic
parameters D, k, and M were determined. The use of nano-clay in the composites was
effective in imparting a substantial reduction in water permeability due to the tortuous path
presented by high aspect ratio clay. Diffusion models for the water uptake behaviour in
polymer composites are reviewed. The effect of accelerated exposure to seawater on the
flexural and impact properties of composites was also investigated. The salient toughening
mechanisms and crack-tip failure processes were identified and discussed in light of observed
microstructures.
Preface xi
Chapter 10 - Densified wood can be effectively utilized as raw material in the production
of wood-base green composites. The viscoelastic thermal compression (VTC) process
enabled the development of a high performance structural wood-based composite with low-
density (undensified) wood in the core, and high-density VTC wood for the faces of the
composite. Increased density of the face layers in these 3-layer VTC composites is
advantageous for their mechanical performance. The aim of this chapter was to present the
VTC process, the VTC wood and the 3-layer VTC composites. Additionally, the viscoelastic
nature of wood and the stress-strain relationship in regard to glass transition temperature and
moisture environment relevant for the density gradient formation in VTC wood are discussed.
Namely, the density gradient of the VTC layer, which is obtained due to the viscoelastic
nature of wood, local environment of moisture content and temperature during the
densification process, affects the bending properties of the VTC composites.
In: Green Composites: Properties, Design and Life… ISBN: 978-1-60741-301-1
Editors: F. Willems, P. Moens, pp. 1-30 © 2010 Nova Science Publishers, Inc.
Chapter 1
STRUCTURE AND PROPERTIES OF GREEN

COMPOSITES BASED ON WHEAT PROTEINS:
A REVIEW
Yihu Song and Qiang Zheng

Department of Polymer Science and Engineering, Zhejiang University; Key Laboratory
of Macromolecular Synthesis and Functionalization of Ministry of Education,
Hangzhou 310027, China
ABSTRACT
Green composites can be prepared by conventionally blending wheat gluten (WG)
and other organic or inorganic components using conventional plastic processing
equipment followed by thermo-molding of the mixture at elevated temperatures to
crosslink the matrix. Glycerol as plasticizer might be used to overcome the brittleness and
improve toughness of the composites. Addition of a secondary component in the filler
form can significantly improve the Young‘s modulus and tensile strength of the
plasticized composites, which is accompanied by a decrease in loss factor in the glass
transition temperature region of the gluten-rich phase. Synthetic biodegradable polymers
have also been used for preparing WG blends by incorporation of reactive compatibilizer
or by chemical modification of WG proteins. The mechanical properties, moisture
absorption, and molecular relaxation of the composites could be tailored by adjusting the
contents of the secondary component and the plasticizer as well as the molding
temperature and time.
INTRODUCTION
Carbohydrates and proteins from plant/crop based renewable agricultural resources
provide a strategic option to meet the growing need for environment-friendly, sustainable
materials [1]. Due to their high yield and low cost, renewable proteins from cultivated crops
such as soy [2, 3], corn [4, 5], cotton [6], and wheat [7-11] show the advantage for
development of edible films or biodegradable plastics using thermoplastic processes such as
2 Yihu Song and Qiang Zheng
compression molding and extrusion. Thermoplastic processing can result in a highly efficient
manufacturing method with commercial potential for large-scale production of the products
due to the low moisture levels, high temperatures, and short times used [12].
The annual production of wheat is about 625 million tonnes in the world [13]. As a
byproduct of starch production, industrial wheat gluten (WG) contains more than 75 %
protein, among which about 40 ~ 50 % is gliadins and 35 ~ 45 % is glutenins. Other
constituents in industrial WG are lipids (3.5 ~ 6.8 %), minerals (0.5 ~ 0.9 %), and
carbohydrates (7 ~ 16 %). There are hundreds of proteins in WG, the molecular weight of the
primary proteins ranging from 20 to 90 kDa [14]. Gliadins are single-chain polypeptides with
a molecular weight of 20 ~ 70 kDa, whilst glutenins are multiple-chain polymeric proteins
interlinked by intermolecular disulphide and hydrogen bonds to give a molecular weight
ranging from 102 kDa to well beyond 105 kDa.
WG, when molded into plastic, has high stiffness in the range of epoxy (1.0 ~ 3.5 GPa)
and reasonable strength (20 ~ 50 MPa). However, WG is quite brittle. Addition of water,
glycerol, sorbitol, sucrose, and other plasticizers allows the proteins to undergo the glass
transition and facilitates deformation and processability without thermal degradation.
Glycerol as a plasticizer can reduce intermolecular forces and glass transition temperature
(Tg) so as to increase chain mobility of proteins [15] and allow WG to form a three-
dimensional network with optimized combination of cohesive and elastic properties [16].
Reactive side groups of WG proteins susceptible to physical and chemical modifications [10,
17-19] make it possible to obtain a crosslinked network with appropriate strength and
functional properties [20]. Heat treatment induces an aggregation reaction by covalent
disulfide bond crosslinking that stabilizes the protein network [21]. The crosslinking reactions
of both gliadins and glutenins are highly dependent on temperature [21, 22]. Gliadins and
glutenins achieve maximum structure buildup at 120 C and 135 C while softening occurs at
temperatures above 130 C and 150 C, respectively. Plasticized WG can be readily
processed into films and bioplastics using conventional plastic processing techniques and
equipment [23-25]. Besides the biodegradability, the wheat protein films exhibit effective
barrier properties against lipids, gases such as oxygen and carbon dioxide, and aroma
compounds, showing an advantage in edible food packaging.
The application of bioplastics is severely limited due to their stiffness and strength
performances, still lower than commonly used petroleum-based plastics [26]. Native fibers or
inorganic fillers have been used to reinforce crop proteins so as to prepare green composites
with improved mechanical properties and water resistance [27, 28]. Biodegradable materials
such as chitin and cellulose whiskers, lignin, as well as natural fibers from grass, pineapple
leaf, hemp and ramie have been reported as reinforcements to prepare composites based on
soy proteins [29-36]. Wood fiber has been used for preparing low cost, biodegradable
composites based on corn gluten meal through extrusion, compression and injection-molding
[37].
Combination of WG and other component (biopolymers and inorganic fillers) shows the
advantage for preparing green composite films with optimized physical properties. Cysteine
could promote the crosslinking reaction between soy protein and WG to increase disulfide
bond formation [38]. The cysteine-mediated soy protein/WG (4/1) blend film casting at pH =
7 gives rise to the best compromise between the barrier and the mechanical properties. Soy
protein/WG film rapidly degrades with 50 % weight loss in about 10 days and with up to 95
% weight loss in 30 days [39]. Tensile strength and strain at break of the bend films
Structure and Properties of Green Composites Based on Wheat Proteins: A Review 3
significantly decreases in 3 days. Methylcellulose (MC) [40], cellulose acetate phthalate [41]
and chitosan [42] have been applied to prepare WG blend films with improved mechanical
strength and reduced water vapor permeability. A low content of montmorillonite
significantly reduces the water permeability of glycerol- plasticized WG films with
appropriate improvement of mechanical properties [43].
In recent years, WG green composites have received much attention for developing
composites that degrade more rapidly in the environment so as to alleviate pollution of non-
biodegradable synthetic polymers. Organic MC microfiber [44], hydroxyethyl cellulose
(HEC) powder [45, 46], hemp and wood fibers [47] and inorganic components such as basalt
yarn [48], silica [49] and calcium carbonate [50] have been investigated to reinforce WG
bioplastis. On the other hand, biodegradable aliphatic polyesters such as polycaprolactone
(PCL) and polylactic acid (PLA) have been used to prepare a blend with WG. This chapter
will address the structure and properties of WG-based green composites prepared using the
conventional mechanical mixing and the thermal molding methods. A conclusion will be
drawn from the progress made so far.
PREPARATION OF WG COMPOSITES
Unplasticized WG is in the glassy state with Tg ranging from 124 C to 145 C. Dry WG
in the powder form does not flow and form a viscoelastic network during the thermal molding
processing. Aqueous dispersant is usually used to facilitate the mixing of WG proteins with
the other components used in the filler form. For preparation of unidirectional WG/natural
filler composites, WG has been dissolved in meta-cresol (0.1 g/10 mL) solution and then the
basalt yarn is soaked in the solution [48]. The soaked yarns are dried in a vacuum oven to
allow WG to penetrate into the yarn. Unplasticized WG/basalt composites are then made by
compression molding the basalt yarns at elevated temperatures. Aqueous dispersant has also
been used to mix polyvinyl alcohol (PVA) and WG for improving the mixing effect [51].
Figure 1. Specific mechanical energy (SME) and pressure during extrusion compounding of PCL/WG
composites with a screw speed of 150 rpm under 127 C [53].
Twin extruder is frequently used to make unplasticized WG blends continuously [52].

The pelletized extrudate can be injection molded into articles using a commercial injection
molding machine. Up to 75 wt % of WG could be incorporated into the WG/PCL blends
without adversely affecting the tensile properties. In the PCL/WG composites with PCL as
the matrix and WG as the filler, specific mechanical energy (SME) during extrusion decreases
while pressure at the extruder die increases in a linear fashion as WG content in the blend
increases (Figure 1) [53]. The particle size of WG lies in 1 ~ 100 m after extrusion and
injection molding while the larger particles become more prevalent in higher filling amounts
as the protein aggregates during processing. PCL matrix in the blend appears continuous up to
20 wt % WG filling. At 75 wt % WG filling, the PCL matrix becomes discontinuous, making
it impossible to use for injection molding.
Plasticized WG composites can be made by blending WG, glycerol and fillers using
three-roll mixer [44-46, 49, 50] or Rheomix 600 mixer [54], followed by a compression
molding at elevated temperatures. During thermal mixing, the plasticized WG could develop
a gel-like elastic characteristic not only due to rearrangement of polymeric proteins to create
new interactions but rather to the growth of clusters due to polymerization reaction. A close
relationship between complex viscosity (at 1 rad/s) and SME has been established for
glycerol plasticized WG bioplastics [55]. The mixing condition (temperature, time, rotor
speed, initial water content and so on) significantly influences the morphology of the mixture
and the ultimate properties of the composites. Torque required to process the WG mixture is
usually used to characterize the mixing processing. Concerning the glycerol plasticized WG,
torque increases to a maximum value rapidly, followed by a decay to a plateau due to the
plasticization effect (Figure 2) [47]. The initial torque increase is associated with a change of
the mixture consistency, from a powder/glycerol dispersion to a cohesive and elastic material.
At the same time, the material temperature increases sharply and stabilizes after torque
reached to the maximum, which is attributed to the thermal energy dissipation due to the high
medium viscosity. In the WG/fiber composites, fiber addition usually accelerates the mixture
consistency change. The maximum and the plateau torques as well as the final temperature
increase as the fiber content increases. The torque increase with the fiber content reflects their
effect on the material viscosity. In the case of the WG composites containing 20 wt % hemp
fiber, the torque gradually increases and become constant at the end of mixing time, which
reflects the glycerol absorption by the fibers during processing.
The molding temperature has significant effects on the crosslinking density of protein and
thereby on mechanical properties of thermo-molded WG bioplastics [56]. The WG
composites are usually prepared by molding at temperatures from 120 C to 150 C. The WG
proteins may degrade at higher molding temperatures while the crosslinking reaction between
proteins may not be sufficient at lower temperatures, both resulting in deterioration in tensile
strength and deformability of the composites. In glycerol plasticized WG/HEC composites
molded at 120 C, the formation of crosslinked protein network is confirmed on the basis of
dynamic rheological measurement at 30 C [45]. The composites exhibit higher storage
modulus (G ) than loss modulus (G ) in the frequency ( ) range from 0.0215 rad s-1 to 100
rad s-1 (Figure 3). At 0.4 rad s-1, both G and G show scaling behavior of G ~G ~ 0.2,
indicating the presence of an elastic network due to chemical crosslinking between WG
proteins [57]. At the terminal zone of < 0.4 rad s-1, both G and G reach to their respective
plateau values nearly independent of . The plateau moduli increase with increasing HEC
content, which can be related to the reinforcement effect of the HEC particles to the WG
matrix.
a b
Figure 2. Torque (a) and temperature (b) evolution during the mixing of 30 wt % glycerol plasticized
WG composites containing 0 wt % (), 5 wt % (), 10 wt % (▲) and 20 wt % ( ) hemp fiber in a two
blade counter-rotating batch mixer turning at a 3:2 differential speed at the mixing chamber temperature
of 30 °C [47].
Figure 3. Storage modulus (G , solid symbols) and loss modulus (G , hollow symbols) as a function of
frequency ( ) for the 30 wt % glycerol plasticized WG composites containing different HEC particles
thermo-molded at 120 C for 5 min [45].
MORPHOLOGY
The compression molded WG bioplastic plasticized with 25 wt % glycerol shows a
coarse and fluctuant fracture surface with spherulite-like inclusions, displaying characteristic
of tough fracture with delamination and corrugation, as observed in the scanning electron
microscope (SEM) micrographs taken at the break surface of tensile fractured WG sheet at
room temperature (Figure 4a). In the WG/MC/glycerol (3/1/2) composites, MC is present as
its original morphology, in the formation of microfibers. The WG matrix also contains
spherulite-like domains and delamination is still the typical characteristic at low MC contents.
Fiber pullout can be observed on the fracture surface of the composites as consequence of the
poor adhesion between the MC fiber and the WG matrix (Figure 4b). In the
WG/HEC/glycerol (7/3/3) composites, large HEC particles with a size of 60~90 m coexist
with spherulite-like domains in the WG matrix (Figure 4c). Both the MC microfibers and the
HEC particles do not influence the morphology of the WG matrix markedly.
Silica is widely used in polymer composites for improving mechanical properties and
reducing cost. Amorphous silica occurred in nature is very weak, whereas it makes very
strong biocomposites when combined with proteins and self-organized into highly ordered
structures [58]. Protein/silica composites or gels have been prepared via in situ
polymerization [59] or sol-gel process [60-62]. In the WG/silica composites prepared by
mechanical mixing and thermo-molding, the content of silica particles with an average
diameter 20 nm influences the morphology the plasticized WG composites significantly.
Introduction of 4 wt % and 6 wt % silica particles in the 30 wt % glycerol plasticized WG
composites leads to a rather homogeneous morphology, the size of the spherulite-like domain
in the WG matrix being reduced considerably (Figure 5a and 5b). At higher silica loadings
such as 10 wt % (Figure 5c), on the other hand, the composites become very inhomogeneous
in morphology and there appear large spherulite-like domains with a size of 8 ~ 25 m,
suggesting that higher silica loadings may promote the phase separation in the WG matrix
with different protein subunits and a wide distribution of molecular weight. Fine calcium
carbonate particles with an average diameter 1.41 m are able to reinforce the glycerol
plasticized WG composites. However, the finely dispersed calcium carbonate particles do not
induce marked changes in morphology of the WG matrix [50], which might be due to the
surface nature of calcium carbonate particles differing form that of silica.
a b
c
Figure 4. Scanning electron microscope (SEM) images taken from tensile break surface of the 25 wt %
glycerol WG plasticized bioplastic (a), the WG/MC/glycerol (3/1/2) composite (b) [44] and the
WG/HEC/glycerol (7/3/3) composite [45].
WG nanocomposites have been produced by dispersing Cloisite-30B nanoclay into the

plasticized WG followed by thermal processing [63]. In the composites, the diffraction peak
of organoclay is significantly reduced in intensity, and the diffractogram shows a similar
pattern to that of WG, indicating the sufficient exfoliation of nanoclay during the thermal
compounding process. Transmission electron microscopy (TEM) images reveal that single
exfoliated silicate layers are the predominant structure in the WG and the WG/PVA(90/10)
nanocomposites containing 3 wt % nanoclay (Figure 6). There also exist some small silicate
tactoids containing 3 ~ 5 particles, but no large agglomerates are visible in the
nanocomposites.
a b
c
Figure 5. Scanning electron microscope (SEM) micrographs taken at the tensile break surface for the 30
wt % glycerol plasticized WG composites containing 4 wt % (a), 6 wt % (b) and 10 wt % silica (c),
respectively [49].
Figure 6. Transmission electron microscopy (TEM) images of 3 wt % methyl tallow bis-2-hydroxyethyl

quaternary ammonium-modified clay filled WG (A) and WG/PVA (90/10) composites (B) thermally
mixed at 90 ~ 95 °C for 5 min at a speed of 100 rpm and compression-molded at 130 °C for 5 min [63].
a b
Figure 7. Influence of MC content on storage modulus (E ) (a) and loss factor (tan ) (b) at frequency (f)
of 1 Hz as a function of temperature T for the 25 wt % glycerol plasticized WG composites thermo-
molded at 127 °C for 8 min [44].
DYNAMIC MECHANICAL AND GLASS TRANSITION BEHAVIORS

Dynamic mechanical analysis (DAM) is frequently applied to characterize the glass
transition, the molecular motion and the reinforcement effect in the WG composites. Figure 7
shows storage modulus (E ) and loss factor (tan ) at frequency (f) of 1 Hz as a function of
temperature (T) for the plasticized WG/MC composites. With increasing temperature, the
composites traverse the glassy, the transition and the rubbery plateau regions in sequence. E
displays a typical value of (3 ~ 7) GPa in the glassy region and a dramatic two-step decrease
is observed in E at the wide glass-to-rubber transition region. Correspondingly, the tan
curves reveal two mechanical loss peaks with the maxima located at the temperature ranges -
31.5 ~ -23.3 C and 51.5 ~ 104.1 C, respectively, depending on MC content.
The wide glass transition of WG bioplastics without MC has been ascribed to the wide
distribution of molecular weight of WG proteins and the presence of a small amount of
residual nonproteinic molecules in WG [64]. The plasticizing effect of glycerol is different for
different protein subunits so that the plasticized WG matrix still presents a wide distribution
of chain mobility [65]. As the MC microfiber do not undergo a glass transition in the test
temperature range, the variations in the dynamic mechanical behavior due to the microfiber
addition can be undoubtedly attributed to the filling introduced variation in the WG matrix.
The high- and the low-temperature mechanical loss peaks are assigned to glass transition
temperatures (Tg1 and Tg2) of the gluten- and the glycerol-rich phases, respectively [66]. In
WG/organoclay namocomposites, the low temperature at -60 ~ -50 C is assigned to the -
transitions that are not influenced by the addition of nanoparticles [63]. Although the WG
composites may absorb some moisture at ambient condition, a transition due to ice melting is
usually not observed at approximately 0 C, indicating that the absorbed water molecules are
strongly hydrogen-bonded with protein macromolecules and there are no free water
molecules existed in the composites. In WG/PVA composites, the low temperature transition
is assigned to the glass transition of bound water and glycerol strongly associated with the
polymer matrix through hydrogen bonding [67]. Both tan peaks of the WG/MC composites
are shifted to high temperatures with increasing MC content, indicating that incorporation of
MC microfibers restricts the mobility of molecular chains in the WG matrix partially due to
the interfacial interaction between the MC microfiber and the plasticized WG matrix. A part
of plasticizer in the composites would be absorbed by MC microfibers especially at high MC
contents, which might be another reason for the increases in Tg1 and Tg2.
MC content influences activation energy (Ea) of glass transitions of the gluten- and the
glycerol-rich phases (Figure 8). Ea(Tg1) associated with Tg1 decreases with addition 3.8 wt %
MC microfibers, which can be ascribed to the improved plasticization effect of glycerol to the
WG matrix as a consequence of fiber filling. Further increasing MC content gives rise to a
significant increase in Ea(Tg1) ascribed to the reinforcement effect. On the other hand, Ea(Tg2)
associated with Tg2 does not vary markedly with MC content, implying that the MC
microfibers interact with WG in the gluten-rich phase and hardly impose sensitivity of
molecular motion in the glycerol-rich phase with respect to temperature.
The content of HEC particles also influences Tg1 and Tg2 and the corresponding peak
values of tan of the composites (Table 1) [45]. In comparison with the WG bioplastic,
increasing HEC content in the composite causes the values of the two tan peaks to decrease
gradually. Loading of 4.8 wt % HEC filler causes Tg1 to decrease by 5 C, suggesting that a
low content of HEC weakens the intermolecular interaction among WG proteins. In fact, the
glycerol plasticizer is not dispersed homogeneously in the WG and the HEC components in
the composites. A large portion of glycerol is inclined to mix with WG so as to plasticize the
WG continuous phase. The enrichment of the plasticizer in the WG matrix leads to an
improved plasticization effect. Further loading of HEC filler results in an increase in Tg1,
which is the same as that found in the WG/MC composites and can be also ascribed to the
interfacial interaction between the HEC particle surface and the WG matrix and the gradual
migration of glycerol from the matrix phase to the filler phase [68]. The interfacial interaction
restricts the molecular motion of protein macromolecules [34] so as to reduce the peak value
of tan corresponding to Tg1 markedly. However, Tg2 of the glycerol-rich phase is located at -
38.7 1.2 C, seeming independent of the HEC content.
Figure 8. Influences of MC content on activation energy (Ea) of Tg1 and Tg2 for the 25 wt % glycerol
plasticized WG composites thermo-molded at 127 °C for 8 min [44].
Table 1. Influence of HEC content on glass transition temperatures and corresponding

tan maximum values for the gluten-rich and the glycerol-rich phases in the 30 wt %
glycerol plasticized WG composites thermo-molded at 120 C for 5 min [45].
HEC content / wt % Tg1 / C tan at Tg1 Tg2 / C tan at Tg2

0 49.2 0.533 -36.7 0.163
4.8 44.0 0.516 -38.2 0.155
9.1 50.0 0.489 -39.8 0.149
13.0 49.2 0.473 -38.3 0.147
16.7 50.4 0.448 -40.0 0.140
23.1 53.3 0.417 -39.0 0.133
DMA test shows that introduction of silica particles to the WG/silica composite causes E
in the rubbery region to increase significantly with respect to the 30 wt % glycerol plasticized
WG bioplastic (Figure 9) [49]. Meanwhile, tan in this region is lowered considerably with
increasing silica content, which is ascribed again to the interfacial interaction between the
silica particle and the WG matrix via electrostatic attraction and hydrogen bonding of silanol
group on silica surface with the reactively polar amine group of WG proteins [68]. The WG
bioplastic shows two high temperature peaks at 53.6 C and 77.3 C, respectively. The
composite containing 2 wt % silica still exhibits two high temperature tan peaks at 32.0 C
and 76 C, respectively. However, the composites containing 8 wt % and 10 wt % silica
shows only one broad and flat tan peak with a maximum located at 55.0 C.
Splitting of the high temperature glass transition peak into two sub-transitions has also
been observed in WG nanocomposites containing 3 wt % exfoliated nanoclay [63]. The
maximum tan of the nanocomposites is significantly lower than that of WG due to the
motional restriction. The peak appearing at around 26 ~ 33 C is attributed to the Tg of the
plasticized matrix. Despite of the significant reinforcement effect of the nanoparticles, the
major high temperature tan peak is shifted only slightly to higher temperatures because
quaternary ammonium as the nanoclay modifier causes an additional plasticization to the
matrix.
There exists only one glass transition in extruded and injection molded PCL/WG
composites. Tg and its corresponding heat capacity are very close to those of pure PCL, which
is one of the indications of miscibility or interaction between the two components [69]. The
nature of the interaction seems to be physical (possibly hydrogen bonding) rather than
chemical, as is revealed from infrared spectra.
Repeated heating-cooling cycling may influence the phase structure of WG blend.
PLA/WG (20/80, 50/50, 80/20) blends show a Tg followed by PLA crystallization and
melting transitions [70]. However, subsequent heating-cooling cycling of the blend leads to
decreases in the crystallization and melting temperatures of PLA and the appearance of a
second Tg, revealing a heating-cooling cycling induced phase separation between the two
polymers that causes a WG aggregation. Heating-cooling cycling also leads to phase
separation and reduction in crystallinity of PLA in the blend made from PLA and
transglutaminase crosskined WG [71].
a b
Figure 9. Temperature dependence of storage modulus E (a) and loss tangent tan (b) for the 30 wt %
glycerol plasticized WG and for the WG composite containing 2 wt %, 8 wt % and 10 wt% silica [49].
MECHANICAL PROPERTIES
The mechanical behavior of thermally processed WG bioplastics might be tailored by
controlling the molding temperature that determines the crosslinking density of the WG
matrix via disulfide formation [56] or by addition of crosslinking agents such as aldehydes
that introduce additional crosslinking bonds between protein macromolecules [66]. The WG
bioplastic may exhibit thermoplastic or elastic deformation characteristic depending on the
crosslinking density and the degree of phase separation.
In the composites with plasticized WG as the matrix, addition another component in the
filler form undoubtedly results in the reinforcement effect. As viewed from stress-strain ( - )
curves, the plasticized WG/MC composites show a yielding like uniaxial stretching
deformation when MC content is below 11.6 wt % (Figure 10). Stress increases rapidly at
small strains but very slowly after yielding. Increasing MC content leads to a significant
improvement in deformational stress at a same strain at the expense of extensibility. The
composite containing 15.8 wt % MC breaks immediately after yielding. The composites
containing more than 24.4 wt % MC become very brittle and break before yielding.
MC content influences Young‘s modulus (E), tensile strength ( b) and strain at break ( b)
of the plasticized WG composites markedly (Figure 11) [44]. E remains almost unvaried
while b decreases slightly with addition of MC microfibers below 8 wt %. Further increasing
MC content gives rise to marked increases in both E and b. b achieves maximum at 33.3 wt
% MC content. E and b at 33.3 wt % MC loading increase by 5.5 and 1.8 times, respectively,
compared to those of the WG bioplastic. On the other hand, b decreases continuously from
132 % to 4 % as increasing MC content from 0 wt % to 42.8 wt %. Correlation analysis shows
that, at the 0.01 level, the mechanical properties are highly related to Tg1. The correlation
coefficients are 0.922, 0.835, and -0.930 for E, b, and b, respectively. Analyzing E as a
function of MC content using the Halpin-Tsai equation for short fiber reinforced composites
[72] yields an aspect ratio of 10.65 0.36 and a Young‘s modulus of 2.73 GPa for the MC
microfiber.
Figure 10. Influence of MC content on stress-strain ( - ) relationship of the 25 wt % glycerol

plasticized WG composites thermo-molded at 127 °C for 8 min [44].
Figure 11. Influences of MC content on Young‘s modulus (E), tensile strength ( b) and strain at break
( b) for the 25 wt % glycerol plasticized WG composites thermo-molded at 127 °C for 8 min [44].
In the WG/HEC composites, E increases slightly and b remains essentially constant with
increasing HEC content below 16.7 wt % (Figure 12). Further addition of HEC filler leads to
significant increases in both E and b. E and b of the 31.8 wt % HEC reinforced composite
improve by 8.8 and 2.0 times, respectively, in comparison with those of the WG bioplastic.
On the other hand, b decreases with increasing HEC content, from 207 % to 43 % as
increasing HEC content from 0 wt % to 31.8 wt %.
Figure 12. Influence of HEC content on Young‘s modulus (E), tensile strength ( b) and strain at break
( b) for the 30 wt % glycerol plasticized WG composites thermo-molded at 120 C for 5 min [45].
From uniaxial tensile test of the WG/silica composites prepared from 30 wt % plasticized
WG, E and b increase from 21.8 MPa to 55.2 MPa and from 3.5 MPa to 5.9 MPa,
respectively, with increasing silica content from 0 wt % to 10 wt % (Table 2) [49]. b does not
vary markedly at silica content below 6 wt % while it decreases rapidly at higher silica
contents, indicating that the strong interfacial interaction restricts the deformability of the WG
matrix. There are discontinuous changes of E, b, and b at a filler content of 6 wt %. At silica
content below 6 wt %, the variation of E as a function of silica content can be fitted to the
Guth-Gold model, suggesting that silica particles are finely dispersed in the WG matrix. On
the other hand, E is considerably higher than the prediction of the Guth-Gold model at higher
silica contents. The strong hydrogen bonding interaction between silanol groups on silica
surface may cause aggregation of silica particles at contents above 6 wt % in the highly
inhomogeneous composites. The silica aggregation significantly influences the mechanical
behavior. The reinforcing effect might be governed by the hydrodynamic effect of the
particles at low silica contents and the percolation mechanism at high silica contents.
Incorporation calcium carbonate into the WG composites causes increases in both E and
b (Table 2) [50]. On the other hand, b decreases from 221 % at 0 wt % to 145 ~ 165 % at
6~10 wt % calcium carbonate, indicating that the interfacial interaction between calcium
carbonate particle and proteins somewhat restricts the deformability of the WG matrix. The
variations in E, b, and b are abrupt at 4 wt % calcium carbonate, suggesting that calcium
carbonate particles may form a filler network together with absorbed WG molecules.
Table 2. Effects of filler content on Young’s modulus (E), tensile strength ( b) and
elongation at break ( b) for the 30 wt % glycerol WG composites containing silica [49]
and calcium carbonate molded at 120 C for 15 min [50]
Filler content (wt %) WG/silica composites WG/calcium carbonate composites

E / MPa b / MPa b/% E / MPa b / MPa b/%
0 21.8 1.6 3.5 0.1 154.5 11.8 12.3 0.8 2.8 0.3 221.1 11.7
2 22.8 3.1 4.4 0.2 184.8 10.4 13.9 1.2 3.3 0.1 230.2 7.3
4 25.6 2.0 4.3 0.3 161.2 19.0 14.4 1.5 3.4 0.1 218.4 17.9
6 25.7 0.5 4.3 0.2 169.0 17.8 22.0 2.1 4.1 0.1 163.4 10.6
8 49.3 4.3 6.7 0.4 138.4 11.2 24.7 1.8 4.4 0.1 151.9 12.5
10 55.2 7.8 5.9 0.1 76.0 21.5 25.9 1.8 4.9 0.1 165.9 4.9
Composites using WG/starch/glycerol as matrix and natural fibers as reinforcement have

been produced by melt-mixing in an intensive batch mixer followed by compression molding
[73, 74]. Sisal, coconut and jute fibers favor an improvement in mechanical properties. Sisal
fiber addition causes increases in E and b by approximately 560 % and 162 %, respectively,
with respect to the WG/starch/glycerol matrix, which is accompanied by reductions in b and
water absorption at equilibrium [74]. Chemical treatment of the fibers by mercerization
affects the mechanical properties of the composites [73]. Alkaline treatment of coconut and
jute fibers not only removes impurities from the surfaces but also partially removes lignin and
hemicellulose, thereby producing a rougher fiber surface, which results in further
improvement in E and b due to the improved interfacial adhesion strength between the fibers
and the matrix.
WG are able to blend with other cysteine-containing proteins such as keratin and
lactalbumin obtained from agricultural sources to form materials with the attributes of each
protein [75]. The cysteine residues allow for the formation of inter- and intramolecular
disulfide bonds among different kinds of proteins. The addition of WG to other cysteine-
containing proteins improves toughness appearing as an increase in b. On the other hand, the
addition of lactalbumin increases E and b of protein blends.
A phase heterogeneity is present in the WG/PVA composites compression molded at 130
C [67]. The composites are characterized with different molecular motion characters in the
WG/PVA miscible phase, the plasticized WG and the PVA phases due to the different extents
of interactions. The glycerol plasticizer predominately associates with the WG component
rather than PVA. In comparison with the WG bioplastics, E and b are improved by 15 ~ 33%
and 21~54 %, respectively, at 10 ~ 25 wt % PVA. Increasing the amount of PVA does not
enhance the intermolecular interactions between the two polymer components so that b is
reduced with increasing the PVA content in the composites.
In the he PCL/WG composites, WG particles do not act as reinforcing filler to PCL. Both
yield stress and b of the PCL/WG composites decrease linearly with increasing WG content.
Up to 20 wt % WG can be incorporated into the PCL/WG composites that exhibit very high
deformability with b above 900 % [53] (Figure 13). After yielding, the composites undergo
stress drop, cold drawing and strain hardening in succession. The composites at 35 ~ 50 wt %
WG content break before appearance of strain hardening because of the formation of voids
and the appearance of failure of the PCL matrix near the WG particles. b decreases
dramatically to less than 100 % at 50 wt % WG. There is a particle-induced transition from an

even distribution of stress in the propagating neck at below 20 wt % WG to fracture without
neck propagation at above 35 wt % WG. In fact, incorporation of WG particles at high
contents restrains the yielding, the necking and the hardening behaviors of the semicrystalline
PCL matrix.
Hydroxyl-functional polyesters are surprisingly compatible with WG proteins [76].
Hydrolyzed WG has been combined with poly(hydroxyl ester ether) to produce thermoplastic
blends with acceptable mechanical properties comparable to commercial thermoplastic
plastics [77]. The blends can be produced by using commercial extrusion and molding
equipments without the addition of plasticizers. Micrographs of fracture surfaces indicate
some degree of moderate adhesion between WG and poly(hydroxyl ester ether) up to 20 ~ 70
wt % WG. E, b and critical stress-intensity factors of the composites fall in the range of 0.8 ~
1.5 GPa, 10 ~ 30 MPa and 2 ~ 9 MPa m1/2, respectively, depending on the amount of WG. As
the WG content is increased, the materials gradually lose ductility and fail in a brittle manner.
The exfoliation of the clay nanoparticles results in significant enhancement of mechanical
properties for the WG, the deamidated WG proteins and the glyoxal crosslinked WG/PVA
blend [63]. At 3 wt % organoclay content, b is improved by 1.2 ~ 1.6 times depending on the
structure of wheat proteins and the composition of the composites. The predominant
interactions between the WG matrix and the nanoparticles in the nanocomposites result in
motional restriction in the mobile phases including lipid, plasticizers, and plasticized
components without significant influence on the mobility of the rigid unplasticized
components.
Figure 13. Stress-strain curves for the injection-molded PCL/WG composites [53].
INFLUENCE OF PROCESSING CONDITION

In WG bioplastics, thermal treatment of WG at elevated temperatures causes a
progressive increase in content of sodium dodecyl sulphate-insoluble fraction due to the WG
aggregation reaction that is highly dependent on both temperature and time [78, 79].
Increasing molding temperature from 100 °C to 130 °C does not effect on Tg markedly
whereas it causes a significant reduction in protein solubility from 38 % to 9 % for the WG
bioplastics [80]. The processing condition influences the crosslinking degree of the WG
matrix, which affects the performance of the WG composites greatly.
For the WG/hemp fibers composites prepared by successive mixing and thermo-molding,
b increases and b decreases with increasing hemp content [80]. However, the mechanical
properties are less sensitive to the molding temperature when the fiber content increases up to
20 wt %. For the composites prepared from unplasticized WG and basalt yarn, b and b
increase simultaneously with increasing molding temperature [48]. On the other hand,
molding temperature has a small effect on E, except at 160 C where the WG proteins
undergo thermal decomposition.
At molding temperature of 120 C, increasing molding time from 5 min to 30 min
improves E and b notably while b remains almost unchanged for the plasticized WG
composites containing 31.8 wt % HEC (Figure 14) [45]. Improvement in mechanical
properties with increasing molding time has been observed in WG bioplastics molded at 90 ~
130 °C [81]. The WG/HEC composites with a molding time of 5 min and 10 min show a
single glass transition of the gluten-rich phase at Tg1 = 48.4 C and Tg1 = 35.6 C, respectively
(Figure 15). On the other hand, the composites thermo-molded for 20 min and 30 min show
splitting of the glass transition of the gluten-rich phase, with a main glass transition peak
located at 67.7 C and a shoulder peak at 38.5 C, which reveals an improved structural
heterogeneity in this phase with extending the crosslinking reaction time of WG proteins. The
tan value at the glass transition region of the gluten-rich phase decreases with increasing
molding time, which is mainly involved in increase in crosslinking density of the WG
network and explains the increases of E and b for the WG/HEC composites.
Figure 14. Influence of molding time on Young‘s modulus (E), tensile strength ( b) and strain at break
( b) for the 30 wt % glycerol plasticized WG composites containing 31.8 wt % HEC compression
molded at 120 C [45].
Figure 15. Influence of molding time on loss factor (tan ) curve for the 30 wt % glycerol plasticized
WG composites containing 31.8 wt % HEC compression molded at 120 C [45].
INFLUENCE OF PLASTICIZER CONTENT
The content of plasticizer imposes on the glass transition and the molecular mobility of
the WG proteins so that it influences the performance of the WG composites markedly. In
general, the plasticizing effect causes a decrease in Tg of the WG matrix and lowers the
cohesiveness of protein chains. A large amount of plasticizer can reduce the strong
intra/intermolecular interactions among WG protein macromolecules and therefore improves
the flexibility and the extensibility of the resultant composites [6].
For the WG/HEC (8/2) composites, increasing glycerol content from 23.0 wt % to 37.5
wt % causes E and b to decrease from 24.1 MPa to 1.0 MPa and from 1.1 MPa to 0.3 MPa,
respectively (Table 3). On the other hand, b increases with increasing glycerol content, from
46 % to 70 % as increasing glycerol content from 23.0 wt % to 37.5 wt %. DMA test shows
that the WG composites with a high glycerol content exhibit high E value in the glassy
region, which can be assigned to the antiplasticization effect [3, 82]. High glycerol content
helps to retain moisture and the water/glycerol mixture crystallizes at this low temperature
range, which stiffens the WG matrix of the composites. In the glassy transition region, both
Tg1 and Tg2 decrease significantly with increasing glycerol content (Table 3). The Tg
depression phenomenon with increasing glycerol content is similar to that observed in the
WG bioplastics [65, 83] and it well accounts for the variation in tensile properties. While the
tan value at Tg1 does not vary markedly, increasing glycerol content brings a gradual
increase in the tan value at Tg2. The Tg2 depression and the increase in the corresponding
tan value distinctly reveal that glycerol addition improves the mobility of the protein
segments in the glycerol-rich domain.
Glycerol content can be used to adjust the processing and mechanical behaviors of the
WG/silica composites. Moisture absorption (MA) and b of the WG/silica (9/1) composite
increase while E and b decrease as the amount of glycerol increases (Table 4), which is in
agreement with the findings in plasticized WG [10, 11, 84]. The glycerol plasticizer is very
hygroscopic and tends to uptake water molecules into the WG composites. Therefore, MA
becomes higher at higher glycerol content.
Table 3. Influence of glycerol content on mechanical and glass transition behaviors for
the WG/HEC (8/2) composites [46]
Glycerol Mechanical properties Glass transition behavior

content (wt %) E / MPa b / MPa b/% Tg1 / C tan at Tg1 Tg2 / C tan at Tg2
23.0 24.2 1.8 1.1 0.10 47 47 82.4 0.482 -31.3 0.087
28.6 8.7 2.0 0.8 0.10 63 3 57.4 0.425 -32.4 0.131
33.3 3.6 0.3 0.5 0.08 71 21 42.0 0.462 -34.6 0.167
37.5 1.0 0.1 0.3 0.05 70 5 30.3 0.460 -36.6 0.201
Table 4. Influence of glycerol content on mechanical properties and moisture absorption

of the WG/silica (9/1) composites [49]
Glycerol content (wt %) Mechanical properties MA / %

E / MPa b / MPa b/% 75 % RH 52 % RH
20 117.0 10.0 10.4 0.3 118 8 17.0 0.3 7.2 0
30 55.2 7.8 3.8 0.1 173 33 20.5 0.4 7.9 0.3
40 3.0 0.4 1.5 0.1 192 11 27.4 0.4 11.8 0.5
The plasticizer content imposes on the morphology and properties of the WG/polymer
blends. A droplet-like structure is formed in the unplasticized WG/aliphatic polyester blends
[85]. E increases slightly with increasing WG loading due to some degree of adhesion
between the WG granules and the polyester matrix. The plasticized WG is more flexible than
polyester, resulting in ductile blends whose ductility is improved with increasing glycerol
content. For the plasticized WG/aliphatic polyester blends, the size of the WG phase reduces
drastically due to large deformations during processing. Consequently, a co-continuous
morphology is formed in the blend prepared from the 50 wt % glycerol plasticized WG.
COMPATIBILIZATION
WG proteins are hydrophillic and are usually immiscible with most synthetic
hydrophobic polymers. The poor interfacial adhesion in the blends really results in inferior
mechanical properties. Compatibilizers have been used to improve the miscibility and thereby
the properties of the WG composites. Polymers with functional groups capable of reaction
can form block or graft copolymers with WG proteins during blending, making the blend
more compatible.
The WG/polymer blends in the absence of compatibilizers usually form a two-phase
structure due to the poor compatibility and interfacial adhesion. Large WG granules are
dispersed in the continuous PCL phase in the extruded WG/PCL blend. Anhydride-modified
polycaprolactone (PCL-MA) could interact with the functional amino groups on the WG
proteins [52]. In the presence of 2.5 wt % PCL-MA, WG granules are well-dispersed within
the PCL matrix, which significantly improves the physical properties over those of simple
mixtures of WG and PCL and causes a shift of tan peak associated with the melting
temperature of PCL and the Tg of WG to higher temperature. Both E and loss modulus (E )
of the compatibilized blends are an order of magnitude higher than the blends of simple
mixtures.
A multifunctional macromolecular thiol obtained by esterification of PVA with 3-
mercaptopropionic acid presents as effective means of improving the strength and toughness
of compression molded native WG bars via disulfide-sulfhydryl exchange reactions [86]. The
addition of just a few mole percent of thiol to PVA is sufficient to dramatically change its
compatibility with WG proteins [51]. There are a gluten-rich phase and a thiolated PVA-rich
phase in the WG/thiolated PVA blend. The phase domains range in size from 10 to 100 nm,
which are roughly 10 times smaller than those of the WG/PVA blend (Figure 16). In the
WG/PVA blend, Tg of the WG phase is not influenced by the PVA content and PVA typically
improves flexibility but lowers modulus. On the other hand, addition of thiolated PVA causes
a reduction in Tg of the WG phase, indicating some incorporation of thiolated PVA into the
portion macromolecules of the WG phase [51]. Thiolated PVA can increase b, b and E
simultaneously by up to 76 %, 80 %, and 25 % over WG [86].
THERMAL DEGRADATION
Thermogravimetric analysis (TGA) is useful to study the thermal stability of a polymer
and its composites. TGA involves continuous weight measurement as the sample temperature
increases and the weight loss at higher temperatures can be related to polymer decomposition.
In the WG/PLA composites, PLA is more heat-resistant than WG. A higher amount of
PLA delays the beginning of the weight loss process and results in a lower ash content [70].
In nitrogen environment, the neat PCL and WG exhibits one degradation profile in TGA
curve, while the WG/PCL composites show a two-step transition devoid of clear line between
the two components [69]. The degradation activation energy increases at higher levels of WG
due to its degradation slower than PCL.
a b
Figure 16. Transmission electron microscopy (TEM) images of compression molded WG blends
containing 20 wt % PVA (a) or thiolated PVA (5.5 mol % thiol) (b) [51]
TGA in air atmosphere reveals that the glycerol plasticized WG/MC composites exhibit a
three-stage decomposition that could be readily realized in the derivative thermogravimetric
(DTA) curves (Figure 17) [44]. The DTA curve of the WG bioplastic displays three isolated
peaks centered at 190 C, 276 C, and 345 C, respectively. The first stage (stage A in Figure
17a) corresponds to the water loss [87] and the temperature at 5 wt % weight loss (T-5%) is
located at 152 C (inset of Figure 17a). Addition of MC microfibers in the composites with
contents below 8.0 wt % leads to a slight decrease in T-5%. Addition of 11.6 wt % MC causes
T-5% to drop sharply by about 70 C. Further addition of MC microfibers cause T-5% to
increase slowly. In comparison with the WG bioplastic, the reduction in T-5% of the composite
is due to the rapid moisture desorption along the interface between the MC microfiber and the
WG matrix. The second stage (stage B in Figure 17a) of weight loss is assigned to the
glycerol evaporation and the WG degradation [87], giving rise to two decomposition peaks at
T1 = 190 C and T2 = 276 C, respectively (stage B in Figure 17b). These two decomposition
peaks are absent in the composites containing more than 11.6 wt % MC microfibers, which
might be ascribed to the significant reduction in rates of the glycerol evaporation and the WG
thermal degradation as a consequence of MC microfiber incorporation. The third stage of
degradation of the WG bioplastic starts from 300 C and gives rise to a decomposition peak at
T3 = 346 C, which corresponds to the oxidation of the partially decomposed protein residues.
The T3 value remains constant at MC contents below 15.8 wt % while it is shifted to high
temperatures at higher MC contents. For 33.3 wt % and 42.8 wt % MC filled composites, T3 is
located at 359 C and 368 C, respectively, being even higher than the decomposition
temperature of pure MC at 354 C [88], suggesting that, at high loading levels, the interaction
between the MC microfibers and the WG matrix might delay the thermal degradation of the
composites.
a b
Figure 17. Influence of MC content on thermogravimetric analysis (TGA) (a) and derivative
thermogravimetric (DTA) (b) curves in air atmosphere for the 25 wt % glycerol plasticized WG
composites thermo-molded at 127 °C for 8 min. The inset in part a shows the influence of MC content
on the temperature at 5 wt % weight loss T-5% [44].
Figure 18. Effect of WG content on weight loss of extruded and injection-molded PCL/WG composite
during enzymatic degradation [69].
BIODEGRADATION
WG bioplastics can fully biodegrade after 36 days in aerobic fermentation and within 50
days in farmland soil without releasing toxic products [89]. When buried in the soil, the
WG/basalt composites undergo biodegradation [48]. The WG component in the composites
could biodegrade completely after 40 day. Moduli of both the WG bioplastics and the
composites decrease steadily versus degradation time. The WG/aliphatic polyester blends are
fairly sensitive to microbial degradation in soil, becoming brittle and fragmented very easily
after 4 weeks [85].
PCL exhibits a low weight loss after enzymatic degradation, whereas presence of WG
ncreases weight loss of the PCL/WG composites [69]. The enzymatic degradation of the
PCL/WG composite is related to the processing method. Proteinase degradation activity on
the extruded composites is much higher than the injection-molded composites as indicated by
a higher weight loss in the extruded samples immersed in enzyme buffer containing
proteinase-K for 4 days (Figure 18). Higher WG amount increases the weight loss following
enzyme treatment.
MOISTURE ABSORPTION
The effect of moisture absorption (MA) on the glass transition as well as the thermal and
mechanical properties is of great importance to the ultimate usability of the biopolymer-based
plastics and composites. MA of the WG composites strongly depends on relative humidity
(RH) (Figure 19), the values at 75 % RH being considerably higher than those at 35 % RH
[44]. Increasing MC content gives rise to only a slight decrease in MA at 35 % RH without
significant difference (P > 0.05) while the reduction in MA at 75 % RH is rather significant
(P < 0.05). The WG bioplastic absorbs about 21.7 wt % moisture at 75 % RH, whereas the
MA value is reduced to about 16.2 wt % for the composite containing 42.8 wt % MC. Though
the HEC filler does not influence the morphology of the glycerol-plasticized WG matrix, MA
of the composites decreases almost linearly with increasing HEC content (Figure 19). The
MA value at 75 % RH is reduced from 14.5 % to 9.6 % as the HEC content is increased from
0 wt % to 23.1 wt % with respect to the total mass of the composites. Similarly, the MA
reduction has also been observed in WG/silica and WG/calcium carbonate composites (Table
5) [49, 50] and also in soy protein isolate based composites containing cellulose or chitin
whiskers [5, 36]. There is a discontinuous change in MA at silica content of 6 wt %, which
might be caused by the change in the dispersion of silica particles in the composite [49]. At
higher silica contents, the aggregation of silica particles causes a reduction in moisture
uptake.
The present investigations disclose that MA of the WG composites could be reduced in
some extent by addition of filler components. However, the WG composites, especially
glycerol plasticized, could not be made into hydrophobic materials essentially. Specific
interactions of water with the WG matrix and the glycerol plasticizer are responsible for the
substantial moisture uptake. Chemical modification of WG should be performed to improve
the hydrophobic nature of the WG composites to restrain the sensitivity of properties with
respect to surrounding humidity.
Figure 19. Influences of filler content on moisture absorption (MA) at equilibrium for the 25 wt %
glycerol plasticized WG/MC composites (solid symbols) [44] and the 30 wt % glycerol plasticized
WG/HEC composites (hollow symbol) [45].
Table 5. Influence of filler content on moisture absorption (MA) at equilibrium for the
WG composites at two different relative humidities [49, 50]
Filler content (wt %) WG/silica composites WG/calcium carbonate

composites
75 % RH 52 % RH 75 % RH 52 % RH
0 22.5 0.6 10.1 0.2 20.4 0.1 10.1 0.1
2 21.7 0.2 9.6 0.4 20.0 0.1 9.9 0.1
4 21.3 0.2 9.4 0.1 19.8 0.1 9.7 0.2
6 20.9 0.1 9.2 0.2 18.3 0.3 8.0 0.3
8 19.8 0.3 8.0 0.1 17.9 0.2 7.6 0.1
10 18.8 0.2 7.7 0.2 16.8 0.2 7.2 0.2
Otherwise, addition of a secondary hydrophobic component for lowering the moisture

sensitivity of casting WG films or thermally processed WG bioplastics has been performed.
For example, mineral oil has been used to lower water vapor permeability of casting WG film
[90]. Hydrophobic liquids such as castor oil have been used to reduce MA and to improve
mechanical strength of thermo-molded WG bioplastics [91]. Some amphiphilic compounds
with a low melting point and a moderate hydrophobicity can plasticize WG during the
thermoplastic processing. The compatible quantity of saturated fatty acids with WG becomes
smaller with increasing the chain length of the fatty acid [92]. Substitution of glycerol by a
fatty acid lowers water vapor permeability of compression molded WG films greatly, from
62.0 ×10-12 mol m-1 s-1 Pa-1 to (5 ~ 21.9) ×10-12 mol m-1 s-1 Pa-1. Addition of octanoic acid
could delay the swelling of WG bioplastics immersed in water [25]. Water vapor permeability
of wheat films can also be reduced by controlling the heat-curing temperature [93]. The use of
hydrophobic and amphiphilic compounds and the adjustment of processing technique open
thus new ways for the improvement of hydrophobicity of WG composites.
CHEMICAL MODIFICATION
The mechanical performance of plasticized WG materials can be significantly modified
through the formation of different chemical and network structures using different
functionalized polymers. This methodology plays a key role in enhancing the hydrophobicity
of the hydrophilic WG proteins to provide high humidity resistance, thus extending its
application.
A cross-linked WG/polymer network has been prepared via grafting poly(ethylene oxide)
diglycidyl ether (PEODGE) onto the protein macromolecules through reactions between the
epoxy groups of PEODGE and the amino groups of WG proteins followed by coupling the
excess PEODGE segments by ethylene diamine [94]. The system at a PEODGE/ethylene
diamine ratio of 1/1 is soluble though the molecular weight of protein is increased. Reducing
the amount of ethylene diamine produces an insoluble cross-linked network. Similarly, a
copolymer containing glycidyl methacrylate (GMA) segments can be grafted onto wheat
proteins in aqueous condition under high sheer rate [95]. Coupling the excess epoxy groups
using ethylene diamine leads to the formation of a crosslinked network. The dried materials
can be made into articles via thermal processing such as compression molding at 130 C. The
crosslinked network shows reduced solubility and water uptake with increasing the content of
the GMA copolymer from 10 wt % to 30 wt %. In comparison with WG, the onset
temperature of glass transition is significantly reduced upon addition of PEODGE or GMA
copolymer and the materials become more flexible at room temperature [94, 95]. The
proportion of mobile protein chains is increased as a result of the plasticization effect from
the mobile modification segments of the PEODGE or the GMA copolymer. The epoxy-
functionalized silane coupling agents such as glycidoxypropyl trimethoxy silane and
glycidoxypropyl methyldiethoxy silane can achieve the same effect to improve mechanical
properties of WG bioplastics [96].
Thiol-containing modifying agents could improve the fracture toughness of WG
bioplastics [97]. Remarkably, mechanical properties of the modified WG formulations stored
in ambient conditions are improved with time. The multifunctional activity of the polythiol-
containing molecules generates the potential for developing fully biodegradable composites
based on modified WG-coated fiber bundle [98]. A reasonably strong interface between the
natural fibers and the WG matrix can form spontaneously after drying the fiber/WG-
dispersing mixture and compression-molding the dried mixture at elevated temperatures.
Modifiers including sodium hydroxide, urea, sodium dodecyl sulfate, sodium
dodecylbenzene sulfonate, and guanidine hydrochloride have been used to modify wheat
protein in aqueous medium for preparing non-petroleum based, biodegradable composites
containing natural fibers derived from straw, corn stalks, sorghum stalks, soybean hulls, and
peanut hulls [99]. Compression molding at elevated temperatures yields composites with a
moisture content of less than about 20 wt % and a compressive strength of at least about 5
MPa.
CONCLUSION
Thermally processed green composites based on WG show promising potential for large-
scale production and their applications will be beneficial to reduce plastic waste and improve
recyclability. The structures and properties of WG composites are dependent on several
parameters such as the content of plasticizer, the structure and nature of the secondary
component, the compatibilizer and the interfacial adhesion, as well as the fabrication method
and condition. The processability and toughness of WG composites could be easily adjusted
through use of plasticizers and appropriate processing equipment. Improvement of
mechanical properties of WG composites by addition of organic and inorganic components
either in the particle or the fiber forms would attract the interest of industry and consumers.
Especially, inclusion of nanoparticles or rigid microfiber in WG composites can improve
tensile strength and modulus significantly, which is accompanied by restriction in molecular
motion and increase in glass transition temperature of the WG phase. Chemical modification
of WG should provide a promising way for controlling the interfacial adhesion strength of the
filled WG composites.
WG can also be used in the filler form to blend with synthetic biodegradable polymers
such as PLA, PCL, PVA and poly(hydroxyl ester ether) to improve the mechanical, thermal
and biodegradation properties. Compatibilizers containing active groups being able to react
with WG proteins are used in the WG blend to produce a stronger, tougher and more
homogeneous material. Usage of compatibilizer and plasticization of WG might lead to a
great change in morphology of the WG blend, leading to the reduction in the size of the WG
domains or the formation of a co-continuous structure.
Further research is still needed to understand how properties are affected by the
plasticizer structure and content, the composite composition, the microstructure, and the
component interactions in the WG green composites. Improvement of hydrophobicity either
by addition of hydrophobic and amphiphilic compounds or by chemical modification of the
WG proteins would be the key for tailoring the structure and properties of the WG composites
and for extending their application in a wide range. Biodegradation of the WG composites
should be evaluated in detail to guide the thermal processing and the control of the
composition, the interfacial interaction and the properties of the final products.
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Chapter 2
FLAX AS POTENTIAL FIBER FOR REINFORCEMENT

IN COMPOSITES
A. S. Singha and Vijay Kumar Thakur*

Applied Chemistry Research Laboratory, Department of Chemistry
National Institute of Technology Hamirpur (H.P.) 177 005, INDIA
ABSTRACT
Among natural fibers, flax fibers are frequently used as reinforcing materials due to
their characteristics properties such as high mechanical properties, low density,
biodegradability, low cost, high specific strength and modulus, no health risk, easy
availability in nature, renew ability etc. On account of its eco-friendly nature, flax fibers
are considered as a future material for preparing reinforced composites. Over the last few
years, there has been an ever-increasing interest in finding new features for flax - fiber-
reinforced composites. This chapter introduces promising applications and recent
developments of flax fiber and its composites. The physical properties of all natural fibers
are mainly determined by the chemical and physical composition, such as the structure of
fibers, cellulose content, angle of fibrils, the degree of polymerization etc. The physical
structure of flax fiber can be modified by various surface treatments such as grafting,
acetylation, silane treatment, mercerization, peroxide treatment etc. These different
treatments modify hydrophilic character of the natural fibers, so that moisture effects in
the composite are reduced. The application of flax fibers as reinforcements in composite
materials requires a strong adhesion between the fiber and the matrix. This chapter also
gives a survey about the chemical composition, various mechanical processes for the
separation of flax fiber, mechanical properties, physical and chemical treatment methods
that improve the flax fiber matrix adhesion, their results and special effects on the various
properties of composites.
Keywords: Natural fiber; structure of flax fiber; surface modifications; coupling agents;
composites; reinforcement; mechanical properties; thermoplastic and thermosetting
matrix.
*
Corresponding authors: Email: assingha@gmail.com, vijaythakurnit@gmail.com
32 A. S. Singha and Vijay Kumar Thakur
INTRODUCTION
Flax (Linum usitatissimum L., Linaceae) is probably the oldest fabric fiber known to
mankind which is very easily cultivated and is being used as a promising reinforcement in
composites on account of its low cost, low density, high specific strength and modulus, non
corrosive, no health risk, easy availability in nature and renew ability. It has been used for
centuries in the manufacture of fine linens [1]. In recent years, there has been an increasing
interest in finding new applications for flax fiber-reinforced composites, which have been
traditionally used for making ropes, mats and carpets, fancy articles and many others usable
goods. In the recent time, there are reports which show that a lot of constructive research is
going on flax fiber [2]. Flax fiber, which has been grown throughout the world for millennia,
is the source of products for existing, high-value markets in the textile, composites, paper/
pulp, and industrial/ nutritional oil sectors [3] .The first expected application has been the use
of the linen stuff by the Egyptians to enfold their mummies. Linen stuff has been found in
graves in Egypt dating from 5000 B.C. [4]. At excavation sites of Stone Age dwellings in
Switzerland, dated at approximately 7000 B.C., flax seeds, twines and fishing nets have been
found. Flax fiber has been used as the basis for panel boards, fabric, for sails, tents, insulating
boards etc [5-6]. Thermal insulation panels have also been prepared by making use of
pinewood stumps and flax fibers. Flax straw has been used for solidifying building industry,
building board, insulating material, paper and non-inflammable building materials. Now a
day, the flax industry has become a very cyclic business and the industry is penetrating for
new, preferably high value steady markets. The waste streams of the flax production like the
woody shives have since long been used for instance chipboards for building applications and
particleboard formation. Only in the last few decades, a renewed interest to use the bast fibers
as reinforcement in plastic matrix composites has risen. Fireproof boards are being prepared
from a mixture of a water-soluble silicate, flax, inorganic hardener, inorganic micro-balloons,
cement, and inorganic aggregates. The use of flax fiber in non-textile applications and
automotive industry has increased to a greater extent recently [7]. Other recent applications
are found in modern cars industry where non-woven fibers mats are used commercially for
interior panels, from time to time in combination with other agro fibers. Flax fiber, which
grows in modest climates, is currently cultivated among large parts of Asia, Western and
Eastern Europe, Canada, USA and in Russia. According to the data available worldwide
approximately 5 million-hectare areas is covered by flax throughout the world.
TECHNICAL APPLICATIONS OF FLAX FIBER

Ecological concern has resulted in a renewed interest in natural materials. An interesting
environmentally friendly alternative to glass fiber as reinforcement in engineering composites
is ligno-cellulosic natural fiber such as flax fiber. Natural fibers like flax fibers are subdivided
on the basis of their origins (coming from plants, animals or minerals). In general, plant or
vegetable fibers are used to reinforce plastics. Plant-fibers may include hairs (cotton, kapok),
fiber-sheafs of dicotylic plants or vessel-sheafs of monocotylic plants, i.e. bast (flax, hemp,
jute, and ramie) and hard-fibers (sisal, henequen, and coir). The availability of large variety of
natural fibers such as flax, sisal, pinus, and hibiscus fibers with well-defined mechanical
Flax as Potential Fiber for Reinforcement in Composites 33
properties is a universal requirement for the successful use of these materials in different
fields with respect to health and safety. Additionally in order to enhance technical
applications, the fibers have to be specially prepared or modified with regard to the following
parameters:
Homogenization of the fiber‘s properties;

Low cost:
Degrees of elementarization;
Degrees of degumming;
Degrees of polymerization;
Good adhesion between fiber and matrix;
Degrees of crystallization;
Eco-friendly nature;
Friendly to health;
Moisture repellence;
Flame retardancy.
In recent years, prices anticipated for natural fibers have not been constant. Flax fibers
demonstrate the highest values of strength, but they are about 30 % more expensive than glass
- fibers assured [8] as shown in Table 1. Supplementary, the price of fiber depends upon
various parameters such as on the level of fiber preparation and pretreatment, e.g. size
finishing including a coupling agent and other surfactants, which are well known for glass-
fibers.
Table.1 Production of plant fiber compared to production of glass-fiber [8].
Fiber Price in comparison to glass-fibers Production (1000t)

Jute 18 3600
E-glass 100 1200
Flax 130 800
Sisal 21 500
Banana 40 100
Coir 17 100
For such types of applications, natural fibers have to be pretreated in a similar way for
their maximum utilization [9-10]. In most of the cases, the substitution of glass - fibers by
natural fibers is generally discouraged because of economic reasons [11]. But, natural
fibers (such as flax fiber) offer a number of advantages over glass-fibers, which are given
below:
I. The natural fibers are very important renewable raw material.

II. These natural fibers are easily available in a number of countries.
III. These natural fibers have non-corrosive nature.
IV. The natural fibers have high specific strength and modulus.
V. When at the end of their life cycle natural fiber reinforced plastics are subjected, to
a number of processes such as a combustion process or landfill, the released
amount of CO2 of the fibers is neutral with respect to the assimilated amount
during there growth.
VI. The low abrasive nature.
VII. There is no health risk.
VIII. Natural fiber reinforced plastics by using biodegradable polymers, as matrices are
the most environmental friendly materials, which can be composted at the end of
their life cycle.
CHEMICAL COMPOSITION OF FLAX FIBER

Like sisal fiber, flax fiber is also a ligno-cellulosic fiber that has been intensely studied
over the last few years. As opposed to man - made fibers, the technical - flax fiber is not a
continuous fiber but is in fact a composite by itself. Mechanical properties of these fibers are
determined by the cellulose content and micro fibril angle. A high cellulose content and low
micro fibril angle are desirable properties of a fiber to be used as reinforcement in polymer
composites [12]. The cells of flax fiber mostly consist of pure cellulose, being cemented as
fascicle bundles by means of non-cellulosic incrusting such as lignin, hemicellulose, pectin,
protein or mineral substances, resins, tannins, dyers and a small amount of waxes and fat [13].
A mature flax cell wall consists of about 70 % to 75 % cellulose, 15 % hemicellulose and
pectic materials. The production of individual fibers without the generation of kink bands will
generate fibers with much higher intrinsic fiber strength, which is extremely helpful for
composite application [14]. Chemical compositions and structural parameters of diverse
fibers vary according to the natural environment and various other conditions [15]. The
compositions of different natural fibers are shown in Table II & III. Different natural fibers
contain different amounts of their basic building block units [16]. Bos et al. [17] have
explored the schematic structure of the flax fiber, from stem to micro fibril. The composition
of the flax fiber, from the stem to the micro fibrils, is very complex.
To reach the micro fibrils (4-10 nm in diameter) from the flax stem (2-3 mm in diameter)
six steps can be considered [17]. The elementary fibers (10-25m) are considered as the
strength provider in the flax plant and are composed of micro fibrils. The micro fibrils are
made up of 30 to 100 cellulose molecules [18]. The higher the cellulose content, higher the
mechanical properties. The cellulose and the lignin represent respectively 71 % and 2.2 % of
the flax fibers chemical constitution [19]. A flax fiber surface is covered with a thin layer of
wax, making the access to the reactive hydroxyl groups difficult [17]. It has been observed
that the technical fibers consist of elementary fibers. They consist of a primary cell wall, a
secondary cell wall and a lumen, which is an open channel in the center of the fiber. The
lumen can be as small as 1.5 % of the cross section. Elementary fibers generally contain 65-
75 % cellulose, approximately 15 % hemicellulose and 10-15 % pectin.
Table II. Chemical composition and structural parameters

of different natural fibers [15].
Fiber Cellulose Hemice- Lignin Extra- Ash Pectin Wax Microfibril/ Moisture
llulose ctives Spiral angle Content
BAST
Jute 61-71.5 13.6-20.4 12-13 - - 0.2 0.5 8.0 12.6
Flax 71-78.5 18.6-20.6 2.2 2.3 1.5 2.2 1.7 10.0 10.0
Hemp 70.2-74.4 17.9-22.4 3.7-5.7 3.6 2.6 0.9 0.8 6.2 10.8
Ramie 68.6-76.2 13.1-16.7 0.6-0.7 - - 1.9 0.3 7.5 8.0
Kenaf 31-39 15-19 21.5 3.2 4.7 - - - -
LEAF
Sisal 67-78 10-14.2 8-11 - - 10.0 2.0 20.0 11.0
PALF 70-82 - 5-12 - - - - 14.0 11.8
Henequen 77.6 4-8 13.1 - - - - - -
SEED
Cotton 82.7 5.7 - - - - 0.6 - -
FRUIT 36-43 0.15-0.25 41-45 - - 3.4 - 41-45 8.0
Coir
WOOD
Soft 40-44 25-29 25-31 5 0.2 - -
Hard 43-47 25-35 16-24 2.8 0.4 - -
Table III. Chemical composition of different natural fiber [15].
Cotton Jute Flax Ramie Sisal

Cellulose 82.7 64.4 64.1 68.6 65.8
Hemi-cellulose 5.7 12.0 16.7 13.1 12.0
Pectin. 5.7 0.2 1.8 1.9 0.8
Lignin _ 11.8 2.0 0.6 9.9
Water soluble 1.0 1.1 3.9 5.5 1.2
Wax 0.6. 0.5 1.5 0.3 0.3
Water 10.0 10.0 10.0 10.0 10.0
The pectin is principally situated in the primary cell wall [14], which further contains
some lignin and hemicelluloses. The primary cell wall is comparatively thin, in the order of
0.2 µm. The fibers in addition contain 2-5 % of waxes, part of which can be found on the
surface of the primary cell wall. The waxes may originate from the plant cuticle, which is
made up of cutin, aliphatic polyester, embedded in soluble waxes, mainly palmitic acid. Van
de Velde and Kiekens [20] demonstrated that natural fibers to a certain degree are wetted out
by water, and as a result that the fiber surface is rather hydrophilic. Singha et al. have also
studied the various properties of flax fibers [21].
The secondary cell wall consists mainly of cellulose and hemicelluloses [21]. Cellulose,
which is known to form strong intra and intermolecular hydrogen bonds, is built up from the
monosaccharide D-glucose units. These hydrogen bonds play major role in strongly
determining both the physical and chemical properties of cellulose. Tensile strength of fiber is
significantly reduced by the removal of the hemicellulose, which causes the fiber bundles to
entirely disintegrate into micro fibrils [15]. Astley and Donald [22] studied the flax cell wall
with small-angle X-ray scattering (SAXS) and derived from the data analysis that the cross
section of the cellulose micro fibrils is approximately 1x5 nm2. Näslund et al. [23] have
reported a micro fibril diameter between 1 and 4 nm, as measured by diffraction contrast
transmission electron microscopy. Astley and Donald [22] have also confirmed a crystalline/
non-crystalline repeat distance of 6 to 7 nm. The fibrils are oriented spirally at approximately
+10° compared to the fiber axis. Briefly different cellulose based natural fibers have different
structural parameters [24]. It has been observed that different natural fibers have different
polymer chain lengths. The degree of polymerization also shows that the length of the
polymer chains varies depending on the type of natural fiber. Degree of polymerization of
diverse natural fibers is found to be different. It has been observed that the physical structure
of flax fibers such as fiber length and fiber volume fraction has the strong influence on the
mechanical properties of flax fiber reinforced composites [25-27].
MECHANICAL PROCESS FOR SEPARATION OF FLAX FIBER

Flax fibers, along with a number of other natural fibers, are being considered as an
environmentally friendly substitute of synthetic fibers in fiber-reinforced polymer composites
[28-31]. Flax is the source of industrial fibers and is currently processed in the form of long
and short fibers. Processes known as retting, breaking, scotching and hackling isolate flax
fibers. Flax fiber plants are not cut but mechanically pulled out from the field. After the de-
seeding step, comes the retting, most of the time achieved on the field itself. Retting, which is
the separation of bast fibers from the core tissues, is most exceptional in flax fiber processing
because it affects quality and yield. Two established methods used commercially to ret flax
for industrial grade fibers are water and dew retting [32].
Water Retting: Water retting results in high quality fiber [33]. In water retting, flax stems
are water logged in rivers, streams and lakes, and anaerobic bacteria colonize the flax stems
and degrade pectin‘s and other matrix compounds. This step helps in freeing fibers from the
core tissues. But the use of this method have been discontinued in western countries a number
of decades ago because of the extensive unpleasant smell and pollution from fermentation
products and the high cost of drying .
Dew Retting: Dew retting is now the established practice in most countries and supplies
the linen used in high quality textiles. This process is dependent mostly upon plant cell-wall
degrading enzymes produced by indigenous, aerobic fungal consortia [34]. Disadvantages of
dew-retting are its dependence on particular geographical regions that have the appropriate
moisture and temperature ranges for retting, coarser and lower quality fiber than water retting,
poor consistency in fiber characteristics, and occupation of agricultural fields for several
weeks. Further, dew retting results in a heavily contaminated fiber that is dusty and
particularly problematic in textile mills.
The next step consists in scutching which separates the fibers bundles from the retted
straw mechanically. Most of the researchers do not however use directly these fibers bundles
because of the weak bonds between the technical fibers, which composed the fibers bundles.
The pectin and lignin inter phase between the technical fibers is comparatively weak and can
be removed during a hackling process. A chemical separation of the fibers has been pointed
out by using enzyme mixture to increase the control during separation processing and to
provide high quality fibers. Chemical retting, enzyme-retting and steam explosion techniques
are fiber extraction methods that have previously been investigated.
Enzyme Retting: Techniques using enzymes have also been considered as a method to
improve retting. Because of problems with both water and dew retting, a long-term objective
for improving the flax fiber industry has been development of enzyme retting. Enzyme retting
produces fibers having the fineness, strength, color, and waxiness comparable to the best
water-retted fibers [33]. Advantages of the enzyme method are: (1) time savings of 4–5 days,
(2) increased yield of 2 % over water-retting, and (3) fiber consistency. Composites using
waste product from flax and hemp retting have also been prepared. Pallensen has also shown
that quality of flax fiber for industrials purposes significantly depends upon the process of
retting [35].
PROPERTIES OF FLAX FIBER

Depending on their origin, natural fibers can be grouped into seed, bast, leaf and fruit
qualities. The bast and leaf (the hard fibers) types are the most commonly used in composite
applications [36]. Examples of bast fibers include hemp, jute, flax, ramie and kenaf. Leaf
fibers include sisal and banana. The strength characteristics of natural fiber such as flax fiber
depend on the properties of the individual constituents, the fibrillar structure and the lamellae
matrix [37]. Jähn et al. [38] have reported that plant fiber properties directly influence the
physical parameters of the fiber-reinforced composites. Quality and other properties of fibers
depend on factors such as size, maturity and processing methods adopted for the extraction of
fiber [39]. Properties such as density, electrical resistivity, ultimate tensile strength and initial
modulus are related to the internal structure and chemical composition of fibers [39]. Natural
fibers have an edge over glass fibers in that they are less expensive, abundantly available
from renewable resources and have a high specific strength [37]. Different properties of
various fibers are shown in Table IV [15].
Table IV. Comparative properties of natural fibers and conventional man-made

fibers [15].
Fiber Density Diameter Tensile Young‘s Elongation at

(g/cm3 (μm) Strength Modulus (GPa) Break (%)
(MPa)
Jute 1.3-1.45 20-200 393-773 13-26.5 7-8
Flax 1.5 - 345-1100 27.6 2.7-3.2
Hemp - - 690 - 1.6
Ramie 1.5 - 400-938 61.4-128 1.2-3.8
Sisal 1.45 50-200 468-640 9.4-22 3-7
PALF - 20-80 413-1627 34.5-82.51 1.6
Cotton 1.5-1.6 - 287-800 5.5-12.6 7-8
Coir 1.15 100-450 131-175 4-6 15-40
E-glass 2.5 - 2000-3500 70 2.5
S-glass 2.5 - 4570 86 2.8
Aramid 1.4 - 3000-3150 63-67 3.3-3.7
Carbon 1.7 - 4000 230-240 1.4-1.8
Mechanical properties of different natural fibers vary to some extent depending upon
their source. Different fibers have different tensile strengths. Compared to other natural
fibers, flax fibers are relatively strong. There is a considerable difference between various
mechanical properties of natural fibers and synthetic fibers [40]. Among natural fibers, flax
has been found to possess the highest tensile strength. This is thought to be due to the fact that
flax has the longest elementary fiber and the smallest micro fibril orientation. The modulus of
flax fibers is investigated thoroughly by Baley and Lamy [41]. Baley reports an average
Young‘s modulus of 54 GPa resulting from numerous tensile tests on single flax fibers [41].
It can be concluded that cellulose is the essential component of all natural fibers. The
mechanical properties of natural fibers depend on its cellulose type, because each type of
cellulose has its own cell geometry and the geometrical conditions, which determine the
mechanical properties.
SURFACE MODIFICATION OF FLAX FIBER

The quality of the fiber–matrix interface is most significant factor for the application of
natural fibers as reinforcement materials for thermoplastics as well as thermosetting
polymers. Mainly two types of methods namely physical and chemical methods can be used
to optimize natural fiber interface [42].
a) Physical Methods
A number of physical methods are used to analyze the properties of the natural fibers.
Physical treatments changes structural and surface properties of the fiber and thereby
influence the mechanical bonding to polymers. Electric discharge (corona, cold plasma) is
one supplementary way of physical treatment of natural fiber. Corona treatment is one of the
most fascinating techniques for surface oxidation activation of natural fibers such as flax
fiber. This process changes the surface energy of the cellulose fibers [43] and in case of wood
surface activation increases the amount of aldehyde groups. The same effects are reached by
cold plasma treatment of various fibers. Marais et al. [44] have studied the effect of cold
plasma and autoclave treatments on mechanical and permeation properties. Depending on
type and nature of the used gases, a variety of surface modification could be achieved.
Surface cross linkings could be introduced, surface energy could be increased or decreased,
reactive free radicals and groups could be produced [43]. Electric discharge methods are
known [44] to be very effective for ‗‗non-active‘‘ polymer substrates such as polystyrene,
polyethylene, polypropylene etc. These are effectively used for cellulose-fiber modification,
in order to reduce the melt viscosity of cellulose-thermoplastic composites and improve
mechanical properties of cellulose-polypropylene composites [43].
b) Chemical Methods
Several studies have been done on the influence of various type of chemical modification
on the performance of natural fiber and fiber-reinforced composites. The different surface
modifications of natural fibers such as mercerization, isocyanate treatment, acrylation, latex

coating, permanganate treatment, acetylation, silane treatment and peroxide treatment with
various coupling agents and others have resulted in improving fiber strength, fiber fitness and
fiber-matrix adhesion in natural fiber composites. Insulating boards have also been prepared
using chemically treated flax fibers. Brief descriptions of some of the important fiber
chemical modifications have been summarized in the following sub-sections.
1. Mercerization
Alkali treatment of cellulosic fibers, also called mercerization, is the common method to
produce high quality fibers [10]. Alkali treatment improves the fiber-matrix adhesion due to
the removal of natural and artificial impurities. Therefore, the development of a rough surface
topography and improvement in aspect ratio offer better fiber-matrix interface adhesion and
an increase in mechanical properties (Figure1).
Jähn et al have found that the cellulosic fine structure of the flax fibers have been
influenced by mercerization treatment [38]. Consequently, mercerization has a lasting effect
on the mechanical behavior of flax fibers, especially on fiber strength and stiffness [40].
Several other studies have also been conducted on alkali treatment. Van de Weyenberg et al.
[46] have reported that although the alkali treatment affects the composite properties in a
positive way, the fiber strength decreases significantly after modification with NaOH. A
slight recovery is recorded for increasing alkali concentration, which can be due to a better
reorientation of the inner fiber structure.
2. Silane treatments
Silane coupling agents are found to be useful in modifying the natural fiber-matrix
interface. Various silanes are effective in improving the interface properties of flax fiber.
Alkoxy silane is able to form bonds with hydroxyl groups. Coupling agents such as toluene
dissocyanate and triethoxyvinyl silane have been tested in fiber treatment in order to improve
the interface properties. Silanes undergo hydrolysis, condensation and bond formation stage
during its treatment reaction. The reaction scheme is given in Figure 2 [47]. Silane treatment
of cellulosic fibers can increase the interfacial strength and therefore the mechanical
properties of the composite. Silane treatment also enhances the tensile strength of the
composites.
Fiber-OH + NaOH Fiber-O--Na+ + H2O
Figure 1 Alkali treatments of cellulosic fibers.
OC2H5 OC2H5
H2O
CH2=CH-Si-OC2H5 CH2=CH-Si-OH
OC2H5 OC2H5
Figure 2. Silane treatments of cellulosic fibers [47].

Figure 3. Reaction Between cellulosic-OH groups and benzoyl chloride [48].
Figure 4. Decomposition Reaction of Peroxide [49].
3. Benzoylation
Manikandan Nair et al [48] have reported that benzoylation of the fiber improved fiber
matrix adhesion; thereby, considerably increasing the strength of composite. Benzoylation
treatment on the surface of flax fibers have been studied by a number of researchers. The
reaction between the cellulosic –OH group of sisal fiber and benzoyl chloride is shown in
Figure 3.
4. Peroxide treatments
The decomposition of the peroxide and the subsequent reaction at the interface is
expected at the time of curing of composites. Figure 4 shows the decomposition of the
peroxides. Sapieha et al. [49] have indicated that the addition of a small amount of benzoyl
peroxide or dicumyl peroxide to cellulose-polymer systems during processing improve the
mechanical properties of the composite.
The improvement of mechanical properties is attributed to the peroxide-induced grafting
of polyethylene onto cellulose surfaces. Sreekala et al. [47] have also reported that peroxide-
treated composites showed an enhancement in mechanical properties due to the peroxide-
induced grafting.
5. Graft co-polymerization
Another effective method of surface chemical modification of natural fibers such as,
rayon, cannabis indica and flax fiber is graft co-polymerization [50-52]. In case of flax fiber,
this reaction is initiated by free radicals of the fiber molecule. The fiber is treated with an
aqueous solution by means of selected ions and is exposed to a high-energy radiation. This
process results in the cracking of the fiber molecule and as results of this radicals are formed.
Afterwards, the radical sites of the fiber are treated with a suitable solution (compatible with
the polymer matrix), like various binary monomer, binary vinyl monomer, methacrylate,
methyl methacrylate, polystyrene [2-4, 6-7] etc. The resulting co-polymer possesses
properties characteristic of both, fibrous cellulose and grafted polymer. For example, the
treatments of flax fibers with binary vinyl monomer mixtures [2-4] contain the properties of
both the fibrous cellulose and grafted polymer. After treatment, the surface energy of the
fibers is increased to a level much closer to the surface energy of the matrix. Thus, a better-
wet ability and a higher interfacial adhesion are obtained.
OTHER METHODS
Various other methods that are used for surface modifications are Isocyanate treatment,
Permanganate treatment, Gamma radiation etc. Some of the researchers have used isocyanate
as coupling agent for surface modification [53]. Isocyanate can act as a promoter or as an
inhibitor of interaction. Permanganate treatment has been carried out to improve the bonding
at the fiber-polymer interface. Sreekala et al. [47] have investigated the fibers, which have
been pre-treated with alkali and then dipped in permanganate solution in acetone. Mustată [13]
has studied the sodium chlorite treatment on the surface of bleached flax. Antiseptics have
also been used to protect composites from fungus. Research on the coating of flax fiber
particleboard with gelatin results in better properties. Stuart et al. [54] have explored the use
of enzymes, chelators and enzyme/ chelator as an environmentally friendly means of
improving the quality of flax fiber for their composite applications. A commercial
pectinolytic enzyme preparation and Ethylene Diamine Tetraacetic Acid (EDTA) have been
used separately and in combination on a commercial flax fiber. An improvement in fiber
cleanliness and separation of the fiber bundles into ultimate fiber has been observed. When
this fiber was subsequently, used as reinforcement in an epoxy matrix, improved composite
properties have been obtained. With the EDTA modified fiber-reinforced composites, tensile
strength improvement in excess of 50 % have been recorded.
DEVELOPMENT OF NATURAL FIBER COMPOSITES

During last 50-60 years study on composites, particularly natural fiber-reinforced
composites have gained greater attention of researchers and manufacturers [55]. The
increased interest in natural fiber-reinforced composites is due to the elevated performance in
mechanical properties, significant processing advantages, excellent chemical resistance, low
cost and low density. They have long served many useful purposes but the application of
material technology for the utilization of natural fibers as reinforcement in polymer matrix
has taken place in recent years. Biocomposites consists of a polymer as the matrix material
and a natural fiber as the reinforcing element. Composites from phosphogypsum have also
been prepared by using flax as reinforcing material [3-4]. Flax-board production requires
closer moisture control, twice as much performing pressure, and a more rugged hot press
design relative to wood particleboard production. Chipboard using flax has also been
prepared. Molding mixtures containing nylon fibers or flax and optionally containing perlite
or borax fireproofing agent and optionally laminating the foams with asbestos paper have
prepared building materials. It has been observed that the resulting foam (cellular in
composition) has good compressive and flexural strength. Fire-resistant polyurethane foams,
useful for building materials, have been prepared by impregnating flax ropes with an
inorganic compound expandable at high temperatures and foaming polyurethane
compositions containing the ropes. Flax fiber is also used as reinforcement in cement mortars
[56], pipes, boards, and profiles with angle moldings. The fibers are being used as a
replacement for asbestos. Flax has been used as an additional component to increase
construction capability of a material prepared with Portland cement, gypsum, multi-
component for building material, gypsum blocks for exterior & interior walls, refractory
panels and moldings used especially for electrical insulators. The effect of flax fiber and
matrix modification has been studied during last decades [3-5, 57]. Kathleen and Kiekens [58]
have concluded that fiber treatment, such as boiling of flax, leads to enhanced mechanical
properties for unidirectional and almost completely compacted multidirectional flax/
polypropylene composites. The use of maleic acid modified polypropylene enhances the
properties of composites due to an increased interaction between the anhydride functions and
the hydroxyl functions on cellulose. A combination of boiled flax with maleic anhydride
modified Poly Propylene (MAA-PP) gives best mechanical properties [58]. Recent studies
indicate that plant-based natural fibers such as flax can be used as reinforcement in polymer
composites [25-27]. Flax fiber helps in replacing the expensive and non-renewable synthetic
fibers such as glass, because of their potential for recyclability. Cellulose based natural fibers
are a potential resource for making low cost composite materials. Cellulosic fillers of fibrous
nature have been of greater interest, because they would give composites with improved
mechanical properties compared to those containing non-fibrous fillers. Ligno-cellulosic
fibers like jute, sisal, coir, and pineapple have been reportedly used as reinforcements in
polymer matrix. According to the types of matrices used in flax fiber reinforced composites,
they can be divided into the two main categories: Thermoplastic Polymers and Thermosetting
Polymers.
a) Thermoplastic Polymers
Thermoplastic polymers constitute an important class of materials with an extensive

variety of applications. They are capable of being re-melted. Polyethylene, polypropylene,
polystyrene and polyvinyl chloride are the most common thermoplastic polymers and are
frequently called commodity polymers [59]. These are being used as matrix polymers.
Polyethylene accounts for more than 80 % of the total production. Polymers have a different
affinity towards the fiber owing to the difference in their chemical structure. In the search for
the most suitable thermoplastic matrix for a flax fiber-reinforced composite, density and
temperature related properties seems to be limiting criteria [39], low-density polyethylene
(LDPE), high-density polyethylene (HDPE) and linear low-density polyethylene (LLDPE)
are used as major matrix for reinforcement.
b) Thermosetting Polymers
Thermosetting polymers also constitute an important class of materials with an extensive

variety of applications. They are not capable of being re-melted but they have mechanical
properties far superior than thermoplastic polymers. Phenolic resins such as Phenol-
formaldehyde, Phenol-Resorcinol formaldehyde, Resorcinol- formaldehyde, Catechol-
formaldehyde and Urea-formaldehyde, Urea-Resorcinol formaldehyde etc. are the most
common thermosetting polymers [60-63]. Flax fiber reinforced composites have been
prepared using Phenolic resin as noble matrix [26-27]. The physical and mechanical
properties of the composites have been determined. Most of the researchers prepared
composites using thermosetting resin as noble matrix [64-66].
MANUFACTURING OF COMPOSITES
A systematic study of the process variables for composites based on different natural
fibers like flax, jute, sisal, ramie, and pineapple have been made with a view to determine the
most suitable processing conditions for such composites by some researchers. Some major
methods of molding are rotational molding [67-68], compression molding, injection molding
and extrusion molding [69-71]. Alternative processing methods of natural fiber-reinforced
composites are an important advancement necessary for their increased use.
Mechanical Properties of Composites
The mechanical properties of natural fibers reinforced composite depend on many

parameters, such as fiber strength, modulus, fiber length and orientation, a good interfacial
bond in addition to the fiber-matrix interfacial bond strength [72-73]. A strong fiber-matrix
interface bond is critical for high mechanical properties of composites. A good interfacial
bond is required for effective stress transfer from the matrix to the fiber where by maximum
utilization of the fiber, strength in the composite is achieved [74]. Modification of the fiber
also improves resistance to moisture-induced degradation of the interface and the composite
properties. In addition, factors like processing conditions/ techniques have significant
influence on the mechanical properties of fiber reinforced composites. Sapieha et al. [75]
have found that the addition of a small amount of dicumyl peroxide or benzoyl peroxide into
the cellulosic fiber-polymer systems during processing has significantly improved the
mechanical properties of the composite. The effect of different chemical modifications, such
as silane treatment and grafting etc. on the mechanical properties and dimensional stability of
cellulosic fiber- thermoplastic composites has extensively studied [76]. It was observed that
the chemically modified cellulosic fiber-reinforced thermoplastic composites offered superior
physical and mechanical properties under extreme conditions even after recycling. Van de
Weyenberg et al. [46] have reported the influence of the different methods on the mechanical
properties of the flax fiber reinforced composites. Their findings have shown a slight decrease
in the relative error when switching from a manual film stacking method to the better-
controlled drum winder method. Moreover, both longitudinal and transverse composite
properties are positively influenced by the change of production process, even when the
difference in fiber volume fraction is taken into account. In some countries flax-waste is
commonly used in furniture manufacturing, as flooring under layment, and as roof sheathing
material. For evaluating the adhesive bonding characteristics of flax-board, shearing strength,
and water resistance of glued joints including the following combinations have been
determined: flax-board/ flax-board, flax-board/ pine wood, flax-board/hard fiberboard.
Protein glues, urea-formaldehyde resin, or phenol-formaldehyde resin have been used as
binder. Phenol-formaldehyde resin gave bonds of particularly high water resistance followed
by urea-formaldehyde resin and casein glue. Sorption isotherms have been determined for
flax and hemp boards prepared with urea-formaldehyde resin straight away after manufacture.
Increases in hygroscopicity during adsorption and a partial decrease during desorption have
been observed. There has been an enhancement in the internal surface of the boards as a result
of flaws rising in the cell walls with changes in humidity, with a resultant increase in
deposition of moisture. Wool et al.[77] have prepared composite panels out of plant oil-based
resin [acrylated epoxidized soyabean oil (AESO)] and natural fiber mats made of flax,
cellulose, pulp and hemp by using vacuum-assisted resin transfer molding or resin vacuum
infusion process. Depending on the nature of the fiber mat the flexural modulus increased to a
range between 1.5 and 6 GPa by room temperature curing with natural fiber reinforcement of
about 10-50 wt %. These eco-friendly natural fiber reinforced composites have been found to
have appropriate mechanical strength and properties suitable for applications in housing
construction materials, furniture and automotive parts. Singha et al. [4-8] have prepared
composites using thermosetting resin, as composite matrix and short ramie, flax, hemp fibers
etc. as reinforcing material. They have made effective use of cardanol as building block for
the development of a thermosetting matrix for composites. Wool et al. [77] have also
prepared composites by the Vacuum Assisted Transfer Molding process with varying
amounts of butyrated kraft lignin dissolved in the unsaturated resin system. Butyrated kraft
lignin has been added to an unsaturated thermosetting resin, consisting of a mixture of
acrylated epoxidized soyabean oil and styrene. Butyrated kraft lignin has improved the
interface between the resin and reinforcing flax fibers. Wambua et al. [78] have investigated
the ballistic properties of flax, hemp and jute fabric reinforced polypropylene composites
processed by hot compression moulding. The composites ballistic limit (V50) has been
determined by subjecting the material to ballistic impact loading by fragment simulating
projectiles (FSPs) using a block manometric cannon interchangeable (BMCI) gun. The
composites ballistic effect has been further examined by investigating the ballistic limit of
composite-steel hybrid systems equipped by gluing thin mild steel plates on the face and rear
of the natural fiber composites. Flax composites exhibited better energy absorption than hemp
and jute composites.
Tensile Properties of Composites
Natural fiber-reinforced composites often show enhancement in tensile properties upon

different modifications owing to the increased fiber-matrix adhesion. Tensile properties can
be explained on the basis of the changes in chemical interactions at the fiber-matrix interface.
The tensile properties of the flax fibers have successfully been determined by a number of
researchers [79-80]. The tensile strength of flax fiber-reinforced composites is determined
both by the tensile strength of the fibers and the presence of weak lateral fiber bonds. Stuart et
al. [54] have performed one of the revolutionary studies on the mechanical performance of
treated and untreated flax fiber-reinforced epoxy composites. They found the use of enzymes,
chelators and enzyme/chelators systems as an environmentally friendly way of improving the
quality of flax fiber for composite applications. A commercial pectinolytic enzyme
preparation and Ethylene Diamine Tetraacetic Acid (EDTA) have been used separately and in
combination on a commercial flax fiber. An improvement in fiber cleanliness and separation
of the fiber bundles into ultimate has been observed. When this fiber has been, consequently,
used as reinforcement in an epoxy matrix, enhanced composite properties have been obtained.
With the EDTA modified fiber reinforced composites, tensile strength improvements in
excess of 50 % have been recorded. Bodros et al. [81] have studied the tensile properties of
flax fiber-biopolymer composites in order to determine whether or not, biocomposites may
replace glass fiber reinforced unsaturated polyester resins. The composites have been
manufactured using a film stacking technique. Preliminary results show that the tensile
properties are improved with the fiber volume fraction. The tensile strength and Young‘s
modulus of L-polylactide acid (PLLA) and polylactic acid (PLA) flax composites are greater
than those of similar PP/ flax fiber composites. The specific strength of composites reinforced
by flax fiber is lower than that of glass fiber composites except for PLLA reinforced with flax
fibers, which exhibit higher specific strength than polyester/ flax fiber composites. These
results are due to the different properties of the polymeric matrix and also to the adhesion
between the fibers and the polymer. The effect of environmental relative humidity and
damage on tensile properties of flax fiber reinforced composites has also been studied by a
number of researchers. Christopher et al. [82] have studied transverse tensile behaviour of
unidirectional plies reinforced with flax fibers. When a unidirectional flax/ polyester ply is
loaded in transverse tension the damage mechanisms are complex; cracks develop in the
matrix, and at the fiber/ matrix interface, but they also appear within the fibers themselves
and in the lamellae within the fiber bundles. This emphasizes highly an isotropic nature of
these flax fibers, whose average longitudinal Young's modulus is found to be 59 G Pa and
whose transverse modulus is found to be 8 G Pa. With a polyester matrix UD composites
reinforced by flax fibers show a higher failure strain than glass-reinforced composites with
the same fiber content.
Impact Properties of Composites
Fibers have a significant effect on the impact resistance through the principle of stress
transfer. When an impact load is applied perpendicular to the reinforcing fibers, good fiber-
matrix adhesion is required for even moderate impact strength. Detailed studies have been
done on the impact resistance of short fiber reinforced composites [83-84]. The impact
resistance of fiber-reinforced composite depends on fiber rigidity, interfacial stress resistance
and fiber aspect ratio. The strength of the matrix, the weakest part of the material, should be
related to the failure process. The involvement of fibers in the failure process is related to
their interaction with the crack formation in the matrix and their stress transferring capability.
The total energy dissipated in the composite before final failure occurs is a measure of its
impact resistance. The total energy absorbed by the composite is the sum of the energy
consumed during plastic deformation and the energy needed for creating new surfaces.
Flexural Properties
Van de Weyenberg et al have studied the influence of the mild fiber treatments on the
flexural properties of the flax fiber reinforced composites [46]. In longitudinal direction, a
slight positive tendency is noticed, while in transverse direction a pronounced effect is
recorded when untreated flax is replaced by 1 % NaOH treated flax. Since the transverse
composite properties are considerably influenced by the interface quality, this leads to the
assumption that the interface between flax fibers and epoxy matrix has improved to a certain
extent through the application of alkali. Many composites using flax fiber as reinforcing
materials have also been prepared.
Table V. Time to ignition of the composites with modar matrix [87].
Matrix Fiber in the composite Time to ignition Total heat evolved MJ/m2)
(TTI) (s)
Modar Glass 62 54.4

Flax 110 104.9
Sisal 52 101.4
Jute 72 74.2
Unsaturated polyester Glass 56 32.3
Jute 51 77.6
Thermal Degradation and Fire Resistance Behaviors
Thermal degradation and fire resistance behaviour of natural fiber reinforced composites
has been studied by few researchers [85-86]. Manfredi et al. [87] have studied the thermal
degradation and fire resistance behaviour of different natural fiber reinforced composites. The
smoke emissions of the materials, their performance against the fire of the biocomposites and
glass-reinforced composites have been compared. Thermal degradation indicated that the
Modar matrix composites showed extra resistant to temperature than the composites with UP
matrix Table V. Flax fiber, due to their low lignin content, exhibits the best thermal resistance
among the different natural fibers (woven jute and sisal) studied as shown in Table V. From
the above study, flax fiber appears to be the best material used, due to the long time of
ignition and the long period to its flashover.
Thermal Properties of Composites
A quick method for determining the threshold values for processing temperature is
thermal analysis. Thermo gravimetric (TG) analyses are carried out with a thermal balance.
The thermo gravimetric degradation curve provides information about the thermal stability of
a material [71, 73]. During thermal study of flax fiber, it has been observed that in case of raw
flax, initial and final decomposition temperature are higher as compared to those of grafted
flax fiber. Differential scanning calorimetric (DSC) studies have also been used to determine
the melting point of the flax-reinforced composites and to collect caloric data. An increased
heating rate leads to a displacement of the melting range to higher temperatures. Nikki et al.
[87] have studied the properties of hemp, flax, kenaf, henequen and glass (15 wt. %)
reinforced epoxy composites composing of diglycidyl ether of bisphenol-A (DGEBA) and
diaminodiphenyl sulfone (DDS) composites. Various methods such as differential scanning
calorimetry (DSC), thermo gravimetric analysis (TGA), environmental scanning electron
microscopy (ESEM), and swept frequency diagnostic method have been used to investigate
material properties. Samples have been processed using both microwave and thermal curing.
Glass and flax composites reached a higher final extent of cure with microwave curing than
with thermal curing. Glass, flax, and hemp cured faster in the microwave as compared to their
convection oven counterparts. Natural fibers and their composites degraded at lower
temperatures than glass and glass fiber composites. Scanning electron microscopy (SEM)
micrographs, used to investigate fiber morphology, have also indicated a lack of bonding at
the interfaces between the fibers, natural and glass, and matrix.
MOISTURE ABSORPTION OF FIBERS

Various researchers have studied the moisture absorption of untreated and treated flax
fibers at different relative humidity‘s. The moisture absorption of the chemically treated flax
fiber has been found to be lower than that of untreated flax fibers [3-7, 25-27]. This shows the
changes in surface chemistry of the fibers. Strong intermolecular fiber-matrix bonding
decreased the rate of moisture absorption in biocomposites. It shows that chemical treatments
of flax fiber can decrease the water absorption of the biocomposites there by making them
moisture resistant.
Effects of Fiber Surface Modifications on Flax Fiber Reinforced Composites
The chemical modification directly influences the cellulosic fine structure of natural fiber
and properties of their respective composites. The mechanical performance of fibers is
dependent upon its chemical composition, chemical structure and cellular arrangement. Joffe
et al. [88] have determined the strength and adhesion characteristics of elementary flax fibers
with different surface treatments. Modifications of the fibers led to major changes on the
fibrillar structure of the fiber. It removed the amorphous components. This changed the
deformation behavior of the fibers. The brittleness of the fiber has been substantially reduced
upon treatments. Bledzki et al. [89] have studied the influence of defined fiber treatments on
unidirectional hemp and flax and PP-composites. Many researchers measured the mechanical
properties of untreated and modified fibers, such as tensile strength, Young‘s modulus and
elongation at break. Treated flax fiber can also be used for preparing composites of superior
properties.
Moisture absorption, Water uptake, Dye up- takes, swelling and Chemical Resistance
Behaviour of flax fibers and respective composites:
Singha et al. have studied different physical and chemical properties of untreated and
treated flax fibers at different relative parameters such as humidity, solvents, conc. etc. [3-7,
25-27]. Fahmy et al. [90] have studied that liquid-phase acetylation of flax straw in a mixture
of Ac2O, AcOH, and HClO4, decreased the water resistance, swelling thickness, and bending
strength of the resulting composites relative to that of non acetylated composites. Some of the
researcher studied the effect of coating on flax fiber reinforced composites. Few researchers
have also studied the effect of the waterproofing impregnating agent GSE-10 on some
properties of flax waste boards. A new waterproofing agent reduced the hygroscopicity of
flax waste boards by 30 percent and swelling by 40 percent, and increased bending strength to
a great extent. The Moisture absorption, Water uptake, Dye uptake, Swelling and
Chemical Resistance Behaviour of chemically treated flax fiber has been found to be lower
than that of untreated fiber [3-7]. This shows that changes in surface chemistry have reduced
the affinity of fibers to moisture. Gouanve´ et al. [91] have studied water vapors sorption
kinetics in natural flax fibers. Baley et al. [92] have studied the influence of the chemical
treatment on the surface tension of flax fibers investigated by wet ability measurements. The
chemical composition of the modified surfaces has been characterized by SEM and infrared
micro spectroscopy and finally on the adherence of resin micro drops has been probed by a
micro bond test. The results obtained from classical sodium hydroxyl plus acetic anhydride
based treatments and with formic acid treatment exhibits a universal increase of the flax
fiber/unsaturated polyester adhesion. It has been pointed out that the complex composite
nature of flax fibers have to be taken into account to get a better understanding of the
adhesion in the multi scale complex composite system built up in flax fibers reinforced
polymers.
CONCLUSION
Natural fibers such as flax fiber can be used as reinforcing materials for low cost
composites due to the economic, biodegradability, light weight, non corrosive, non abrasive
to health and greater environmental advantages of such materials. Flax fiber is most important
effective reinforcement material for polymer, rubber, gypsum, cement matrices and
automotive industries. Recently the use of flax fiber has created a new range of technological
applications away from its traditional usage as ropes, carpets, mats, etc. However, flax fiber is
highly hydrophilic due to the presence of hydroxyl groups from cellulose and lignin.
Chemical treatment can reduce the hydrophilic character of the fiber by treating these fibers
with suitable chemicals to decrease the hydroxyl groups in the fibers. Fiber-surface treatment
can improve the adhesion properties between flax fiber and matrix and simultaneously reduce
water absorption. Composites obtained by chemically treated fiber offered better physical and
mechanical properties. Mechanical properties of flax fiber-reinforced plastic composites
could be improved by the use of surface treatments. The hydrophilic nature of bio fibers leads
to biocomposites with high water absorption characteristics that can be overcome by treating
these fibers with suitable chemicals to decrease the hydroxyl groups of the fibers. The water
absorption and swelling of the treated flax fiber composites have been lower than those of
untreated flax fiber composites. Environmental effects easily influence the moisture
sensibility of flax fibers. Generally speaking, rising moisture content lowers the mechanical
properties. Natural fibers when used as reinforcement can replace technical-fibers, such as
glass-fibers or carbon fibers because of their eco-friendly nature and other advantages. The
advantages of technical-fibers are good mechanical properties, which vary only little. The
mechanical properties of composites are influenced mainly by the adhesion between matrix
and fibers. As in the case of glass-fibers, pre-treating the fibers can change the adhesion
properties. So, special processing‘s, such as chemical and physical modification methods
have been evolved. Moisture repellency, resistance to environmental effects, and not last, the
mechanical properties are improved by these treatments. Various applications of natural fibers
as reinforcement in plastics have proved encouraging. Several natural fiber composites reach
the mechanical properties of glass-fiber composites, and they are being used in automobile
and furniture industries. A lot of research is going in the area of synthesis of biodegradable
natural fiber reinforced composites. This will add a new dimension to the green chemistry,
which has become a need of the hour.
ACKNOWLEDGMENT
We express our sincere thanks to Prof. B.N Mishra & Prof. I. K. Mehta, Department of
Chemistry H.P.U. Shimla for their consistent help & guidance in carrying out the research
work and literature review. We would also like to thank the authors of references for the
information obtained from their paper.
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Chapter 3
REVIEW ON NATURAL FIBERS /HDPE COMPOSITES:

EFFECT OF CHEMICAL MODIFICATION ON THE
MECHANICAL AND THERMAL PROPERTIES
Daniella R. Mulinari1, Maria Odila H. Cioffi1

and Herman J. C. Voorwald1
1
Fatigue and Aeronautic Materials Research Group, Department of Materials
and Technology, UNESP/FEG, Guaratinguetá/SP, Brazil.
ABSTRACT
In the recent years, great attention has been dedicated to the exploitation of natural
fibers as reinforcement for plastics, replacing fibers synthetic materials. Objectives are
not just environmental concerns and consumer pressure but also a unique combination of
high performance, great versatility and processing advantages at low cost. However,
certain drawbacks such as incompatibility with a hydrophobic polymer matrix, the
tendency to form aggregates during processing and poor resistance to moisture reduce
greatly the potential of natural fibers to reinforce polymers. On the other hand, various
treatments are being used to improve fibre-matrix compatibility. This process is
considered critical as a development phase of these materials due to strong interfiber
hydrogen bonding, which holds fibers together. Methods for surface modification can be
physical or chemical according to superficial modification approach of the fibre. In this
review, the main results presented in the literature are summarized, with specific attention
on the properties in terms of physical and chemical structure of natural fibers, thermal
and mechanical properties, processing performance and final properties of natural fibers
reinforcing high density polyethylene matrix. The use of physical and chemical
treatments for the improvement of fibers-matrix interaction was also considered.
INTRODUCTION
Natural fibers are gaining progressive account as renewable, environmentally acceptable,
and biodegradable starting material for industrial applications, technical textiles, composites,
54 Daniella R. Mulinari, Maria Odila H. Cioffi and Herman J. C. Voorwald
pulp and paper, as well as for civil engineering and building activities. Natural fibers
reinforced composites combine acceptable mechanical properties with a low density. Such
composites offer a number of well-known advantages, which include low cost, availability of
renewable natural resources and biodegradability [1-3].
The utilization of this biomass for processing of novel composites has attracted growing
interest due to eco-friendly and renewable nature characteristics. Indeed, enormous interest in
the development of new composite materials filled with natural fibers has been shown by
important industries such as the automotive, construction or packaging industry [4-6].
Compared to inorganic natural fibers present advantages such as lower density and cost,
less abrasive to the processing equipment, harmless, and the mechanical properties are
comparable to those of inorganic fibers [7]. The consequence of incompatibility with a
hydrophobic group results in inadequate bonding with the polymer matrix to produce the
composite.
1. NATURAL FIBERS
1.1. Types of Natural Fibers
Natural fibers are subdivided based on origins, coming from plants, animals or minerals.
All plant fibers are composed of cellulose while animal fibers consist of proteins (hair, silk,
and wool). Plant fibers include bast (or stem or soft sclerenchyma) fibers, leaf or hard fibers,
seed, fruit, wood, cereal straw, and other grass fibers [8]. Some examples are cotton (seed
hairs), ramie, jute, and flax (bast fibers), and sisal and abaca (leaf fibers). The most
commonly fibers used for reinforce polymer are jute, ramie, flax, and sisal. Natural fibers in
the form of wood flour have also been often used for preparation of natural fiber composites.
The properties of these fibers are presented in Table 1.
As can be seen in Table 1, the tensile strength of glass fibers is substantially higher
compared to natural fibers for the same order of modulus. However, when the specific
modulus of natural fibers (modulus/specific gravity) is considered, natural fibers show
comparable values to or higher than those of glass fibers. These higher specific properties are
one of the major advantages of using natural fibers composites for applications where
properties as weight reduction are required.
Table 1. Mechanical properties of natural fibers [9].
Fibre Fiber type Density Tensile strength Young‘s Elongation at Moisture

(g.cm-3) (MPa) modulus (GPa) break (%) absorption
(%)
E-glass Mineral 2.5-2.55 1800-3500 70-73 2.5-3.0 0
Flax Bast 1.4-1.5 345-1500 27.6-80 1.2-3.2 7
Hemp Bast 1.48 550-900 70 1.6 8
Jute Bast 1.3-1.45 400-800 10-30 1.16-1.8 12
Ramie Bast 1.5 400-938 44-128 1.2-3.8 12-17
Coir Seed 1.15-1.25 131-220 4-6 15-40 10
Sisal Leave 1.35-1.45 468-700 9.4-38 2-7 11
Curaua Leave 1.4 500-1150 11.8 3.7-4.3 ----
Review on Natural Fibers /HDPE Composites: Effect of Chemical… 55
Figure 1. Structure cellulose fibrils [11].
Table 2. Cellulose fibrils [12].
Fiber source Species Origin

Abaca Musa textilus Leaf
Bagasse - Grass
Bamboo (> 1250 species) Grass
Banana Musa indica Leaf
Coir Cocos nucifera Fruit
Curaua Ananás erectifolius Leaf
Hemp Cannabis sativa Stem
Jute Corchorus capsularis Stem
Kenaf Hibiscus cannabinus Stem
Piassava Attalea funifera Leaf
Pineapple Ananus comosus Leaf
Ramie Boehmeria nivea Stem
Sisal Agave sisilana Leaf
1.2. Microstructure of the Fibers
Natural fibers can be considered cellulose fibrils reinforced materials, which consist of
microfibrils in an amorphous matrix of lignin and hemicellulose [10,11]. The cell wall in a
fiber is not a homogenous membrane (Figure 1).
Each fibril has a complex layered structure consisting of a thin primary wall that is the
first layer deposited during cell growth encircling a secondary wall. The secondary wall is
made up of three layers and the thick middle layer determines the mechanical properties of
the fibre. The middle layer consists of a series of helically wound cellular microfibrils formed
from long chain cellulose molecules: the angle between the fiber axis and the microfibrils is
called the microfibrillar angle. The characteristic value for this parameter varies from one
fiber to another [10].
Such microfibrils have typically a diameter of about 10– 30 nm and are made up of 30–
100 cellulose molecules in extended chain conformation and provides the fiber mechanical
strength. The amorphous matrix phase in a cell wall is very complex and consists of
hemicellulose, lignin, and, in some cases, of pectin. The hemicellulose molecules are
hydrogen bonded to cellulose and act as cementing matrix between the cellulose microfibrils,
forming the cellulose– hemicellulose network, which is thought to be the main structural
component of the fiber cell. The hydrophobic lignin network affects the properties of other
network acting as a coupling agent and increases the stiffness of the cellulose/hemicellulose
composite.
The structure, microfibrillar angle, cell dimensions, defects, and the chemical
composition are the most important variables that determine the overall properties of the
fibers [12]. Generally, fibers tensile strength and Young‘s modulus are higher with increasing
cellulose content whereas the stiffness is determined by microfibrillar angle. When
microfibrils have a spiral orientation in relation to the fiber axis, the plant is more ductile, for
parallel orientation fibers will be rigid, inflexible and have high tensile strength. Some of the
important cellulose fibrils are listed in Table 2.
1.3. Chemical Composition of Natural Fibers
The chemical composition of natural fibers varies depending upon their type. The main
components of natural fibers are cellulose, hemicellulose, lignin, pectins, and waxes [11].
Cellulose is a natural polymer consisting of D-anhydroglucose (C6H11O5) repeating units
linked by 1,4- -D-glycosidic linkages at C1 and C4 position [13]. The degree of
polymerization (DP) is around 10.000. Each repeating unit contains three hydroxyl groups
(Figure 2). These hydroxyl groups have ability to hydrogen bond, which play an important
role for crystalline packing and also govern cellulose physical properties.
Cellulose forms is a microcrystalline structure with regions of high order i.e. crystalline
regions and amorphous regions of low order. Cellulose is also formed of lamella like
crystalline microfibrils. The crystal nature (monoclinic sphenodic) of naturally occurring
cellulose is known as cellulose. Cellulose is resistant to strong alkali (17.5 wt%) and
relatively resistant to oxidizing agents but is easily hydrolyzed by acid to water-soluble sugars
[14].
Hemicellulose is a group of polysaccharides composed of a combination of 5- and 6-
carbon ring sugars, called as a misnomer. It differs from the cellulose in three aspects,
presents several different sugar units in contrast of cellulose which has only 1,4– -D-
glucopyranose units, exhibit a considerable degree of chain branching with pendant side
groups contributing to a non crystalline nature, whereas cellulose is a linear polymer and
finally the degree of polymerization (DP) of native cellulose is 10–100 times higher than that
of hemicellulose that is around 50–300 [15]. Hemicellulose forms the supportive matrix for
cellulose microfibrils and is very hydrophilic, soluble in alkali and easily hydrolyzed in acids
[15].
Figure 2. Repetitive unit of cellulose [13].

Lignin is a complex hydrocarbon polymer with both aliphatic and aromatic constituents,
amorphous and hydrophobic in nature. It is totally insoluble in most solvents and is
responsible for the characteristic of rigidity from the plants. It is thought to be a complex,
three-dimensional copolymer of aliphatic and aromatic constituents with very high molecular
weight. Hydroxyl, methoxyl and carbonyl groups have been identified, containing five
hydroxyl and five methoxyl groups per building unit. Structural units of lignin molecule are
derivatives of 4-hydroxy-3-methoxy phenylpropane [15].
Considering the vegetal separation process, it was observed that the native state lignin in
isolated form is very difficult, which justify the interest in cellulose application. Lignin is
considered to be a thermoplastic polymer, which exhibits a glass transition and melting
temperature of around 90 oC and 170 oC respectively [16]. It cannot be hydrolyzed by acids,
but is soluble in hot alkali, readily oxidized, and easily condensable with phenol [17].
Pectins are a collective name for heteropolysaccarides, responsible for plants flexibility.
Waxes, the last part of fibers, consist of different types of alcohols [15].
Constituents properties contribute to the full property of the fiber. The percentage
composition of each one varies for different fibers. Generally, fibers contain 60–80%
cellulose, 5–20% lignin, and up to 20% moisture [18].
2. NATURAL FIBER COMPOSITES

The matrix phase plays a crucial role concerning the performance of polymer composites.
Both thermosets and thermoplastics are attractive as matrix materials.
In thermoset composites the formulation is complex because of a large number of
components involved as base resin, curing agents, catalysts, flowing agents and hardeners.
These materials are chemically cured to a highly cross-linked production with consequent
three-dimensional network structure. Due to the cross-linked structures, materials are tough
solvent and creep resistant. Reinforcement will be accommodated until 80% and, considering
the fibers alignment, the enhancement in properties is remarkable [8,19].
Thermoplastics offer advantages over thermoset polymers, as the low processing cost,
design flexibility and molding easiness of complex parts. Simple methods such as extrusion
and injection molding are used for the processing of these composites [20-23]. In
thermoplastics most of the work reported so far deals with polymers such as polyethylene,
polypropylene, polystyrene, and poly(vinyl chloride). The main reason is the processing
temperature, which is restricted to 200 0C in order to avoid thermal degradation of natural
fibers.
For thermoplastic composites, fibers distribution is an important parameter to be
considered with respect to mechanical, thermal and microscopic properties. Thermoplastic
composites are flexible and tough and exhibit good mechanical characteristics. However, the
amount of reinforcement is limited by the processability of the composite. The fiber
orientation is random and, as a consequence, properties are lower than that observed by
thermoset composites [22].
Fibers properties, the aspect ratio, and the fibre–matrix interface govern the composites
final properties. Reinforcement supports almost all the applied load and the role of the matrix
is to attach and protect the fibers. Futhermore, transfers loading across the interface and so
contribute with the performance of the composite [24-31].
Another important aspect is the thermal stability of these fibers, which are lignocellulosic
and consist of mainly lignin, hemicellulose, and cellulose. The cell walls undergo pyrolysis
with increasing processing temperature and contribute to char formation. These charred layers
help to insulate the lignocellulosic from further thermal degradation. Since most of
thermoplastics are processed at high temperatures, the thermal stability of the fibers at the
processing temperatures is important. The key issues in development of natural reinforced
composites are (i) thermal stability of the fibers, (ii) surface adhesion characteristics of the
fibers, and (iii) dispersion of the fibers in the case of thermoplastic composites [24, 32].
3. MAJOR ISSUES IN DEVELOPMENT OF NATURAL

FIBERS/HDPE COMPOSITES
3.1. Thermal Stability of Natural Fibers
In general natural fibers have low degradation temperatures (~200 oC), which for
thermoplastics processing where temperatures are above 200 oC is a problem. Thermal
analysis of polymers is an important study, used to understand the structure–property relation
with respect to viscoelasticity parameters in order to prove the technology for industrial field
of different polymeric materials, especially reinforced polymer composites [22].
One of the accepted methods to study polymeric materials thermal properties is
Thermogravimetry (TG). Both TG and Derivative Thermogravimetry (DTG) provide
information about the nature and degradation of the material. Some works apply this
technique for characterization after chemical modification of lignocellulosic materials [35].
In Differential Scanning Calorimetry (DSC), the heat flow rate associated with a thermal
event can be measured as a function of time and temperature resulting in quantitative
information about melting and phase transitions of the composite system [36]. For composites
based on semicrystalline matrix polymers, crystallinity is an important factor that determines
the stiffness and the fracture behavior of the crystallized matrix polymer [37]. Current studies
have revealed that the presence of natural and chemically modified fibers acts nucleating
agents of semicrystalline thermoplastics, which causes change in crystallization and melting
heat of the final composite [32, 38].
One of the most important effects of natural fiber addition in a polymeric matrix is the
increase of crystallinity. This effect can happen in two different ways: transcrystallinity, with
heterogeneous nucleation generating a layer of fiber surface, and cylindrical crystallization
caused by self-nucleation, a kind of homogeneous nucleation generating the form from a form
crystals [39]. Depending on the system, some fiber treatments can avoid the formation of
transcrystallinity or improve its occurrence. Various natural fibers such as sisal, flax, kenaf,
and bamboo, present active surfaces sites susceptible to form the transcrystalline regions [39-
41]. Due to the interaction of the polymeric chains and the fiber surface, transcrystallinity
improve fiber/polymeric matrixes adhesion [39].
3.2. Moisture Content of the Fibers
Cellulosic fibers are hydrophilic and absorb moisture, which content vary between 5 and
10%. This phenomenon proves dimensional variations affecting composites mechanical
properties. During composites processing based on thermoplastics, moisture may produce
porous. Treatment of natural fibers with chemicals or grafting of vinyl monomers may reduce
the moisture gain [42, 43].
3.3. Processing of Thermoplastic Composites
The processing of natural fiber thermoplastic composites involves extrusion of the

components at melt temperatures, followed by shaping operations such as injection molding
and thermoforming [44-47]. Fiber–fiber interactions as well as fibre–matrix interactions play
a crucial role in determining the properties of such composites [48-55]. Many times, it is
observed that these fibers do not work as an effective reinforcement system due to poor
adhesion at the fibre–matrix interface. Cellulose fibers also tend to aggregate and therefore
the fibers do not disperse well in a hydrophobic polymer matrix and thus prove difficulties in
achieving a uniform distribution of fiber in the matrix11. The surface characteristics of the
reinforcing fiber are important in the stress transfer from the matrix to the fiber. The
pretreatment of the fiber with suitable additives prior to processing proves good dispersion
and significantly improved composites mechanical properties [56-60].
3.4. Dispersion of the Fibers in the Matrix
The incorporation of cellulosic fibers in thermoplastics produces a low dispersion fiber

due to strong interfiber hydrogen bonding, which holds the fibers together [8]. Treatment of
the fibers and/or use of external processing supports reduce this problem. Various processing
aids/coupling agents such as stearic acid, mineral oil, and maleated ethylene have been used
[61-64]. The concentration of the additive is approximately 1% by weight of fibers. The
stearic acid is highly effective in dispersing, reducing fiber-to-fiber interaction. Mineral oil
works as a lubricant that is adsorbed on the fibers and this facilitates the disentanglement of
individual fibers.
3.5. Chemical Modification in Natural Fibers

Natural fibers are incompatible with the hydrophobic polymer matrix and have a
tendency to form aggregates [65]. These are hydrophilic fibers and thus exhibit poor
resistance to moisture. To eliminate the problems related to high water absorption, treatment
of fibers with hydrophobic aliphatic and cyclic structures has been attempted [48-55]. These
structures contain reactive functional groups that are capable of bonding with reactive groups
in the matrix polymer. Thus, modification of natural fibers is attempted to produce fibers
hydrophobic in order to improve interfacial adhesion between the fiber and the matrix
polymer.
Treatment of fibers to improve adhesion is a critical phase in the development of such

composites, and bleaching, grafting of monomers and acetylation are used in this way. In
addition to the surface treatment of fibers, the use of a compatibilizer or a coupling agent for
effective stress transfer across the interface can also be explored. This compatibilizer is, in
general a polymer with functional groups grafted onto the chain of the polymer. The coupling
agents are tetrafunctional organometallic compounds based on silicon, titanium, and
zirconium and are commonly known as silane, zirconate, or titanate coupling agents [65].
3.5.1. Silane treatment

Coupling agents usually improve the degree of crosslinking in the interface region
resulting in a perfect bonding. Various silanes were found to have effectively improved the
interface properties of wood-polypropylene, mineral filled elastomers, and fiber reinforced
epoxies and phenolics [66].
Silanes having reactive alkyl groups bond chemically in order to form adhesives reacting
with appropriate groups and thus promote adhesion. Silanes having non-reactive alkyl groups
have no chemical coupling activity and, in such cases adhesion appers to arise from improved
interfacial compatibility. Silanes have been used to promote adhesion to hydrophilic
adherents, such as glass, aluminum, clay, talc, calcium carbonate etc [67]. A possible
mechanism of bonding formation of alkosilanes with cellulosic fibers is shown in Figure 3.
Figure 3. A possible mechanism of bond formation of alkosilanes with cellulosic fibers [67].
The silane coupling agents were found to be effective for modified natural fibre-polymer
matrix interface. Gonzalez et al. [68] investigated the effect of silane coupling agent and
alkaline treatment on the interface performance of henequen reinforced high-density
polyethylene composites. The fiber-surface silanization results in a better interfacial stress
transfer without improve the fiber wetting. The alkali treatment increases the surface
roughness resulting in improved mechanical interlocking with higher surface area to bonding.
The silane treatment enhances the tensile strength of the composite.
3.5.2. Mercerization
For Mercerization, which is an alkali treatment of cellulose fibers, parameters as type and
concentration of the alkalic solution, operational temperature, temperature treatment time,
material strength, as well as the applied additives are considered [61]. Optimal conditions of
mercerization ensure the improvement of tensile properties and absorption characteristics,
which are important in the process [69-71].
Alkali treatment improves the adhesive characteristics of the fiber surface by removing
natural and artificial impurities, thereby producing a rough surface topography. Moreover,
alkali treatment provides fiber fibrillation, i.e. breaking down of the composite fiber bundle
into smaller fibers. In others words, alkali treatment reduces fiber diameter and thereby
increases the aspect ratio. Therefore, development of a rough surface topography and
enhancement in aspect ratio offer higher fibre-matrix interface adhesion with consequent
increase in mechanical properties [71].
3.5.4. Maleic anhydride treatment

Composites of polyethylene reinforced by natural fibers or fillers have been studied by
several authors [72-74]. Araújo et al. [39] studied high density polyethylene composites with
curaua fibers, which were prepared using an intermeshing corotating extruder and two
different coupling agents. The components thermal stability was studied by
thermogravimetric and differential scanning analysis, as well as by the oxidation induction
time. Results showed that maleic anhydride grafted polyethylene, used as coupling agent,
affected the composite stability more markedly that for poly(ethylene-co-vinyl acetate). One
explanation is that the compatibilized composites present more interfacial interaction due to
the reaction between acid groups of the maleic anhydride groups and hydrophilic groups on
the fiber surfaces, Figure 4. This higher interaction promotes an interaction degradation
processes between both components, i.e. the degradation of one component may accelerate
the other one.
Also due to the presence of peroxide residues which is used to graft maleic anhydride to
polyethylene. However, oxidation induction times were analogous for composites with and
without coupling agents. Results also indicated that a higher fibre–matrix interaction exclude
the possibility of crystallinity development by the fiber.
3.5.5. Modification of metallic oxide coated cellulose fibers

In the recent years, procedures for the modification of metallic oxide coated cellulose
fibers, Cell/MxOy, have been studied [75, 76]. This material type has been used for specific
applications: TiO2 for bactericidal activities [77], ZrO2 for retention and analysis of Cr(VI)
[78] of sulphate [79], Nb2O5 for adsorption of phosphate ions [75] and Al2O3 for adsorption of
some metal halides from ethanol solution [80].
Figure 4. Representation of the interface rection between the curaua fiber surface and the PE-g- MA
[39].
The experimental methodology of the fibers coating process depends on the form in
which the cellulose is obtained, as fiber or membrane. As fiber form, the cellulose treatment
with a precursor reagent can be made in aqueous or non-aqueous solvent [81].
Figure 5 shows the schematic representation of the Lewis acid with cellulose [81]. The
reaction is carried out under anhydrous conditions in the first step due to the supposition of
primarily a donor-acceptor bond is formed between ZrOCl2.8H2O and the oxygen of the C1-
O-C5 and C1-O-C4 bonds. The attack to the standard oxide bond provides a ring opening
resulting in a molecule rupture process in order to form micro fibers. Ammonium solution is a
required mean to promote the chemical link of metallic oxide with fiber surfaces.
Figure 5. Reaction of the Lewis acid with cellulose and formation of the donor-acceptor bond [81].
Mulinari et al. [82] studied the effect of the sugarcane bagasse cellulose modification
using zirconium oxychloride to reinforce high-density polyethylene in order to improve
mechanical properties. Results showed a successfully performance and that the reinforcement
of high-density polyethylene presented a tensile strength value higher than that with non-
modified sugarcane bagasse cellulose. Modification in the sugarcane bagasse cellulose was
crucial to increase the mechanical properties of the composite material.
3.5.6. Others types treatments

Deslignification (dewaxing) is generally carried out by extracting using alcohol or
benzene reagents and with NaOH followed by drying at room temperature. Many oxidative
bleaching agents such as alkaline calcium or sodium hypochlorite and hydrogen peroxide are
commercially used. Bleaching generally results in weight loss and improved tensile strength.
Weight losses are mainly attributed to the action of the bleaching agent or alkali or alkaline
reagent on the noncellulosic constituents of fibers as hemicellulose and lignin [78,79].
Physical methods, such as stretching, calendering, thermotreatment, and the production of
hybrid yarns do not change the chemical composition of the fibers. Physical treatments
change structural and surface properties of the fiber and thereby influence the mechanical
interlocking with matrix [83]. Electric discharge (corona, cold plasma) is another way of
physical treatment. Corona treatment is one of the most interesting techniques for surface
oxidation activation. This process changes the surface energy of the cellulose fibers, and in
the case of wood, surface activation increases the amount of aldehyde groups [65].
The same effects are reached by cold plasma treatment. Depending on the type and nature
of the used gases, a variety of surface modifications can be achieved. Surface crosslinkings
may be introduced, surface energy increased or decreased, and reactive free radicals and
groups could be produced.
Electrical discharge methods are known to be very effective for ―nonactive‖ polymer
substrates as polystyrene, polyethylene, and polypropylene for exemple, which are
successfully used with modificated cellulose fiber in order to decrease the melt viscosity of
cellulose-polyethylene composites and to improve mechanical properties of cellulose-
polypropylene composites [83,84].
4. MECHANICAL PROPERTIES OF NATURAL FIBERS COMPOSITES

The properties of natural fibers reinforced composites are dependent of parameters as
volume fraction of the fibers, fiber aspect ratio, fiber–matrix adhesion, stress transfer at the
interface, and fiber orientation [85-87]. Most of the studies on natural fiber composites
involve mechanical properties characterization as a function of fiber content, effect of various
treatments of fibers, and the use of external coupling agents.
Both the matrix and fiber properties are important to improve mechanical properties of
composites. The tensile strength is more sensitive to the matrix properties, whereas the
modulus is dependent on the fiber properties. To improve the tensile strength, a strong
interface, low stress concentration, fiber orientation is required whereas fiber concentration,
fiber wetting in the matrix phase, and high fiber aspect ratio determine tensile modulus. The
aspect ratio is very important to determine the fracture properties. In short-fibre-reinforced
composites, there exists a critical fiber length that is required to develop its full stress
condition in the polymer matrix [88-90]. Fiber lengths shorter than this critical length lead to
failure due to bonding at the interface at lower load. On the other hand, for fiber lengths
greater than the critical length, the fiber is stressed under applied load and thus results in a
higher strength of the composite. For impact strength, an optimum bonding level is necessary.
The degree of adhesion, fiber pullout, and a mechanism to absorb energy are some of the
parameters that can influence the impact strength of a short-fibre-filled composite.
The properties mostly vary with composition as per the rule of mixtures and increase
linearly with composition. However, it has been observed that this linear dependence on
percentage of fiber content does not hold at high percentage (80%) of the fibre, probably due
to lack of wetting of the fiber surface by the polymer.
5. EFFECT OF MODIFICATION ON MECHANICAL AND THERMAL

PROPERTIES OF NATURAL FIBERS/HDPE COMPOSITES
The mechanical and thermal properties of thermoplastic composites can be improved by
the use of compatibilizers between the fiber and matrix and modification of surface fibers.
5.1. Silane and Oxidization Treatments
Li et al. [24] studied two types of fiber surface treatment methods, namely chemical
bonding and oxidization to improve fiber/HDPE matrix interfacial bonding properties.
In the chemical coupling method two kinds of silanes are used diluted to a 6%
concentration in acetone, i.e. 3-aminopropyltriethoxy silane (silane 1) and gamma-
methacryloxypropyltrimethoxy silane (silane 2), to modify the sisal fiber surface. The sisal
fibers were immersed into silane solution for 24 h and then cleaned by acetone and dried in
the oven at 60 oC for 4 h to remove the excessive solvent. The chemical formulae of the
silanes are:
Silane1: 3-aminopropyltriethoxy silane, H2N– (CH2)3– Si(OC2H5)3.

Silane 2: gamma-methacryloxypropyltrimethoxy silane, CH2CH3CCOO(CH2) 3Si(OCH3)3.
In the presence of moisture, silanes 1 and 2 react with water to form silanol and alcohol:
Silane 1: NH2 (CH2)3Si(OC2H5)3 + 3H2O = (HO)3Si(CH2)3NH2 + 3(C2H5OH)

Silane 2: CH2CH3CCOO(CH2)3Si(OCH3) 3 + 3H2O = (HO)3Si(CH2)3OOCCCH3CH2 +
3(CH3OH)
Silanol reacts with the hydroxyl groups attached to the glucose units, G, of the cellulose
molecules in the fiber cell-wall, thereby bonding itself to the cell-wall, rejecting water:
Silane 1: NH2(CH2)3Si(OH)3+GOH=NH2(CH2)3 Si(OH) 2OG + H2O

Silane 2: (HO)3Si(CH2)3OOCCCH3CH2+GOH=CH2CH3CCOO(CH2) 3Si(OH)2OG + H2O
When combined with the matrix resin, other functional groups of the silane molecule,
such as NH2 for silane 1 and C=C groups for silane 2, react with suitable groups of the resin.
As a consequence fiber/matrix chemical bonding occurs improving interfacial properties.
In the oxidization method permanganate (KMnO4) and dicumyl peroxide (DCP) were
selected as the oxidants to treat the fiber surface. Sisal fibers were immersed in a 0.055%
permanganate acetone solution for 2 min, cleaned with acetone, and dried at 60 oC for 4 h to
remove excessive solvent. For the DCP treatment, sisal fibers were immersed into a DCP
acetone solution (6% concentration) for 1.5 h and washed with acetone. Drying was
performed in the same way as for the permanganate treatment. All fibers were heated in an
oven at 120 oC to remove the moisture before treatment and all treated fibers were stored in
sealed plastic bags before being used.
Results showed that permanganate and DCP treated sisal fiber reinforced HDPE
presented a stable debonding process. On the other hand, silane treated sisal fiber reinforced
HDPE showed an unstable debonding process. Figure 6 shows load– displacement curves
obtained for the treated and untreated sisal fibers with the HDPE matrix during single fiber
pull-out tests.
Two different types of load – displacement curves have been observed. The load–
displacement curves of untreated, the DCP and KMnO4 treated sisal fibers are typical of ‘
stable’ pull-out for a mainly mechanically bonded interface. The rising portion of the
debond load versus displacement curve is typically linear without apparent ‘ stick-slips’
and there is no significant load drop after complete debonding. Due to the oxidization
function of the permanganate and DCP, the sisal fiber surface was etched and became quite
rough, as shown in Figure 7.
5.2. Maleic Anhydride Treatment
Araújo et al. [39] studied crystallization phenomenon and the interaction between the
degradative processes of the HDPE/curaua fibers composites with and without coupling
agent, prepared using an intermeshing corotating extruder. Two different coupling agents
(poly(ethylene-co-vinyl acetate), EVA (UE-2866/32 with 28% of vinyl acetate) provided by
Polietilenos União (Triunfo, Brazil) and maleic anhydride grafted polyethylene PE-g-MA
(MEGHWAX SAW X-01) provided by Megh Ceras & Emulsões (São Paulo, Brazil), with
40–60 mg KOH/g as acidity level were used.
Thermogravimetric results of composites present a decrease in the fiber degradation
Temperature in comparison with that isolated fiber, while insignificant differences are
associated to the HDPE. It was observed an antagonistic fiber/HDPE interaction, considering
that in general an increase in the fiber degradation temperature as reinforce is expected. The
composite without coupling agent and that with EVA had part of the fiber weight loss process
occurring at higher temperatures, close to the HDPE weight loss, as shown the Table 3. A
higher char residue formation was observed when using PE-g-MA as coupling agent.
Figure 6. Load-displacement curves of single fiber pull-out tests for sisal/HDPE composites with
different surface treatments [24].
Figure 7. SEM photograph showing a sisal fiber after being treated by permanganate [24].
Table 3. Temperatures when the weight loss reaches 3 wt% (Ti) and when the larger
rate of weight loss occurs (Tmax) [39]
Samples Ti (value at 3 Tmax curaua Tmax HDPE process

wt% weight loss) fiber process
HDPE 427 ------ 476
Natural fibre 266 363 ------
Calculated 315 363 476
Composite 337 8 346 4 470 6
Composite + PE-g-MA 288 8 350 5 473 6
Composite + EVA 316 8 351 3 471 6
The compatibilized composite shows a higher interfacial interaction due to the reaction
between acid groups of the maleic anhydride groups and hydrophilic groups on the fiber
surfaces. As a consequence the degradation of one component accelerates the degradation of
the other.
Also the increase of the composites crystallinity occurred due to the transcrystallinity
effect, as shown the Table 4, which at the same time is decreased by the presence of the
coupling agents due to the reactions with the fiber surface OH groups.
5.3. Alkali Treatment
Isothermal crystallization behavior and mechanical properties of ionomer-treated sisal

fibers reinforced high-density polyethylene (HDPE) composites have been investigated by
Choudhury [85]. Short sisal fibers (length ~4.0 mm) were thoroughly washed by aqueous
detergent solution to remove dirt followed by cleaning with distilled water and dried in
vacuum oven at 70 oC for 1 day. The washed fibers were immersed in 5% aqueous NaOH
solution for a period of 1 h at 40 oC, followed by washing with 0.1N acetic acid and distilled
water. The alkali-treated fibers were than dried in vacuum oven at 70 oC for 2 days to obtain
mercerized fibers .
The mercerized sisal fibers were immersed in hot 5% Surlyn ionomer solution (in
toluene) at 70 oC for 30 min to obtain ionomer treated fibers. Composites were prepared by
the melt mixing of the ionomer treated short sisal fibers with HDPE in a HAAKE rotor
mixture (Model Rheomix 600, Dreieich, Germany) at 120 oC with roller blades and a mixing
chamber with a 60 cm3 volumetric capacity. The process was carried out for 10min at an
optimum speed of 50–60 rpm, which depended on the quantity of the fibers by weight. Each
batch contained various plastic to fiber weight ratio (95:5, 90:10, 85:15 and 80:20) [85].
The present investigation showed the application of sisal fiber as a good reinforce and
Surlyn ionomer as an effective coupling agent for composite fabrication with polyethylene
matrix. Figure 8 shows hypothetical model of fiber modification with Surlyn ionomer and
reaction with HDPE matrix.
DSC analysis demonstrated that the presence and the concentration of short sisal fibers
affect significantly the crystallization behavior of HDPE matrix. A noticeable decrease to half
time of HDPE crystallization was observed by the incorporation of short sisal fiber to HDPE.
This could be attributed to the fact that the sisal fibers surfaces act nucleating sites for the
crystallization of the matrix polymer, promoting growth and formation of transcrystalline
layer in the composites.
The concentration of nucleating sites in the HDPE/sisal composites increased with the
increase of fiber content, which was reflected in higher composites crystallinity. The
phenomenon was observed for mechanical properties of HDPE/sisal composites with
increasing fiber content, which was attributes to the reinforcing effect imparted by the
ionomer treated fibers, which allowed a uniform stress distribution from the polymer matrix
to the dispersed fiber phase.
5.4. Modification of Metallic Oxide Coated Cellulose Fibers
Mulinari et al. [82] studied the modification effect of sugarcane bagasse cellulose with
zirconium oxychloride to reinforce HDPE in order to improve mechanical properties.
Cellulose from sugarcane bagasse was obtained by pre-treatment with 10% sulfuric acid
solution, followed by centrifugation, deslignification with 1% sodium hydroxide solution and
bleaching with sodium chloride. Modified cellulose from sugarcane bagasse was obtained by
dissolution of 2 g of zirconium oxychloride in 100 mL of aqueous hydrochloric acid solution
(0.5 mol L-1), in which 5 g of cellulose were immersed in this solution. The material was
precipitated with ammonium solution (1:3) at pH 10.0, under stirring, filtered under vacuum,
exhaustively washed with distilled water for the complete removal of chloride ions (negative
silver nitrate test) and dried at 50 ºC for 24 h. The resulting material was designated as
Cell/ZrO2.nH2O [78]. The effect of modification on fibers was evaluated by scanning electron
microscopy and X-ray diffraction techniques.
Figure 9 shows sugarcane bagasse cellulose fibers non-modified and modified
diffractograms. It is possible to observe a major diffraction peak for 2θ ranging between 22o
and 23 o, which corresponds to the cellulose (0 0 2) crystallographic planes.
X-ray diffraction peaks for both materials can be attributed to crystallinity scattering and
the diffuse background to disordered regions. Materials tested are semicrystalline. The
spectrum corresponding to the non-modified sugarcane bagasse cellulose fibers shows
diffraction peaks at the following 2θ angles: 15.7º and 22.82º. For modified sugarcane
bagasse cellulose the same peaks can be observed at 15.9º and 22.82º. The presence of the
peaks at 15º and 22º are an evidence of the modification on fiber. The position of these peaks
indicates an increase of the interplanar distance in relation to the modified fibre. This
behavior occurs due to the generation of disorder when fibers are modified. The projection
substituting groups along the axis is associated with an increase in the interfibrillar distance.
Patterns for both materials are similar; however non-modified fiber is less crystalline than
the modified one. The crystallinity index (CI), which is an amount of crystalline cellulose
measurement with respect to the global amount of amorphous materials, was evaluated using
Segal empirical method according to following equation (1):
I(002) I(am)
CI 100 (1)
I(002)
where I002 is the maximum intensity of the 002 lattice reflection of the cellulose I and Iam
is the maximum intensity of X-ray scattering broad band due to the amorphous part of the
sample. According to this method, non-modified and modified fiber presented 47% and 53%
of crystallinity, respectively. These values can be attributed to the fibers modification.
Also it was observed a change in the morphological structure of the cellulose fibers from
sugarcane bagasse after the modification by SEM. Cellulose fibers micrographs non-modified
show fibers of flattened forms and different sizes (Figure 10A). On the other hand, cellulose
fibers modified showed the presence of oxide, however, it was noticed that the oxide was not
deposited in a homogeneous way on the cellulose surface (Figure 10B).
Table 4. Tc, Hc, Tm, Hm and Xc for the formulation [39].
Sample Tc Hc Tm Hm (J/mol) Xc (%)

(oC) (J/mol) (oC)
Obtained Calculateda Desviation Obtained Calculateda,b Desviation
HDPE 113 185 138 190 ---- ---- 65 ---- ----
Composite 111 179 138 188 152 + 24% 81 52 + 56%
Composite 112 149 135 162 148 + 10% 62 51 + 41%

+ EVA
Composite 110 129 137 136 148 - 8% 60 51 + 18%
+ PE-g-MA
Figure 8. Hypothetical model of fiber modification with Surlyn ionomer and reaction with HDPE
matrix [85].
Table 5. Mechanical properties of the materials [86].
Samples Properties
Elongation at break (%) Tensile strength (MPa) Tensile modulus (MPa)
HDPE 8.9 0.8 15.7 1.1 732.45 90.6
CB5% 5.4 0.4 16.2 0.7 942.5 98.6
CB10% 5.5 0.2 15.6 0.3 897.4 27.5
CB20% 5.7 0.3 15.8 0.3 1140.7 62.5
CM5% 7.2 0.1 20.8 0.4 1177.7 25.0
CM10% 7.4 0.4 21.9 0.6 1238.5 41.0
CM20% 6.5 0.2 20.9 0.4 1306.4 26.9
Reinforcement in wt% (CB = non-modified cellulose; CM = modified cellulose).
Results showed that modification effect on sugarcane bagasse cellulose with zirconium
oxychloride was successfully accomplished and that this reinforcement material with HDPE
showed tensile strength higher than non-modified sugarcane bagasse cellulose. Modification
in the sugarcane bagasse cellulose influenced directly the mechanical properties of the
composite material, as can be observed in Table 5.
1400
(a)
(b)
1200
1000
Intensity (cps)
800
600
400
200
0
10 20 30 40 50 60 70
2 (degree)
Figure 9. X-ray patterns for sugarcane bagasse cellulose fibers non-modified (a) and (b) modified [82].
Figure 10. Morphology of cellulose fibers: (A) non-modified (500X); (B) modified (500X) [82].
The reinforcement amount contributes also to variation of the tensile modulus as

indicated in Table 5. Fibers insertion improves the modulus, because the fibers Young‘s
modulus is higher when compared to the thermoplastic modulus. However, to obtain a
significant increase, a good fiber/matrix interfacial bond is necessary.
5.5. Hot Water Treatment
Sato et al. [87] evaluated the effect of sapegrass fibers treated with hot water on mechanical
properties sapegrass fibers/HDPE composites. Results were successfully accomplished and it
was verified an effectively improvement in the tensile strength and modulus compared to the
HDPE isolated, as shown Table 6. This treatment increase the fibers roughness, confirmed by
scanning electron microscopy technique, promoting a mechanical interlocking.
SEM provides an excellent technique for examining the surface morphology of sapegrass
fibers. The morphology of sapegrass fibers in nature can be observed in Figure 12, which shows
the longitudinal and cross sections of fibers. These fibers show a superficial layer with high
percentage of extractives.
By longitudinal observation, the sapegrass fibers show a kind of spiral elements in the inner
parts (Figure 11B and 11D). On the other hand, the surface of fiber is not extremely smooth in
nature as some knots like drip wax appears on the surface. It is also possible to observe in
Figure 11A and 11C a superficial layer of parenquimas cells.
After the treatment with hot water on sapegrass fibers in nature the removal of extractives
on surface fibers and spiral elements in the inner parts is observed. These images can be
observed in Figure 12. It was also verified that, with the elimination of superficial layer, the
contact area for the exposition of fibrils (reentrance) and globular marks (salience) increased. As
a consequence, it was observed an increase in the fiber roughness, which contributes to increase
the fiber/matrix adhesion.
Table 6. Mechanical properties of the materials [87].

Samples Elongation at Tensile Tensile Modulus (MPa)
break (tensile) (%) Strenght (MPa)
HDPEr 8.9 ± 0.8 15.7 ± 1.1 733 ± 91
Sapegrass 5% /HDPE composite 6.6 ± 0.3 23 ± 0.9 1412 ± 119
(Reinforcement in wt%)
Sapegrass fibers insertion in matrix after extractives removal increased tensile strength as
well as tensile modulus, when compared with those for HDPE. Results obtained for tensile
strength and modules are excellent considering that a simple treatment in fibers was
responsible for a mechanical strength improvement. Table 6 evidences the mechanical tests
results obtained for HDPE and treated sapegrass fibers/HDPE composite.
Composites presented an increase of 45% in the tensile strength and 93% in the tensile
modulus compared to the HDPE.
SEM micrographs of the fractured surface for the composite can be observed in Figure
13. This micrograph shows clearly that the fibers and matrix interfacial adhesion was good.
Of this way proposed treatment in sapegrass fibers was satisfactory.
Figure 11. Morphology of sapegrass fibers in nature: (a) cross section (500X); (b) longitudinal section
(1000X); (c) cross section (2000X) and (d) longitudinal section (5000X) [87].
Figure 12. Morphology of treated sapegrass fibres: (a) cross section (500X); (b) longitudinal section
(1000X); (c) cross section (2000X) and (d) longitudinal section (5000X) [87].
Figure 13. SEM fracture surface of sapegrass fibers/HDPE composite [87].
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Chapter 4
BAMBOO, SOYBEAN AND CORN AS RESOURCES

FOR GREEN COMPOSITES
Kuichuan Sheng1, Mehrdad ADL2, Hui Wang, Rui Chang

and Kun Fang
Bio-energy and Biomaterials Laboratory, School of Bio-systems Engineering
and Food Science, Zhejiang University, China
ABSTRACT
Bamboo, a well known plant has a broad application in nutrition, construction,

handicrafts as well as furniture and decoration. A huge amount of bamboo wastes are
disposed continuously as a byproduct of its utilization in various purposes especially in
wood and furniture industries. A wide variety of researches and activities have been
performed on utilization of bamboo wastes in manufacturing of green composites and
hence, a wide assortment of substances have been tested to act as the supplementary
components such as Portland cement, petrochemical polymers (e.g. poly-ethylene, poly-
vinyl chloride, poly-propylene, polyester resins), and recently biodegradable polymer
matrices such as poly-lactic acid, plant proteins and poly-butylene-succinate. Scientific
efforts have been studied the different combinations of bamboo wastes with polymer
matrices and/or coupling agents. The most important items in these researches have been
the mixing ratios of materials as composite components, physical and chemical properties
of ingredient materials, production techniques and qualitative properties of composites
such as physical characteristics, mechanical strength, durability, water and moisture
resistance, abrasion resistance and external appearance. Effects of pre-treatment of
ingredients have been extensively investigated by purpose of modification and
improvement of composite characteristics. Extractable proteins from soybean and corn
have also been studied as polymer matrix for making green composites. Zein, a plant
protein found in corn that is widely applicable as coating agent or adhesive, is an example
that has fulfilled experiments for making particle boards. Further similar experiences
have been carried out on making composites from wood or bamboo sawdust or fibers
with soybean proteins. The more common objectives through the above mentioned
Corresponding authors : No. 268 Kaixuan Rd., 310029, Hangzhou, China- email: kcsheng@zju.edu.cn
2
- Email: madl49@yahoo.com
80 Kuichuan Sheng, Mehrdad ADL, Hui Wang et al.
researches have been to find the best mixing ratios, the most effective coupling agents
and/or modifiers, the optimum operational parameters in manufacturing processes, the
qualitative measures such as tensile strength, bending strength, internal bond, modulus of
elasticity, water absorption, thickness swelling, density and porosity. This chapter
reviews technical and scientific attempts on making composites from bamboo wastes and
various matrices and coupling agents especially those which have been performed in
Zhejiang University and academic organizations cooperating with.
INTRODUCTION
Bamboos as a group of evergreen perennial woody plants are naturally grown in a lot of
parts of the world such as east Asia, India, sub-Saharan Africa, Northern Australia,
southeastern United States and Latin Americas. According to its indigenous characteristics
bamboo is distinguished from woods and can be considered as a composite material itself
because cellulose fibers can be found embedded in lignin matrix [1]. Bamboo forests are
widespread in China from Sichuan in the heart of mainland to the east until the Yellow Sea
shores and to the south until the China Sea and Indo-China peninsula. For thousands of years
bamboo has been playing an outstanding role in the life of eastern Asian people not only in
the form a construction material but also in culinary and medical purposes as well as basic
material for handicrafts. China has the largest area and richest resource of bamboo containing
more than 500 species in 39 genera and has experienced a rapid development in bamboo
utilization industry [2]. The surface area of bamboo forests reportedly extends 5 million ha
over China [3,4]. Zhou et al., described the ecological functions and socio-economical
benefits of bamboo forests including soil protection, water resources conservation, river
banks protection, land rehabilitation and carbon sequestration [2]. Predominant famous native
species in China are phyllostachys pubescens that covers some 20,000 km2 (40% of total
bamboo forests) and usually grows in sub-tropical climates with 1200-1800 mm annual
precipitation and 13-20 °C mean annual temperature, phyllostachys bumbusoides that
produces good quality woods and is more cold-tolerant, phyllostachys bissetii that is plentiful
in Sichuan province [5]. Mature bamboo plantations have considerable biomass productivity.
For example, above-ground net primary productivity for phyllostachys bumbusoides has been
reported as 24.6 t.ha-1.yr-1 including leaves over a 6 year period in Japan while woody
biomass increment had been 15.5 t.ha-1.yr-1 [6]. This quantity has been reported for
phyllostachys bumbusoides as 18.1 t.ha-1.yr-1 in Japan while another research has reported the
average above-ground woody biomass of this species as 7.7 t.ha-1.yr-1 for a semi-natural
lowland stand in Zhejiang province, China [7].
Bamboo culms are the most applied part of these plants in industry. Although bamboo
culm has highly anisotropic characteristics but its significant tensile strength and elasticity,
makes it widely applicable in structural, furniture and decorative purposes. Cellulose,
hemicellulose and lignin are the main constituents of bamboo culm having the percentages of
35-50%, 15-20% and 15-27% respectively [1,5,10]. Though Jain and Kumar et al., reported
the contents of cellulose and lignin in bamboo equal to 60.8% and 32.2% respectively [13], it
may corresponde to the composition of an Indian species they tested. They described the
microstructure of bamboo in which, cellulose constitutes most of fibers that have been
surrounded by an amorphous matrix of lignin and hemicellulose.
Bamboo, Soybean and Corn as Resources for Green Composites 81
Bamboo plywood is one of important industrial products of bamboo in China that has a
lot of applications such as decorations, flooring of living spaces and interior parts of
automobiles. The total production capacity of bamboo plywood was reported as much as
200,000 cubic meters annually in 1994 [8]. Utilization of bamboo culms as poles for
scaffolding is another major application of this plant. The value of China‘s bamboo products
reached to US$ 1.1 billion among 30 bamboo producers and exporters in October 2007 [9].
Bamboo wastes are produced in different types from different utilizations. They are
available in the form of leaves, roots and culm residues. Culm residues are usually in the form
of chips, fibers and particles that belong to ligno-cellulosic materials. Large amounts of
bamboo wastes are generated in China every year. Over 50,000 tonnes of bamboo scaffolding
waste each year is dumped as construction wastes only in Hong Kong [11].
There are several ways to manage and utilize bamboo wastes. Conversion to energy is
one of the management options for bamboo wastes. Bamboo culm residues have higher
energy content than most agricultural wastes but lower than woods. Various references have
reported the heating value of bamboo culm in the range of 15 to 18 MJ per kg of oven dried
matter [5,10,12]. Moreover to energy generation from bamboo wastes, there are other
approaches to make value adding products from these sources of waste. This article concerns
the application of bamboo culm residues in production of composites.
Characterization of Bamboo-Based Composites
Each composite may have several components through which, at least two components
are essential, a matrix and a reinforcing agent. Composites utilizing bamboo fibers or bamboo
particles as reinforcement have been introduced to the commercial world since at least two
decades ago. These kind of composites are being constituted from bamboo-derived materials,
a main matrix in the form of polymer or adhesive or other material, and additive materials by
various purposes such as coupling agents, surface treatment agents, polymer improvement
agents and so on. Brief descriptions on above mentioned components will be discussed
hereafter. Before that, it‘s necessary to mention a brief essay about qualitative assessment
parameters for bamboo-based composites. They can be categorized into mechanical
properties, physical characteristics, thermal properties and chemical properties. Each category
includes several parameters and characteristics. Some parameters are commonly used in most
research works about bamboo-based composites or their components such as tensile strength
or modulus of elasticity while some others have only been assessed in a few numbers of
experiences. Most applicable and important parameters for qualitative assessment of these
composites have been summarized in Table 1 as follows.
Bamboo Culm’s Wastes as Reinforcement for Green Composites
As mentioned before, residues of bamboo culms are classified as ligno-cellulosic

resources and according to appropriate mechanical properties of bamboo fibers they have a
good ability to act as reinforcement within the composite matrix. Several researches have
been carried out on physical, chemical and mechanical properties of bamboo and its fibers.
Some selected parameters of bamboo have been summarized in Table(2) as follows.
Table 1. Influential parameters for quality assessment of bamboo-based composites.
Category Parameter Application target

Composite polymer bamboo fibers or
matrix particles
Tensile strength + + +
Modulus of elasticity (Young‘s + + +
modulus)
Modulus of rapture + + +/-
Mechanical Elongation at failure + + +/-
Bending strength + + -
Shear strength + + -
Internal bond + - -
Abrasion resistance + +/- -
Density + + +
Porosity + +/- +/-
Water absorption + +/- +/-
Physical
Thickness swelling + - -
Morphology and micro-structure + +/- +
General appearance + - -
Glass transition temperature + + -
Melting temperature + + -
Crystallization temperature + + -
Thermal Apparent melt viscosity + + -
Activation energy for flow +/- + -
Thermal degradation + + -
Thermal gravity analysis + + -
Enzymatic degradation + + +
Activation energy for flow + + -
Chemical Chemical composition + + +
Lignin and hemicellulose content +/- - +
Solvents‘ resistance + + -
Table 2. Selected parameters of bamboo fibers.
Fiber bundle Diameter (μm) Tensile Young‘s Failure Ash content (%)
density strength modulus (GPa) strain (%)
(g/m3) (MPa)
800a 88-125b 441 220b 35.9 13.1b 1.3b 0.6 – 2.1c
a
according to Ref.[13]
b
adopted from Ref.[14]
c
data are referred to Ref.[5]
Figure 1. Mature bamboos and their culms in a bamboo forest in Zhejiang, China.
Size analysis of bamboo particles

100
90
Cumulative percent
80
70
60
50 passed
40
30
20
10
0
1000 400 200 100 10
size in micron
source: Bio-energy and biomaterials Laboratory, Zhejiang University
Figure 2. A sample of size distribution for bamboo particles.
The wastes of bamboo culms can be applied in different forms in making composites.
They may be used in the coarse form without any processing or adopt some degrees of
treatment such as grinding, screening, fiber extrusion, chemical treatment or thermal
treatment and so on. By the way, the adhesion between reinforcement (i.e. bamboo particles
or fibers) and matrix materials plays a very important role in mechanical properties and other
qualitative characteristics of composites. It has been proved that bamboo fibers act more
effectively than raw bamboo particles in fabrication of bamboo-based polymer composites
and the method of bamboo fibers extraction is very important as well due to the brittle nature
of these fibers because they are originally covered by lignin [14]. K. Okubo and his
colleagues have concluded in this reference that lignin removed fibers presents a better
reinforcement function in polymer matrix. There are mechanical or hydrothermal procedures
to extract bamboo fibers from bamboo culms. Okubo et al., applied steam explosion
technique in order to extract bamboo fibers and measured their mechanical properties as
mentioned in Table 2 and obtained satisfying results from utilization of these fibers in
polymer matrices [14]. However, they found through their scanning electron microscopy
(SEM) analysis that the steam-exploded fiber bundles have not separated sufficiently from
lignin matrix therefore they used a mixing machine by purpose of mechanical rubbing on
fiber bundles as a further treatment for removal of lignin from surface of fiber bundles and
obtained consequently better mechanical properties by using mechanically rubbed steam-
exploded bamboo fibers as reinforcement in polymer composites.
Particle size distribution and particles‘ shape are other important parameters that affect
reinforcing behavior of bamboo and consequently the characteristics of bamboo-based
composites. A proposed appropriate parameter on this aspect can be effective size that is
widely applied in soil mechanics and other granular materials behavior. According to
scientific definition, the effective size of a granular medium is the size from which, 85% of
particles are smaller. This size will be usually found from size distribution graph of particles
or granular materials. An example of size distribution graph for bamboo culms particles has
been presented in Figure 1. As a case example, Wang et al., found in their experience on
composite fabrication from raw bamboo particles and poly(vinyl chloride) (PVC) that
optimum effective size of bamboo particles (as shown in Figure 2) was 0.42mm (40# mesh)
in which, bamboo and PVC could get a fixed composition because the size ratio between
bamboo and PVC seemed to be the best fitted for PVC granules to enter the lumens of
bamboo particles [15]. They found higher water absorption and thickness swelling as well as
lower tensile strength in their examined composites which had been made by coarse bamboo
particles and suggested that larger lumens, more fine pores and more available hydrogen
bonding sites in coarser bamboo particles have been the main reasons for increase in water
absorption and drop in mechanical strength.
According to the research of Shibata et al., Young‘s modulus of bamboo fibers were
rather decreased from 20-25 GPa to 10-11 GPa by increase in fiber diameter from 0.15 mm to
0.4 mm [16]. It has been mentioned in their article as well that Young‘s modulus of fiber-
polymer composites decreases with decreasing in fiber length.
The content of bamboo fibers or particles is another effective parameter in qualitative
properties of composites. The role of bamboo fraction in a relevant composite has been
comprehensively investigated in a number of research works including the experiments of
this chapter‘s authors. Shibata et al., studied the effect of volume or weight fraction of
bamboo fibers on flexural modulus and their results showed an ascending trend with increase
of fiber volume fraction [16]. Lee and Wang found through their works on making
biodegradable composites from bamboo with poly(Lactic acid) (PLA) or bamboo with
poly(butylene succinate) (PBS) that increase in bamboo flour (BF) content had a direct effect
on Young‘s modulus in BF/PLA and BF/PBS composites and water absorption was increased
in both categories as well [17]. Tensile strength followed quite different trend for different
utilized polymer matrices and coupling agents, for example it was decreased with increase of
BF content in BF/PBS but increased vice versa when a coupling agent was added. This fact
has been demonstrated in Figure 2. Ge and Li et al., used bamboo flour with an effective size
of 0.1 mm (120 mesh) with PVC for making composites and found a descending trend in
tensile strength with increase in bamboo flour (BF) content in the composite but Young‘s
modulus showed an increase for the same trend in BF content [18]. It has also experienced in
the research of this chapter‘s authors that water absorption and thickness swelling in
bamboo/PVC composites increased by increase in bamboo fraction and its particle size [15].
It can be related to hydrophilic behavior of bamboo fibers. Internal bond showed a relative
decrease with increase of bamboo particles‘ fraction in above mentioned composites.
The nature of the particles or fibers will also influence the physical and mechanical
properties of fabricated bamboo-based composites. Raw and untreated bamboo fibers have
been proved to cause more porosity and water absorption in natural fiber reinforced
composites due to presence of hydroxyl groups and other polar groups on bamboo fibers
[19,20]. Water absorption in natural fiber-polymer composites has been proven to be a
function of volume fraction of fibers in the composite and availability of free hydroxyl groups
on those natural fibers [20]. Moisture content of natural fibers and particles is another
important parameter in consequent characteristics of fabricated composite. The experiences in
bio-energy and biomaterials laboratory of Zhejiang University as well as other references
showed that moisture content more than 10% in bamboo particles will significantly impact
the quality of fabricated composite in the form of more porosity and lower water resistance
because the excess moisture would not have the possibility to leave the mold during hot
pressing process for bamboo/polymer composite fabrication. Results on tensile properties of
bamboo-based composites made by PVC and untreated bamboo particles in this laboratory
showed a decrease in average tensile strength of samples with increase in bamboo weight
fraction in composites as presented in Figure 4, but they did not show a linear relationship
with moisture content of bamboo particles [16].
●: without coupling agent, ○: with coupling agent
Figure 3. Effects of bamboo flour content and addition of coupling agent on tensile strength of
bamboo/PBS composites.
8 3% moisture
Tensile strength (MPa)

5% moisture
6 8% moisture
4
2
0
40 50 60 70 80
Bamboo wt%
Figure 4. Tensile strength of bamboo/PVC composite samples vs bamboo weight fraction
In order to overcome the limitations induced by water absorption and internal bond in
bamboo-based composites some techniques are exploited such as surface treatment or
modification of interface between bamboo particles and matrix. As a further enhancement,
development of cross linking between fibers and matrix can also be used by application of
supplementary materials named as coupling agents.
Matrix
Matrix in bamboo-based composites is usually selected from polymers however there are
some reported activities on making composites from bamboo particles and Portland cement as
well. There are several articles and reports available concerning various types of polymer
matrices used in fabrication of bamboo-based composites. The Bio-energy and Biomaterials
Laboratory of Zhejiang University has investigated PVC, Zein and soybean protein as
polymer matrices so far as well as poly(lactic acid) in its collaborative work with Bio-
materials and Technology Laboratory of Kansas State University, USA.
Portland Cement as a Matrix for Bamboo Composites
Ling Fei Ma described in his article the manufacturing of particle board from chips of
phyllostachys pubescens (moso bamboo) and Portland cement [21]. He performed these
activities along with Nagadomi, Kuroki and other colleagues in Wood Research Institute of
Kyoto University, Japan. They utilized chips from different parts of bamboo culm and mixed
with cement and water in a weight ratio of 15:200:100 respectively [22]. They tested cold
pressing, hot pressing as well as steam injection pressing for fabrication of bamboo/cement
composites. They also applied some additives including sodium bicarbonate, sodium
carbonate, sodium silicate, calcium chloride and magnesium chloride in order to investigate
their effects on hydration rate, internal temperature, density and mechanical properties of
composites. For cold pressed composites calcium chloride had the most effective influence on
rising mechanical properties at its 15% additive content (ratio to weight of cement) resulting
in 16.91 MPa, 3.37 GPa and 0.55 MPa for MOR, MOE and internal bond (IB) respectively.
Sodium silicate (Na2SiO3) was found the most effective additive at 15% additive/cement ratio
in hot pressing process that contributed to higher mechanical properties and better cement
hydration. It was obtained in turn by substitution of 5% of cement weight by silica fume, 11
minutes hot pressing at 110 °C and 24 hours treatment at 100 °C. The optimum results of
cement hydration and mechanical strength of composites in steam injected pressing process
were obtained by addition of 10% Na2SiO3 and 5% MgCl2 to the cement at the operational
condition of 11 minutes hot pressing at 110 °C including steam injection at 147 kPa pressure.
The MOR and IB were obtained over 12 MPa and 0.4 MPa respectively [22].
Polymers as Matrix for Bamboo Composites
Polymers are widely used for wood-plastic composites (WPC). Bamboo-based

composites can be categorized as a branch of WPCs. The more experienced polymers that
have been applied as matrix in bamboo-based composites can be seen in Table 3.
Poly(lactic acid) PLA is a crystalline and transparent biological-based polymer made
from monomers of lactic acid [CH3CH(OH)COOH] that its biodegradability makes it
environmental friendly. This material has relatively high melting point, high strength but low
elongation at break [33] and has been investigated in a number of scientific literature and
applied as polymer matrix for bamboo-based or wood-based composites. According to some
weaknesses in its mechanical behavior in composites, it is usually applied after modification
or in combination with other chemical agents. The latter agents have the duty of making
better adhesion or cross linking between polymer molecules and reinforcement fibers. They
will be discussed in more details in another section.
Poly(butylene succinate) (PBS) is a white crystalline thermoplastic polymer that can be
produced from butanediol (HOCH2CH2CH2CH2OH) and succinic acid
(COOHCH2CH2COOH) as raw materials which in turn are available from renewable
resources. This polymer has melting point of about 90-120 °C and glass transition
temperature of about -45 to -10 °C. It was applied in bamboo-based composites by Lee and
Wang [17].
Table 3. Some investigated polymer matrices for bamboo-based composites from

literature review.
Polymer Production Reference

origin
Poly(lactic acid) (PLA) Biological [17]
Poly(butylene succinate) (PBS) Biological [17]
Poly- propylene (PP) Chemical [14]
Methyl-methacrylate (MMA) Chemical [23]
Poly-vinyl chloride (PVC) Chemical [15,18]
Soy protein adhesive (SPA) Biological [31,32]
Methyl methacrylate with chemical formula (CH2=C(CH3)CO2CH3)is a colorless organic

liquid that is ester of methacrylic acid and is largely used as a monomer for production of
poly(methyl methacrylate). Bashar et al., made bamboo-plastic composites from bamboo
powder of an Indian species (Tala bamboo) using methyl methacrylate (MMA) as the bulk
monomer combined with methanol at different proportions [23]. They applied different
additives to improve the performance of polymer matrix. The effect of those additives such as
lithium nitrate (LiNO3) and urea (CO(NH2)2) on tensile strength and bending strength was
investigated. Their results showed that lithium nitrate increased the tensile and bending
strength by 43% and 59% respectively. The mixture of urea and lithium nitrate had the
highest effect on tensile strength value.
Soy protein
Soy protein is a biologically extracted substance from soybean containing sorts of natural
amino acid polymers with a wide variety of applications in food industry such as non-dairy
creamer or imitation meats as well as other industrial functions such as emulsifier, adhesive
or resin. It is commercially available in three grades: soy flour with about 50% protein, soy
protein concentrate (SPC) with some 70% protein and soy protein isolate (SPI) containing
more than 90% protein. Due to its large quantities, renewable nature and biodegradability,
soybean protein has been considered as a substitute for petroleum polymer in the manufacture
of various binders. Soy-based adhesives have been used primarily for plywood [24]. In recent
years, increased demand for adhesives, limited resources of petroleum-based binders, and
increasing interest in developing environmental friendly products have resulted in expanded
application of soybean-based adhesives[25,26]. Both SPC and SPI should preferably be
modified in order to improve their mechanical characteristics prior to use as resin or polymer
matrix in fabrication of green composites. As both soy protein and cellulose have highly polar
groups, it is expected a strong interface between soy protein and natural fibers. The role of
improving agents is the increase of bonding and linking ability between protein molecules
and reinforcing fibers. In order to improve the properties of soybean-based adhesives, many
kinds of denaturants have been used. Netravali and his colleagues experienced fabrication of
biodegradable composites from flax-yarn fibers and soy protein [27]. They made
unidirectional flax-yarn fiber composites using both SPC and SPI. They applied
glutaraldehyde (C5H8O2) and poly-vinyl alcohol (PVA) as cross-linking agents for
modification of SPC and stearic acid as modifier for SPI and obtained considerably better
mechanical properties and lower moisture absorption in their fabric reinforced composites.
Alkali substances, such as sodium hydroxide (NaOH), are the most common chemical used to
increase the adhesion strength and water resistance of soy-based protein adhesives. Soy
protein or modified soy protein can be used as adhesives in making particleboard and other
composites.
As a research work in Bio-energy and Biomaterials Laboratory (BBL) of Zhejiang
University, the application of sodium hydroxide modified soy protein adhesive (SPA) as a
polymer matrix for bamboo particleboard was studied. During this research soy protein was
modified by NaOH and mixed with bamboo fibers in order to form medium density
composite under 5 MPa pressure in hot pressing process. The effects of pressing temperature,
pressing time and moisture content on physical and mechanical properties of bamboo-based
soy protein composites were investigated by Gu-lai Lv et al., [31]. The mathematical
assessment of obtained results was carried out by the use of response surface methodology.
According to this evaluation optimal properties of composites were obtained at moisture

content of 34.2% and press temperature of 167 °C with 7.8 min. press time. At this optimal
condition, MOR, MOE, tensile strength and 24 hours thickness swelling reached to 16.5 MPa,
1032.6 MPa, 10.4 MPa and 31.0% respectively. In order to prepare the adhesive, soy protein
isolate (SPI) having 90% purity was added to 0.2% NaOH solution at a ratio of 16.5 g : 150
mL with further addition of 1.6 g potassium sorbate (C6H7KO2) as preservative agent. The
mixture was stirred for 2.5 h at room temperature. The resultant adhesive was then ready to be
mixed with the bamboo shavings that were in turn prepared from a bamboo plywood factory
in Hangzhou, Zhejiang with a size variation of 10 to 20 mm. The bamboo shavings were
mixed with the modified SPI at room temperature. In all cases, the adhesives were mixed with
bamboo shavings using a paddle mixer for 15 minutes. The moisture content of the mixture
was adjusted to various pre-established value ranging from 15% to 30%. Hot pressing process
was adopted fabricate bamboo particleboard samples at 5MPa pressure. Different values of
pressing times from 5 to 10 minutes and temperatures from 150 to 180 °C were selected as
testing parameters. Coating ratio was an important factor affecting the particleboard qualities.
Four coating ration of 9%, 11%, 13% and 15% were tested. The press time and press
temperature were 7.5 min and 175 ℃ respectively. The moisture content of the bamboo
shavings was adjusted to 10% and then the bamboo shavings were blended with modified SPI
adhesive. The mixture was dried to 26% moisture content and then pressed. The particleboard
using 13 % coating ratio had the highest MOR, IB values and lowest 24h-ts value (Table 4).
MOR and IB showed little significant difference among 9%, 11%, or 15% coating ratio.
Because the particleboard with 13% coating ration had the most desirable quality, 13%
coating ration was used for all other experiments.
In this study, the Box- Behnken factorial design with three factors was chosen to find out
the effects of press time, press temperature and moisture content on particleboard properties.
The above mentioned design has been devised by George E.P. Box and Donald Behnken in
1960. Mathematical models, describing the relationships between the factors and the
particleboard properties, were developed. The 3D response surface was made by keeping one
independent variable at constant level, changing the other two independent variables, and
then calculating the response variables. The effects of press time, press temperature and
moisture content on MOR have been shown in Figure 5. The next Figure shows the effects of
same parameters on MOE [31].
Table 4. Effect of soy protein adhesive coating ratio on particleboard properties.
Coating ratio (%) MOR (MPa) IB (MPa) 24h thickness swelling (%)
9 10.15 0.30 17.11
11 11.52 0.35 15.48
13 15.37 0.42 13.20
15 12.68 0.35 24.62
Figure 5. Surface plot of the effects of temperature, pressing time and moisture content on MOR of
bamboo/SPA particleboards.
Figure 6. Surface plot of the effects of temperature, pressing time and moisture content on MOE of
bamboo/SPA particleboards.
Figure 7. Effects of temperature, pressing time and moisture content on 24h-ts of bamboo/SPA
particleboards.
Surface plots for thickness swelling after 24 hours (24h-ts) have been demonstrated in
Figure 7 as follows. Based on the surface plots, 24h-ts decreased with the increase of press
temperature, increased with the increase of press time, and decreased then increased with the
increase of moisture content. As press temperature increased, some hygroscopic components
of particles, such as hemicelluloses, would be hydrolyzed to furfural, which improved the
bond and water resistance between particles [31].
Figure 8. Surface plots of effects of temperature, moisture content and pressing time on IB of
bamboo/soy protein adhesive composites.
Another research activity was carried out by Fang et al., in BBL in order to develop an
environmental friendly bamboo particleboard with modified soy protein isolate (SPI) through
which, effect of coating ratio of SPI modified by sodium dodecyl sulfate (C12H25SO4Na) on the
physical and mechanical properties of bamboo particle board was studied [32]. The bamboo
particles in the size range of 2 – 5mm were utilized in this study and SPI was modified by 1%
solution of sodium dodecyl sulfate (SDS). The physical and mechanical properties of bamboo
particle board based on SDS-modified SPI as affected by coating ratio were studied. The results
showed that the optimal coating ratio of SPI adhesive was 13%. The mechanical properties and
water resistance of particle boards affected by moisture content, press time and press temperature
were tested by response surface methodology. Optimal properties of particleboards were obtained
with moisture content of 26%, press temperature of 175 °C and press time of 8.5 minute. Under
the optimal condition all the physical and mechanical properties of particleboards achieved the
requirements of Chinese standard for particleboards GB 4897-2003 with internal bonding 0.65
MPa, modulus of rapture 16.8 MPa and thickness swelling rate 6.7% [32]. The surface plots for
effects of pressing time, moisture content and temperature on internal bonding (IB) of
particleboards have been shown in Figure 8.
Poly-vinyl chloride
Poly-vinyl chloride (PVC) has been investigated as well by purpose of fabricating
bamboo-based composites. Ge et al., performed experimental fabrication of wood-plastic
composites using pine flour with PVC and bamboo flour with PVC [18]. They used
unplasticized PVC granules blended with bamboo flour and pine flour in two distinct
compounding experiments. They utilized some additives to PVC as well, by purpose of heat
stabilization, processing aid, impact modification and coupling agent. Both bamboo flour
(BF) and pine flour (PF) increased the stiffness of PVC composites significantly while
decreased tensile strength to some extent comparing to neat PVC. Pine flour showed a better
influence on mechanical properties of composites than bamboo flour with the same particle
size at the same loading level. None of BF and PF had obviously adverse effect on the
thermal stability of these composites. Tensile strength decreased from 45MPa (for neat PVC)
with increase in bamboo flour content to 24MPa (at 50% BF content) while Young‘s modulus
increased from 1610MPa to 2160MPa at the same correspondences.
Comprehensive experiments are ongoing in BBL, Zhejiang University on fabrication of
composites from PVC and bamboo wastes. The results on mechanical properties of initial
experiments had been considerably lower than those in preceding research in Ref.[18]. For
example the range of tensile strength (TS) values was 1.5 to 7.5MPa [15] comparing to the
range of 24 to 41MPa for BF/PVC composites in previously mentioned research. It may be
justified by this fact that no pre-treatment was done on bamboo particles and no additive or
coupling agent was used in initial set of experiments in BBL. Recent investigations are being
performed on bamboo/PVC composites in BBL in order to improve qualitative properties. A
part of these activities are focused on surface treatment of bamboo particles. Scanning
electron microscopic (SEM) images of a smooth slice interface of bamboo/PVC composite
depicts a well dispersion of bamboo particles inside the PVC matrix as well as compatibility
between bamboo and PVC. However, a cross section of sharp bending interface of
bamboo/PVC composite sample as shown in Figure 9 demonstrates that some bamboo
particles had been pulled out from matrix resin and reveals probable bonding weakness
between bamboo and PVC [15].
Figure 9. SEM image of bamboo/PVC composite with 50% bamboo content.
Surface treatment of natural fibers as an approach to improve the water resistance of

fibers or fiber reinforced composites has attracted great attentions in recent years. Vilay &
Cui et al. concluded that chemical treatment reduced the hydroxyl group in structural
molecules of the cells‘ wall in natural fibers and resulted in lower water absorption of the
composites [34, 35]. Chemical agents such as sodium hydroxide, sodium silicate, sodium
bisulfite, sodium carbonate and so on have been tested in order to modification of bamboo
particles‘ surfaces in BBL so far and satisfying results have been obtained that are still under
publishing. An overall look to these results reveals that water absorption could be decreased
to below one-fourth of initial value by chemical surface treatment. The results also suggest a
direct relationship between hemicellulose content and water absorption and a resembling
trend in decrease of both mentioned parameters.
Zein
Zein is a biochemical substance that belongs to prolamine proteins and is extractable
from corn (maize). It should be mentioned that prolamins are a group of proteins with high
proline (C5H9NO2) content which are found in cereal grains such as wheat, barley, rye and
corn. Zein is insoluble in water but a lot of organic compounds especially alcohols, ketones
and aromatic hydrocarbons can be applied as a solvent for it either in their neat form or
sometimes mixed with water[28]. Zein has been demonstrating a wide variety of applications
over a nearly one century as a binder, an adhesive, a plastic coating agent, film or fiber in
various industries. A comprehensive essay about zein, its properties and applications is
available in Ref. [28]. Pure zein has strong adhesive properties but it needs supplementary
compounds as plasticizers in order to convert into films or fibers or act as a suitable polymer
matrix. Eight groups of plasticizers have been identified by Hansen (1938) including glycols,
sulfonamides, fatty acids, amides, amines, glyceryl esters, glycol esters, esters and
miscellaneous organic compounds [29]. An investigation on processing and properties of a
polymer composite of zein and gluten was carried out by Sanghoon Kim in 2006 [30]. He
introduced a developed process through which, microscopic scale wheat protein (gluten)
material were coated with zein in room temperature and then compressed to form a rigid
coherent material. The compressive strength of this polymer composite was found around
40MPa comparable with poly-propylene [30]. Nevertheless, pure zein is an expensive
substance that is available for US$ 20-58 per kg[28]. It restricts its application as a bulk
polymer for composites therefore, corn gluten meal, a by-product from corn starch processing
has been considered as an alternative for utilization in green composites. Unrefined corn
gluten meal contains 67% to 70% protein on a dry basis. Beg et al., studied the application of
corn gluten meal (CGM) as a biodegradable matrix in wood-plastic composites [36]. They
examined several plasticizers including octanoic acid, glycerol, polyethylene glycol and water
with different composition of mixtures. The content of CGM, plasticizers and wood fiber in
their composition mixtures varied from 30% to 70%, 20% to 50% and 0% to 20%
respectively. The best mechanical properties were obtained with a matrix containing 10%
octanoic acid, 30% water and 20% wood fibers, which resulted in a tensile strength and
Young‘s modulus of 18.7MPa and 4GPa respectively.
Research activities are currently under development in BBL in order to extract zein from
low cost residues of corn starch processing and utilize it in manufacturing of environmental
friendly particleboards. In one of these researches, methylene dichloride was applied as
plasticizer and effects of methylene dichloride content, zein content and the temperature of
making glue on the mechanical properties of zein/bamboo particleboard were investigated.
The results showed that when the volume percentage of methylene dichloride was increased
from 10% to 50%, the values of mechanical properties of particleboard, such as modulus of
rupture, modulus of elasticity, tensile strength and internal bond strength, were initially
increased and then decreased. The optimal volume percentage was obtained about 20%
corresponding to 15.85MPa and 2353.44 15.62MPa for TS and Young‘s modulus
respectively. When the percentage of zein was increased from 20% to 40%, the values of
mechanical properties of particleboard also showed initial increases and then decreases, the
optimal percentage of zein was found about 30%. When the temperature of making glue
increased from 25℃ to 65℃, the value of mechanical properties of particleboard decreased, so
the optimal temperature was found 25℃. Similar experiments have been performed using
other plasticizers in this laboratory such as oleic acid or glycerol. The optimal percentage
content for oleic acid and glycerol has found 9% and 10% respectively. Although mechanical
properties have been found satisfying in above mentioned experiments but more
investigations are still needed to improve water resistance of bamboo/zein composites.
Figure 10. General appearance of composite samples of zein adhesive and bamboo particles.
Coupling Agents
Coupling agents are chemical substances having the task of improving the coupling and
adhesion between matrix and reinforcing agent in composites. A lot of materials have been
examined as coupling agents in bamboo-based composites. Their molecular structure has
usually the capability of reacting with both polymer matrix molecules and fiber molecules.
Some researchers preferred to utilize biodegradable and bio-based coupling agents.
Table 5. Summary of effects of LDI addition to biodegradable bamboo-based

composites.
Effect on Type of composite

Target parameter BF/PLA BF/PBS
Tensile strength Improve by up to 50% Improve by up to 90%
Young‘s modulus Increase by up to 17% Little increase
Elongation at failure No significant change Increase by up to 60%
Water absorption Decrease by up to 30% and Decrease by up to 54% and
retarding the absorption speed retarding the absorption speed
Crystallization temperature Increase by up to 4% Increase by up to 10%
Activation energy for flow Increase Increase
Thermal degradation Improve thermal stability Improve thermal stability
Enzymatic degradation Decrease in degradation rate Decrease in degradation rate
Source: [17]
Lysine is an essential amino-acid with two amino groups and one carboxyl group from
which, some polymers can be derived to act as coupling agents. lysine-based diisocyanate
(LDI) is based on lysine and can react with hydroxyl or carboxyl groups in bio-polymer
molecules. Seung-Hwan Lee and Siqun Wang applied LDI as a coupling agent in fabrication
of biodegradable composites made by bamboo fibers with poly(lactic acid) (PLA) or with
poly(buthylene succinate) (PBS) [17]. They studied the effects of LDI on tensile strength,
water resistance, interfacial adhesion, thermal properties and biodegradability of the
fabricated composites.
Okubo et al., used poly-propylene (PP) as polymer matrix in their research work and
modified it by maleic anhydride [14]. Maleic anhydride acted as a coupling agent between
bamboo fibers and PP as they reported, because it provides polar interactions and links PP to
the hydroxyl groups on the cellulose fiber. They mixed 5 weight percent of maleic anhydride
modified poly-propylene (MAPP) with 95 percent poly-propylene and applied the mixture as
polymer matrix in fabrication of bamboo-based composites.
Cross-Linking Agents
Cross linking agents have the ability of making links or bonds with both polymer matrix
and reinforcements. Silane is an example of cross linking agents. Bamboo flours in the
research work of Ge and Li et al., were treated with A-1100 silane by purpose of improving
the adhesion between BF and PVC matrix [18]. They mentioned two interactions for silane
treated surfaces of BF, the first one between silanol groups of silane and hydroxyl groups of
BF by hydrogen bonding, and another one between the silane chain and PVC by Van der
Waals bonding.
Glutaraldehyde is frequently used in biochemistry applications as an amine-reactive
homobifunctional crosslinker. It was successfully used in research works of Netravali et al.,
on fabrication of green composites [27].
Research activities are undergoing in BBL as well on influences of cross linking agents
on mechanical properties and physical qualities of bamboo-based composites.
CONCLUSION
Utilization of bamboo residues in production of composites is an appropriate option for
management of huge amounts of this kind of wastes in societies and industries who concern
bamboo culms. Bamboo-based composites should meet some requirements in mechanical
properties, thermal strength, water resistance and other qualitative attributes depending on
their purpose of application. Properties of bamboo-based composites are function of several
parameters from which, mixing ratio between bamboo particles and matrix, characteristics of
matrix, characteristics of coupling agents, operational conditions of composite processing and
type of modifications on bamboo particles are the most important. Hence the mechanical
properties and water resistance of bamboo-based composites may obtain a wide range of
variations depending on above mentioned parameters. The investigations are being followed
to
a) find more appropriate and environmental friendly substances (including polymer
matrices, coupling agents and cross-linkers) for bamboo-based composites with
better quality and higher stability
b) decrease the material costs and manufacturing expenses in this field as much as
possible
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[15] Wang, H; Chang, R; Sheng, KC; Adl, M; Qian, XQ. ‗ Impact response of bamboo-
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[27] Netravali, AN. ‗Green composites from cellulose fabrics and soy protein resin‘,
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[29] Hansen, DW. Plasticized prolamine base composition. U.S. patent, 1938, 2,115,716.
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based on modified soy protein adhesive‘- Journal of Materials Science and
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[33] Garlotta, DA. ‗Literature review of poly (lactic acid)‘, Journal of Polymer
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loading on the properties of bagasse fiber-reinforced unsaturated polyester composites.
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Chapter 5
VEGETABLE OIL-BASED POLYMERS

AND LIGNOCELLULOSIC DERIVED COMPOSITES
Mirta I. Aranguren*, Norma E. Marcovich and Mirna A. Mosiewicki

INTEMA, Facultad de Ingeniería,
Universidad Nacional de Mar del Plata, Argentina.
ABSTRACT
The growing environmental concerns together with the reduction of petroleum
resources have been a motor for revitalizing the interest in using raw materials from
renewable resources. Among those, vegetable oils constitute a valuable renewable source.
Their chemical modification is a promising alternative to substitute (at least partially)
petrochemical materials used in polymer formulations. In this chapter, the focus will be
on the use of castor and tung oils to synthesize polyols for the polyurethane industry. The
polymers derived from these polyalcohols present different properties depending on the
vegetable sources, synthesis path for the polyol, additives, etc., and thus, polyurethanes
can be produced to fit the requirements for different applications. The addition of
lignocellulosic reinforcements like wood flour or plant fibers noticeably affect the
properties of the polyurethanes due to the strong interaction that these
fillers/reinforcements develop with the polar polyurethane matrix. The biocomposites
prepared from the bio-based polymers and biofillers/biofibers can be a useful alternative
to substitute synthetic composites (from solid composites to filled foams) reducing the
environmental impact usually associated to traditional polymers. The physical, thermal
and mechanical properties of the neat polyurethanes and derived composites are
presented and analyzed in this chapter.
INTRODUCTION
The use of renewable sources in the preparation of various industrial materials has been
revitalized because of environmental concerns (persistence of plastics, gas emissions,
*
Corresponding author : Email: marangur@fi.mdp.edu.ar
100 Mirta I. Aranguren, Norma E. Marcovich and Mirna A. Mosiewicki
reduction of landfill space) together with the shortage of petroleum resources. In particular,
vegetable oils are an important worldwide available renewable source of polymer precursors.
Oils are presently obtained from naturally occurring (mostly) or genetically modified plants,
such as sunflower, cotton, linseed oil flax, etc.
The chemical modification of vegetable oils is a promising alternative to substitute (at
least partially) petrochemical materials used in polymer formulations. Extensive works have
been carried out by groups at Delaware [1-4] and Iowa [5-8], on the investigation of different
reaction paths leading to the synthesis of different polymers from epoxy to alkyd resins and
polyalcohols [2,4]. In this chapter, the focus will be on the use of vegetable oils in the
synthesis of polyols for the polyurethane industry. A possible path of reaction consists in the
hydroxylation of the carbon-carbon double bonds of the triglyceride molecules and/or the
alcoholysis with glycerin or triethanolamine. The polymers derived from these polyalcohols
present different properties depending on the selected raw materials (vegetable sources,
synthesis path for the polyol), additives, polymerization reaction, etc., and thus, polyurethanes
can be produced to fit requirements for different applications.
The addition of lignocellulosic reinforcements like wood flour or plant fibers can affect
significantly the properties of the polyurethanes due to the strong interaction that these
fillers/reinforcements develop with the polar polyurethane matrix. The combination of the
bio-based polymers with biofillers/biofibers, usually called biocomposites, can be a useful
alternative to substitute synthetic composites reducing the environmental impact usually
associated to traditional polymers.
This chapter describes the modification of castor and tung oils to obtain hydroxylated
monomers. These modified oils were used as the polyol component in the formulation of rigid
polyurethanes, PU (solid and foamed). Wood flour (WF) and hemp fibers were subsequently
incorporated to obtain composite formulations with enhanced properties. The physical,
thermal and mechanical properties of the neat polyurethanes and the reinforced composites
were measured and analyzed, and are also summarized in this chapter.
POLYURETHANES FROM VEGETABLE OILS

Vegetable oils consist on triglyceride molecules (Figure 1) that can be readily modified
chemically to obtain different useful monomers for the production of polymeric materials.
From the many available routes that have been described and reviewed in the specialized
literature [1-9] two are going to be referred in this chapter. One of them consists on the
hydroxylation of an unsaturated vegetable oil (tung oil), followed by the alcoholysis of that
intermediate product. Solid polyurethane -wood flour composites were derived from a
polyurethane prepared from this polyol.
The second approach was simply the alcoholysis of another vegetable oil (castor oil),
further applied to the formulation of polyurethane foams and low-density natural fiber
composites.
Vegetable Oil-Based Polymers and Lignocellulosic Derived Composites 101
R1
O
O
O
O O R3
R2
O
Figure 1. Scheme of a triglyceride molecule.
HOOC CH CH CH CH CH CH
elaeostearic acid
HO
HOOC CH CH CH2 CH CH2 CH2
ricinoleic acid
Figure 2. Schematic molecular structures of the elaeostearic and ricinoleic acids.
Tung oil (TO, also known as China wood oil) is obtained from the tung tree, a plant that
can be found in Asia, South America (Argentina and Paraguay), United States and Africa.
The fatty acid chains that form this oil are more than 80 % elaeostearic acid (Figure 2), a
molecule containing three conjugated unsaturations. Because of this high degree of
usaturations tung oil is traditionally used as a drying oil, with excellent performance as basis
for wood varnishes.
On the other hand, the composition of castor oil (CO) is such that about 90 % of the fatty
acid chains correspond to the ricinoleic acid (Figure 2). Castor oil and its derivatives have
been used frequently for different applications from industrial (soaps, lubricants, hydraulic
and brake fluids, paints, dyes, coatings, inks, waxes, shampoos) to pharmaceutical (laxative,
lip balm). As tung oil, castor oil is also an unsaturated oil, but additionally, it has hydroxyl
groups in its structure (the ricinoleic acid has one hydroxyl group in its chain).
Synthesis of the Vegetable Oil Based Polyols
Hydroxylated tung oil (HTO)

The double bonds in the highly unsaturated TO can be reacted to incorporate hydroxyl
groups in the triglyceride structure. These hydroxyl groups are by themselves polymerizable
but they can also be used to attach other interesting reactive groups to the molecule, as it has
been reported by Wool et al [1].
OOC CH CH O
HC
OOC R + OH
OOC R
HO OH
OH OH
OOC C C
OOC R
OOC R
R: unsaturated fatty acid
Figure 3. Hydroxylation reaction scheme of unsaturated vegetable oils.
Table 1. Formulation used in the hydroxylation reaction of tung oil.
Reactants Weight %
Tung oil 54.7
Hydrogen peroxide 15.6
Formic acid 29.7
Hydroxylated oils can be synthesized from the reaction of the unsaturated oils with
performic acid (obtained by the in situ reaction of hydrogen peroxide and formic acid), which
leads to the conversion of the double bonds in the oil to hydroxyl groups. The reaction is
carried out at a temperature of 40-50°C for 3h. Initially, the unsaturated oils undergo an
intermediate process of epoxydation, but since the epoxide group is unstable under the strong
acid conditions, it opens to form hydroxyl groups [9-11] (Figure 3). Table 1 shows the weight
percentage of reactants used in the modification of tung oil.
Alcoholyzed hydroxylated tung oil (AHTO) and alcoholyzed castor oil (ACO)
Alternatively or complementary to the hydroxylation reaction, the concentration of
hydroxyl groups in the oil-based resins can be increased by carrying out an alcoholysis
reaction, which reduces the triglyceride molecules to monoglycerides and diglycerides
(Figure 4). Alcoholyzed oils are prepared from the reaction of the oils with polyalcohols. This
step of reaction consisted mainly in a transesterification of the triglyceride molecules with
excess of triethanolamine and the final products are a mixture of different polyalcohols
containing one or two fatty acid chains. The reaction is carried out at 150°C for 2.5h [9-11].
Any unreacted triethanolamine remains in the reactive mixture; thus, the final composition of
the derived polyol is complex, but all the species are reactive in further steps to form
polyurethanes. Table 2 summarizes the formulation used in the modification of castor oil and
hydroxylated tung oil.
OOC R CH2 CH2 OH

OOC R + N CH2 CH2 OH
OOC R CH2 CH2 OH
R: unsaturated fatty acid or Triethanolamine

hydroxylated fatty acid 150ºC
LiOH
H2C R´
CH2 CH2 R´
N CH2 CH2 R´ HC R´
CH2 CH2 R´ H2C R´
R´: unsaturated fatty acid, hydroxylated

fatty acid or hydroxyl group
Figure 4. Alcoholysis reaction scheme of unsaturated vegetable oils.
Table 2. Weight percentage of the reactants used in the alcoholysis reaction.
weight %
CO or HTO* 67.3
Triethanolamine 32.5
Hydroxide lithium 0.2
* Castor Oil or Hydroxylated Tung Oil
Physical and Chemical Characterization of the Oils and Derived Polyols
The measurement of the OH values was a useful technique to assess the modifications
achieved by reacting the oils. The results are summarized in Table 3.
Tung oil having no hydroxyl groups in its original structure shows a zero hydroxyl value.
On the other hand, the structure of the castor oil is usually reported as having about 90% of
the fatty acid chains corresponding to ricinoleic acid. From that proposed structure a
theoretical hydroxyl value of 163 mg KOH/g can be calculated, which is in very good
agreement with the experimental value reported in Table 3. After the chemical modifications
of the TO and CO, the resulting polyols have higher hydroxyl values, in the range commonly
reported for polyols used in the synthesis of rigid polyurethanes (434 and 449 mg KOH/ g,
respectively).
The viscosity of the oils and polyols is also reported in Table 3. The comparison between
the viscosities of CO and TO shows that the former (more polar due to the presence of
ricinoleic acid in the structure) presents higher flow resistance due to larger intermolecular
forces. The viscosities of the oils increase significantly after the chemical modification,
mainly in the AHTO that reach a paste-like consistency. The incorporation of hydroxyl
groups in the oils generates species with higher intermolecular interactions by hydrogen
bonds.
Table 3. Physical and chemical properties of the oils and its modifications
TO* HTO AHTO CO** ACO

Hydroxyl value (mg KOH/g) 0 287 434 169 449
Viscosity (cp) 397 - 97000 422 670
* supplied by Cooperativa Agrícola Limitada de Picada Libertad, Argentina
** Parafarm®, Argentina,
Absorbance
CO
TO
4000 3500 3000 2500 2000 1500 1000 500

cm-1
Figure 5. FTIR spectra of the unmodified TO and CO.
The natural polyol based on CO presents a relatively low viscosity as compared to that of
commercial synthetic polyols used in the production of rigid foams [12]. This is an advantage
when reinforced foams are being produced, since the mixing times, as well as the filler
agglomeration, are reduced (better dispersion is reached faster because of the lower viscosity
of the reactive suspension medium) [12].
The differences between the oils and the further changes resulting from the chemical
modifications were also investigated by FTIR. Figure 5 shows the comparison of the FTIR
spectra of the unmodified TO and CO. One important difference between them is that the TO
spectrum shows a negligible absorption at 3000-3500 cm-1. On the contrary, CO shows a
clear band in this spectral region because of the high percentage of ricinoleic acid in the
molecular structure of the triglyceride. The observation is in agreement with the measured
OH values of TO and CO (Table 3).
Both spectra show also similarities related to the triglycerides structures. The peak at
3010 cm-1 corresponding to the C=C unsaturations is clearly observed, although slightly
clearer for TO, which also shows the C=C wag peak at 991 cm-1. The peak at 1745 cm-1
corresponds to the absorption of the ester groups in the triglyceride molecules.
After the chemical modification of the vegetable oils, the most important change in their
spectra is the increase in the band intensity at 3450 cm-1 corresponding to the O-H absorption.
In the case of the tung oil, the hydroxylation reaction of the double bonds that occurs during
the first step of the modification is responsible for the disappearance of the bands at 3010 and
991 cm-1 (Figure 6).
ACO
Absorbance AHTO
HTO
4000 3500 3000 2500 2000 1500 1000 500

cm-1
Figure 6. FTIR spectra of the HTO, AHTO, ACO.
AHTO
HTO
TO
10 12 14 16 18 20 22 24 26 28
Time (minutes)
Figure 7. Size exclusion chromatograms for TO, HTO, AHTO [from ref.10].
In the alcoholysis step (AHTO and ACO) different reactions can take place, which lead
mainly to the breakage of the molecules to give species of lower molecular weight. Again, the
clearest change occurs in the 3300-3500 cm-1 region. As already mentioned, the intensity of
this band grows due to the increase of the concentration of hydroxyl groups [10]
Unlike the HTO and AHTO, the ACO spectrum shows no alteration of the peak
absorption at 3008 cm-1 after the chemical modification, indicating the preservation of the
C=C during the alcoholysis reaction.
As indicated previously, the chemical modifications of the oils necessarily generated a
mixture of species of different molar masses, so the changes were also followed by size
exclusion chromatography (SEC). Figure 7 illustrates these changes for the case of the tung
oil chemical modifications (TO, HTO, AHTO).
The SEC curve of the tung oil shows essentially a single peak for the triglyceride
(indicating that the molecular composition is rather homogeneous in this oil, and that it is
practically monodisperse. However, as the modification proceeds, the size exclusion
chromatograms of the modified oil present several peaks corresponding to different products.
The chromatogram corresponding to the HTO shows lower retention volumes and wider
peaks compared to TO without chemical modification. Although the retention times indicate
the right expected trend of increasing molar mass and the probable appearance of oligomeric
species at this step (association of molecules through strong H-bonding), the resulting curve
suffers some aberration already described by John et al [13]. They reported that although the
determination of the molar mass of single fatty acids does not show this problem when using
polystyrene (PS) calibration in the SEC measurements, the triglyceride samples suffer
aberration, resulting in the determination of much larger molar mass values than the
theoretically expected ones. The proposed reason for this effect was the difference between
the linear molecular structure of PS and the three arms - molecular structure of the
triglyceride molecules (Figure 1) [13].
In the chromatogram corresponding to AHTO the effect is less important due to its lower
molar mass, although there is still a large contribution from high molar mass species.
VEGETABLE OILS- BASED POLYURETHANES

The plant oil-based polyols can be reacted with isocyanate containing reactants to
produce polyurethanes (Figure 8). These polymers are highly attractive because of the large
variety of properties that can be achieved by varying the nature of the polyol and the
isocyanate components, the stoichiometric ratios and the preparation process that can lead to
solid pieces (from elastomeric to thermoset) or to foamed materials (from hard to soft foams
depending on the chemical structures of the reactants).
Structural Materials: Wood Flour Composites
In the present case, solid composite materials were prepared from PU based on the tung
oil-derived polyol and pine wood flour (WF, particle size < 64 m) as reinforcement. The
composites were prepared by initially mixing the reinforcement with the polyol (a mixture 1:1
of the polyol and tetrahydrofurane to reduce the viscosity) and then adding and mixing the
isocyanate component, a polymeric MDI (pMDI, Rubinate 5005, Huntsman Polyurethanes,
USA). No catalyst was used in this reaction in order to maintain a low reaction rate that
allowed a good WF dispersion. The mixture was cured in a mold after solvent evaporation
using a heated press (75°C, 4 MPa, 1 hour).
H O
R - N = C = O + R’ - O H R - N - C - O - R’
Figure 8. Schematic of the polyurethane reaction from an isocyanate and a hydroxyl containing
components.
(a) (b)
Figure 9. Scanning electron micrographs of the composite with 10 wt% of wood flour at 100x (a) [10],
and 500 x (b).
The comparison between the experimentally measured density of the composites and the
density calculated from a simple rule of mixtures indicated that the composites were
essentially free of voids [11]. This is an indication of good wetting quality of the
filler/reinforcement by the matrix. Further on, the analysis of the images obtained by scanning
electronic microscopy (SEM) of fracture surfaces of these composites showed very good
dispersion of the wood flour and excellent interfacial adhesion (Figure 9) with no separation
of the fibrous wood flour particles from the matrix. There is essentially no pull out of the
irregular wood fibers and fracture occurs at the same level in the matrix and filler.
The incorporation of wood flour concentrations up to 30 wt.% lead to well dispersed
particle-composites, but higher WF contents produced some agglomeration and appearance of
voids that were the consequences of the initially high viscosity that made difficult the WF
dispersion and the insufficient volume of matrix to wet the surface of the wood particles.
Thermo-mechanical behavior
It is to be expected that a strong interfacial adhesion had some effect on the thermal-
dynamic-mechanical properties of the polymer acting as the composite matrix. In the present
case, the comparison of the tan δ curves obtained for the neat polyurethane and composites
(Figure 10) clearly shows an important shift of the polymer transition (mechanical
relaxation related to the polymer glass transition) towards higher temperatures. Although this
is the usual behavior of polymers after addition of rigid fillers (chain mobility is hindered by
the presence of the fillers), that effect usually accounts for a shift of a few degrees. Figure 10
shows that by the addition of 30 wt.% of wood flour, the polymer T is shifted by ca. 20°C.
Such a large increase is indicating a strong interfacial interaction, and the logic explanation is
the obvious reaction between isocyanate groups from the pMDI with the hydroxyl groups in
the wood flour, which become chemically bonded to the matrix by this reaction. This
interfacial reaction explains also the excellent polymer -filler compatibility observed in this
system, leading to good dispersion and wetting of the filler. The width of the peak also
increases suggesting a more heterogeneous structure of the network formed in the presence of
the filler. There is also tailing of the peak in the region of higher temperatures, suggesting
that there are relaxation processes of tightly cross-linked chains or chain segments.
To support this reasoning, it must be considered that in the formulation of the composites
the ratio NCO/OH was always maintained equal to 1.1, and that the calculation of the OH
concentration included the groups coming from the tung oil-based polyol as well as the
groups coming from the wood flour [10,11]. Thus, a fixed stoichiometric ratio was used in the
comparison.
0,45
0,40
0,35
0,30
0,25
tan
0,20
0,15 30% WF
0,10
0% WF
0,05
0,00
20 40 60 80 100 120 140 160 180 200
Temperature (ºC)
Figure 10. tan -T curves for the polyurethanes with 0 and 30 wt.% of wood flour.
1E9
Storage modulus (Pa)
1E8 30% WF
0% WF
1E7
20 40 60 80 100 120 140 160 180 200
Temperature (ºC)
Figure 11. Storage modulus curves for the polyurethanes with 0 and 30wt% of wood flour.
The storage modulus plot gives additional information regarding the increase of the
rigidity of the system as more wood flour is added (Figure 11). There is an increase of about
54 % of the room temperature (glassy) modulus when 30 wt.% of filler is added, and the
increase is as high as 600 % in the rubbery plateau. The relaxation that results in the drop of
the rigidity of the material is shifted well above room temperature, which widens the
applicability of the composite as structural material.
Thermal stability
The thermal stability of the unreinforced and reinforced polyurethane from tung oil was
examined by thermogravimetry. Figure 12 shows the curve of weight loss versus temperature
for the unreinforced polyurethane, the wood flour and a composite with 30wt% of wood
flour.
100
80
60
weight %
PU
40 comp.
WF
20
0
0 100 200 300 400 500 600
Temperature (°C)
Figure 12. Weight loss vs temperature for the unreinforced polyurethane, the wood flour and the
composite containing 30 wt.% of wood flour.
The curve that corresponds to the unreinforced polyurethane presents two main
degradation steps. The first step starts at about 200ºC and is associated with the breakage of
urethane links [10,14,15]. The second step at temperatures higher than 400ºC can be
attributed to the polyol decomposition.
On the other hand, the wood flour shows a loss of mass at a relatively low temperature
(below 100°C), which is due to the loss of moisture, since lignocellulosic materials are very
hydrophilic. At higher temperatures (ca. 300°C), wood flour degrades in a wide range of
temperatures as the result of the many interacting components in its structure [16,17,18].
The polyurethane reinforced with 30 wt.% of wood flour shows an intermediate curve
and the loss of mass is rather monotonous. Clearly, the reinforced polyurethane presents
higher residual mass than the neat polyurethane or the WF. Apparently, the interfacial
reactions between pMDI and the hydroxyl groups in the WF lead to a more thermally stable
material [10].
Figure 13 presents the experimental and calculated curves of the thermogravimetric result
(weight %) for the 30 wt.% WF composite, as well as the derivate curves versus temperature.
The theoretical curve was obtained according to the equations below, which implicitly
assume that there are no interactions between matrix and reinforcement:
TGcomposite TGWF WWF TGpolyurethaneWpolyurethane

dTGcomposite dTGWF WWF dTGpolyurethaneWpolyurethane
where W's are the weight fractions of the matrix (polyurethane) and the wood flour (WF).
Figure 13. Experimental and calculated curves of the TG weight % and derivate signal for the 30 wt%
WF composite.
The prediction is far from the experimental results, indicating that strong new interactions
are formed in the composite. The experimental moisture loss appears at higher temperatures
than predicted, which may occur because it is strongly adsorbed into the network. The
experimental degradation peaks also appear at higher temperatures than calculated (except the
last one), overlapping and with relatively lower intensity than expected from the calculations.
The overall result is that the composite begins to degrade at higher temperatures than
expected, at a lower rate and leaving higher char content. All these characteristics are
welcome as improvements with respect to the unfilled polyurethane.
Mechanical properties
The tensile properties of these composites are shown in Table 4. Noticeable
improvements in the tensile modulus (as it had also been observed in the room temperature
storage modulus by DMA) and strength were observed, as well as in the ultimate tensile
deformation of the material at low WF% (Table 4). This last observation is not usual when a
polymer is compounded with rigid particles /short fibers, although it is a looked-for
characteristic for most applications.
The increase in properties is quite remarkable; at room temperature the tensile modulus
of the 30 wt. % wood flour -composite is more than three times the value of the polymer
modulus (it must be remember that due to the excellent compatibility filler -polymer no
additives were needed for compounding). Tensile strength increases by 70 % in the same
conditions, while deformation (although small) seems to go through a maximum at
intermediate wood flour concentrations.
Table 4. Tensile properties of structural composites with different wood flour contents.
Wood flour (wt%) Tensile modulus (GPa) Tensile strength (MPa) Tensile ultimate
deformation (x1000)
0 0.91 0.12 26.00 2.56 34.5 1.8
10 1.23 0.13 35.65 1.75 45.9 3.5
30 3.03 0.40 44.90 3.06 20.9 4.0
Table 5. Impact properties of structural composites with different concentrations of

wood flour.
Wood flour (wt%) Ei (J/m) Et (J/m) d (MPa)
0 24.4 4.1 122.8 6.6 164.9 25.0
10 29.3 1.9 180.2 32.8 229.0 21.9
30 33.0 1.9 388.7 36.3 279.3 36.2
This excellent balance of properties is the result of the good interfacial interactions
(including covalent bonding). Generally, the failure of the composites is the result of
debonding of the filler at multiple sites, followed by the coalescence of the cracks up to the
final rupture. In the case of the tung oil-based PU, the debonding mechanism is essentially
absent as already discussed in the analysis of the SEM pictures, which delays the rupture of
the materials towards larger elongations. It has also been advanced in the literature, than the
micron sized filler may be acting as a chain extender when added in small concentrations
[11]. As more filler is added and the rigidity of the composites increases, the behavior turns to
be the usual one: higher modulus and lower elongations at fracture.
To further investigate the toughness of the PU and derived composites, impact tests were
performed using the falling dart technique that characterizes the material response in the
thickness direction. In Table 5, the results are reported as the energy required for crack
initiation, Ei, and the total energy for fracture, Et, (initiation and propagation), as well as
resistance to fracture, d.
The results show the same trend discussed from the tensile characterization of the
materials, which is, increased toughness as the amount of wood flour is increased. With the
addition of 30 wt.% of wood flour, the energy to initiate a crack is 35 % higher than in the
neat PU network, while the total energy is more than three times the value measured for the
unreinforced PU. This is indicating that it is more difficult to initiate a crack in the cross-
linked composite, and that the propagation is much restrained by the very well dispersed
wood flour, that act arresting the advance of the crack. Alternatively, if the comparison is
made on the fracture resistance the improvement is of 70%.
The overall effect of adding the wood flour into the reacting tung oil-based precursors has
shown to be outstanding. The composites show improved tensile properties (increased
modulus and strength with little (or no) detriment of the ultimate elongation), improved
thermal behavior (the relaxation is shifted above room temperature) and improved impact
properties (a completely unusual behavior in microcomposites); features that widen the range
of possible applications for the composites, since the balance of properties with respect to the
neat PU results positive for all the performed mechanical tests.
Moisture Sorption
The equilibrium moisture content (EMC) is the humidity content reached by the material
under controlled ambient conditions of constant temperature and relative humidity, expressed
as the percentage of increased weight with respect to the weight of the dry material measured
at time zero.
Table 6 shows the equilibrium moisture content of composites with 0, 10 and 30 wt.% of
wood flour conditioned at 90% relative humidity (RH). As expected, EMC increases as the
wood flour concentration increases due to the hygroscopic nature of the wood flour [19].
Table 6. EMC at 90% RH of structural composites with different concentrations of
wood flour.
Wood flour (wt%) Experimental EMC (%) Calculated EMC (%)

0 4.12 0.16 4.12
10 4.27 0.07 5.53
30 5.80 0.16 8.34
A simple rule of mixtures was also used to predict the EMC of the composites, as:
EMC WWF EMCWF (1 WWF) EMCpolyurethane
using the experimental measured EMCpolyurethane and a reported value of 18.2% for the
EMCWF [20]. The simple weighed addition of the equilibrium humidities leads to higher
EMC for the composites that the experimental measured values (Table 6). This result is in
agreement with the already discussed good wetting of the wood flour by the polyurethane, as
well as the presence of strong interactions filler-matrix that reduces the hygroscopicity of the
filler, by reducing the concentration of available OH surface groups in the WF.
Partially Foamed-Natural Fiber Composites from Castor Oil
To reduce the density of the PU composites the matrix can be partially foamed. This
alternative was investigated using the castor oil derived PU. The modification of the
triglyceride consisted only in the alcoholysis step, which leads to polyols that preserve the
original unsaturations of the fatty acids that formed the molecules of the oil. In the
formulation of these composites, the same polymeric isocyanate (pMDI) used in the
preparation of the compact composites from tung oil, was utilized. The fillers used in the
composite production were wood fibers (Pine sp., average size from sieving: 840 m) and
hemp fibers (continuous) that are shown in Figure 14. In this case the formulation required a
surfactant agent (Tergostab B 8404, Huntsman Polyurethanes, USA), but no catalyst was
added in order to have a relatively low reaction rate that allowed for the fibers incorporation.
The foaming agent, on the other hand, was the moisture content of the plant fibers (even after
drying at 110°C overnight, some moisture is present, and the same is true for the polyol). One
of the envisioned applications of these materials is as highway -noise insulator, although it
could be utilized in other structural applications where low weight and medium mechanical
performance is required (car or construction panels).
Figure 15 shows the effects of the addition of wood particles and continuous, one-
directional hemp fibers on the dynamic-mechanical properties of the composites.
Figure 14. Images of the utilized reinforcements. a: wood fibers; b: hemp continuous fibers [from ref.
21].
As in the case of the solid composites, the DMA results show a large shift in the T of
the polymer matrix [21]. The tan peak is wide indicating that there are different mechanisms
active in the relaxation. Although the width of the peak increases in the composites (as
compared to that of the neat PU), its height decreases due to the dilution effect of the fiber
addition and the increased rigidity of the composites. There is also a clear shift of the
relaxation peak towards higher temperatures as plant fibers are added. On the other hand, in
the case of these foamed composites, the storage modulus at room temperature does not
increase, the reason being the higher density of the unfilled material with respect to the
partially foamed one. Although the addition of the rigid wood fibers should contribute to the
modulus of the material, the presence of bubbles in the matrix reduce the overall modulus of
the composite. Finally, the effect of the fibers high modulus overcomes the foaming effect at
the rubbery state of the materials.
Since the long hemp fibers were essentially continuous (considering the maximum size of
the samples (15 cm), the one directional hemp-fiber composites showed the highest modulus,
as it was theoretically expected. The samples prepared with this fiber arrangement and
partially foamed PU matrix showed densities in the range of 0.75-0.8 g/cm3, with bending
modulus of 1.5 - 2.0 GPa, and low ultimate strains (0.035-0.04 mm/mm).
0.6
109
Matrix
Matrix 0.5 WF
WF
1D-Hemp
Storage modulus (Pa)
1D-Hemp 0.4
Tan
108 0.3
0.2
0.1
107 0
40 60 80 100 120 140 160 180 200 40 60 80 100 120 140 160 180 200
Temperature (ºC) Temperature (ºC)
Figure 15. DMA results of the partially foamed castor oil -based polyurethane and composites
containing 20 wt. % WF and 20 wt.% of continuous 1D hemp fibers.
The presence of unsaturations in the polymer precursor is a feature that should be

considered carefully when working with triglyceride-based polymers and composites. In the
case of the castor oil-low density composites, unsaturations are still present in the fatty acid
fragments after the chemical modification of the oil. The C=C unsaturations do not participate
in the polyurethane reaction and remain in the final composite/polymer network. As it is well
known from the behavior of drying oils, diffusing oxygen from air produces a series of
complex reactions when in contact with the polymer unsaturations, which lead to further
polymer chain cross-linking. In the studied composites, this chemical aging affected the
properties of the materials increasing the modulus and strength of the materials, but also and
quite interestingly, increasing the deformation at break and thus, increasing the toughness of
the material. An increase of up to three times was measured on the bending modulus after one
year from preparation of the 1D hemp composite, with about a 15% increase in the average
value of the ultimate strain. Most of the changes due to aging occurred during the first 6
months after preparation [21].
Polyurethane Foams from Castor Oil
Polyurethane polymers are also commonly used as foamed materials. Thus, the
possibility of using the vegetable oil-based polyols as raw material for the production of rigid
foams and composite foams was also investigated. Polyurethane rigid foams are commonly
used for their low density and low thermal conductivity, which is due to the presence of a
more or less regular skeleton of cells (open or closed) [22]. The semi-structural materials that
can be obtained can also find application as panels for acoustic insulation. The mechanical
response of these cellular materials depends on the architecture of the cell walls (shape of the
cells, size distribution and wall width) and the intrinsic properties of the polymer constituent
and additives [22].
For the present case, the foams and composite foams were formulated from the castor oil
derived polyol, the polymeric isocyanate and the surfactant agent also utilized in the
production of the partially foamed-natural fiber composites. Additionally, a catalyst (tertiary
amine, Tergoamin DMCHA, Hunstman Polyurethanes) and a foaming agent (HCFC, 141b,
Hunstman Polyurethanes) were also incorporated to the formulation. In this case, the selected
reinforcement/reactive filler was again pine wood-flour, with average particle size 64 m.
The index (moles of NCO groups/moles of OH groups) was adjusted for each system in
order to obtain stable non-collapsing foams, considering the contributions of both, polyol and
wood flour, since isocyanate groups were also consumed in the heterogeneous covalent
reaction with the surface OH groups of the vegetable particles. The system was mechanically
mixed for 20 seconds and then the foam was allowed to freely rise in an open mold, at room
temperature.
The characteristic foaming times measured for the oil based system were higher than
those measured for other commercial systems [23], but still in the range of operation
conditions for preparing rigid polyurethanes foams. For example, the cream times were in the
range of 64-77 s, while the end of rise times were 155-166 s for the castor oil-based foams.
The foaming reaction rate was reduced as the wood flour concentration increased, probably
because of steric hindrance effects that control the chemical reaction between the isocyanate
and the OH groups in the filler.
Scanning electron micrographs of the rigid foams (Figure 16) revealed that there was not
a preferential orientation of the cells in the growing direction (sample taken from the center of
the foamed piece), being the cellular structure of the unfilled foams predominantly spherical
and evenly distributed, with few broken cells. In general, the cells appear closed in the
unfilled foam. The addition of WF to the formulation is responsible for an increase in the
viscosity of the mixture. This causes the mixture to be less expandable, giving rise to a more
distorted structure of cells, with a larger cell size distribution (less uniform sizes) [23]. This
effect increases with the filler content, since WF particles are large enough to interfere with
the cell development. The integrity of the cell walls in the composite foam appears more
compromised, probably due to the presence of the wood flour, while there is also a wider
distribution of cell sizes. The densities of the foams were between 37.6 and 38.8 Kg/m3, in
the range expected for this type of foams [24]. The thermal conductivity of the oil-based foam
increased with WF content, reaching a 15% increase with respect to the unfilled material
when filled with 15 wt.% WF (39.4 to 45.3 mW/mºC, measured with a transient technique
[25-27]). The thermal conductivity of the cellular materials depends on their cell structure,
which was distorted by the addition of wood-flour. The effect of having small and/or
clustered-small cells resulted in an increase in the thermal conductivity of the foam.
The effect of the foam density in the mechanical properties was investigated for the
unfilled foam. The compression modulus and strength increased with density, since in
compression the stiffness arises from buckling of cell walls [28]. The higher density is related
to more compact cellular structures, thus there is more material per unit area and the modulus
and strength increase [29]. The yield strain also shows a slight increase with density, with
measured values in a narrow range of 5.4 to 6.7 % strain.
0% WF 15% WF
Figure 16. Scanning electronic micrographs of unfilled and 15 wt% wood flour rigid foams [from ref.
23].
For the filled foams, it was found that the compression modulus decreased as wood flour
concentration increased (3.4 and 2.1 MPa for the 0 and 15 wt.% samples respectively). Since
in the filled foams, the isocyanate groups are consumed not only in the reaction between the
polyol and the pMDI, but also between the wood flour hydroxyls and the isocyanate groups in
the pMDI, the reduction in mechanical properties could be attributed to more fragile cell
walls in the filled foams, with respect to the cells of the neat PU foams. A non-uniform
distribution of filler would also contribute to the embrittlement effects, since areas of high
stress concentration can be induced, which lead to the failure of samples in an unexpected
manner at random locations in the samples [30]. Unfortunately, wood flour incorporation
causes a severe disruption of the foam morphology, since the average wood flour particle size
is larger than the cell wall width. This change in the cell structure reduces the resistance to
fracture under load during the compression test and thus, decreases the composite
compression strength [23].
Although foamed composites could become a valuable alternative for semi-structural
applications where low weight is desirable, it is necessary to minimize the cell disruptions
introduced by a micro-sized filler (WF), the use of a nano-bio-filler/reinforcement with
compatible chemical functional groups, such as cellulose nanocrystals, could be a valuable
alternative to be investigated.
CONCLUSIONS
The polyols obtained from vegetable oils by different chemical modifications are
appropriate to prepare rigid polyurethanes from solids to foams. Through these modifications,
the hydroxyl group concentration in the modified tung and castor oils increases, as compared
to the initial oils, reaching values high enough to prepare rigid polyurethanes.
Wood flour was revealed as an attractive reactive reinforcement for polyurethane
composites production, with good compatibility with the oil-derived matrix. Natural
composites with unusual high deformation at break and strength were prepared from wood
flour and tung oil based-polyurethane. Addition of wood flour also has a positive effect on
impact properties in agreement with tensile and DMA behavior.
The partially foamed materials prepared from castor oil derived polyurethanes are
interesting alternatives to consider for structural applications where low weight and medium
mechanical performance is required. These composites suffer important aging due to a

secondary reaction of the unsaturations present in the vegetable oil-based polyol. As a result,
the modulus and strength of the material improve with time. It is very interesting that there
was no decrease of the deformation to rupture, and for this reason aged materials showed
improved modulus and toughness than original composites, under the test conditions reported.
Rigid foams and wood flour filled-rigid PU foams were also prepared. The wood flour
reacts with the pMDI and thus, acceptable foams can be prepared using up to 15% wt of filler,
although the compression properties decrease and the thermal conductivity increases slightly
as wood flour concentration increases.
To minimize the cell disruptions introduced by a micro-sized filler, the use of a nano-bio-
reinforcement with compatible chemical functional groups, such as cellulose nanocrystals is
suggested.
ACKNOWLEDGMENTS
The authors thank the financial support from the Universidad Nacional de Mar del Plata
(UNMdP), the National Research Council from Argentina (CONICET) and the National
Agency for the Promotion of Science and Technology, Argentina (ANPCyT). Thanks are also
due to the Cooperativa Agrícola Limitada de Picada Libertad, Argentina, and to Huntsman
Polyurethanes for gently supplying the tung oil and other polyurethane reactants, respectively.
REFERENCES
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H; Wool, RP. J. Appl. Polym. Sci, 2001, 82, 703.
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[3] Bunker, SP; Wool, RP. J. Appl. Polym. Sci., 2002, 40, 451-458.
[4] La Scala, J; Wool, RP. JAOCS, 2002, 79, 59-63.
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[6] Li, F; Larock, RC. Biomacromolecules, 2003, 4, 1018-1025.
[7] Li, F; Hanson, MV; Larock, RC. Polymer, 2001, 42, 1567-1579.
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Polym. Sci., 2002, 84, 591-597.
[10] Mosiewicki, MA; Casado, U; Marcovich, NE; Aranguren, MI. Polym. Eng. Sci., 2009,
49, 685-692.
[11] Casado, U; Marcovich, NE; Aranguren, MI; Mosiewicki, MA. Polym. Eng. Sci., 2009,
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[12] Woods, G. The ICI Polyurethanes Book, John Wiley & Sons, NY.
[13] John, J; Bhattacharya, M; Turner, RB. J. Appl. Polym.Sci., 2002, 86, 3097-.
[14] Jellinek, NH. G; Dankle, SR. Degradation and Stability of Polymers, Elsevier
Publication, London, 1983, 91.
[15] David, DJ; Staley, MP. Analytical Chemistry of Polyurethane, Part III (High Polymers);
Wiley Interscience, N Y; 1974, Vol. XXI, 365.
[16] Huang, M.-R.; Li, X. –G. J. Appl. Polym. Sci. 1998, 68, 293-304
[17] Flaqué C., Montserrat S. J. Appl. Polym. Sci. 1991, 42, 3205-3213
[18] Marcovich, NE; Reboredo, MM; Aranguren, MI. Termochim. Acta, 2001, 372, 45-57.
[19] Mosiewicki, M; Borrajo, J; Aranguren, MI. Polym. Intern., 2007, 56, 779-786.
[20] Marcovich NE., Reboredo MM., Aranguren MI., Polymer 1999, 40, 7313-7320.
[21] Aranguren, MI; Rácz, I; Marcovich, NE. J. App. Polym. Sci., 2007, 105, 2791-2800.
[22] Saint-Michel, F., Chazeau L., Cavaillé, J.-Y. Compos. Sci. Technol., 2006, 66, 2709-
2718.
[23] Mosiewicki, MA; Dell'arciprete, GA; Aranguren, MI; Marcovich, NE. J. Compos. Mat.,
Early view, published October 6, 2009, doi: 10.1177/0021998309345342.
[24] Jin, JF; Chen, YL; Wang, DN; Hu, CP; Zhu, S; Vanoverloop, L; Randall, D. J. Appl.
Polym. Sci., 2002, 84, 598-604.
[25] Carslaw, H.S. and Jaeger, J.C. Conduction of Heat in Solids, Claredon Press, Oxford,
1959, pp.149-156.
[26] Barrera, M; Zaritzky, NE. Conductividad Térmica de Hígado Vacuno Congelado,
CIDCA, Universidad Nacional de La Plata, 1981.
[27] Aranguren, MI; Borrajo, J; Williams, RJJ. SAMPE J. 1984, 20,18-23.
[28] Gibson, LJ; Ashby, MF. Cellular solids: structure and properties, Pergamon Press,
Oxford, 1988, pp. 94, 183.
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[30] Maharsia, RR; Jerro, HD. Mat. Sci. Eng. A, 2007, 454-455, 416-422.
Chapter 6
CHICKEN FEATHER FIBER/POLY(LACTIC ACID)

GREEN COMPOSITES: MECHANICAL, THERMAL
AND BIODEGRADABLE PROPERTIES1
Hu-Lin Lia*, Yong-Qing Zhaoa*, Kin-Tak Laub

and Hoi-Yan Cheungb
a
College of Chemistry and Chemical Engineering, Lanzhou University,
Lanzhou, 730000, China.
b
Department of Mechanical Engineering, The Hong Kong Polytechnic University,
Hung Hom, Kowloon, Hong Kong, China.
ABSTRACT
To reinforce poly(lactic acid) (PLA) and take full advantage of chicken feather, the
first time we used chicken feather fiber (CFF) as reinforcement for PLA, and prepared
completely biodegradable PLA/CFF biocomposites by using melting compound method.
By means of tensile test, dynamic mechanical analysis (DMA), differential scanning
calorimetry (DSC), thermogravimetric analysis (TGA), thermomechanical analysis
(TMA), enzymatic degradation test and scanning electron microscopy (SEM), the effect
of CFF on the structural, thermal and mechanical properties and enzymatic degradation
behavior of PLA matrix was investigated. As CFF was incorporated into PLA matrix, the
tensile modulus of the PLA matrix was slightly increased, and the storage modulus
(bending mode) could be remarkably enhanced at glass and rubbery regions of PLA.
DMA results showed the motion of PLA chain segments could be effectively restricted
when 10 wt% of CFF was added into the PLA matrix. On the other hand, the thermal
stability and dimension stability of the PLA matrix became poorer with the addition of
CFF. Moreover, the presence of CFF also significantly enhanced the enzymatic
degradation ability and crystallization ability of the PLA matrix. The content of this
chapter is believed to assist the development of environmentally-friendly composites
from biodegradable polymers, especially for converting agricultural waste – chicken
feather into useful products.
1
This project was supported by The Hong Kong Polytechnic University and Innovative Technology Fund (ZP22).
*
Corresponding author : Fax: +86-931-891-2582, Email:lihl@lzu.edu.cn, zhaoyongq04@lzu.cn
120 Hu-Lin Li, Yong-Qing Zhao, Kin-Tak Lau et al.
INTRODUCTION
In recent years, with emphasis of growing environmental awareness and scarcity of oil
resources, composites composed of biodegradable polymer from renewable resources as
matrix and natural fibers as reinforcement have attracted great interests in composite science.
Poly(lactic acid) (PLA) is a thermoplastic polymer which can either be synthesized by
condensation of lactic acid or ring opening polymerization of lactide which is the diester of
lactic acid. Lactic acid is produced by fermentation of dextrose which itself is gained from
annually renewable resources like corn [1]. Due to its good biocompatibility,
biodegradability, mechanical properties and light weight, PLA has been widely used in many
aspects, such as medical applications [2,3] and automotive parts [4]. The commercial market
for high molecular weight PLA has increased substantially in recent years, ascribed to
advanced industrial technologies of polymerization.
PLA offers advantages of relatively high strength and ability to be processed in most
equipment, however, reinforcement is usually needed for practical applications [5,6]. One
way to improve the properties of PLA is the addition of fibers materials [5-7]. The use of
traditional fiber like glass, aramid or carbon fiber has been discussed critically due to the
environmental problem, although these fibers usually show remarkable reinforcing effect.
Compared with traditional fibers, natural fiber offer many advantages, such as low cost, low
density, renewable, high toughness, acceptable specific strength properties, non-abrasive
behavior and biodegradability [8-10], and thus natural fiber is a promising candidate for
reinforcing PLA. Natural fibers can be classified into plant-based and animal-based fibers. In
general, plant-based natural fibers are lignocellulosic in nature and are composed of cellulose,
hemicelluloses and lignin, whereas animal-based fibers are of proteins [11]. Natural fibers
like flax, abaca, bamboo and silk fibers have been used as reinforcements to enhance the
mechanical properties of PLA [12-17]. However, hardly any researcher has attempted the use
of chicken feather fibers (CFF) as reinforcement for this kind of biodegradable polymer.
Chicken feather is approximately 91% protein (keratin), 1% lipids, and 8% water, and its
amino acid sequence is largely composed of cystine, glycine, proline and serine [18]. Keratin
is a special form of fibrous protein found in wool, nails, claws, horns and feathers, which
protects animals against environmental conditions [19]. It is distinguished from other fibrous
proteins due to the high stability of its structure, which is granted not only by the hydrogen
bonds and van der Waals forces, but also by their high content of the aminoacid cystine
[20].Therefore, this protein is durable, insoluble, chemically unreactive and pliable;
moreover, it may recover its original mechanical properties with little loss, after repeated
deformations [19,21]. As part of chicken feather, CFF also mainly consists of keratin. One
surprisingly important feature of CFF is the special semi-crystalline and cross-linked structure
[22]. Its tensile strength, Young‘s modulus and melting point are about 100~200 MPa, 1~4
GPa, 240 °C, respectively [18,23,24]. In addition, CFF has a high aspect ratio, and is
hydrophobic, durable, renewable and biodegradable. All of the afore-mentioned good
properties contribute to the promising advantage of using CFF as polymer reinforcement. On
the other hand, chicken feather is often treated as a waste product from the poultry sector. For
example, approximately 2 × 109 kg of chicken feather is generated and abandoned in the
United States every year [25]. In most cases, the feathers are disposed of by burial, whereas
Chicken Feather Fiber/Poly(Lactic Acid) Green Composites: Mechanical… 121
an improved, more effective, and hopefully profitable utilization of the chicken feather waste
is desirable.
This chapter is aimed at investigating the feasibility of using CFF/PLA composites, in
terms of their mechanical and thermal properties and biodegradable behavior. Results
obtained from dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC),
thermomechanical analysis (TMA), thermogravimetric analysis (TGA), tensile test and
enzymatic degradation experiment will be presented in this chapter.
Preparation of CFF/PLA Composites
Poly (lactic acid) (PLA) pellets were obtained from East Link Degradable Materials Ltd.,
Hong Kong. The weight-average molecular weight (Mw) of 143K dalton and polydispersity of
1.38 were determined by gel permeation chromatography (GPC). Differential scanning
calorimeter (DSC) determined its glass transition temperature (Tg) and melting temperature
(Tm) to be ca. 60 °C and 170 °C, respectively.
Chicken feather was purchased from Cixi Minghui Feather Products Co., Ltd., Zhejiang,
China. Before use, chicken feather was washed with ethanol several times and dried to have
them clean white, sanitized and odor-free, and this procedure was referred to an U.S. patent
[26]. CFF with a length of 10~30 mm was separated from the shaft of chicken feather and
used as reinforcement for PLA. Two different types of CFF－flight feather fiber and down
feather fiber can be obtained from a chicken feather. Figure 1 shows the images of the cross-
section of these fibers captured with a scanning electron microscope (SEM). These fibers are
cylindrical in shape. The diameter of flight feather fiber is about 5 times to that of the down
feather. The former has a hollow cross-section, while the latter has a solid core, with little
protrusions at certain intervals along its length. Judging from the different physical structures
of two types of CFF, the down feather fiber is believed to perform better as reinforcement for
PLA (This conclusion can be confirmed by results of tensile test of composites reinforced
with two types of CFF. The results are not shown here). Therefore, CFF/PLA composite
materials for subsequent experiments were prepared with down feather fiber which is denoted
by CFF unless otherwise stated.
Figure 1. SEM images of (a) down feather fiber and (b) flight feather fiber.
CFF/PLA composites were fabricated by melt compounding with a Thermo Haake

MiniLab twin-screw micro extruder (Germany) at 180 °C. The screw speed and the mixing
duration were set to 100 rpm and 10 minutes, respectively. Before extrusion, PLA pellets and
CFF were dried at 80 °C in an oven for 4 h and 24 h, respectively. CFF/PLA composites with
2, 5, 8 and 10 wt% of CFF were prepared. These composites were indicated as XCFF/PLA (X
is the CFF weight ratio in the PLA matrix), e.g., the composites with 2 wt% CFF was
shortened as 2CFF/PLA. Standard dumbbell shape specimens (ASTM D638) were prepared
by a Thermo Haake small scale injection-molding machine (Germany). The injection barrel
and the mold were pre-heated to desired temperature of 200 and 45 °C, respectively.
Tensile Properties of CFF/PLA Composites
Tensile tests were conducted to compare the mechanical tensile properties of neat PLA
and CFF/PLA composites with the use of a 50-kN MTS Alliance RT-50 tensile machine and
25 mm extensometer according to the ASTM standard. The crosshead speed of 1 mm/min
was employed. At least three replicates were tested for each sample to obtain an average
value. Fracture surfaces of samples from tensile tests were observed by using scanning
electron microscopy (SEM, Leica Stereoscan 440, accelerating voltage 20 KV). All
specimens were sputter coated with gold prior to examination.
Figure 2 shows the effect of CFF content on the tensile properties of PLA matrix. As seen
in Figure 2a, the tensile strength of PLA decreases with increasing the content of CFF. This
phenomenon has also been reported by other researchers [17,27], and can be ascribed to the
fact that the strength of CFF is insufficient. However, the decrement is less than 10 MPa
when the CFF content varies from 2 wt% to 10 wt%, which is acceptable for applications that
do not require high load-bearing capability. It is believed to be a reasonable compromise for
the improvement of the tensile modulus as demonstrated in Figure 2b. It is shown in Figure
2b that the tensile modulus of all the CFF/PLA composites is higher than that of neat PLA. A
maximum value of 4.2 GPa (increment of 16 %) is achieved for the CFF/PLA composite with
CFF content of 5 wt% (5CFF/PLA). Figure 2c shows the elongation at break of CFF/PLA
composites, and the value obtained at 2 wt% of CFF content (2CFF/PLA) is 56 % higher than
that of the neat PLA. It implies that the ductility of PLA matrix can be effectively improved
by the incorporation of CFF with certain amount which is less than 8 wt%.
The morphology of fracture surfaces of CFF/PLA composites was investigated by SEM.
The micrographs in different magnification for 5CFF/PLA are shown in Figure 3. It can be
seen that there are many CFF like pins which could bridge PLA matrix, as indicated by
arrows in Figure 3a. The bridging effect could prevent crack propagation effectively. Besides,
many CFF together with the PLA matrix were broken rather than draw out, and the details
could also be observed in Figure 3b. This shows the fact that CFF have good adhesion to the
PLA matrix, and thus the stress can be transferred from the PLA matrix to CFF. This may be
attributed to the hydrophobicity of CFF and the interactions between CFF and the PLA
matrix.
Due to the bridging effect and good adhesion, to some extent the mechanical tensile
properties of PLA can be improved by adding CFF into it.
70
a 5 b
Tensile Modulus (GPa)

Tensile Strength (MPa)
60
50 4
40 3
30
2
20
1
10
0 0
0 2 4 6 8 10 0 2 4 6 8 10
CFF Content (wt%) CFF Content (wt%)
6
Elongation at Break (%) c
5
0
0 2 4 6 8 10
CFF Content (wt%)
Figure 2. The effect of CFF content on the tensile properties of PLA matrix.
Figure 3. SEM images for tensile fracture surface of the 5CFF/PLA.
Dynamic Mechanical Properties of CFF/PLA Composites
Dynamic mechanical analysis (DMA) is a sensitive and versatile thermal analysis

technique, which has been widely employed for investigating the structures and viscoelastic
behavior of polymeric composites for determining their relevant stiffness and damping
characteristics for various applications as the materials are deformed under periodic stress or
strain [28-30]. DMA results are composed of three parameters: dynamic storage modulus (E'),
loss modulus (E") and dissipation factor (tan δ＝E"/ E').
DMA for neat PLA and CFF/PLA composites were conducted under nitrogen atmosphere
with a Perkin-Elmer Diamond DMA Lab System at oscillation amplitude of 10 μm and three
frequencies of 0.5, 2 and 10 Hz. Nitrogen was adopted as protective gas. Temperature scans
were carried out with bending mode and a heating rate of 2 °C/min from 25 to 140 °C. DMA
specimens were cut from injection molded samples in rectangular shape with dimensions of
50 mm in length, 5mm in width and 1.5 mm in thickness.
Effect of temperature on the dynamic properties of CFF/PLA composites

The dynamic storage modulus (E') is the most important parameter to assess the load-
bearing capability of a composite material. Figure 4a shows the storage modulus of the neat
PLA and CFF/PLA composites with different CFF content. Despite of whether the addition of
CFF in the PLA matrix, E' decreases gradually upon heating from 25 °C and it drops rapidly
in the glass transition region of PLA. However, the increase of E' can be observed around 85
°C, which reflects the increase of the structure stiffness due to the cold crystallization during
DMA measurements with a slow heating scan rate (2 °C/min). And the rubbery plateau of
PLA appears around 100 °C.
10.0
PLA a
2CFF/PLA 9.0
PLA
2CFF/PLA
b
9.6 5CFF/PLA
5CFF/PLA
8CFF/PLA 8CFF/PLA
10CFF/PLA 8.5
10CFF/PLA
9.2
logE" (Pa)
logE' (Pa)
8.0
8.8 7.5
8.4 7.0
6.5
8.0
20 40 60 80 100 120 140 20 40 60 80 100 120 140
Temperature ( C) Temperature ( C)
1.2 PLA c
2CFF/PLA
1.0 5CFF/PLA
8CFF/PLA
10CFF/PLA
0.8
0.6
tan
0.4
0.2
0.0
20 40 60 80 100 120 140

Temperature ( C)
Figure 4. The representative DMA curves (test frequency is 0.5 Hz) of the neat PLA and CFF/PLA
composites with different CFF content: (a) log E'; (b) log E" and (c) tan δ curves.
Moreover, it can be seen from the Figure 4a that the E' of all the CFF/PLA
composites is higher than that of the neat PLA in the glass region and rubbery plateau.
For example, the E' of 10CFF/PLA at 35 °C and 120 °C is 72% and 148% higher than
that of the neat PLA, respectively. This may be attributed to the combination of the
hydrodynamic effects of CFF embedded in the PLA matrix and the mechanical restraint
introduced by CFF, which reduce the mobility and deformability of the PLA matrix.
The loss modulus E" is the viscous response of the material. Figure 4b shows the loss
modulus of CFF/PLA composites with different CFF loading. It can be seen that the E" of
neat PLA and composites has a maximum in the glass transition region and shows the
similar tendency as the storage modulus E' in the glass and rubbery region.
The addition of CFF into PLA matrix would intensify the friction of the system, and
thus there is more energy to be consumed in the form of heat.
Tan δ is a damping term which can be related to the impact resistance of a material.
In a fiber reinforced composite system, damping is affected by the presence of fibers.
This is mainly due to shear stress concentrations at the fiber ends in association with the
additional viscoelastic energy dissipation in the matrix material. Another reason could be
the elastic nature of the fiber [30]. Figure 4c shows the tan δ curves of neat PLA and
CFF/PLA composites. Accompanied with the appearance of a great drop in the E' curves
and a maximum in the E" curves, the tan δ curves also shows a maximum in the glass
transition region, and the temperature position of this maximum was used to determine
the glass transition temperature (Tg). Generally, the tan δ peak value of composites will
decrease due to the fact that fibers can restrict the mobility of polymer chains. However,
the tan δ peak values of all the CFF/PLA composites are higher than that of the neat PLA,
and the Tg values of all the CFF/PLA composites except for 10CFF/PLA are slightly
lower than that of the neat PLA, which can be seen from Table 1. These suggest that CFF
has plasticization effect on the PLA. On the other hand, it is noted from Table 1 that the
Tg value of 10CFF/PLA is higher than that of the neat PLA. Therefore, it is believed that
the Tg value of CFF/PLA composites can be adjusted by controlling the content of CFF in
the PLA matrix.
Table 1. Tg values from tan δ curves for the neat PLA and CFF/PLA composites.
Sample Tg (°C)
0.5 Hz 2 Hz 10 Hz
Neat PLA 63.1 65.3 69.2
2CFF/PLA 62.6 64.8 68.0
5CFF/PLA 62.4 64.5 67.7
8CFF/PLA 63.1 65.2 68.3
10CFF/PLA 64.1 66.3 69.4
Effect of frequency on the dynamic properties of CFF/PLA composites

The viscoelastic properties of a material are dependent on temperature, time and
frequency. For example, if a material is subjected to a constant stress, its elastic modulus
will decrease over a period of time. This is attributed to the fact that the material
undergoes molecular rearrangement in an attempt to minimize the localized stress.

Modulus measurements performed a short time (high frequency) will result in higher
values whereas measurements taken over long time (low frequency) result in lower values
[31].
The variation of E' with frequency of the neat PLA and 5CFF/PLA is shown in
Figure 5a and 6a, respectively. It is found that increase of frequency can slightly increase
the E' values, and the glass transition of PLA is delayed. Figure 5b and 6b show the effect
of frequency on the E" of the neat PLA and 5CFF/PLA, respectively. The peak of the loss
modulus curve tends to shift to higher temperature with increase of frequency. The tan δ
values measured over a range of frequencies for the neat PLA and 5CFF/PLA are shown
in Figure 5c and 6c, respectively. The tan δ peak is also found to shift to higher
temperature with increase of frequency. Tg values of all the sample with variation of
frequency are summarized in Table 1. It is clear that Tg of all the sample increases with
increase of frequency, that is to say, the relaxation movement of PLA chains is delayed
when high frequency is used. In fact, high frequencies can induce more elastic-like
behavior. A material will behave stiffer than it can be, if the frequency is chosen to be
high enough.
9.0
0.5 Hz a 0.5 Hz
b
9.5 2 Hz 2 Hz
10 Hz 8.5 10 Hz
8.0
logE" (Pa)
9.0
logE' (Pa)
7.5
8.5
7.0
6.5
8.0
20 40 60 80 100 120 140 20 40 60 80 100 120 140
0.8
0.5 Hz c
2 Hz
10 Hz
0.6
0.4
tan
0.2
0.0
20 40 60 80 100 120 140
Temperature ( C)
Figure 5. The effect of frequency on DMA curves of the neat PLA: (a) log E'; (b) log E" and (c) tan δ
curves.
10.0
0.5 Hz a 9.0
0.5 Hz
b
2 Hz 2 Hz
10 Hz 10 Hz
9.5
8.5
logE" (Pa)
logE' (Pa)
9.0 8.0
7.5
8.5
7.0
8.0
6.5
20 40 60 80 100 120 140 20 40 60 80 100 120 140
1.0
0.5 Hz c
2 Hz
10 Hz
0.8
0.6
tan
0.4
0.2
0.0
20 40 60 80 100 120 140

Temperature ( C)
Figure 6. The effect of frequency on DMA curves of 5CFF/PLA: (a) log E'; (b) log E" and (c) tan δ
curves.
Cole-cole plot
The single relaxation peaks are inadequate to describe the viscoelastic response of
polymer. The magnitude of polarization within a material is represented by dielectric
constant, which can be represented by the Debye and Onsager equations [32]. Cole-Cole is a
particular treatment of dielectric relaxation data obtained by plotting E" against E', each point
corresponding to one frequency [32].
Structural changes taking place in composites after fiber incorporation to polymer matrix
can be studied by means of the Cole-Cole method. The dynamic mechanical properties when
investigated as a function of temperature and frequency are represented on the Cole-Cole
complex plane,
E"= f (E') (1)
Figure 7 shows the Cole-Cole curves of CFF/PLA composites, where log E" are plotted
as a function of the log E'. The nature of the Cole-Cole curve is used to indicate the nature of
the composites. A semi circle diagram represents the composite systems are homogeneous.
The Cole-Cole curves presented in the figure are imperfect semi circles. The shape of the
curves implies the relatively good fiber-matrix adhesion.
9.0
8.5
logE'' (Pa)
8.0
2CFF/PLA
7.5 5CFF/PLA
8CFF/PLA
10CFF/PLA
7.0
6.5
8.0 8.4 8.8 9.2 9.6
logE' (Pa)
Figure 7. Cole-Cole plots of CFF/PLA composites with different CFF content.
Crystallization and Melting Behavior of CFF/PLA Composites
Crystallization and melting behavior of neat PLA and CFF/PLA composites were
investigated by Differential scanning calorimetry (DSC) on a Perkin-Elmer DSC 7 system.
The specimens were sliced from injection molded samples and sealed in aluminum crucibles.
All the specimens were scanned from 30 °C to 200 °C at 10 °C/min and kept isothermally at
200 °C for 10 minutes to eliminate previous thermal history. They were then quenched to 30
°C at 25 °C/min and subsequently scanned from 30 to 200 °C at 10 °C/min again. All the runs
were under nitrogen atmosphere.
Heat flow (mW)
10CFF/PLA
8CFF/PLA
5CFF/PLA
2CFF/PLA
PLA
Endo.
80 100 120 140 160 180 200

Temperature ( C)
Figure 8. DSC traces of the neat PLA and CFF/PLA composites with different CFF content.
Figure 8 shows the DSC thermograms of the neat PLA and CFF/PLA composites in the
second heat scan after fast cooling at 25 °C/min from the molten state, and the relative data
are listed in Table 2. It is found that the addition of CFF in PLA matrix will decrease the cold
crystallization temperature (Tcc) of PLA. For example, the Tcc of 10CFF/PLA is 10 °C lower
than that of the neat PLA. And the enthalpy of crystallization (ΔHcc) of CFF/PLA composites
increases with increasing the CFF content. These indicate that crystallization ability of PLA
can be enhanced due to the presence of CFF which may behave as nucleating agent.
Moreover, the enthalpy of fusion (ΔHm) of all the CFF/PLA composites is higher than that of
the neat PLA, which implies that the crystallinity (Χc, Χc=ΔHm/ΔHo, in which ΔHo is the
melting heat of 100% crystalline PLA) of PLA slightly increases with addition of CFF in it.
Table 2. DSC results of the neat PLA and CFF/PLA composites.
CFF Content (wt%) Tcc (°C)a ΔHcc (J/g)b Tm (°C)a ΔHm (J/g)b
0 112.9 38.8 163.4 169.5 43.2
2 112.2 42.1 164.0 171.9 44.7
5 112.4 42.6 163.7 170.0 43.7
8 112.0 43.5 163.5 170.0 44.7
10 102.9 44.5 152.0 166.7 46.9
a
Tcc and Tm are taken from the maximum position of crystallization and melting peaks, respectively.
b
ΔHcc and ΔHm are corrected for the content of PLA in the composites.
Tcc: cold crystallization temperature, ΔHcc: enthalpy of cold crystallization, Tm: melting temperature,
ΔHm: enthalpy of fusion.
From Figure 8 and Table 2, it can be seen that the melting point (Tm) of PLA is about 169
°C. And PLA shows double melting peaks. It can be due to the fact that the less perfect
crystals have enough time to melt and reorganize into crystals with higher structural
perfection, and melt again at higher temperature [33,34]. Moreover, there is almost no
difference between the Tm of CFF/PLA composites and that of the neat PLA when CFF
content is lower than 10 wt%. However, the Tm of 10CFF/PLA is obviously lower than that of
the neat PLA. This suggests that there will be enough less perfect crystals nucleating at CFF
surface in this case. These crystals reorganize into better form and melt again at higher
temperature, and thus the melting peaks of 10CFF/PLA shift to lower temperature. This
means that the addition of CFF over 10 wt% into PLA matrix can decrease Tm of PLA.
Thermal Stability of CFF/PLA Composites
Thermal stability of neat PLA and CFF/PLA composites was investigated by means of
Thermogravimetric analysis (TGA), which was carried out with a Netzch TGA/DSC system.
The specimens were heated from 30 to 600 °C at a rate of 10 °C/min under a flow of argon.
100
a b
PLA
2CFF/PLA
PLA
80 5CFF/PLA
2CFF/PLA
DTG (%/min)
8CFF/PLA
Mass (%) 5CFF/PLA
10CFF/PLA
60 8CFF/PLA
CFF 10CFF/PLA
CFF
40
20
0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Figure 9. TGA curves of the neat PLA and CFF/PLA composites with different CFF content: (a) TG
and (b) DTG curves.
TGA curves as a function of temperature of the neat PLA and CFF/PLA composites are
shown in Figure 9. It can see from TG curves (Figure9a), the thermal degradation behavior of
either the neat PLA or CFF/PLA composites goes through three stages. From 30 °C to 240
°C, there is nearly no difference in thermal stability between the neat PLA and CFF/PLA
composites. However, the difference of thermal stability can be easily observed within the
major degradation region from 240 °C to 375 °C, in which all the CFF/PLA composites
display lower thermal stability than the neat PLA. This conclusion can be confirmed by the
difference of TDi (the initial degradation temperature), TD (the temperature at which 50% of
12
the sample weight is lost) and Tp (the temperature at which there is the maximum of the DTG
curves) (Figure 9b) between the neat PLA and CFF/PLA composites. Their values are
summarized in Table 3. It is obvious that TD , TD and Tp value of all the CFF/PLA
i 12
composites are lower than that of the neat PLA, and they decreases with the increase of CFF
content. In general, the thermal stability of a composite material is determined by the
component which has the lowest thermal stability. As for CFF/PLA composites, the thermal
stability of CFF is lower than that of the neat PLA in this region. For example, the TD , TD
i 12
and Tp of CFF are 255.0 °C, 342.3 °C and 331.6 °C, respectively. But that of the neat PLA are
346.3 °C, 366.6 °C and 372.1 °C, respectively. Therefore, the addition of CFF can accelerate
the thermal degradation of PLA matrix in this region. On the other hand, the water molecular
remained on CFF surface may promote the ester bonds scission of PLA [35]. In the third
region (375~600 °C), however, it is found that the presence of CFF can slightly increase the
char residue at 600 °C ( wtR ) (Table 3) of the PLA matrix. The char of CFF/PLA
600
composites with 2~10 wt% CFF is 0.1~4.9 wt% higher than that of the neat PLA. Thus, the
thermal stability of PLA can be slightly improved in this region. This is due to the fact that
the thermal stability of CFF is better than that of the PLA matrix in this region (as shown in
Figure 9a) and it may act as barrier minimizing the permeability of volatile degradation
products in the composites.
Table 3. TGA results of the neat PLA and CFF/PLA composites.
Sample Tp (°C)a TDi (°C)b TD1 2 (°C)c wtR600 (%)d

Neat PLA 372.1 346.3 366.6 0.4
2CFF/PLA 369.1 342.4 362.3 0.5
5CFF/PLA 364.2 338.3 358.3 1.6
8CFF/PLA 356.7 329.3 349.3 2.6
10CFF/PLA 347.9 322.2 342.2 5.3
CFF 331.6 255.0 342.3 25.4
a
the temperature at which there is the maximum of the DTG curves.
b
the initial degradation temperature is the intersection temperature of the baseline for lower temperature
range and the tangent line for TG curve.
c
the temperature at which 50% of the sample weight is lost.
d
weight percentage of the residue at 600 °C.
Dimensional Stability of CFF/PLA Composites
Dimensional stability is critical for a composite material in different applications. Poor

dimensional stability will cause warping and other changes in shape during service. The
coefficient of thermal expansion (CTE), a parameter used to evaluate the thermal stability of
materials, can be obtained from TMA test. The lower the CTE value, the higher the
dimensional stability. Generally, the CTE of a fiber reinforced polymer matrix composite
may be lower than that of the neat polymer matrix because polymers thermally expand with a
greater extent than most reinforcing fibers. Lowering the CTE value is desirable in
minimizing thermo-dimensional changes in composites exposed to temperature variation
during composite fabrication or use [11].
CTE of samples was obtained using a Perkin-Elmer 7/DX Thermomechanical Analyzer
(TMA). The force applied was 5 mN and it was heated at rate of 10 °C/min from 30 to 160
°C.
150
140
CTE ( m/m C)
130
120
110
100
0 2 4 6 8 10
CFF Content (wt%)
Figure 10. The coefficient of thermal expansion (CTE) of the neat PLA and CFF/PLA composites with
different CFF content.
Figure 10 shows the CTE of CFF/PLA composites with different CFF content. All the
CFF/PLA composites have values of CTE higher than that of the neat PLA. This suggests that
the dimensional stability of PLA matrix will deteriorate due to the presence of CFF. This may
be caused by the weak thermal stability of CFF, or composite defects including interface
debonding, fracture of matrix and reinforcements, which has a significant influence on the
elasto-plastic behavior of the composites [36-38]. Among the CFF/PLA composites with
different CFF content, 5 wt% CFF/PLA composite has the best dimensional stability.
Enzymatic Degradation Behavior of CFF/PLA Composites
The environmental applications of CFF/PLA composites require fundamental information

concerning its degradation properties. A well-known enzyme Proteinase K was used to
degrade the composites in order to examine their degradation behavior.
The details of the enzymatic degradation experiments are as the follows. Specimens for
the experiment were cut from injection molded samples with dimensions of 5 mm in length, 5
mm in width and 1.5 mm in thickness. The enzymatic degradation experiments were carried
out according to previous literature methods [39]. A specimen was placed in a vial containing
5 mL of Tris-HCl buffer (pH=8.6), 1.0 mg of proteinase K and 1.0 mg of sodium azide.
Deionic water was used to prepare the above solutions. For a given experiment, three
replicate specimens in separate vials were used for weight loss measurements at a specified
degradation time. The degradation experiments were carried out at 37 °C in a rotary shaker
(100 rpm). The buffer/enzyme solution was replaced every 24 h to ensure that enzyme
activity remained at a desired level throughout the experiment duration and that the solution
pH did not drop below pH=8.0 [39,40]. Up to a specified degradation time, the specimens
were withdrawn from and washed with distilled water. After wiping, the specimens were
weighed and vacuum dried at room temperature for one week before being subjected to
analysis.
The surfaces of samples from enzymatic degradation were observed by using scanning
electron microscope (SEM, JEOL Model JSM-6490, accelerating voltage 20 KV). All
samples were sputter coated with gold prior to examination.
SEM observation
SEM was used to observe the changes of surfaces of the samples before and after
enzymatic degradation. Figure 11 shows the surface of neat PLA. Before degradation, the
surface of the neat PLA is smooth as shown in Figure 11a. After degradation, it can be seen
from Figure 11b, c, d that many holes are formed on the surface, and the diameter of these
holes increases with the degradation time, indicating very pronounced degradation. SEM
images of the surfaces of 2CFF/PLA, 8CFF/PLA and 10CFF/PLA before and after
degradation are shown in Figure 12, Figure 13 and Figure 14, respectively. Compared Figure
12a, Figure 13a and Figure 14a with Figure 11a, it is found that the surfaces of the composites
are rougher than that of the neat PLA before degradation. The rough surfaces would promote
the degradation process ascribed to increasing surface area to contact enzyme solution. After
degradation, CFF exposes on the composites due to the enzymatic degradation of PLA
(Figure 12b-d, Figure 13 b-d and Figure 14b-d). With increasing the degradation time and
CFF content, the surfaces of the composites become more and more rough. This indicates that
the addition of CFF into PLA matrix can accelerate the enzymatic degradation process.
Besides, it is noted that degraded PLA from 10CFF/PLA is likely less than that of 8CFF/PLA,
although there are more CFF exposed on 10CFF/PLA than that of 8CFF/PLA after 120 h
enzymatic degradation (Figure 13d and Figure 14d). The enzymatic degradation of the
polymeric materials occurs predominantly on their surfaces [41,42]. However, it is clearly
observed that the enzymatic degradation of CFF/PLA composites occurs along CFF as shown
in Figure 14b and 14d. That is to say, the degradation not only occurs on the surface of the
composites but also at the interface between CFF and PLA matrix, which allow the PLA
chain in the composites to become more susceptible to enzymatic degradation. As a result, the
enzymatic degradation can occur inside the composites as well as on their surfaces.
Figure 11. SEM images of the neat PLA after 0 (a), 24 (b), 72 (c) and 120 h (d) enzymatic degradation.
Figure 12. SEM images of 2CFF/PLA after 0 (a), 24 (b), 72 (c) and 120 h (d) enzymatic degradation.


Water absorption ratio analysis

Water absorption ratio of polymeric material is one of important factors which are
responsible for the weight loss in enzymatic degradation [43]. The water absorbed by
polymeric material will increase the free volume within the polymer matrix and then facilitate
the enzymatic attack. Therefore, enzymatic degradation is promoted. The water absorption
ratio can be calculated according to the following equation:
Water absorption ratio% (Ww Wd )/Wd (2)

2.0
PLA a
2CFF/PLA
5CFF/PLA
Water absorption ratio (%)

1.6
8CFF/PLA
10CFF/PLA
1.2
0.8
0.4
0.0
0 20 40 60 80 100 120 140 160

Degradation time (h)
1.0
1.3
24 h 48 h 1.4 72 h
0.8 1.2
1.2
1.1
0.6 1.0 1.0
0.9
0.4 0.8
0.8
0.7 0.6
0.2
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
CFF content
2.0 2.0 1.9
1.8 96 h 120 h 144 h

1.8 1.8
1.6
1.7
1.4 1.6
1.2 1.6
1.4
1.0 1.5
0.8 1.2 1.4
0.6
1.0 1.3
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
CFF content
b
Figure 15. The effect of degradation time (a) and CFF content (b) on the water absorption ratio of
CFF/PLA composites during enzymatic degradation.
Where Ww and Wd represent the wet and dry weight of the sample after degradation,
respectively. Figure 15 shows water absorption ratio profiles of neat PLA and CFF/PLA
composites. The water absorption ratio of all the samples exhibits increasing tendency with
increasing the degradation time (Figure 15a). However, the water absorption ratio of
2CFF/PLA, 8CFF/PLA and 10CFF/PLA nearly become a constant after 96 h degradation,
especially the water absorption ratio of 10CFF/PLA hardly change after 72 h degradation.
This suggests that the water absorption of CFF/PLA composites may have saturation.
Moreover, the water absorption ratio of CFF/PLA composites will increase first, and decrease
afterwards with increasing CFF content (Figure 15b). 8CFF/PLA has the maximum. And the
water absorption ratio of CFF/PLA composites is higher than that of the neat PLA. This
implies that CFF can contribute to enhance water absorption ratio of the composites, which
may be due to the fact that the random dispersion of CFF in PLA matrix does a structural
favor for enzymatic solution diffusing into the inside of CFF/PLA composites. However, the
water absorption ratio of CFF/PLA composites will decrease as the CFF content is more than
8 wt%. This may be ascribed to the hydrophobicity of CFF. At this case, the hydrophobicity
of CFF may become the predominant factor for the water absorption ratio of CFF/PLA
composites.
Weight loss analysis

Weight loss is a very important parameter for measuring degradation ability of polymeric
material. It can be obtained from the following relationship:
25 PLA
a
2CFF/PLA
5CFF/PLA
20 8CFF/PLA
Weight loss (wt%)
10CFF/PLA
15
10
0 20 40 60 80 100 120 140 160

Degradation time (h)
5.4 10.5 14
24 h 48 h 72 h
5.1 10.0
Weight loss (wt%)
4.8 9.5
13
4.5 9.0
8.5
4.2
8.0 12
3.9
7.5
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
CFF content
17.5 22 26
96 h 120 h 144 h
Weight loss (wt%)
25
17.0
21
24
16.5
23
20
16.0 22
0 2 4 6 8 10 0 2 4 6 8 10 0 2 4 6 8 10
CFF content
b
Figure 16. The effect of degradation time (a) and CFF content (b) on the weight loss of CFF/PLA
composites during enzymatic degradation.
Weight loss% (W0 Wd )/W0 (3)
Where W0 is the initial weight, and Wd is the dry weight of the samples after degradation.
The variation of weight loss of neat PLA and CFF/PLA composites during enzymatic
degradation is shown in Figure 16. The weight loss of the composites is mainly due to
degraded PLA and released CFF. The weight loss of all the samples increases with increasing
degradation time (Figure 16a). At the same degradation time, the weight loss of CFF/PLA
composites increases first, and decreases afterwards with increase of CFF content (Figure
16b). The maximum appears at 8 wt% of CFF content. Besides, the weight loss of CFF/PLA
composites is higher than that of the neat PLA. These imply that the presence of CFF can
accelerate the enzymatic degradation of the composites. The variation of weight loss of
CFF/PLA composites is on the whole consistent with the variation of water absorption ratio,
it is thus clear that the effect of CFF on the water absorption ratio results in the variation of
the weight loss.
CONCLUSION
From the aforementioned results, the following conclusions can be summarized for the
mechanical, thermal and biodegradable properties of CFF/PLA composites.
(1) When 5 wt% CFF (down feather fiber) is added into PLA matrix, CFF/PLA
composites has the best mechanical tensile properties. Due to the bridging effect and
good adhesion, mechanical tensile properties of PLA can be somewhat improved by
incorporation CFF into it.
(2) In the glassy and rubbery region of PLA, the addition of CFF will significantly
enhance the storage modulus of PLA. The Tg value of CFF/PLA composites is likely
to be adjusted by controlling the content of CFF in the PLA matrix, and will increase
with increasing frequency.
(3) The presence of CFF will improve crystallization ability of PLA. CFF can act as
nucleating agent for the crystallization of PLA. And the Tm value of PLA will be
slightly increased as the CFF content is 2~8 wt%.
(4) The addition of CFF will reduce the thermal stability and the dimensional stability of
PLA.
(5) The enzymatic degradation of CFF/PLA composites occurs not only on their surface,
but also into the internal; the water absorption ratio of PLA can be enhanced by the
addition of CFF, and thus the enzymatic degradation of PLA will be accelerated.
However, CFF will hinder the enzymatic degradation of PLA, when the CFF content
is more than 8 wt%.
(6) CFF-reinforced PLA composites are capable to offer favorable mechanical and
thermo-mechanical properties for real applications that do not require high load-
bearing capability.
Further study should be focused on the improvement of interfacial bonding and thermal
stability of CFF/PLA composites.
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Chapter 7
MECHANICAL AND MOISTURE ABSORPTION

OF CORN AND WHEAT FLOUR COMPOSITES
FOR DEVELOPING COUNTRIES
Thimothy Thamae, Shanil Vaja, Yiyi Shangguan, Claire Finoro,

Nick Stefano and Caroline Baillie
Department of Chemical Engineering, Queens University, 19 Division Street,
Dupuis Hall, Kingston, K7L 3N6, Ontario, Canada
ABSTRACT
Low cost processing methods for natural fibre composites could be suitable for
developing countries context. The challenge is to make composites with properties that
are not overly compromised by the use of low technogly. Composites were made using
corn/wheat stalk flour and waste high density polyethylene and were tested for moisture
absorption, impact, tensile and flexural properties. The composites made from outer ring
corn stalk flour absorbed more water than those made from whole corn stalk flour. When
wheat stalk flour composites were extruded before being moulded, they absorbed about
15% less water at equilibrium than when they were just layered, shredded and moulded.
The above mentioned parameters in both corn and wheat stalk composites did not make
significant differences on impact properties of the composites. Sealing the wheat straw
composites had the unexpected effect of absorbing about 5% more water at equilibrium
than the unsealed wheat straw composites. Neither silane nor sodium hydroxide
treatments improved the tensile or flexural properties of the corn stalk composites, likely
due to poor mixing governed by the selected processing methods. By careful selection of
the processing techniques and materials, it is possible to make composites that may be
affordable without overly sacrificing their properties.
INTRODUCTION
Due to their abundance and low cost, natural fibres and waste plastic could potentially be
used for making plastic composites in developing countries. However, the complex and
expensive processing approaches traditionally used to make composites may be economically
unfeasible. In developing countries the composite manufacturing approaches require more than
just substituting conventional fibres with green fibres. The methods need to reflect the economic
142 Thimothy Thamae, Shanil Vaja, Yiyi Shangguan et al.
and social contexts of these countries if they are to succeed as products and to to benefit
marginal socio-economic groups (Baillie, 2006, Medina, 2007). Waste-for-Life (Wfl) is a not-
for-profit network which works to bring poverty reducing solutions to environmental problems.
The beneficiaries of these programs are those who are marginalized and vulnerable. Waste-for-
life works with the communities who scavenge plastic, who grow crops, who form community-
based cooperatives and work to survive. Engineers and researchers working with Waste-for-life
are attempting to develop low cost manufacturing processes which are feasible in these
communities (Thamae and Baillie, 2009). The challenge is to create composites using these low
technologies which have comparable properties to their industrially produced counter parts.
Natural fibres as lignocellulosic materials are known for their affinity for moisture.
Consequently, the composites made from them also take up more moisture. What makes
natural fibres hydrophilic is the presence of free hydroxyl groups on their chemical structure
which generate polarity and attract naturally polarized water molecules. Moreover, these fibres
have a porous structure which allows for a free movement of water (Sreekala et al, 2002). In
composites, additional factors that increase water absorption include micro voids and
indentations on the fibre-matrix interfaces (Beg and Pickering, 2008). Hydrophobic plastics
alone absorb very little water. Therefore the water enters the composites mainly through fibres
exposed on the composite surfaces.
As the water molecules move and lodge into the interfibrillar spaces, they begin to enter
and build up in the plant cell walls. This can cause fibre swelling and affect mechanical
properties of the composites (Yadav et al, 2004). Therefore, it is very important to understand
the water absorption behavior of different composites when fully submerged in water. It is also
critical to understand the effects of the processing methods on the impact properties.
Since natural fibres and thermoplastics are poorly compatible, many approaches have been
devised to increase stress transfer efficiency at the interface. These approaches include using
alkali treatment of natural fibres, or chemically coupling the two materials using silane coupling
agents. The alkali treatment transforms the morphology of fibres by dissolving lignin,
hemicelluloses and other substances (Mwaikambo and Ansell, 1999, Thamae and Baillie,
2007). It also reorganizes fibre cellulose bonds; transforming them from cellulose I to cellulose
II. The cellulose-II lattice is thermodynamically more stable than that of cellulose-I. These
processes result in improved tensile strength of the fibres and the composites (Van de
Weyenberg et al, 2006). Silane coupling agents have functional groups that can bond covalently
with polymers, and hydrolyze to form bonds with natural fibres (Kokta et al, 2004). These
bonds theoretically improve the strength of the interface, hence they improve the strength of the
composites. However, these kinds of chemical treatments may not be affordable in developing
countries. Thus, the important question is; would these chemical treatments be effective given
the simple processing methods used? Are they worth the additional cost and/or impact on the
environment?
In this chapter, we determine the influence of varying processing parameters to make
composites suitable for Waste-for- life contexts. Basic compression moulding techniques based
on the capabilities of a low-cost Kingston hot press specially designed for developing countries
by Dr Darko Matovic were used (Thamae and Baillie, 2009). Also explored is the impact of the
addition or removal of the extrusion/mixing step in the processing for contexts where extruders
cannot be purchased. Composites are processed using raw materials that are normally discarded,
waste plastic bags and straw. The expensive processing techniquies of the straw to retrieve the
fibres is avoided. Instead, the stalks of wheat and corn are milled into flour particles and used as
Mechanical and Moisture Absorption of Corn and Wheat Flour… 143
fillers. Moisture absorption, impact, tensile and flexural properties of these materials are
determined and compared.
METHODOLOGY
Materials
Corn and wheat stalks were obtained from local farmers. Both stalks were milled into
flour using Thomas Wiley laboratory mill containing a sieve with holes 2 mm in diameter.
For corn stalk, it was necessary to determine the influence of the whole stalk against the outer
ring (Thamae at al, 2008). The ―woody‖ outer ring of corn stalk was peeled from the pith with
a knife. Then, the outer ring was cut into pieces small enough to be fed into the mill and
milled into flour. The same procedure was followed to make the whole corn stalk flour. Some
tensile and chemical properties of corn straw pith and corn and wheat straw fibres are given in
Table 1.
The waste High Density Polyethylene (HDPE) bags were collected from users or
obtained from recycling bins. To ensure consistency, only plastic bags from local grocery
stores such as A&P, Food Basics and Loblaws were used. These stores have the same bag
manufacturers (Hillex and Hymopack) and all have the Resin Identification Code of 2
(HDPE). The plastic bags were then cleaned using water and a dish washing liquid and then
air dried before use. 1N solution of sodium hydroxide was obtained from Fisher Scientific
while 97% triethoxyvinylsilane solution came from Sigma Aldrich.
Composites manufacturing
The path followed for the processing of all composites in this chapter is identified in
Figure 1 (see the dotted line). The composites were varied by the weight fraction of the
corn/wheat stalk flour in HDPE. Composites of the following flour weight fraction: 10, 20,
30, 40 and 50% were made. Pure HDPE was used as a control sample. To make each
composite layer, corn or wheat straw flour was sandwiched between two thin single layers of
HDPE bags. Each sandwich was then placed between two Teflon sheets and two metal plates.
Then it was hot pressed for 2 minutes at a temperature of 150 ºC and a pressure of 6.7 MPa.
The products of this process were thin composite layers which were cut into very small
diamond shaped pieces by an office paper shredder.
Table 1. Tensile and chemical properties of wheat and corn fibres and corn pith.
Material Tensile properties (MPa) Chemical properties (%)

Strength Modulus Cellulose Hemicellulose Lignin
Wheat stalk fibres (Hornsby et al, 0.17-29.68 1030-2.67 35 22.3 15.6
1997, Petersen et al, 2009)
Corn stalk fibres (Reddy and _ _ 38–40 7-21 28
young, 2005)
Corn pith (ZuoDong, 2007) 0.89 49.5 24.6 19.1 12.3
The pieces were fed into a Wayne single screw laboratory extruder to enhance mixing
and to improve flour-matrix adhesion. The extruder has five heating zones that were set at the
following temperatures: 140, 150, 160, 170 and 180 ºC. The screw speed was varied between
25 and 65 rpm to comply with the machine‘s pressure limits. The composites exited the
extruder through a circular nozzle with a diameter of approximately 5 mm in a rope-like form.
They were then cut into small cylindrical pellets (approximately 3 cm in length) and placed in
a 20 × 20 × 0.32 cm steel mould. The mould was then placed between the Teflon sheets and
hot pressed for 3 minutes at a temperature of 150 ºC and a pressure of 6.7 MPa. After heating,
the composite tile was removed from the mould and cold pressed to reduce warping in the
tiles as they cooled off. This processing procedure will be referred to as tv in this chapter. The
letters t (shredding, extrusion and pelletizing) and v (press moulding the pellets into
composites) represent the last two stages followed in the production process shown in Figure
1. The above process was the basis for making some of the wheat stalk flour composites
(WSFCs) and all of the corn stalk flour composites (CSFCs).
For some WSFCs, the thin composites were only shredded and pressed into 20 × 20 ×
0.32 cm tiles without being extruded. This processing procedure will be referred to as sv in
this chapter because extrusion step is excluded (see Figure 1). For water absorption tests, the
sv and tv WSFC test specimens were wrapped in a layer of pure HDPE on all six sides. The
two larger sides of the specimens were sealed by pressing them between two heated plates
covered with Teflon sheets. The plates provided only enough pressure for the film to adhere.
The four specimens‘ edges were sealed by gently pressing them against the hot plates covered
with Teflon sheets.
For chemical treatments, corn stalk flour was immersed in 1N solution of NaOH over a
period of 24 hours. The solution was filtered with a sieve and the flour was washed with
water to a neutral pH. It was then dried in a vacuum oven at 50ºC until dry. Composites of
two flour contents, 20 and 30%, were made. For treatment with triethoxyvinylsilane, this
solution was added to water to a concentration of 4% by weight in a beaker. Acetic acid was
added until the solution was at pH 5.5. The flour was then immersed in this solution and
agitated over a period of 5 minutes. The pH was monitored and kept below 6 for the duration
of the immersion. The solution was then filtered by sieve and dehydrated in a vacuum oven at
50ºC until dry.
Water Absorption Tests
Water absorption tests were carried out according to ASTM D 570-98 for all the
composites. The test specimens were cut into the dimensions of 76.2 ×25.4 ×3.2 mm using a
waterjet saw. Three specimens per flour content for each variable were made. The specimens
were conditioned by drying in an oven at 50 ºC for 24 hours, cooled and weighed to the
nearest 0.001 g. Then they were submerged in a container with distilled water at room
temperature for twenty-four hours. At the end of this period, they were wiped with a dry clean
cloth and immediately weighed again. From then onwards, they were weighed every two
weeks until some of the specimens, especially those of higher flour content reached
equilibrium (time could not permit weighing until all specimens reached equilibrium).
Figure 1. Different stages of processing using different fillers in our lab. The dotted lines represent the
path followed by the straw composites used in this chapter.
The percent increase in weight during immersion was calculated using the following
equation:
(1)
Where Mt is the percentage of moisture absorbed, W(t) is the wet weight of a composite at
time t, W(0) is the conditioned weight.
Mechanical Tests
The ASTM D4812-06 standard test method for unnotched cantilever beam impact
resistance of plastics was followed. The dimensions of the test specimen were 63.50 mm long
by 12.70 mm deep by 3.2 mm wide (where the width is the thickness of the sheet). Ten
specimens for each type of composite at each weight fraction were tested using a laboratory
impact testing machine.
Tensile and flexural tests for the composites were performed using Instron 3369
Universal Tester connected to a Bluehill Merlin Software. They were made according to
ASTM D 638-08 and ASTM D790-07 respectively, making 5 tests per weight fraction per
variable. For all tests, the specimens were cut from the composite tiles using a waterjet saw.
Tensile specimens were tested at a rate of 5mm/min at 50 mm gauge length and tensile
strengths were calculated using:
(2)
where Wmax is the maximum load and A is the original cross-sectional area of the specimen.
The tensile modulus (MPa) was calculated as the slope of the initial linear section of a stress-
strain graphs. Rectangular specimens measuring 127× 12.7× 3.2 mm were cut out for flexural
testing. For these tests, the support span L was calculated using a ratio L/d of 16:1 where d is
the depth if the beam (mm). The rate of crosshead motion was determined using:
(3)
Where L is the support span (mm), d is the depth of the beam (mm) and Z is the rate of
straining of the outer fibre (mm/mm/min) – taken to be 0.01. The flexural strength (MPa) was
given by:
(4)
Where P is the load applied (N), b is the width of the beam (mm) and. The flexural modulus
was obtained using:
(5)
Where m is the slope of the initial straight-line portion of the load-deflection curve (N/mm).
Table 2 gives a summary of the tests made and the rationale behind them.
Table 2. Questions asked and investigations made.
Questions Composites made Tests

If it is less expensive to use the whole corn stalk rather than to use Outer ring CSFCs vs. whole Moisture
the outer ring only in composites, how does using the whole stalk CSFCs absorption
affect composite properties (Thamae et al, 2008)? and impact
Path sv in Figure 1 may be more affordable in developing sv-WSFCs vs. tv-WSFCs Moisture
countries due to absence of extrusion path used in tv. To what absorption
extend does the path sv sacrifice composite properties over tv? and impact
Using waste plastic sheets for sealing to reduce water absorption Sealed- WSFCs vs. non- Moisture
could be less expensive than the use of normal coating. How well sealed-WSFCs absorption
does this procedure prevent moisture absorption?
To what extent does the use of chemical treatments on the flour Corn whole stalk untreated vs. Tensile and
improve composite properties in the context of low-tech NaOH and silane treated flour flexural
processing methods relevant to the developing countries used in
this study?
Microscopy
Fracture surfaces of the tensile and impact samples, cross-sections of corn and wheat
stalks and their flour particles were observed using a Scanning Electron Microscope (SEM).
The specimens were all gold plated and observed on a JEOL JSM 840 SEM.
RESULTS AND DISCUSSION

Water Absorption
Moisture absorption behaviour of CSFCs and WSFCs are shown in Figures 2 and 3 (all error
bars in this chapter represent standard deviations). Both types of composites have a number of
similar trends. Water absorption increases with flour content while pure HDPE takes in very little
water over time. As lignocellulosic materials have a high concentration of hydroxyl groups (OH),
they are very hydrophilic. In addition, as the filler content increases given the same average
particle size, the interfacial area increases. The interfacial area can be a pathway for movement of
water molecules (Espert et al, 2004).
Additionally, as opposed to the use of pure technical fibres, milled corn and wheat stalks
particles contain a spongy parenchymal tissue called pith. This tissue has hexagonal and
sometimes quadrangular shaped cells (if viewed from the vertical cross-section of the stalks as
opposed to the transverse section) (ZuoDong, 2007) Figure 4 (a-b). The particles of both corn and
wheat stalks contain some components of the pith (Figure 4 (c-d)). These components are
sometimes not apparent in wheat stalk particles due to the thinner layer of pith in wheat stalk. This
cellular, porous structure possibly adds to the water retention abilities of the composites although
it is partly destroyed during processing, especially during extrusion.
The water absorption properties of CFSCs were an exception as they took more water at 40%
than at 50% flour content (Figure 3 (b)). This could be due to increased thermal degradation
(burning) of the flour at higher flour content during extrusion. Adding more flour to HDPE
decreases the composite‘s melt flow index. Addition of fibres (outer ring flour has much more
concentration of fibres than the whole stalk) to plastics may increase their viscosity (and reduce
melt flow index) in the same manner as a reduction in their temperature, (Czarnecki and White,
1980).This results in more time spent by the composite in the extruder under heat (composites at
the 40% and 50% flour content were darker as a sign of burning). This thermal degradation
probably modified the flour chemical structure in a manner that reduced its hydrophicility.
There is a flour content at which the water uptake begins to increase rapidly, especially in
WSFCs (Figures 2 and 3). In Figure 2, there is a huge gap between water uptake at 30 and 40%
flour content for all the graphs. In Figure 3 (a), this gap is between 20 and 30% flour content
while the gap is not clearly defined in Figure 3 (b). This phenomenon may be explained by the
percolation concept detailed in Wang et al, (2005). Figure 5 can be seen as a cross-section of a
composite, showing grey squares occupied by flour particles and white squares occupied by
plastic at different flour contents. When flour content is very low (Figure 5(a)), there is greater
percentage of particles that are likely to be fully encapsulated by the plastic. Except for the
particles that are exposed at the composite surface, the encapsulated particles do not come in
contact with water. Therefore, they are less likely to take part in transmitting water through the
composite.
Increasing flour content increases the chances of having flour particles against one
another, forming agglomerates which are encapsulated in the plastic (Figure 5(b)). This is
because lignocellulosic materials have strong intermolecular hydrogen bonding forces
between their particles. Therefore there is a ―critical flour content (CFC)‖ (Wang et al,
2005), at which these agglomerates form continuous clusters that span from one end of
the composite to the other end. These clusters serve as passages for water movement. It is
at CFC that the composite water uptake abruptly jumps to levels higher than those of
previous trends as water molecules have largely unrestricted movement. In this study, the
CFC possibly lies between 30 and 40% flour content for the WSFCs. More tests may be
needed to make similar conclusions about the CSFCs.
It is obvious why sv-WSFCs absorb more water than tv-WSFCs (about 15% more
moisture content for both sealed and non-sealed samples at equilibrium) (Figure 2). Due
to the hotpress-only method used in sv-WSFCs case, the samples made in this way had a
large number of wheat particle agglomerates which increased water conductivity. Many
of these agglomerates were even exposed to the surface. For tv-WSFCs, the probability of
having each flour particles encapsulated by the plastic was high because of
extrusion/mixing process. The encapsulation reduced water absorption. However, it is not
as obvious why the sealed samples took up more water than the unsealed samples (Figure
2). Sealed samples had about 5% more moisture content than the unsealed ones in both
the sv and tv samples at equilibrium. The results are quite the opposite of what the sealing
was intended to do. It is possible the sealing merely magnified surface flaws on the
composites instead of healing them. Further surface analyses would be needed for a
meaningful explanation.
The outer ring-CSFCs absorb more water than the whole CSFCs (which constitute
both the outer ring and the pith) (Figure 3). A major reason could be the differences in
chemical nature of the two fillers. The outer ring is rich in fibres. These fibres have a
greater concentration of cellulose compared to pith (Table 1). Cellulose has a high
concentration of OH groups that make it hydrophilic. It is true that both the outer ring
only and whole stalk have these hydrophilic fibres. However, they are more concentrated
in the outer ring composites given the same flour content.
There seems to be declining water content at higher flour contents in Figure 3 (b) for
what is supposed to be an equilibrium range. This may further signify the influence of
thermal degradation of the flour which results in more substances dissolving and leaching
out of the composites, reducing the weight of specimens.
There is a substancial difference between the water absorption of CSFCs and WSFCs.
Compared to composites of other lignocellulosic fillers, wheat stalk based composites
have been observed to absorb more water (Panthapulakkal and Sain, 2007 and Patil et al,
2000). This observation has been associated with the loose crisscrossed structure of
cellulose and lignin in wheat straw which allow for easier penetration by water
molecules.
The diffusion coefficients, which measure the ability of the water molecules to
penetrate the composites, are given in Table 3. These coefficients were calculated using
equation 6 developed by Shen and Springer (1976 ), where Mt is the moisture content at
time t, M∞ (taken to be the average of the last three moisture content values for each
specimen) is the moisture content at the equilibrium, D is the diffusion coefficient and h
is the thickness of the sample:
(a) (b)
(c) (d)
Figure 2. Moisture absorption properties of WSFCs: (a) sv- sealed-WSFCs (b) sv-non- sealed-WSFCs
(c) tv -sealed WSFCs (d) tv-non-sealed-WSFCs.
(a) (b)
Figure 3. Moisture absorption properties of CSFCs, (a) whole CSFCs (b), Outer ring-CSFCs.
(6)
Equation 6 can be rearranged to
(7)
(a) (b)
(c) (d)
Figure 4: SEM pictures of: (a), a cross-section through a corn stalk, (b) cross-section through
a wheat stalk, (c) particles of untreated corn stalk flour (d) particles of untreated wheat stalk flour.
Figure 5. A simplified cross-section through a straw flour plastic composite where black squares
represent an area covered by flour and white squares represent an area covered by plastic: (a), low flour
content, below CFC (b) high flour content above CFC
The values of D can be obtained from the slope of the linear component of the graphs of
Mt against the square root of time t. The graphs in Figures 2 and 3 reveal that most of the
composites did not reach equilibrium between 0-20% flour content. Therefore without a more
reliable M∞, the D values were not calculated at this range of flour content. In all cases,
diffusion coefficients increased with increasing flour content. As expected, the wheat sv-non-
sealed WSFCs provided little resistance to water flow, registering the high D values. What
was unexpected was that the outer ring-CSFCs registered similar values of D to the sv-non-
sealed WSFCs.
Table 3. Diffusion coefficients of selected specimens (mm2/s).
Specimen Flour content (%)

30 40 50
tv-non-sealed WSFCs 7.352 ×10 -12 1.021×10 -11 1.416×10 -11
sv-non-sealed WSFCs 2.813×10 -11 3.260×10 -11 4.117×10 -11
Whole CSFCs 8.474×10 -12 1.233×10 -11 1.540×10 -11
Outer ring CSFCs 1.883×10 -11 3.108×10 -11 5.357×10 -11
Impact Properties
The impact properties of the composites are shown in Figure 6. There were no significant
differences between parameters compared within both CSFCs and WSFCs. CSFCs were more
brittle especially at lower flour contents compared to WSFCs. The impact strengths of all the
composites rapidly declined with flour content but began to level off between 20-30% flour
content. Polymer molecular chains have the ability to uncoil under load, absorbing energy in
the process. Adding stiffer fillers like the flour in this case reduces the polymer chain
mobility, hence the capacity of the composites to absorb energy. Also, there are normally
stress concentrations at the ends of the fillers, in areas of poor interface, and in regions where
fillers contact one another. The formation of these stress concentrations make materials
brittle.
(a) (b)
Figure 6. Impact properties of (a) tv-WSFCs vs. sv WSFCs (b) Outer ring CSFCs vs. whole CSFCs.
(a) (b)
Figure 7. SEM images of impact fracture surfaces of (a) CSFCs and (b) WSFCs.
The SEM pictures of the fracture surfaces of both CSFCs and WSFCs at 20% flour
content are shown in Figure 7. Both pictures reveal rough fracture surfaces, some fractured
flour particles and indentations left by flour particles as they dislocated from the matrices.
These kinds of morphologies increase stress concentrations and partly explain the rapid
decline of fracture strengths upon adding the flour.
Tensile and Flexural Properties
Tensile and flexural properties of WSFCs have been reported elsewhere (Thamae and
Baillie, 2009). Untreated milled whole corn stalk flour contain a variety of components:
fibres, woody components of the outer ring (which contain fibres) and pieces of pith (Figure 4
(c)). The irregular shapes of some of these particles do not maximize interfacial surface area.
That, together with the weak interfacial chemical bond between the flour and the matrix may
have resulted in declining tensile strengths of untreated CSFCs as shown in Figure 8 (a).
Unlike tensile strength, which normally registers at higher forces when the interface fails,
tensile modulus is less dependent on the interface, depending more on the filler content. The
tensile modulus of untreated CSFCs improved by about 50% from 0 to 20% flour content and
leveled off from then (Figure 8 (b)). The leveling might be due to agglomeration of flour
particles at a higher content which opposed further improvement in modulus.
(b)
(a)
(c)
(d)
Figure 8. Tensile and flexural properties of CSFCs and the effect of silane and NaOH treatment.
Flexural strength, a combination of tensile and compressive strengths (Pak and Case,
1997), improved by 31% with flour content from 0 to 30% flour content (Figure 8 (c)). The
improvement could be a reflection of the compressive component of the flexural strength
which is not interface dependent and responds to flour content. However, there is a decline of
the flexural strength at 40-50% flour content, possibly signaling the agglomeration of
particles. Flexural modulus improved the most, nearly doubling at 40% flour content before
declining at 50% content (Figure 8(d)).
In all cases, it can be seen that treating the flour with NaOH or triethoxyvynilsilane did
not improve any of the properties. This fact may say more about the selected processing
methods than the chemical treatments used. A single-screw extruder used in making the
composites is more of a conveyor of molten polymers than a mixer of polymers and fillers
together into composites. Thus without proper mixing, chemical treatments may have made
little differences in terms of improving the interface. The SEM pictures of the tensile fracture
surfaces of the both NaOH and silane treated CSFCs show loosely held corn flour particles
within the matrix and eveidence of particle pullout (Figure 9 (a-b)). Interestingly, the NaOH
treatment of the flour resulted in agglomeration of the woody corn particles, with pith acting
as a glue (Figure 9 (c)). The treatment also modified the structure of the parenchyma cells in
the pith, largely destroying the shapes of its cells (Figure 9 (d)), compare with Figure 4(c))
(a) (b)
(c) (d)
Figure 9. SEM picture of tensile fracture surface of (a) NaOH treated CSFCs (b) Silane treated CSFCs
(c) NaOH treated corn stalk flour particles (d) portion of NaOH treated corn stalk pith.
CONCLUSIONS
The outer ring CSFCs absorbed more water than the whole CSFCs. These two
composites did not have significant differences in their impact properties. Therefore whole
CSFCs may be a preferable choice since it is less costly to process.
sv-WSFCs resulted in much more water absorption than tv-WSFCs, that is, about 15%
more moisture content for both sealed and non-sealed specimens at equilibrium. Therefore
tv-WSFCs would be a more preferable option in terms of moisture absorption but less
affordable for use in developing countries.
Sealed WSFC samples had about 5% more moisture content than the unsealed ones in
both the sv and tv samples at equilibrium. Thus the composites would be better without film
sealing.
None of the treatments improved the tensile or flexural properties, probably due to poor
mixing governed by the selected processing methods.
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Chapter 8
GREEN COMPOSITES BASED ON BIODEGRADABLE

POLYMERS AND WOOD FLOUR
R. Scaffaro, M. Morreale, G. Lo Re, A. Maio

and F. P. La Mantia
Università di Palermo, Dipartimento di Ingegneria Chimica dei Processi e dei Materiali,
Viale delle Scienze, 90128 Palermo (Italy)
ABSTRACT
The use of natural-organic fillers for polymer composites is mainly due to
environmental and economical reasons. In fact, natural-organic fillers are usually cheap
and easily available (often coming from wastes), are less abrasive to processing
equipments, give less hazard concerns regarding health of production workers, provide a
fundamental help in reducing the use of non-renewable sources throughout the life-cycle
of the material. On the other hand, in order to achieve fully environmental-friendly
products, a complete biodegradability is required. This can be obtained only by using
polymer matrices which are biodegradable as well. One of the most widely known is the
Mater-Bi® family.
In this work, we have investigated on the preparation and characterization of Mater-
Bi®/wood flour green composites. Since the actual composition of the Mater-Bi® grade
used was proprietary, statistical analysis was carried out in order to individuate the most
influential processing variables and their optimal values. Mechanical, rheological and
morphological tests were carried out as well. Based on these results, another Mater-Bi®
grade with the most suitable amount of wood flour was tested, and the analysis was
focused mainly on the determination of the best processing technique. The investigation
was completed by performing biodegradation tests which allowed assessing the actual
biodegradability of the prepared green composites.
158 R. Scaffaro, M. Morreale, G. Lo Re et al.
INTRODUCTION
The use of polymer composites attracted considerable attention over the last decades,
because of the very wide range of properties achievable through the addition of fillers to
commodity polymer matrices. More recently, increasing attention has been focused on
polymer composites filled with natural-organic particles. These include several fillers coming
from wood, hemp, jute, kenaf, rice, maize, tapioca, sago, olives, etc [1-15]. There is a number
of reasons justifying their utilization, among which the reduced cost and specific weight of
the fillers (often coming from wastes), lower health hazards for the production workers in
case of inhalation, aesthetic improvements, and several environmental issues regarding
basically the reduction in the use of oil-based resources throughout the entire life-cycle of the
product [5, 16-18] and the inner biodegradability of the fillers. The applications can be
numerous and interesting, including panels, automotive components, packaging, furnishing,
decking, etc. [19-22]. However, a main environmental drawback is that commodity polymers
are not usually biodegradable. Therefore, during the last years, a straightforward solution has
been found in replacing non-biodegradable polymer matrices (like polyethylene,
polypropylene, polystyrene, etc.) with biodegradable ones [23]. These composites are often
referred to as ―green composites‖ and the biodegradable matrices used include polyesters,
polyvinyl alcohol, polyester amides, polyhydroxyalcanoates, starch and its derivatives,
polylactic acid, etc. [19, 24-26]. Starch and derivatives, in particular, find interesting
commercial applications, like the Novamont‘s Mater-Bi® family. These polymers are usually
based on modified starch and synthetic polymers (aliphatic polyesters in prevalence) [18, 23,
26, 27]. The mechanical properties of Mater-Bi and related composites can be interesting but
variable according to the type of Mater-Bi used, the filler, its weight percent and the
processing methods [23, 27-35]. In particular, it can be quite complicated to get a reliable
knowledge of the relationships between processing variables and final properties in
multiphase systems like Mater-Bi/natural organic filler composites, prior to preparation and
processing. It would be therefore very useful to implement a reliable tool for investigating the
properties of a polymer composite, in order to obtain data which can be considered exact at a
chosen confidence level [36]. This can be, in turn, useful to build new predictive models. In
the scientific literature, some examples of statistical approaches in the investigations of the
properties of Mater-Bi/natural organic fillers are available. Johnson et al [35, 37] carried out
mechanical tests on Mater-Bi/myscanthus composites and processed the collected data
through a two-level factorial design and Box-Cox transformations [38], in order to correlate
the impact strength of the composites and the main processing variables like temperature,
processing speed, filler content and filler size. The full factorial design, although disturbed by
the presence of strong noise, revealed that interaction existed between temperature and speed,
and Box-Cox transformations allowed stating that temperature was the most important
variable, followed by processing speed. Morreale et al [36] also implemented a two-level full
factorial design with the aim to assess the statistical significance of the main processing
variables (filler size, filler content, presence of humidity, processing temperature and speed)
on mechanical properties and morphology of Mater-Bi/wood flour composites [36]. The
variables were chosen as the main that influence film and panel production, and the study
allowed evaluating the critical properties and verifying the validity of some theoretical
predictive models.
Green Composites Based on Biodegradable Polymers and Wood Flour 159
Another major issue is the actual biodegradability of these materials. The first studies on
Mater-Bi by Bastioli [27] indicated that starch promotes the biodegradation under composting
conditions. As for Mater-Bi based ―green composites‖, Di Franco et al. [26] conducted
biodegradation tests (in soil and biotic aqueous media) on Mater-Bi/sisal composites, finding
a good fiber stability and a weight loss up to 50% (in soil). More soil burial tests were
performed by Alvarez et al. [39], confirming a potential biodegradability in landfills and
finding a significant interaction between fibers and matrix, which resulted in a reduced water
absorption; nevertheless, for longer burial times, the composites endured higher weight
losses, due to the fact that fibers may have acted as support for the bacterial growth. The role
of bacterial activity is fundamental, as well as the actual environmental conditions.
Rutkowska et al. [40, 41] tried therefore to study the degradation of Mater-Bi under different
environments like sea or sewage sludge, reporting a fast and complete biodegradability after
four weeks. As for the composites, Scaffaro et al [23] prepared several Mater-Bi/wood flour
composites by different processing techniques and investigated on their biodegradation in
active sewage sludge, finding also the relationships between the main processing variables,
the environmental conditions (summer or winter) and the actual biodegradation.
In this chapter, a two-level full factorial design of experiments will be applied in order to
assess the critical processing variables for Mater-Bi/wood flour green composites. In a second
part, the actual biodegradation processes of the green composites will be investigated.
THEORETICAL BACKGROUND
The two-level full factorial model used to interpret the data obtained by changing the
values of the processing variables was built according to the method described by Box and
Hunter [38]. The main goal of this kind of analysis is to provide a powerful tool for
evaluating the effects of several operating variables on the main observed properties of the
system, the contribution of each variable, the interactions between the variables and thus their
optimum combinations.
Given
P = P (x1, x2, …, xn) (1)
a generic system property, P, depending on (x1, x2, …, xn) variables, it can be described by
selecting two levels for each of the n variables, obtaining 2n combinations to be taken into
account in the experimental analysis. The combinations are thus summarized in a ―matrix of
contrasts‖, where each row represents a specific conditions set, while the columns allow
determining the ―main effect‖ of the variable and the interaction between the variables
themselves.
In detail, the ―main effect‖ (ME) of a variable is the difference between two averages
(one calculated by considering the superior level of the variable, the other by the inferior
level) and allows appreciating the influence of every single variable on the selected property
(keeping the other variables constant): in other words, the main effect of the xi variable
provides the increment that the selected ―P‖ property undergoes upon changing the value of
the variable from the inferior to the superior level.
For the statistical calculations, the matrix of contrasts needs to be filled with ―+‖ and ―-‖
signs, which represent, respectively, the superior and inferior level assumed by the considered
variable. Finally, the last column of the table reports the actual numerical values that the ―P‖
property assumes for each of the 2n conditions sets.
It is possible to demonstrate that the main effect, ME, of the generic xi variable can be
calculated as the algebraic sum of the values ―P‖ assumes in the previous column, each taken
as positive or negative according to the sign appearing in the table column corresponding to
that specific variable. In symbols:
k
ME = Mi (2)
i 1
Where i = (1,…, k) are the selected sets of conditions (k = 2n) and Mi is the average value of
the selected property. Indeed, the result should be further divided by four, because of the
definition itself of ME as the difference between two averages.
However, an accurate analysis cannot rely just on the calculation of the main effects and
their significance. Such an approach could be misleading, since the variables can interact
between themselves, with important consequences on the system behavior. Therefore, it is
fundamental to calculate also the significance of possible interactions; this can be performed
by including the column of interactions in the table of contrasts. Each interaction column can
be obtained by simply multiplying the sign arrays of the corresponding variable columns, e.g.
the x1-x2 interaction column is obtained by multiplying, two-by-two, the signs of each array
of x1 and x2 columns.
Defining as di the difference between the highest and the lowest value the ―P‖ property
assumes in the generic i experimental condition set, the estimated experimental run variance
s² is calculated as follows:
s² = ∑ (si²/g) = ∑ (di²/g) (3)
where g is the number of degrees of freedom. This allows calculating the mean variance of
the effect, VE, as follows:
VE = (1/g+1/g) s² (4)
Defining the ―Standard Error of the Effect‖, SE, as
SE = VE (5)
the significance of a variable (or of an interaction) can be determined by calculating the

ME/SE ratio, which is distributed according to a t distribution with g degrees of freedom.
Thus, by selecting a proper confidence level (e.g. 95%), a Student‘s t-test allows determining
the statistical significance of the variable (or of the interaction) at the chosen confidence
level.
Finally, it is important to point out that, in order to assure validity to the statistical model,
the tests must be conducted randomly.
EXPERIMENTAL
A Mater-Bi® grade, produced by Novamont (Italy), was used in this work. Its measured
melt flow index (at 150 °C under 5 kg load) was equal to 49 g/10 min and it was used for both
the implementation of the statistical model and the assessment of the biodegradation rates.
However, the composition is proprietary, so no further data are available.
The wood flour, indicated throughout the chapter as SDC, was kindly supplied provided
by La. So. Le. (Italy). Its main characteristics are: average particle diameter 350-500 µm,
aspect ratio L/D ≈ 3.9.
For the validation of the statistical model, the materials were processed by a Brabender
(Germany) PLE330 batch mixer, and prepared by changing three process variables, i.e.
mixing temperature, filler content and mixing speed, between two possible levels (inferior
and superior). In particular, lower and upper levels were, respectively, 120 °C and 140 °C, 15
wt% and 30 wt%, 20 rpm and 30 rpm. Mixing was followed by compression molding in a
Carver (U.S.A.) laboratory press set at 140 °C for about 3 minutes, in order to obtain the
samples for the following IZOD impact tests (ASTM D256), using a Ceast (Italy) 6545
machine, and tensile tests (ASTM D882) for the determination of the elastic modulus, using
an Instron (U.S.A.) 3365 universal testing machine.
Taking into account the results of the statistical model, the specimens for biodegradation
tests were prepared via different techniques such as, of course, mixing (in the same Brabender
PLE330 mixer), extrusion in a single-screw Brabender extruder, equipped with a slit die and a
Collin (Germany) calendering system and extrusion in a OMC (Italy) twin-screw extruder.
The materials coming out of these devices were grinded on line and compression molded for
forming the specimens, except for single-screw extruded specimens that were directly cut off
the calendered films. Some of the granules coming from the twin-screw extruder were also
fed to a Sandretto (Italy) injection molding machine, in order to produce injection molded
specimens. All the samples were subjected to biodegradation tests, based on weight loss
measurements after immersion in an active sewage sludge reactor. Before immersion, the
samples were dried at 60°C for approximately 20 h, weighing and surface roughness
measurements using a Zeiss (Germany) Handysurf E35 apparatus, according to the methods
described by Rosa et al [42]. Weight loss measurements were performed every week, over a
period of 16 weeks, both in the winter and in the summer season, in order to compare the
effect of the environmental temperature on the biodegradation kinetics, In particular, the
average temperature was 25 °C and 12 °C, respectively. Percent weight variations were
calculated according to the following:
% WL = 100 (Wt – W0)/W0 (6)
Where Wt is the measured weight at t time and W0 is the initial weight. The data
reproducibility was satisfactory (max. +/- 8% in the summer, +/- 4% in the winter). In fact,
the process parameters of the plant (not reported here for sake of conciseness) although being
slightly different from winter to summer, were substantially homogeneous within each
season. It is important to point out that weight loss measurements were calibrated by using
samples immersed in distilled water for the same time duration. Furthermore, in order to
assess the effects of biodegradation on the mechanical properties, tensile tests were performed
on the specimens extracted from the active sewage sludge, by using an Instron 3365 universal
testing machine. Data reproducibility was adequate (max. scattering +/- 7%). Finally, SEM
micrographs were taken by means of Philips (Netherlands) ESEM XL30 apparatus.

Statistical Analysis
The analysis was performed adopting a 23 full factorial design and taking the impact
strength as reference property. In fact, impact strength is often a critical property in
wood/polymer composites [43]. The three monitored variables were filler content, mixing
speed and mixing temperature. The 8 experimental conditions and the average values of
impact strength are summarized in Table 1.
The execution of the analysis of variance and the Student‘s t-test allowed determining
that the minimal significance value (with 8 degrees of freedom) is 2.3, therefore, based on the
calculations performed on the matrix of contrasts, by considering the main effect and the
standard error of the effects as described above (not reported here in detail, for sake of
brevity), all the three variables proved to be significant.
Table 1. The 8 investigated experimental conditions (impact tests).
Filler wt% Temperature, °C Mixing speed, rpm IS (J/m) max min

A 15 120 20 74 81 70
B 15 120 30 90 94 85
C 15 140 30 110 115 107
D 30 140 30 99 107 94
E 30 140 20 61 62 57
F 30 120 20 66 74 61
G 15 140 20 70 74 58
H 30 120 30 72 73 70
Table 2. Matrix of contrasts.
c T v cT cs Ts IS (J/m)
A - - - + + + 74
B - - + + - - 90
C - + + - - + 110
D + + + + + + 99
E + + - + - - 61
F + - - - - + 66
G - + - - + - 70
H + - + - + - 72
Based on the experimental results, it is also possible to prepare the matrix of contrasts
(Table 2), according to the methods previously described. In particular, filler content is
indicated as ―c‖, mixing temperature as ―T‖ and mixing speed as ―s‖; ―cT‖, ―cs‖ and ―Ts‖
represent the binary interaction between the corresponding variables.
Figure 1. Effects of filler content, mixing temperature and mixing speed on the impact strength.
A graphical representation is provided in Figure 1, where the highest the slope, the higher
is the statistical weight of the processing variable. In particular, a strong significance is
observed for filler concentration and mixing speed and, in particular, it is better to use lower
concentrations and higher mixing speeds. Therefore it is strongly advised, on the basis of the
statistical model, to operate at 15 wt% filler content and 30 rpm. However, also temperature
is statistically significant, in particular by improving the impact strength, thus the optimum
set of conditions includes a mixing temperature equal to 140°C.
With regard to the variable-variable interactions, it was found that no significant
interaction is present, except for a moderate significance of the speed-temperature one. This
can be also observed in Figures 2-4, which are the binary interaction plots for the couplings
concentration-temperature, concentration-speed and speed-temperature, respectively. In the
concentration/temperature (Figure 2) and concentration/speed interaction plots (Figure 3) the
lines are almost parallel, i.e. there is no interaction. Differently, in the case of the speed-
temperature plot (Figure 4), the lines are not parallel indicating a weak interaction between
the two variables. Actually it is less important as the intersection would occur just out of the
investigated range.
It can be concluded that the behavior of the investigated system is fully described by the
3
2 full factorial model, which allows establishing a statistical significance of concentration,
temperature and speed, in particular an optimum set of conditions as follows: filler weight% =
15%, mixing speed = 30 rpm, mixing temperature = 140°C.
A similar 23 full factorial design was performed also with regard to the elastic modulus.
The variables were, once more, filler concentration, mixing speed and mixing temperature,
with the same inferior and superior levels as before. The 8 sets of experimental conditions
and the results of the tensile tests are reported in Table 3.
The matrix of contrasts is reported in Table 4, where the symbols have the same meaning
as above.
The calculations on the matrix of contrasts (determination of the main effects and the
standard error of the effects, not reported here in detail for sake of conciseness) proved that,
of the three variables, only concentration is statistically significant. In particular, the increase
of filler content has a positive influence on the elastic modulus. A graphical representation is
reported in Figure 5.
Figure 2. Concentration/temperature binary interaction plot.
Figure 3. Concentration/speed binary interaction plot.
Table 3. The 8 investigated experimental conditions (tensile tests).
Filler wt% Temperature, °C Mixing speed, E (MPa) max min

rpm
A 15 120 20 470 480 462
B 15 120 30 446 385 540
C 15 140 30 537 587 451
D 30 140 30 760 790 691
E 30 140 20 706 727 631
F 30 120 20 636 653 609
G 15 140 20 435 509 417
H 30 120 30 622 679 602
Figure 4. Speed/temperature binary interaction plot.
Table 4. Matrix of contrasts.
c T v cT cs Ts E (MPa)
A - - - + + + 470
B - - + + - - 446
C - + + - - + 537
D + + + + + + 760
E + + - + - - 706
F + - - - - + 636
G - + - - + - 435
H + - + - + - 622
Figure 5. Effects of filler content, mixing temperature and mixing speed on the elastic modulus.
With regard to the variable-variable interactions, it was found that no significant

interaction is present in the investigated ranges of the variables (Figures 6 and 7), except for
mixing speed and temperature, as shown in Figure 8, where the lines are clearly not parallel
and an intersection occurs at approximately 124 °C. However, it should be observed that,
according to the same plot, the most favourable conditions are those represented by the higher
speed and the higher temperature, i.e. 30 rpm and 140°C, which were also the optimum
values with concern to the impact strength.
Figure 6. Concentration/temperature binary interaction plot.
Figure 7. Concentration/speed binary interaction plot.
The only discrepancy between the results of the two statistical designs regards the filler
concentration. In fact, according to the one regarding impact strength, concentration should
be kept at its lowest value (15 wt%), while the highest level (30 wt%) should be used in order
to achieve the optimum conditions for higher moduli. However, in this specific case, we have
chosen to prefer impact strength (as pointed out previously), thus the optimum conditions set
appears to be: filler content = 15 wt%, mixing speed = 30 rpm, mixing temperature = 140°C.
These values were, therefore, chosen as the reference processing parameters for the following
section, regarding the preparation of different systems by different processing techniques, and
the execution of the biodegradation tests.
Figure 8. Speed/Temperature binary interaction plot.
Biodegradation tests
It should be pointed out that compression molded specimens, prepared by using the
material coming out of the batch mixer, were obtained via two different ways: in the first
case, a cellulose-based sheet was used as non-stick medium between the material and the
mould plates, thus they were labelled ―cellulosic‖, while in the second case a teflon sheet was
used and the samples consequently labelled. This was done in order to assess the influence of
different surface smoothness.
In order to properly comment the results, it is better to take into account separately the
unfilled polymer and the composites.
Table 5 reports the weight losses for the unfilled polymer samples after 4, 12 and 16
weeks of immersion in the active sewage sludge during winter [23] for all the materials. The
symbols in Table 5 will be further used in the rest of the chapter.
It can be observed that the polymer is biodegradable up to a maximum value of 43.9% for
the MC samples. Other processing techniques led to slightly lower biodegradation, especially
in the case of IM samples. These results can be explained considering the surface roughness
of the different obtained samples, which we investigated in our previous works [23] and is
reported in Figure 9.
Table 5. Weight losses of the unfilled samples (winter).
Processing technique Week 4 Week 12 Week 16

Mixer-Cellulosic (MC) 1.9 29.8 43.9
Mixer-Teflon (MT) 0.3 14 30.5
Single Screw (SS) 1.3 13.3 28.9
Twin Screw (TS) 2 20.4 38.6
Injection Molding (IM) 0.8 5.7 16.3
Figure 9. Average surface roughness of the neat samples.
Table 6. Weight losses of the unfilled samples (summer).
Processing technique Week 4 Week 12 Week 16

Mixer-Cellulosic (MC) 7.2 52.7 71.1
Mixer-Teflon (MT) 7.9 42.4 55
Single Screw (SS) 5 57.6 73
Twin Screw (TS) 2.9 18.7 28
It can be easily observed that the higher the surface roughness, the higher the
biodegradation rate the material underwent. This is likely to be due to the fact that higher
surface roughness provides higher surface extension and thus easier support for the bacteria to
attack the material, start and grow the biodegradation process. In fact, MT samples, although
being virtually the same as MC ones, provided significantly lower biodegradation rates; the
only difference between the two materials is the overall surface roughness, therefore this
parameter has a significant influence on the biodegradation process. A contradiction may
seem to arise if comparing the roughness values of IM, SS and MT to the corresponding
weight loss values. This was explained by considering the way how the automatic equipment
measures the average surface roughness, underestimating the presence of deep and random
cavities (as the ones which were detected on the surface of the SS samples) which of course
are not neglected by the bacteria, and by taking into account that surface roughness cannot be
the only morphological parameter to influence the bacterial attack (and thus the
biodegradation rate). In fact, morphological analysis showed that the bulk morphology of IM
samples was significantly improved in comparison to MT samples, probably due to the high
pressure achieved in the mould, and thus it can provide higher resistance to the bacterial
attack and penetration [23].
The weight losses of the samples treated during summer [23] are reported in Table 6.
The conclusions which can be drawn are quite similar to those regarding the winter
season test. The most interesting difference is the significantly higher biodegradation rates
observed. Weight losses were almost doubled, with a maximum of about 70%. This
remarkable effect is to be attributed to the increase of environmental temperature during
summer which, in turn, increases the bacterial metabolism and thus the presence of the
enzymes which hydrolyze the organic substrate needed for the metabolism itself.
The weight loss plots for the composites as a function of immersion time are shown in
Figures 10 and 11 for the winter and the summer season, respectively, while surface
roughness values are reported in Figure 12.
It can be observed that, during the winter season, weight losses are significantly higher
than in the case of the corresponding neat polymer samples immersed in the same conditions.
The trends are similar to the ones observed in Table 5 for the unfilled samples: the higher the
surface roughness, the higher is the biodegradation rate. The exception represented by IM
samples is due, in complete analogy to the case of the unfilled samples, to the way the
average surface roughness is measured by the automatic equipment, and to the higher packing
degree achieved by injection molding, thanks to the higher pressure attained in the mold.
Figure 13 a-d show some examples of the bulk morphologies of MT, SS, TS and IM samples,
respectively, obtained by Scanning Electron Microscopy. It can be easily observed how MT
and SS samples show uneven, poorly packed morphologies.
Figure 10. Weight loss of the composites immersed in active sludge during winter.
Figure 11. Weight loss of the composites immersed in active sludge during summer.
Figure 12. Average surface roughness of the SDC composites.
a b
c d
Figure 13. a-d. Bulk morphology micrographs of MT (a), SS (b), TS (c) and IM (d) samples.
The other important result regards the comparison between summer and winter. During
the summer period, the biodegradation rates are significantly higher and, in the case of TS
and MC composites, weight loss in 16 weeks reaches a 100% level, i.e. complete
biodegradation is achieved in a 16 weeks time frame. This remarkable results points out that
the presence of wood flour enhances the biodegradability of Mater-Bi® by acting as a support
for the microbial growth, in agreement with previous studies [23, 26, 39]. Furthermore, the
increase of the weight loss (and thus, biodegradation) rates are likely to be due also to the
voids and interstices at the matrix-filler interfaces, which can be observed also in the SEM
micrographs above reported.
CONCLUSION
In this chapter, an extensive study on biodegradable polymer/wood flour composites has
been presented. The biodegradable polymer belonged to the Novamont‘s Mater-Bi® family
and the study was carried out on two consecutive stages. The first stage included the
implementation of a full factorial statistical design, which allowed assessing, on the base of
preliminary measurements, the optimum set of conditions for production of the composites
through a batch mixer. The statistical model was described and validated, and it was shown
how such a model can be a powerful instrument to investigate, in an objective way, the
relationships between composite properties and processing variables; furthermore, it allows
overcoming the problems related to experimental noise when performing experiments which
involve a large number of variables, allowing to find the optimum set of variables for the
achievement of a selected property (e.g. elastic modulus, impact strength, etc.) of the product.
Once validated the model, samples were prepared through batch mixing, by setting the
processing variables to the values obtained by the statistical model, and they were directly
compared to the ones produced by different processing techniques. The comparison was
based on the determination of the actual biodegradability of the unfilled polymer and the
composites, performed through weight-loss measurements on sample immersed in a real
biodegrading environment such as active sewage sludge. It was found that biodegradation
depends significantly on the environmental conditions (faster in summer) and that the
composites achieved higher biodegradation rates than the unfilled polymer. This is likely to
be due to wood fibers, which provided a support for the bacterial attack and growth, and also
led to changes of the surface and bulk morphologies. As regards the processing technique
selected, this showed to exert a significant influence on the biodegradation, because of the
direct effects it can have on the surface and the bulk morphologies. In particular, injection
molding, also due to the higher pressure achieved during the process, led to higher resistance
to better, more compact bulk morphologies and thus to improved resistance to bacterial
attack, while twin-screw and mixer processed samples experienced significantly higher
biodegradation rates.
ACKNOWLEDGMENTS
The Authors wish to thank Novamont (Novara, Italy) for providing the material and
technical support, and AMAP (Palermo, Italy) for providing the access to the active sewage
sludge reactor.
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Chapter 9
MECHANICAL PROPERTIES AND MOISTURE

ABSORPTION BEHAVIOUR OF CELLULOSE-FIBRE
REINFORCED POLYMER COMPOSITES
H. Alamri, A. Alhuthali and I. M. Low

Centre for Materials Research, Department of Imaging & Applied Physics, Curtin
University of Technology, GPO Box U1987, Perth, WA 6845, Australia.
ABSTRACT
Epoxy and vinyl polyester matrix composites reinforced with cellulose fibre were
fabricated and characterized with respect to their flexural, fracture and impact properties.
Reinforcement of the polymer by cellulose fibres resulted in a significant increase in the
strain at failure, fracture toughness and impact toughness but only a moderate increase in
flexural strength and flexural modulus. Moisture absorption of the composites in water
was analysed. The kinetics of sorption-diffusion process was investigated and typical
kinetic parameters D, k, and M were determined. The use of nano-clay in the composites
was effective in imparting a substantial reduction in water permeability due to the
tortuous path presented by high aspect ratio clay. Diffusion models for the water uptake
behaviour in polymer composites are reviewed. The effect of accelerated exposure to
seawater on the flexural and impact properties of composites was also investigated. The
salient toughening mechanisms and crack-tip failure processes were identified and
discussed in light of observed microstructures.
Keywords: Cellulose fibres, epoxy resin, vinyl-ester resin, moisture absorption, fracture
toughness, crack-bridging.
176 H. Alamri, A. Alhuthali and I. M. Low
INTRODUCTION
When compared to their synthetic counterparts, natural fibers represent an
environmentally friendly alternatives by virtue of their attractive attributes which include
lower density, lower cost, non-toxicity, ease of processing, renewability and recyclability [1-
3]. Natural fibers used in polymer composites can lead to materials with high specific strength
and specific modulus because of their low density. Numerous researchers have recently
reported advances in the use of various natural plant fibers within polymeric composites [4-
8]. Natural fibres have been considered for use in high technology industries such as
transportation and construction as potential replacement materials for glass fibres, talc and
mica in composite materials and for forming structural components of low cost, low density,
high toughness [9, 10] and acceptable specific strength [11].
Growing environmental awareness and societal concern, the unsustainable consumption
of petroleum, and new environmental regulations have provided an increasing demand for
environmentally friendly materials with the desire to reduce the cost of traditional synthetic
fiber reinforced composites [1-3]. These conditions have created the need for new materials,
products and processes that are compatible with the environment. Attention is now focussed
on natural fiber or ―green‖ composites, which are composed of natural or synthetic resins,
reinforced with natural fibers. Inevitably, the driving force for this initiative is the automotive
industry due to the imposed pressures to produce vehicles that are lightweight, fuel-efficient
and emit less pollution [12, 13].
Hitherto, most studies of cellulose or plant fibre reinforced composites have been based
on thermoplastic resins [14-23] and very few on thermosetting resins [24-27]. In addition, the
method of mixing the fibres into the resins is usually based on mechanical blending or
stirring, a process which does not allow the incorporation of large volume fraction of fibres
and has the tendency to cause fibre damage, fibre agglomeration or generation of air-bubbles.
In this paper, we describe the fabrication, characterization and properties of epoxy
composites reinforced with recycled cellulose fibre (RCF). The potential use of these
composites as a material in marine environments was investigated through the study of
seawater soaking on the mechanical and fracture properties. The moisture absorption of these
composites in water was analysed. The kinetics of sorption-diffusion process was investigated
and typical kinetic parameters D, k, and M were determined. The use of nano-clay in the
composites was effective in imparting a substantial reduction in water permeability due to the
tortuous path presented by high aspect ratio clay. Various diffusion models for the water
uptake behaviour in polymer composites are reviewed. The effect of accelerated exposure to
seawater on the flexural and impact properties of composites was also investigated. The
micromechanisms of toughening and crack-tip failure processes were identified and discussed
in the light of observed microstructures.
MODELS OF MOISTURE DIFFUSION

Moisture absorption is determined by the diffusion coefficient and the boundary
condition at the surface of the material. In practice, water absorption or penetration into
polymeric composites is caused by three different processes [28, 29]. Firstly, water diffusion
Mechanical Properties and Moisture Absorption Behaviour… 177
inside the microgaps between polymer chains. Secondly, capillary transport takes place into
the gaps and flows at the interfaces between the fiber and the polymer. Thirdly, transport by
microcracks in the matrix [28]. The third mechanism increases during the wet/dry cycle
exposure [29]. Water diffusion into polymer composites has been examined in many studies.
In general, water diffusion models can be grouped into three categories [30].
In Fickian diffusion, the moisture absorption is independent of moisture concentration as
follows:
Mt ⎡ ∞
8 ⎡ − D (2n + 1) 2 π 2t ⎤ ⎤
= ⎢1 − ∑ exp ⎢ ⎥⎥ (1)
n ( 2n + 1) π
2 2
M∞ ⎣ ⎣ 4l 2 ⎦⎦
where M∞ is maximum moisture uptake, Mt is moisture uptake in time, D is diffusivity, 2 l is

the sample thickness, and n is the number of terms in the Prony series. When immersion
times at the primary stage of diffusion are short, the solution of equqtion (1) will give the
famous Ficks law of diffusion given as;
1
Mt ⎛ Dt ⎞ 2
= 2⎜ 2 ⎟ (2)
M∞ ⎝ πl ⎠
However, the Ficks law cannot be generalized because in some situations the diffusion
behavior is anomalous when the moisture mobility within the composite material does not
obey Ficks law coefficient or the exponent value. This case happens in glassy polymer [28].
In Ficks law the diffusion rate is small when compared to the polymer segment mobility.
However, in the non-Fickian state the viscosity of polymers, the microcrack and the leaching
from the composite can lead to higher rate in the polymer segment mobility when compared
with the diffusion rate into composites [28, 29].
Hence, other models consider those variables to obtain valid prediction for the diffusion
behavior. One of these models is Langmuir Model for diffusion (LMD). This model assumes
that the water molecules diffusion inside the composite material consist of mobile and bound
phases [30]. The equation of the Langmuir Model is:
Mt γ 8 α ∞
1 ⎧⎪ ⎡ π (2n + 1)⎤ 2 ⎫⎪
M∞
= 1−
γ +α
e −αt − 2
π α +γ
∑0 (2n + 1)2 exp⎨⎪− ⎢⎣ 2l ⎥⎦ Dt ⎬⎪ (3)
⎩ ⎭
In this model the key variables are the trapped molecules probability per unit volume (γ)
and the mobile molecules probability per unit volume (α). At equilibrium, when the trapped
molecules become mobile molecules, it will satisfy the relation:
γC∞ = α C∞ (4)
Another model is Diffusion with Time Varying Diffusivity (DTVD) which can be
obtained from the analogy with a relaxation modulus for viscoelastic model [30]. As is clear
from the comparison between this model and the Fick’s model, the time decreasing function
is replacing the diffusion coefficient constant:
⎧−(2n+1)2π2 ⎡ ⎤⎫
[ ( )]
∞
Mt 8 m
=1−∑ exp
⎨ ⎢D t + ∑ D t +τ e−t /τr
−1 ⎥⎬ (5)
0 (2n+1) π
2 2 2 0 r r
M∞ ⎩ 4l ⎣ r=1 ⎦⎭
More models have been proposed in order to study the kinetics of moisture absorption in
composite materials. The mobility of water molecules inside the composite material can be
considered analogically to the thermal conductivity through the materials [30]. By knowing
the matrix diffusivity (Dm) and the fiber diffusivity (Df) the transverse diffusivity is obtained
as moisture kinetics, given by following relations:
D 11 = D m (1 − ν f ) + D f ν f (6)
⎡ ⎤
⎛
B ν ⎞
2
⎢ 1− ⎜ ⎟ ⎥
D f
⎢ ⎜ π ⎟ ⎥
⎛
= ⎜1 − 2
ν ⎞
⎟ D ⎢π − 4 −1 ⎝ ⎠ ⎥
D D
f
+ m
× tan
⎜ π ⎟ ⎢ ⎥
22
⎝ ⎠
m
B D
⎢ ⎛
B ν
2
⎞ ⎛
B ν
2
⎞ ⎥
1− ⎜ ⎟ 1+ ⎜ ⎟
D f D fr
⎢ ⎜ π ⎟ ⎜ π ⎟ ⎥
⎣⎢ ⎝ ⎠ ⎝ ⎠ ⎦⎥ (7)
where D11 is the diffusivity parallel to the fiber (longitudinal direction), D22 is the diffusivity
normal to the fiber (transverse direction), and BD can be defined as:
⎛ ⎞
= 2⎜ D − 1⎟ (8)
B ⎜
m
⎟
D
⎝ D f ⎠
When the diffusivity of fibers is small compared with the diffusivity of the matrix, i.e. υf <
0.785, then equations (6) and (7) can be reduced to [30]:
D 11 = D m (1 − ν f ) (9)
⎛
= ⎜1 − 2
ν f
⎞
⎟ (10)
D 22 ⎜ π ⎟ D m
⎝ ⎠
Other researchers suggest a model for composites which depend on the analogy with the
shear stiffness [30]. In this model the parallel diffusivity (D11) follows equation (9) while the
diffusivity in transverse direction is given by:
1 + ξη ν f
D 22
= D m
1 − ην
(11)
f
Df
−1
Dm
η= (12)
Df
+ξ
Dm
where the diffusivity of the matrix is larger than the fibers (e.g. glass or carbon) and ξ is the
aspect ratio of the fiber.
In the Barrier Model, the diffusion in fillers is assumed perfectly parallel to the surface
[30] and the permeability of the composite is dependent on the aspect ratio of the filler which
consists of an average face length (L) and an average thickness (W). At a particular clay
loading, other parameters are related to the volume fraction of the polymer (υp) and the fibre
(υf). The result of this model is permeability ratio between the polymer (Pu) and the filler (Pf)
[30]:
Pf
Pu (
= υp + L
2w )υ f (13)
From the formulae previously described and assuming a uniform distribution of aligned
and exfoliated clay platelets, the Diffusion Model for Exfoliated Nanocomposite (DMEN)
can be written as follows:
Dn 1
= (14)
Dm ⎛ 2ξυ c ⎞ 2
⎜1 + ⎟
⎝ 3π ⎠
where Dn is the diffusivity of a nanocomposite at random orientation, and υc is the volume

fraction of the composite. When the nanocomposite is considered as intercalated
nanocomposite, it will consist of agglomerates with n platelets. The diffusion model (DMEN)
will have a similar formula when compared with Model (8) but it includes the number of
platelets n:
Dn 1
= (15)
Dm ⎛ 2ξυ c ⎞ 2
⎜1 + ⎟
⎝ 3nπ ⎠
EXPERIMENTAL PROCEDURE
Sample Preparation
Three sources of cellulose fibres were used for the reinforcement of epoxy resins and
vinyl-ester resins. The first was based on recycled cellulose fibre (RCF) paper supplied by
Amcor Pty. Ltd. (Canning Vale, WA). The second was based on newspapers (NPF) and the
third was based on cupboards (CBF). General purpose vinyl ester resin and epoxy resin
supplied by Fibreglass & Resin Sales Pty Ltd, Perth were used for the fabrication of the
composites. Commercial nanoclay (Cloisite 30B) supplied by Southern Clay Products in the
United States was used to investigate its effect on the moisture absorption behaviour and
impact fracture properties of cellulose-fibre reinforced polymer composites.
Two methods were used to fabricate the cellulose-fibre reinforced polymer composites.
The first method involved dispersing processed loose fibres of NPF and CBF of different
loadings (0 - 20wt%) within the polymer matrix. These samples of dimensions 25 mm × 25
mm × 6 mm were fabricated for the moisture absorption measurements. In order to
investigate the effectiveness of nanoclay in reducing the moisture absorption of the
composites, the samples were coated with a thin layer of nanoclay (1 & 5 wt%) dispersed in
either epoxy or vinyl-ester. The second method involved direct casting sheets of epoxy-
soaked RCF or NPF in a well-greased medium-density fibreboard (MDF) mould, followed by
a vacuum treatment for several minutes at room temperature to assist in the removal of any
air bubbles. Once this process was completed, a lid was placed on top of the mould and a 20
kg weight was used to ensure dense compaction of the RCF or NPF sheets within the epoxy
matrix. All the samples were subsequently cured overnight at room temperature. Typical
dimensions of the resulting composite plates were 200 mm × 200 mm × 8 mm and they were
subsequently machined to rectangular bars for flexural property measurements. Compositions
of the various samples are shown in Table 1 whilst typical microstructures showing the
dispersion of cellulose fibres within the epoxy matrix are presented in Figure.1
Figure 1. Optical and scanning electron micrograph showing a typical microstructure of sample
RCF440. (a) cross-section view (bright-field); and (b) planar view.
Table 1. Compositions of the various samples.
Sample RCF or NPF Sheets (wt%) Epoxy (wt%)

Pure Epoxy 0 100
RCF 30 70
NPF 30 70
As these composites have the potential for use in marine environments, the influence of
seawater on their mechanical properties was investigated by carrying out accelerated
absorption tests in which specimens of size 100 mm × 50 mm × 8 mm were soaked in
seawater at 60°C over a period of up to 2 weeks. The flexural properties (i.e. strength and
modulus) and impact properties (i.e. strength and toughness) of the samples before and after
soaking in seawater were measured.
Moisture Absorption Measurements
Rectangular bar specimens with dimensions of 20 mm × 20 mm × 6 mm were used for

the measurements of moisture absorption. The samples were soaked in tap water at room
temperature (23°C) and periodically removed for measurement of mass change using a digital
scale (AA-200, Denver Instrument Company, USA) with a 0.1mg weighing precision. The
following equation was used to determine the amount of moisture uptake or absorbed (MA) by
the specimens over a period of 51.5 days or 1236 hours;
MA = m −m
t D
× 100 (16)
m D
where MD is the dry mass and Mt is the mass of sample soaked for time t.
Diffusion Coefficient
The moisture absorption behaviour of polymer composites tends to follow the Fick’s law
of diffusion as follows:
Mt ⎡ ∞
8 ⎡ − D (2n + 1) 2 π 2 t ⎤ ⎤
= ⎢1 − ∑ exp ⎢ ⎥⎥ (17)
n ( 2n + 1) π
2 2
M∞ ⎣ ⎣ 4h 2 ⎦⎦
where M∞ is maximum water uptake, Mt is water uptake at time t, h is sample thickness, and D
is diffusion coefficient. At the linear relationship period of moisture diffusion, the solution of
Fick’s law will give the following equation:
1
Mt Dt 2
16 2 (18)
M h
From equation (18), the diffusion coefficient (D) can be determined found from the initial
slope of the plotted curve of water absorption percentage versus the square root of immersion
time, i.e.
2
Mt / M
D (19)
16 t /h
Porosity and Hardness Measurements
The apparent porosity (Pa) of a sample refers to the ratio of open pores in the material to
its bulk volume. The Australia Standard 1774.5, 2001 was used to determine the apparent
porosity of samples using the following equation:
P m m
m m
a
s
s
d
i
100 (20)
where Md is dry mass, Mi is mass of sample immersed in water, and Ms is the mass of soaked
sample.
A Rockwell hardness tester (Avery, Type 6407; England) was employed to investigate
the effect of NPF and CBF loading and water absorption on the hardness of these composites.
Values of Rockwell hardness were measured using the ‗H‘ scale or 1/8th inch steel ball
indenter at load of 100 kg.
Measurements of Flexural Properties
Rectangular bars of dimensions 60 mm 10 mm 8 mm were cut from the fully-cured

samples for three-point bend and Charpy impact tests to evaluate the flexural strength ( f),
flexural modulus (E f), fracture toughness (Kic), impact strength ( i) and impact toughness
(Gic). Flexural testing was carried using the 3-point bend configuration according to the
ASTM D790-03 standard [31] on a universal testing machine (Instron® 5500R) equipped
with an adjustable-span flexural test fixture. Testing was carried out utilising span-to-depth
ratio of 16 and a crosshead speed of 1.0 mm min-1. A minimum of three specimens of each
sample were used were used for both flexural and Charpy impact tests. In these
measurements, the samples were tested with the RCF sheets normal to the applied load.
Values of flexural strength, σf, were calculated as follows:
3Pmax S
f (21)
2bd 2
where Pmax is the maximum load, S is the span, b is the specimen width, and d is the specimen
depth. Values of flexural modulus, Ef, were calculated using the initial slope of the load-
displacement curve, ΔP/Δx, according to:
S3 P
Ef (22)
4bd3 x
For KIC measurements, a razor blade was used to initiate a sharp crack at the notch of
single edge notch beam (SENB) specimens (notch width approximately 2.5 mm) with the
values of KIC being determined using the methods described by Atkins & Mai [32]. The
values of KIC were measured for samples with sheets of RCF being normal to the applied
load.
Measurements of Impact Properties
Charpy impact measurements were conducted using a Zwick impact tester to measure the
response of a material to dynamic loading. Values of impact strength (σi) were from:
E
i (23)
A
where E is the impact energy to break a sample with a ligament area A.
For impact toughness (GIC ) measurements, a razor blade was used to initiate a sharp
crack at the notch of single edge notch beam (SENB) specimens (notch width approximately
2.5 mm) with the value of GIC being determined using the methods described by Plati &
Williams [33].

Effect of Cellulose Fibres on Porosity and Hardness
Figures 2 & 3 show that increasing the content of cellulose fibres resulted in an increase
in apparent porosity. The presence of more fibres probably caused an increase in the viscosity
of the resin, thus rendering the tendency of air-bubbles or pores to be trapped during mixing
of fibres in the polymer matrix. As a result the porosity of samples increased as more fibres
were introduced into the matrix. A closer examination of these results show that epoxy
composites (Figure. 2) appeared to exhibit a slightly higher values of porosity when
compared to vinyl-ester composites. The presence of pores in the composites is expected to
increase the likelihood of water uptake by virtue of reduced resistance to moisture diffusion
within the matrix.
Figure 2. Porosity of epoxy/NPF and epoxy/CBF composites with different loadings of cellulose fibres.
Figure 3. Porosity of vinyl-ester/NPF and vinyl-ester /CBF composites with different loadings of
cellulose fibres.
Results of Figures 4 & 5 show that increasing loading of both NPF and CBF resulted in a
decrease in hardness of the composite samples. This reduction in hardness can be attributed to
an increase in porosity as more fibres were dispersed in the polymer matrix. A further
softening was observed when the samples were soaked in water for about 52 days. The source
of this softening can be attributed to the plasticisation of the polymer matrix by prolonged
exposure to water. Alternatively, the swelling of cellulose fibres due to water exposure may
cause the hardness to decrease because fibre swelling can lead to micro cracking within the
brittle matrices such as epoxy resin and vinyl ester resin [34]. It is worth-noting that samples
with a low content of cellulose fibres are expected to have better interfacial bonding with the
matrix, low values of porosity and thus more resistant to water uptake. The reverse is true for
samples with high loading of cellulose fibres.
Figure 4. Effect of cellulose fibre loading and water absorption on the hardness of epoxy/NPF
composites.
Figure 5. Effect of cellulose fibre loading and water absorption on the hardness of vinyl-ester/NPF
composites.
Characteristics of Moisture Absorption
A Fickian diffusion behaviour was observed for all the samples immersed in water for a
prolong period. Water absorption occurred w rapidly in the beginning of exposure of the
matter with water, but as time progressed the rate of moisture absorption slowed down until it
reached the point of equilibrium. Figures 6 & 7 show the moisture absorption behaviour for
epoxy composites containing various loading of NPF and CBF. As would be expected, water
absorption increased with an increase in content of cellulose fibres. It is worth-noting that the
rate of water uptake was quite rapid in the first 225 hours, thereafter, the rate levelled off
gradually. A similar behaviour in moisture absorption was displayed by vinyl-ester
composites (Figures 8 & 9) although the rate levelled off at a shorter time of 120 hours. These
results concur with the findings of others [35-37] who also investigated the moisture
absorption behaviour of polymers reinforced with natural fibres. The enhanced water uptake
in natural fibre reinforced polymer composites can be attributed to hydrophilic nature of the
fibred due to the presence of hydroxyl groups which attract water molecules, and bind with
them through hydrogen bonding [37-40]. The addition of cellulose fibres also increases the
interfacial area which allows water to be absorbed along the fibre-matrix interfaces as a result
of the capillary effect [34, 39]. Hence, the higher the content of cellulose fibres, the higher the
water absorption rate.
Figure 6. Water absorption behaviour of epoxy/NPF composites with different NPF loading. (■) 0%; (
♦ ) 5%; (▲) 10%; (●)15%; (×) 20%.
Figure 7. Water absorption behaviour of epoxy/CBF composites with different CBF loading. (♦ ) 5%; (
▲) 10%; (●)15%; (×) 20%.
Figures 10 & 11 show that when compared to epoxy composites, vinyl-ester composites
have better resistance to moisture absorption. This is because epoxy resin is more hydrophilic
and has a higher content of hydrophilic hydroxyl groups in its chemical structure, while vinyl
ester resin has less of polar ester moieties and therefore is less hydrophilic [41]. In addition,
water is more readily absorbed in composites which have flaw such as voids or cracks. What
occurs is that the water molecules come in contact with cellulose fiber cell walls and then
gain access to the voids made during preparation within the composite. Voids can often arise
when micro-bubbles are created during the preparation process. These imperfections in the
composites, although hard to avoid, make it easier for the water to enter and occupy the
material [39, 42].
Figure 8. Water absorption behaviour of vinyl-ester/NPF composites with different NPF loading, (■
)0%RCF,(♦ )5%RCF,(▲)10%RCF,(×)15%RCF, (●)20%.
Figure 9. Water absorption behavior of vinyl-ester/CBF composites with different CBF loading, (■)
0%; (♦ ) 5%; (▲) 10%; (×) 15%; (●) 20%.
Figure 10. Comparison of maximum water uptake between epoxy/NPF composites and vinyl-ester/NPF
composites.
Figure 11. Comparison of maximum water uptake between epoxy/CBF composites and vinyl-ester/CBF
composites.
Diffusion Coefficients
The diffusion coefficients were calculated for the samples using equation (19) and the
results are listed in Tables 2 & 3. The results indicate that moisture diffusion rate (D)
increases with increasing NPF and CBF content. Similar results have also been reported by
other studies , an observation, these results are supported by other studies findings [34, 37].
As previously mentioned, increasing the content of cellulose fibres can lead to an increase in
(a) the hydrophilic state of the composites, (b) the number of voids, and (c) the interfacial
area between the fibre and the matrix, which can in total generate more pathways for water
molecules leading to increased velocity of the diffusion process inside the composites.
Table 2. Diffusion coefficients, D, of epoxy-RCF composites.
Sample NPF (wt%) CBF (wt%) M∞ (%) Slope D (mm²/sec)

Epoxy (E) 0 0 1.93 0.07 4.13 x 10-6
E/NPF5 5 3.46 0.15 5.24 x 10-6
E/NPF10 10 5.26 0.24 5.88 x 10-6
E/NPF15 15 7.73 0.41 7.54 x 10-6
E/NPF20 20 11.9 0.71 9.55 x 10-6
E/CBF5 5 3.7 0.17 5.63 x 10-6
E/CBF10 10 5.5 0.27 6.8 x 10-6
E/CBF15 15 7.94 0.42 7.7 x 10-6
E/CBF20 20 12.32 0.73 9.5 x 10-6
Table 3. Diffusion coefficients of Vinyl ester resin-RCF composites.
Samples M∞ (%) Slope D (mm²/sec)

Vinyl-Ester (VE) 0.74 0.0301 3.25 x 10-6
VE/NPF5 2.23 0.0678 1.81 x 10-6
VE/NPF10 3 0.0964 2.03 x 10-6
VE/NPF15 5.76 0.2127 2.68 x 10-6
VE/NPF20 7.81 0.2996 2.89 x 10-6
VE/CBF5 1.71 0.0725 3.5 x 10-6
VE/CBF10 2.9 0.1309 3.99 x 10-6
VE/CBF15 5.1 0.2371 4.2 x 10-6
VE/CBF20 6.99 0.3263 4.8 x 10-6
Table 4. Mechanical and fracture properties of the various samples.
Sample σF (MPa) EF (GPa) KIC (MPa·m1/2) σI (kJ·m-2) GIC (kJ·m-2)

Pure Epoxy 171 ± 9 4.1 ± 0.1 1.2 ± 0.2 0.4 ± 0.1 1.3 ± 0.1
Epoxy/RCF 179 ± 5 6.4 ± 0.3 2.4 ± 0.2 1.2 ± 0.4 6.3 ± 3.0
Table 5. Effect of soaking in seawater for two weeks on the flexural strength
(σF), flexural modulus (EF), impact strength (σI) and impact toughness (GIC)
of the composite samples.
σF (MPa) EF (GPa) σI (kJ·m-2) GIC (kJ·m-2)

Sample
Before After Before After Before After Before After
Epoxy 171 ± 9 - 4.1 ± - 0.4 ± - 1.3 ± -
0.1 0.1 0.1
Epoxy/RCF 179 ± 5 92 ± 6.4 ± 2.3 ± 1.2 ± 1.5 ± 6.3 ± 25.4 ±
7 0.3 0.2 0.4 0.3 3.0 3.6
Effect of Nano-Clay on Moisture Absorption
As can be seen in Figures 12 & 13, the water uptake of samples with nanoclay-coating is
significantly decreased. The addition of the nanoclay has been shown to impart significant
improvements in water absorption resistance. This is because nanoclay platelets have an
extremely high aspect ratio, where the water molecules path is disturbed [43]. The water
molecules path is changed from the direct fast diffusion into the polymer matrix to a maze
like path or tortuous zigzag pathway with the presence of the nanoclay platelets [44, 45] and
that leads to water molecules having to take a long way around the nanoclay layers.
Consequently, this leads to a reduction in water uptake.
Figure 12. Effect of coating with different nanoclay loading on the maximum water uptake of
epoxy/CBF composites.
Figure 13. Effect of coating with different nanoclay loading on the maximum water uptake of vinyl-
ester/CBF composites.
Mechanical Properties
The mechanical and fracture properties of the pure epoxy and RCF-reinforced epoxy
composites are summarized in Table 4. When compared to the pure epoxy, several interesting
features are worth noting for the composites. Firstly, the presence of RCF significantly
improved the fracture toughness (KIC) and impact toughness (GIC). As will be shown later, the
enhanced fracture resistance can be attributed to energy dissipation due to crack-deflection at
the fibre-matrix interface, fibre-debonding, fibre-bridging, fibre pull-out, and fibre-fracture.
Secondly, moderate gains were observed for flexural strength and flexural modulus but the
gain for impact strength was quite significant. As previously reported [25, 26], the gains in
these properties are dependent on the volume fraction or number of RCF sheets in accordance
with the rule-of-mixture equations. Thirdly, samples tested with the RCF sheets parallel to the
applied load achieved a higher KIC when compared to samples with the RCF sheets parallel to
the applied load. The higher fracture toughness in the former case can be attributed to the
pronounced display of interfacial crack-deflection, leading to a very tortuous crack-path.
Lastly, whilst the epoxy sample underwent catastrophic failure (Figure. 14a), the composite
samples failed in a more graceful manner with: (i) discontinuous or multiple ―stick-slip‖
fracture when the RCF sheets are normal to the applied load (Figure. 14b), and (ii) slow and
continuous crack growth when the RCF sheets are parallel to the applied load (Figure. 14c).
The phenomenon of multiple ―stick-slip‖ fracture can be attributed to the repeating
occurrence of crack initiation, arrests and de-bonding at the CRF/epoxy interfaces
Fracture Processes
The processes of fracture in composite samples during three-point bending showed

distinct differences depending on the orientation of RCF sheets to the applied load.
Micrographs in Figure 15 show the typical tortuous crack paths for samples with the RCF
sheets aligned normal to the applied load. The RCF sheets provided a gross crack deflection
of the growing crack at the fibre-epoxy interface as the principal mode of crack-tip failure.
This resulted in desirable energy dissipation processes such as crack-tip blunting and
interfacial de-bonding. Microcracks were also initiated within the RCF sheet in the high stress
region in the vicinity of the propagating crack.
A different mode of principal crack-tip failure was displayed for samples with RCF
sheets aligned parallel to the applied force. Here the crack-path is more continuous and less
tortuous due to the absence of gross crack deflection (Figure. 16). The crack advances
through the formation of a heavily damaged zone ahead of the crack-tip [26]. The damage
zone is initiated at fibres in the high stress region in the vicinity of a propagating crack. The
crack propagation follows a local trajectory through resin and deflected around the cellulose
fibres. This formation of localised damage ahead of the growing crack shields the crack by
activating multiple crack tips and by reducing the local stress intensity through crack
deflection and leads to the formation of crack bridges from ―uncracked ligaments‖ due to the
incomplete coalescence of these microcracks with the main crack tip [26].
Figure 14. Load versus deflection plots during three-point bending for (a) pure epoxy sample; (b)
Epoxy/RCF sample with RCF sheets normal to the applied load, and (c) Epoxy/RCF sample RCF
sheets parallel to the applied load.
a b
c
(a) crack-tip deflection during initial fracture; (b) multiple crack-deflections during final fracture, and
(c) formation of microcracks within the RCF sheets.
Figure 15. Optical and scanning electron micrographs of Epoxy/RCF with RCF sheets normal to the
applied load.
Figure 16. Scanning electron micrograph showing the crack path during the initial fracture of
Epoxy/RCF with RCF sheets parallel to the applied load.
CONCLUSIONS
Epoxy and vinyl-ester composites reinforced with cellulose fibres have been fabricated
and characterised. The moisture absorption behaviour of the composites in water was
analysed and the kinetics of sorption-diffusion process was investigated. The diffusion
coefficient (D) of the composites increased in proportion with an increase in the cellulose
fibre loading. The use of nanoclay in the composites was effective in imparting a substantial
reduction in water permeability due to the tortuous path presented by high aspect ratio clay.
Significant improvements in fracture properties, together with moderate increases in flexural
properties, were achieved through the reinforcement of cellulose fibres. However, the long-
term exposure of these materials to seawater had a detrimental effect on the flexural
properties, although their impact properties were significantly improved. The crack-tip failure
micromechanisms in theses composites were strongly dependent on the orientation of CRF
sheets with respect to the applied load.
The avoidance of fibres by the advancing crack-tip is accomplished by the initial tilting
and subsequent twisting of the crack front between the fibres, thus resulting in a non-planar
crack-path and extensive fibre pull-outs on the fracture surface (Figure. 17).
(a)
(b)
Figure 17. Scanning electron micrographs showing the fracture surface of sample (a) Epoxy/RCF and
(b) Epoxy/NPF.
ACKNOWLEDGEMENTS
This work forms part of the doctoral theses of H. Alamri and A. Alhuthali. Both are
particularly grateful to the Saudi government for providing the PhD scholarships. The authors
wish to thank Amcor Pty. Ltd in Canning Vale, W.A. for providing the recycled cellulose
fibres for this study. We are also very grateful to H.S. Kho for kindly providing Figs. 14-16
and to Dr. I.J. Davies for useful discussion. Ms. E. Miller and Dr. B.A. Latella kindly assisted
with the experimental work on SEM and flexural testing respectively.
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Chapter 10
DENSIFIED WOOD FOR GREEN COMPOSITES
Andreja Kutnara* and Frederick A. Kamkeb

a
University of Primorska, Primorska Institute for Natural Sciences and Technology,
Muzejski trg 2, 6000 Koper, Slovenia; Oregon State University, Department of Wood
Science and Engineering, 119 Richardson Hall, Corvallis, Oregon, USA.
b
Oregon State University, Department of Wood Science and Engineering,
119 Richardson Hall, Corvallis, Oregon, USA.
ABSTRACT
Densified wood can be effectively utilized as raw material in the production of
wood-base green composites. The viscoelastic thermal compression (VTC) process
enabled the development of a high performance structural wood-based composite with
low-density (undensified) wood in the core, and high-density VTC wood for the faces of
the composite. Increased density of the face layers in these 3-layer VTC composites is
advantageous for their mechanical performance. The aim of this chapter was to present
the VTC process, the VTC wood and the 3-layer VTC composites. Additionally, the
viscoelastic nature of wood and the stress-strain relationship in regard to glass transition
temperature and moisture environment relevant for the density gradient formation in
VTC wood are discussed. Namely, the density gradient of the VTC layer, which is
obtained due to the viscoelastic nature of wood, local environment of moisture content
and temperature during the densification process, affects the bending properties of the
VTC composites.
1. INTRODUCTION
Most mechanical properties of wood are correlated to its density. Although other
anatomical factors are important, such as microfibril angle, high density wood is typically
preferred for structural applications and where wear resistance is important. Since increasing
*
Corresponding author : E-mail address: andreja.kutnar@siol.net, Tel.: +386 31240 121.
198 Andreja Kutnar and Frederick A. Kamke
the density of wood enhances its mechanical properties and improves the hardness of wood,
many attempts have been made to develop a suitable process for the densification of wood
(Blomberg and Persson 2004). Densification makes it possible for low-density and
commercially uninteresting wood species to be modified into high performance and high
value products. A recently developed method for wood densification using the viscoelastic
thermal compression (VTC) process enabled the processing of thin materials (less than 10
mm) in the production of wood-base green composites (Kamke and Sizemore 2008; Kutnar et
al. 2008a). A simple application is a 3-layer laminated composite, with VTC wood in the two
outer layers, and a layer of untreated low-density wood in the core.
The VTC process may be applied to any wood species, although it is intended for low-
density species. Laboratory tests have been conducted with eastern cottonwood (Populus
deltoides), aspen (Populus tremuloides), yellow-poplar (Liriodendron tulipifera), sweetgum
(Liquidamber styraciflua), loblolly pine (Pinus taeda), radiata pine (Pinus radiata), and
Douglas-fir (Pseudotsuga menziesii). Recent application has focused on rapidly-grown hybrid
poplar clones (ie. Populus deltoides x Populus trichocarpa). Intensive silviculture can yield
harvest rotation at 10 years or less – dramatically increasing forest productivity. However,
rapid growth of softwood species typically results in low density wood. Hardwood species
that are amenable to rapid growth, also have low density, and consequently are not suitable
for structural applications. Densification processes, and subsequent composite manufacture,
improves the value of these timber resources and reduces the demand on mature forests.
2. VISCOELASTIC BEHAVIOUR OF WOOD

Wood is termed viscoelastic because it can exhibit a range of properties from viscous
fluids to linear elastic solids. Owing to the viscoelastic nature, mechanical properties of wood
depend on time, temperature and moisture. In relative terms, at short times, low temperatures
and low moisture contents, wood exhibits glassy behaviour that can be characterized as stiff
and brittle. At long times, high temperatures and high moisture contents, wood exhibits
rubbery behaviour that can be characterized as compliant. The transition phase occurs
between these two distinct regions; the temperature associated with the phase change being
typically called the glass transition temperature Tg (Wolcott et al. 1994). The Tg, also known
as the softening temperature, characterizes the softening behaviour of amorphous polymers.
When the temperature of the polymer approaches Tg, the stiffness of the material decreases
rapidly, corresponding to a marked increase in molecular motion (Wolcott 1989). Many
properties of amorphous polymers, such as the elastic modulus, change dramatically when the
material passes this softening point (Figure 1).
The viscoelastic nature of wood plays an important role in compression and densification.
Structure changes during the compression strongly depends on the moisture content and
temperature of the wood. Brittle fractures in wood occur when the hemicelluloses and lignin
are in the glassy phase, and the polymers are brittle. Temperatures higher than Tg promote
polymer mobility and permit rearrangement of the molecules. When the wood temperature is
above the Tg of both amorphous polymers, large deformation can occur without fractures or
with ductile fractures (Wolcott et al. 1990).
Densified Wood for Green Composites 199
Figure 1. Variation of the relaxation modulus with temperature for an amorphous polymer (Lenth
1999).
Figure 2. The glass-transition temperature of lignin as a function of moisture content (Morsing 2000).
The softening temperature of wood is strongly influenced by its water content (Morsing
2000). Increasing moisture content decreases the Tg of the amorphous components of wood,
and vice versa (Figure 2). Water molecules plasticize wood polymers. Moisture forms
secondary bonds with the polar groups in the polymer molecules, and swells the polymer
network, thus reducing the secondary bonding between the polymer chains and increasing
mobility for the polymer molecules. Moisture thus increases the free volume of the system.
The wood becomes more easily deformed and the transition temperature is lowered.
Viscoelastic behaviour results in densification due to the transverse compression of the
constituent wood elements and associated buckling of the cell wall in the radial or tangential
directions. The strain-time curve of wood under a compressive load can be divided into four
parts: initial elastic deformation, viscoelastic deformation, final elastic springback and time-
dependent springback or creep recovery (Tang and Simpson 1990). Wood densification can
have both permanent and recoverable components, which together have a significant
influence on the physical and mechanical properties of the composite product (Lenth and
Kamke 2001a). Because of its viscoelastic nature, wood also exhibits rheological properties
such as creep and relaxation.
3. PROCESS OF VISCOELASTIC THERMAL COMPRESSION

(VTC) OF WOOD
The VTC process increases the density of wood by compression perpendicular to the grain.
Pre-conditioning the wood components, by heat and steam, to exceed Tg softens the cell wall. A
rapid moisture loss just prior to mechanical compression promotes a mechano-sorptive affect
that further softens the wood components. A subsequent heat treatment reduces the potential for
water sorption and stabilizes the material. The degree of densification is controllable, with a
maximum density of approximately 1.4 g/cm3.
Densification of wood by VTC involves five steps (Kamke and Sizemore 2008). First, the
wood is heated and conditioned to an elevated temperature and moisture content, such that the
wood substance reaches or exceeds its glass transition temperature. The desired temperature
range is about 160°C to 175°C. Pronounced softening of the wood follows, which is caused by
inducing rapid vapor decompression and removal of the bond water in the cell wall. The
purpose of the rapid vapor decompression is to induce transient moisture content in the
specimen and promote mechano-sorption behavior in the second phase compression. This
softening dramatically reduces the compression modulus of the wood. This movement of
moisture retards the cell‘s ability to transfer stress and resist strain. In effect, the polymer
molecules are able, to a great extent, to deform under the applied load without cleaving. While
the wood is in a softened state, it is compressed perpendicular to the grain. The mechanical
compression is within the range of 650 and about 2000 kPa depending on the degree of
densification desired.
In the next step annealing the wood to allow relaxation of the remaining stresses is
performed. The temperature is increased, which increases molecular motion, and assists stress
relaxation. High temperature exposure also induces some thermal degradation - primarily of the
hemicellulose component, which is believed to reduce the hydrophilic nature of wood. Thermal
degradation products may also result in additional polymer crosslinking reactions. The
temperature is set within the range about 175°C and about 225°C, and compressed wood is held
under a mechanical pressure of between approximately 650 and about 2000 kPa.
The VTC process is completed with cooling the wood, while still under mechanical
compression, to below Tg.. When the VTC wood is conditioned to the ambient temperature and
humidity the equilibrium moisture content is significantly lower than the virgin wood.
The degree of densification depends upon the initial basic wood density (Currier 1963;
Kamke and Sizemore 2008; Lenth and Kamke 2001a, 2001b) and also on the species and type
(adult, juvenile) of wood (Kultikova 1999). Other factors to consider include the thickness of
the product, form of the wood in the product (i.e. on the size and shape of the wood elements),
on previous treatments of the wood product, such as pressure and/or heat treatment, infusion
with resin, and on the desired final density. Depending on these factors, the increase in density
may be in the range of about 25% to 500%, though preferably in the range of about 100% to
200%.
Transient heat and mass transfer in the wood results in temperature, gas pressure, and
moisture content gradients in the wood during the VTC process, which causes a variation in
compression modulus with respect to the thickness direction. Consequently, some regions are
compressed more than others and a density profile is created. Generally the formation of a
density profile can be attributed to the combined action of time, temperature, moisture,
compression force, and stress relaxation of wood during the densification process (Kamke and
Casey 1988; Wolcott et al. 1990; Kutnar et al. 2009).
4. VTC WOOD CHARACTERISTICS

VTC processing of wood has a dramatic affect on many properties. The morphology of
VTC wood changes significantly and depends strongly upon the degree of densification
(Figure 3). Densification is achieved by a reduction of the void space, which is largely cell
lumen volume. The high strain which occurs in the VTC process drastically reduces the void
volume and causes cell wall buckling without fracturing (Kutnar et al. 2009). The strength
and stiffness of the VTC wood material are increased approximately in proportion to the
increase in density (Kutnar et al. 2008a). Unbroken cell walls are a major factor for improved
properties of VTC wood, while the type and amount of cell collapse has a very important
effect on the mechanical and physical properties of the densified material (Wolcott 1989;
Kultikova 1999; Navi and Girardet 2000; Kamke and Sizemore 2008).
Due to temperature and moisture gradients, and their relationship to Tg at the time the
compression stress is applied, a density profile is formed, which varies with the degree of
densification (Kutnar et al. 2009). An examination of the cross-section of VTC specimens
reveals that low and high density layers can be distinguished by the varying amount of void
space across the thickness (Figure 3).
Major chemical changes induced by the VTC process are the polymerization reactions of
lignin and partial degradation of hemicellulose (Kutnar et al. 2008b). The VTC process
reduces the hydrophilic nature of the wood (Jennings et al. 2006). Surface free energy
decreases significantly. Although this seems to be driven by thermal affects, since the level of
densification has limited influence on the surface properties of VTC wood (Kutnar et al.
2008b).
Figure 3. Photomicrographs of VTC wood specimens in transverse view having different degrees of
densification. The specimen blocks were polished after embedding in oil. Compression was applied in
the vertical direction, as indicated by the arrows.
VTC
wood
Untreated wood
VTC
wood
Figure 4. The 3-layer VTC composite. The other laminas are 2.5 mm thick VTC wood laminas,
whereas the core is 6 mm thick untreated wood.
VTC processing affects adhesive flow and penetration (Kutnar et al. 2008c). The
effective penetration (EP) of phenol-formaldehyde (PF) adhesive differs upon the level of
densification; the EP decreases with the increasing densification. Although the surface
properties of VTC wood and adhesive penetration properties are changed significantly, the
bonding performance of VTC wood with PF adhesives is comparable with or better than in
the case of the virgin wood (Kutnar et al. 2008a; Kutnar et al. 2008c; Jennings et al. 2005).
Additionally, bonding of the VTC wood to untreated wood is not problematic, although the
penetration of the adhesive is mainly into the untreated wood (Kutnar et al. 2008a).
Good bonding characteristics has made it possible to develop a new wood-based
composite with low-density undensified wood in the core and high-density VTC wood in the
face layers (Figure 4) (Kamke and Sizemore 2008; Kutnar et al. 2008a; Jennings et al. 2005).
The high density VTC wood surface layers resist in-plane and bending loads, whereas the low
density core determines the product thickness, moment of inertia, and carries the shear loads.
Kutnar et al. (2008a) and Kamke (2006) determined that the modulus of rupture (MOR) and
modulus of elasticity (MOE) of the 3-layer VTC composites are significantly improved due to
the increased density of the VTC wood in the face layers of the 3-layer composites. In
addition, the MOE values of 3-layer VTC composites are comparable to commercially
existing structural composite lumber (SCL) (Kutnar et al. 2008a). This means the VTC
process offers the possibility of manufacturing structural wood composites from non-
structural timber species, like low density hybrid poplar.
5. CONCLUSIONS
Knowledge of the viscoelastic behavior of wood, utilized in the VTC densification
process, greatly benefits the forest products industry, since it results in the manufacture of
high performance, high value composite products from rapidly grown raw material. The VTC
process increases the density of wood without cell wall fracture, thus the strength and
stiffness of the wood material is increased. The improved mechanical properties, and the
ability to control them, provide a variety of potential uses for VTC wood. Low-density and
juvenile wood with lower mechanical properties can be used in new high-performance wood-
based composite products for structural components in buildings, transportation systems, and
casework.
6. REFERENCES
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(Pinus sylvestris) during densification with the CaLignum process. Journal of Wood
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compression densified wood. Part 1: Bond performance. Journal of Adhesion Science and
Technology, 19(13-14), 1249-1261.
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compression densified wood. Part 2: Surface energy. Journal of Adhesion Science and
Technology, 20(4), 335-344.
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technologia, 8, 2, 83-92.
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wood relevant for structural composites. Holz als Roh- und Werkstoff, 66, 6, 439-446.
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thermal compression on the chemistry and surface energetics of wood. Colloids and
Surfaces A: Physicochemical and Engineering Aspects, 329, 82-86.
Kutnar, A., Kamke, F. A., Nairn, J. A. & Sernek, M. (2008c). Mode II fracture behavior of
bonded viscoelastic thermal compressed wood. Wood and Fiber Science, 40, 3, 362-373.
Kutnar, A., Kamke, F. A. & Sernek, M. (2009). Density profile and morphology of
viscoelastic thermal compressed wood. Wood Science and Technology 43, 1, 57-68.
Lenth, C. A. (1999). Wood material behavior in severe environments. Ph.D. Dissertation.
Virginia Tech, Blacksburg, Virginia, 122.
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temperature pressurized environments. Wood and Fiber Science, 33, 1, 104-118.
Morsing, N. (2000). Densification of wood - The influence of hygrothermal treatment on
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INDEX
agents, 11, 23, 31, 39, 56, 57, 58, 59, 60, 61, 63, 65,
A 67, 76, 79, 81, 84, 86, 87, 88, 92, 94, 95, 142
aggregates, 4, 32, 53, 59
absorption, 1, 4, 17, 18, 21, 22, 44, 47, 48, 54, 61,
aggregation, 2, 10, 13, 16, 22
82, 84, 85, 88, 92, 94, 104, 105, 134, 135, 137,
aging, 114, 117
141, 143, 144, 146, 147, 149, 154, 155, 175, 176,
agricultural, 1, 14, 36, 81, 119, 155
177, 178, 180, 181, 185, 186, 187, 194
aid, 91
acceptor, 62
air, 20, 114, 143, 176, 180, 183
acetate, 3, 27, 61, 65, 73, 75
alcohol, 28, 30, 63, 64, 88
acetic acid, 67
alcoholysis, 100, 102, 103, 105, 112
acetone, 41, 64, 65
aldehydes, 11, 26
acetylation, 31, 39, 47, 60, 74, 75, 77
alkali, 39, 41, 46, 56, 57, 61, 63, 67, 74, 142, 155
achievement, 171
alkaline, 61, 63, 97, 155, 156
acid, 3, 19, 23, 25, 29, 35, 42, 45, 48, 56, 59, 61, 62,
alternative, 32, 93, 99, 100, 112, 116
67, 68, 78, 79, 84, 86, 87, 88, 93, 94, 97, 101, 102,
aluminum, 60, 128
103, 104, 114, 119, 120, 121, 138, 144, 158
Aluminum, 78
acidity, 65
amine, 10, 95, 115
acoustic, 114
amino, 18, 23, 29, 88, 94, 120
activated carbon, 96
amino groups, 18, 23, 94
activation, 9, 19, 38, 63
ammonia, 27
activation energy, 9, 19
ammonium, 7, 10, 68
additives, 59, 61, 75, 86, 88, 91, 99, 100, 110, 115
amorphous, 47, 55, 56, 57, 68, 80, 198, 199
adhesion, 5, 14, 15, 18, 24, 29, 31, 33, 39, 40, 41, 44,
amorphous polymers, 198
45, 47, 48, 58, 59, 60, 61, 63, 64, 71, 74, 83, 87,
amphiphilic compounds, 23, 24
88, 94, 107, 122, 127, 137, 144, 155
amplitude, 124
adhesion properties, 48
anaerobic, 36
adhesion strength, 24, 88
anaerobic bacteria, 36
adhesive properties, 92
analysis of variance, 162
adhesives, 60, 88, 89, 97, 202
animals, 32, 54, 120
adjustment, 23
annealing, 200
adsorption, 44, 61, 78
anomalous, 177
adult, 200
antagonistic, 65
aerobic, 21, 36
aqueous solution, 40
Africa, 80, 101
Argentina, 99, 101, 104, 117
ageing, 154
argon, 129
agent, 33, 41, 47, 56, 60, 61, 63, 65, 67, 75, 79, 81,
aromatic hydrocarbons, 92
84, 85, 89, 91, 92, 94, 112, 115, 155
206 Index
asbestos, 41 biopolymer, 21, 28, 45

ash, 19 biopolymers, 2, 25, 30, 74, 138
Asia, 32, 80, 101 biotic, 159
Asian, 80 bleaching, 60, 63, 68
aspect ratio, 11, 39, 45, 57, 61, 63, 120, 161, 175, blend films, 3
176, 179, 190, 194 blends, 1, 4, 10, 14, 15, 18, 19, 21, 28, 29, 30, 75
assessment, 73, 81, 82, 88, 161 blocks, 42, 201
ASTM, 122, 144, 145, 161, 182, 196 boiling, 42
atmosphere, 20, 124, 128 bonding, 8, 10, 13, 38, 41, 43, 47, 53, 54, 59, 60, 61,
Australia, 80, 175, 182 64, 65, 84, 88, 91, 95, 148, 186, 191, 199, 202
automobiles, 81 bonds, 11, 14, 35, 36, 39, 43, 44, 62, 94, 142, 199
availability, 31, 32, 54, 85 Boston, 138
avoidance, 194 branching, 56
awareness, 120, 176 Brazil, 53, 65, 74
Brazilian, 27, 74, 78
bubbles, 113, 176, 180, 183, 187
B
buffer, 21, 132
buildings, 202
bacteria, 36, 168
burning, 147
bacterial, 159, 168, 169, 171
banks, 80
barley, 92 C
barrier, 2, 30, 78, 130
barriers, 74 calcium, 3, 6, 13, 14, 22, 28, 60, 63, 86
Bax, 138 calcium carbonate, 3, 6, 13, 14, 22, 28, 60
behavior, 4, 8, 11, 13, 18, 25, 27, 29, 39, 47, 58, 67, calibration, 106
68, 74, 77, 78, 84, 85, 87, 107, 111, 114, 116, 119, Canada, 32, 141
120, 121, 123, 126, 128, 130, 132, 142, 160, 163, cannabis, 40
177, 187, 200, 202, 203, 204 capillary, 177, 186
Beijing, 95 carbohydrates, 2
bending, 47, 80, 88, 91, 114, 119, 124, 191, 192, carbon, 2, 48, 56, 80, 96, 100, 120, 179
197, 202 carbon dioxide, 2
benefits, 80, 202 carbonates, 96
benzene, 63 carboxyl groups, 57, 94
benzoyl peroxide, 40, 43 cardboard, 97
bicarbonate, 86 carpets, 32, 48
biochemistry, 95 casein, 44
biocompatibility, 120 cast, 25, 26
biodegradability, 2, 25, 26, 31, 48, 54, 87, 88, 94, casting, 2, 23, 27, 30, 180
120, 157, 158, 159, 170, 171 castor oil, 23, 100, 101, 102, 103, 112, 114, 115, 116
biodegradable, 1, 2, 3, 23, 24, 25, 26, 28, 29, 30, 34, catalyst, 106, 112, 115
49, 53, 74, 79, 84, 88, 93, 94, 96, 97, 119, 120, cavities, 168
121, 137, 157, 158, 167, 171 cell, 34, 35, 36, 38, 44, 55, 56, 58, 64, 114, 115, 116,
biodegradable materials, 25 117, 142, 155, 187, 199, 200, 201, 202
biodegradation, 21, 24, 27, 157, 159, 161, 166, 167, cell growth, 55
168, 169, 170, 171 Cellulose, 35, 42, 49, 55, 56, 59, 68, 74, 80, 143, 148,
bioethanol, 155 175, 183
biofilms, 27 cellulose fibre, 76, 175, 176, 179, 180, 183, 184,
biomass, 54, 80, 95 185, 188, 191, 194, 195
biomaterials, 30, 85 cellulosic, 30, 32, 34, 39, 40, 42, 43, 47, 59, 60, 78,
biomimetic, 29 81, 154, 167
Index 207
cement, 32, 42, 48, 79, 86, 96 consumers, 24

chain branching, 56 consumption, 155, 176
chain mobility, 2, 8, 107, 151 control, 24, 36, 41, 115, 143, 202
charcoal, 96 convection, 47
chelators, 41, 44 conversion, 96, 102
chemical agents, 87 cooling, 10, 129, 200
chemical interaction, 44 copolymer, 23, 57
chemical properties, 35, 47, 79, 81, 104, 143 corn, 1, 2, 24, 27, 79, 92, 93, 120, 141, 142, 143,
chemical structures, 106, 138 144, 146, 147, 150, 152, 153, 154
chemicals, 48, 59, 155 corona, 38, 63, 78
chicken, 119, 120, 121 correlation coefficient, 11
China, 1, 79, 80, 81, 83, 95, 96, 101, 119, 121 corrosive, 32, 33, 48
chitin, 2, 22, 27 costs, 95
chitosan, 3, 27 cotton, 1, 32, 54, 78, 100
chloride, 40, 42, 57, 68, 78, 79, 84, 86, 87, 91, 155 coupling, 23, 31, 33, 39, 41, 56, 59, 60, 61, 63, 64,
chromatograms, 105, 106 65, 67, 75, 76, 79, 81, 84, 85, 86, 91, 94, 95, 96,
chromatography, 105 142, 155
civil engineering, 54 covalent, 2, 111, 115
classical, 48 covalent bond, 111
clay, 7, 15, 60, 175, 176, 179, 194 covalent bonding, 111
cleaning, 67 crack, 45, 111, 122, 175, 176, 183, 191, 193, 194
clusters, 4, 148 cracking, 40, 184
CO2, 34 CRC, 74, 138, 139
coatings, 101 creep, 57, 199
coconut, 14 crops, 1, 142, 154
cohesiveness, 17 crosslinking, 2, 4, 11, 16, 26, 30, 60, 88, 114, 200
combustion, 33 cross-sectional, 146
commodity, 42, 158 crystalline, 36, 56, 68, 87, 120, 129
communities, 142 crystallinity, 10, 58, 61, 67, 68, 75, 129
community, 142 crystallization, 10, 33, 58, 65, 67, 75, 77, 78, 119,
compaction, 180 124, 129, 137
compatibility, 18, 19, 53, 60, 76, 91, 107, 110, 116 crystals, 58, 129
components, 1, 3, 9, 10, 14, 15, 19, 22, 24, 47, 56, culm, 80, 81, 86
57, 59, 61, 79, 81, 90, 106, 109, 147, 152, 155, curing, 23, 40, 44, 47, 57, 96
158, 176, 199, 200, 202 cuticle, 35
composition, 15, 24, 25, 31, 34, 35, 37, 41, 47, 48, cutin, 35
56, 57, 63, 64, 75, 80, 82, 84, 93, 97, 101, 102, cycling, 10
106, 157, 161 cysteine, 2, 14, 27, 29
composting, 159 cystine, 120
compounds, 2, 23, 36, 60, 92
compressive strength, 24, 92, 153
D
concentration, 39, 59, 61, 63, 64, 65, 67, 102, 105,
108, 112, 115, 116, 144, 147, 148, 163, 166, 177
dairy, 88
condensation, 39, 120
damping, 123, 125
conditioning, 200
data analysis, 35
conductivity, 114, 115, 117, 148, 178
dating, 32
confidence, 158, 160
decay, 4
configuration, 182
decomposition, 16, 19, 20, 40, 46, 109
conservation, 80
decompression, 200
construction, 42, 44, 54, 79, 80, 81, 113, 176
defects, 56, 132
208 Index
definition, 84, 160 durability, 79

deformability, 4, 13, 14, 125 duration, 122, 132, 144, 161
deformation, 2, 11, 45, 47, 110, 111, 114, 116, 117, dust, 155
198, 199, 203, 204 dyes, 101
degradation, 2, 19, 20, 21, 43, 46, 57, 58, 61, 65, 67, dynamic mechanical analysis, 119, 121, 139
74, 75, 82, 94, 109, 110, 119, 121, 130, 131, 132, dynamic-mechanical properties, 76, 107, 113
133, 134, 135, 136, 137, 147, 148, 159, 200, 201
degradation process, 61, 132
E
degradation rate, 94
degrading, 36
Eastern Europe, 32
degrees of freedom, 160, 162
ecological, 80
degumming, 33
ecosystems, 96
Delaware, 100
Egypt, 32
Denmark, 203
elastic deformation, 11, 199
density, 4, 11, 16, 31, 32, 37, 41, 42, 54, 61, 63, 67,
elasticity, 80, 81, 82, 93, 202
73, 76, 77, 80, 82, 86, 88, 97, 100, 107, 112, 113,
elastomers, 60
114, 120, 155, 176, 180, 197, 198, 200, 201, 202
electrical characterization, 75
deposition, 44
electrolytes, 28
depression, 17
electron, 5, 6, 7, 19, 36, 46, 68, 71, 84, 91, 107, 115,
derivatives, 57, 101, 158
119, 121, 122, 132, 180, 193, 194
desorption, 20, 44, 155
electron microscopy, 7, 19, 36, 46, 68, 84, 119, 122
developing countries, 141, 142, 146, 154, 155
elongation, 14, 47, 87, 111, 122
dew, 36, 37
email, 79
dextrose, 120
emulsifier, 88
DGEBA, 46
encapsulated, 147, 148
Diamond, 124, 143
encapsulation, 148
dielectric constant, 127
energy, 3, 4, 9, 19, 38, 40, 44, 45, 64, 79, 81, 82, 85,
differential scanning, 46, 61, 119, 121
86, 88, 94, 111, 125, 151, 191, 203
Differential Scanning Calorimetry (DSC), 58
England, 182
diffraction, 7, 35, 68
environment, 1, 3, 19, 25, 34, 142, 171, 176, 197
diffusion, 148, 150, 175, 176, 177, 178, 179, 181,
environmental advantage, 48
182, 183, 185, 188, 190, 194
environmental conditions, 120, 159, 171
diffusion process, 175, 176, 188, 194
environmental impact, 99, 100
diffusivity, 177, 178, 179
environmental issues, 158
diglycidyl ether of bisphenol, 46
environmental regulations, 176
disentanglement, 59
enzymatic, 21, 119, 121, 132, 134, 135, 136, 137
disorder, 68
enzymes, 36, 37, 41, 44, 169
dispersion, 4, 22, 58, 59, 91, 104, 106, 107, 135, 180
epoxy, 2, 23, 41, 44, 46, 100, 175, 176, 179, 180,
displacement, 46, 65, 66, 183
183, 184, 185, 186, 188, 189, 190, 191, 192
distilled water, 67, 68, 132, 144, 161
epoxy groups, 23
distribution, 6, 8, 15, 29, 57, 59, 67, 83, 84, 115, 116,
epoxy resins, 179
160, 179
equilibrium, 14, 22, 112, 141, 144, 148, 150, 154,
disulfide, 2, 11, 14, 19
177, 185, 200
disulfide bonds, 14
ester, 15, 24, 29, 88, 104, 130, 175, 179, 180, 182,
donor, 62
183, 184, 185, 186, 187, 188, 189, 190, 194
double bonds, 100, 101, 102, 104
ester bonds, 130
drying, 24, 36, 63, 101, 112, 114, 144, 203
esterification, 19, 76
DSC, 46, 58, 67, 119, 121, 128, 129
esters, 92
DTA curve, 20
ethanol, 61, 78, 121
ductility, 15, 18, 122
ethylcellulose, 25
Index 209
ethylene, 23, 30, 59, 61, 65, 76, 79 flow, 3, 58, 82, 94, 103, 129, 147, 151, 154, 161, 202
ethylene oxide, 23, 30 flow rate, 58
evaporation, 20, 106 fluctuant, 5
evolution, 5 foams, 41, 99, 104, 106, 114, 115, 116, 117
exclusion, 105, 106 food, 2, 25, 26, 27, 88
execution, 162, 166 food industry, 88
exfoliation, 7, 15 Forestry, 95, 96
experimental condition, 160, 162, 163, 164 forests, 80, 95, 198
exploitation, 53 formaldehyde, 42, 43, 155, 202
exposure, 175, 176, 177, 184, 185, 194, 200 fracture, 5, 15, 23, 29, 58, 63, 73, 107, 111, 116,
extraction, 36, 37, 83, 155 122, 123, 132, 152, 153, 154, 175, 176, 180, 182,
extrusion, 2, 3, 4, 15, 43, 57, 59, 75, 83, 122, 142, 189, 191, 193, 194, 202, 203
144, 146, 147, 148, 161 fractures, 198
free energy, 201
free radicals, 38, 40, 63
F
free volume, 134, 199
freedom, 160, 162
fabric, 32, 44, 88
friction, 125
fabricate, 89, 180
FTIR, 104, 105
fabrication, 24, 67, 83, 84, 85, 86, 88, 91, 94, 95,
fuel, 176
131, 176, 180
functionalization, 78
factorial, 89, 158, 159, 162, 163, 171
fungal, 36
failure, 14, 45, 64, 82, 94, 111, 116, 175, 191, 194
fungus, 41
family, 157, 158, 171
furniture, 43, 49, 79, 80
FAO, 96
fusion, 129
farmers, 143
farmland, 21
fat, 34 G
fatty acids, 30, 92, 106, 112
fermentation, 21, 36, 120 Gamma, 41
fiber bundles, 35, 41, 44, 84 gas, 99, 124, 201
fiber content, 4, 16, 45, 63, 64, 67 gases, 2, 38, 63
fibrillar, 37, 47 gasification, 96
fibrillation, 61 gauge, 146
fibrils, 31, 34, 35, 55, 56, 71 gel, 4, 6, 25, 28, 121
Fick’s law, 181 gel permeation chromatography, 121
fillers, 4, 26, 42, 61, 99, 100, 107, 112, 143, 145, gelatin, 41
148, 151, 153, 157, 158, 179 Gelatine, 28
film, 2, 23, 25, 27, 30, 43, 45, 92, 144, 154, 158 gels, 6, 28
films, 1, 2, 23, 25, 26, 27, 29, 30, 75, 92, 161 generation, 34, 68, 81, 176
filtration, 25 Georgia, 138
financial support, 117 Germany, 67, 122, 155, 161
fire, 46, 74 glass, 1, 2, 8, 9, 10, 16, 17, 18, 21, 23, 24, 29, 32, 33,
fishing, 32 37, 42, 45, 46, 48, 54, 57, 60, 73, 87, 107, 119,
fitness, 39 120, 121, 124, 125, 126, 154, 155, 176, 179, 197,
flax fiber, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 198, 199, 200
42, 43, 44, 45, 46, 47, 48, 75 glass transition, 1, 2, 8, 9, 10, 16, 17, 18, 21, 23, 24,
flexibility, 17, 19, 57 57, 87, 107, 121, 124, 125, 126, 197, 198, 200
flexural strength, 41, 146, 153, 175, 182, 189, 191 glass transition temperature, 1, 2, 8, 10, 24, 87, 121,
flight, 121 125, 197, 198, 200
flooring, 43, 81 glass-fiber, 33, 48, 155
210 Index
glassy state, 3 hemp fiber, 4, 5, 16, 27, 44, 100, 112, 113, 114
glucose, 35, 64 heterogeneity, 14, 16
glutaraldehyde, 88 heterogeneous, 58, 107, 115
glycerin, 25, 100 high density polyethylene, 53, 61, 74, 75, 76, 78, 141
glycerol, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, high pressure, 168
17, 18, 20, 22, 23, 27, 28, 29, 30, 93 high tech, 176
glycine, 120 high temperature, 2, 8, 10, 20, 41, 58, 198, 203
glycol, 92 Hm, 69
gold, 122, 132, 147 homogenous, 55
GPC, 121 Hong Kong, 81, 119, 121
GPO, 175 hot pressing, 85, 86, 88
grades, 88 hot water, 71
gradient formation, 197 House, 95
grafting, 23, 30, 31, 40, 43, 59, 60 housing, 44
grain, 200, 203 humidity, 21, 22, 23, 44, 45, 47, 75, 112, 158, 200
grains, 92 Hungarian, 51
granules, 18, 84, 91, 161 hybrid, 44, 63, 198, 202
graph, 84 hydration, 86
grass, 2, 26, 54, 96 hydro, 23, 31, 35, 48, 56, 59, 60, 61, 67, 85, 92, 109,
gravimetric analysis, 46 142, 147, 148, 186, 188, 200, 201, 203
gravity, 54, 82 hydrocarbon, 57
groups, 2, 13, 18, 23, 24, 34, 38, 39, 40, 48, 56, 57, hydrochloric acid, 68
59, 60, 61, 63, 64, 65, 67, 68, 85, 88, 92, 94, 100, hydrodynamic, 13, 125
101, 102, 103, 104, 105, 107, 108, 109, 112, 115, hydrogen, 2, 8, 10, 13, 35, 53, 56, 59, 63, 84, 95,
116, 117, 142, 147, 148, 186, 199 102, 103, 120, 148, 186
growth, 4, 34, 55, 67, 159, 170, 171, 191, 198 hydrogen bonds, 2, 35, 103, 120
guidance, 49 hydrogen peroxide, 63, 102
hydrolysis, 39, 77
hydrolyzed, 56, 57, 90
H
hydrophilic, 23, 31, 35, 48, 56, 59, 60, 61, 67, 85,
109, 142, 147, 148, 186, 188, 200, 201
hardener, 32
hydrophilic groups, 61, 67
hardening, 14
hydrophobic, 18, 22, 24, 30, 53, 54, 56, 57, 59, 120
hardness, 182, 184, 185, 198
Hydrophobic, 23, 142
harvest, 198
hydrophobic polymer matrix, 53, 59
hazards, 158
hydrophobicity, 23, 24, 122, 136
H-bonding, 106
hydrothermal, 83, 155
HDPE, 42, 53, 58, 64, 65, 66, 67, 68, 69, 70, 71, 73,
hydroxide, 24, 68, 88, 92, 141, 143
74, 77, 78, 143, 144, 147, 155
hydroxyl, 15, 24, 29, 34, 39, 42, 48, 56, 57, 64, 85,
healing, 148
92, 94, 101, 102, 103, 105, 106, 107, 109, 116,
health, 31, 32, 33, 34, 48, 157, 158
142, 147, 186
heart, 80
hydroxyl groups, 34, 39, 48, 56, 64, 85, 94, 101, 102,
heat, 2, 10, 19, 23, 58, 91, 125, 129, 147, 200, 201
103, 105, 107, 109, 142, 147, 186
heat capacity, 10
hydroxylation, 100, 102, 104
heating, 10, 46, 81, 124, 144
hydroxypropyl, 26
heating rate, 46, 124
height, 113
hemicellulose, 14, 34, 35, 55, 56, 58, 63, 80, 82, 92, I
200, 201
hemp, 2, 3, 4, 5, 16, 27, 32, 37, 44, 46, 47, 75, 100, ice, 8
112, 113, 114, 155, 158
Index 211
images, 6, 7, 19, 71, 91, 107, 121, 123, 132, 133, interfacial adhesion, 14, 18, 24, 41, 59, 71, 74, 94,
134, 152 107, 155
imitation, 88 interfacial bonding, 64, 137, 184
immersion, 144, 145, 161, 167, 169, 177, 182 interfacial properties, 65, 75
immobilization, 28 intermolecular, 2, 9, 14, 17, 35, 47, 103, 148
impact energy, 183 intermolecular interactions, 14, 17, 103
impact strength, 45, 64, 151, 158, 162, 163, 166, intrinsic, 34, 115
171, 182, 183, 189, 191 ions, 40, 61, 68, 78
implementation, 161, 171 isotherms, 44
impurities, 14, 39, 61 isotropic, 45
in situ, 6, 102 Italy, 157, 161, 171
inclusion, 24
incompatibility, 53, 54
J
independent variable, 89
India, 80
Japan, 80, 86, 96
Indian, 80, 88, 96
JI, 171
indication, 107
joints, 43
indigenous, 36, 80
Jung, 30
induction, 61
induction time, 61
industrial, 2, 27, 32, 36, 53, 58, 76, 81, 88, 99, 101, K
120, 155
industrial application, 53, 155 keratin, 14, 120
industrial fibers, 36 ketones, 92
industry, 24, 32, 37, 54, 73, 80, 88, 95, 96, 99, 100, kinetic parameters, 175, 176
176, 202 kinetics, 29, 48, 161, 175, 176, 178, 194
inertia, 202 knots, 71
infrared, 10, 29, 48 KOH, 65, 103, 104
inhalation, 158
inhibitor, 41 L
initiation, 111, 191
injection, 2, 4, 10, 15, 21, 43, 57, 59, 75, 86, 96, 122, lactic acid, 29, 79, 86, 87, 94, 97, 119, 120, 121
124, 128, 132, 161, 169, 171 lakes, 36
innovation, 73 lamella, 56
inorganic, 1, 2, 3, 24, 32, 41, 54 lamellae, 37, 45
inorganic filler, 2 laminated, 198
inorganic fillers, 2 land, 80
insertion, 71 landfill, 33, 100, 159
Instron, 145, 161, 182 Langmuir, 29, 177
insulation, 32, 114 latex, 39
insulators, 42 Latin America, 80
integrity, 115 lattice, 68, 142
interaction, 9, 10, 13, 20, 24, 41, 42, 45, 53, 58, 59, laundering, 78
61, 65, 67, 107, 158, 159, 160, 162, 163, 164, 165, law, 177, 181
166, 167 leaching, 148, 177
interactions, 4, 14, 15, 17, 22, 24, 28, 44, 59, 94, LEAF, 35
103, 109, 110, 111, 122, 155, 159, 160, 163, 165 legislation, 73
interface, 20, 24, 38, 39, 40, 41, 43, 44, 46, 57, 59, LHC, 28, 29
60, 61, 62, 63, 65, 74, 75, 86, 88, 91, 132, 133, life cycle,
142, 151, 152, 153, 155, 191 life-cycle, 33, 34, 157, 158
212 Index
ligament, 183 melt, 14, 38, 59, 63, 67, 82, 122, 129, 147, 161
lignin, 2, 14, 26, 34, 35, 36, 44, 46, 48, 55, 56, 57, 58, melt flow index, 147, 161
63, 80, 83, 120, 142, 148, 198, 199, 201 melting, 8, 10, 19, 23, 46, 57, 58, 87, 119, 120, 121,
likelihood, 183 128, 129
limitations, 86 melting temperature, 10, 19, 57, 121, 129
linear, 4, 42, 56, 64, 77, 85, 106, 146, 150, 181, 198 metabolism, 169
linear dependence, 64 methacrylic acid, 88
linen, 32, 36 methanol, 88
links, 94, 109 methyl methacrylate, 40, 88
lipids, 2, 120 methylcellulose, 27
liquids, 23, 30 methylene, 26, 93
lithium, 88, 103 mica, 176
loading, 9, 11, 18, 20, 44, 57, 75, 76, 91, 96, 97, 125, microbial, 21, 170
179, 182, 183, 184, 185, 186, 187, 190, 194 microcrystalline cellulose, 76
localised, 191 microscope, 5, 6, 7, 121, 132
London, 75, 96, 117, 154, 155 microscopy, 7, 19, 47, 107
long period, 46 microstructure, 24, 26, 77, 80, 155, 180
losses, 63, 159, 167, 168 microwave, 47, 75
Louisiana State University, 95 migration, 9
Low cost, 33, 141 minerals, 2, 32, 54
low tech, 141, 142 Ministry of Education, 1
low temperatures, 198 misleading, 160
low-density, 42, 76, 77, 97, 100, 155, 197, 198, 202 missions, 99
low-tech, 146 mixing, 3, 4, 5, 6, 14, 16, 67, 79, 84, 95, 104, 106,
low-temperature, 8 122, 141, 142, 144, 148, 153, 154, 161, 162, 163,
lubricants, 101 165, 166, 171, 176, 183
lumen, 34, 201 MMA, 87, 88
lysine, 94 mobility, 2, 8, 15, 17, 107, 125, 151, 178, 198, 199
models, 89, 158, 175, 176, 177, 178
modules, 71
M
MOE, 87, 89, 90, 202
moieties, 186
macromolecules, 8, 9, 11, 17, 19, 23
moisture, 1, 2, 8, 17, 18, 20, 21, 22, 23, 24, 25, 27,
magnesium, 86
31, 36, 41, 43, 47, 48, 53, 57, 59, 64, 65, 79, 85,
maize, 92, 158
88, 89, 90, 91, 109, 110, 112, 141, 142, 145, 146,
management, 81, 95
148, 154, 175, 176, 177, 178, 180, 181, 183, 185,
man-made, 37
186, 188, 194, 197, 198, 199, 200, 201, 203
manufacturing, 2, 43, 73, 79, 86, 95, 141, 143, 202
moisture content, 24, 25, 48, 85, 88, 89, 90, 91, 112,
marine environment, 176, 181
148, 154, 197, 198, 199, 200, 201, 203
market, 120
mold, 85, 106, 115, 122, 169
markets, 32
moldings, 42
mass transfer, 201
mole, 19
mastication, 154
molecular mobility, 17
MDH, 97
molecular structure, 94, 101, 104, 106
MDI, 106
molecular weight, 2, 6, 8, 23, 57, 105, 120, 121
measurement, 4, 19, 68, 103, 181
molecules, 8, 13, 18, 23, 34, 55, 64, 87, 88, 92, 94,
measures, 80, 168
100, 102, 104, 105, 106, 112, 142, 147, 148, 177,
mechanical behavior, 8, 11, 13, 17, 39, 74, 77, 78,
178, 186, 187, 188, 190, 198, 199, 200
87, 107
monomer, 40, 88
mechanical energy, 3, 4
monomers, 59, 60, 87, 100
media, 159
Index 213
monosaccharide, 35
montmorillonite, 3, 30
O
morphological, 68, 75, 157, 168
oil, 23, 32, 44, 59, 100, 101, 102, 103, 104, 105, 106,
morphology, 4, 5, 6, 18, 22, 24, 47, 71, 74, 75, 116,
108, 109, 111, 112, 114, 115, 116, 117, 120, 155,
122, 142, 158, 168, 170, 201, 203
158, 201
motion, 8, 9, 14, 24, 119, 146, 198, 200
oils, 99, 100, 102, 103, 104, 105, 114, 116
moulding, 44, 142, 144
oleic acid, 93
movement, 126, 142, 147, 148, 200
oligomeric, 106
MTS, 122
olives, 158
Oregon, 197
N organ, 7, 8, 15, 60
organic, 1, 24, 88, 92, 157, 158, 169
nanocomposites, 7, 10, 15, 28, 77 organic compounds, 92
nanocrystals, 116, 117 organoclay, 7, 8, 15
nanoparticles, 8, 10, 15, 24, 28, 78 organometallic, 60
National Research Council, 117 orientation, 38, 43, 56, 57, 63, 115, 179, 191, 194
native species, 80 oscillation, 124
natural, 2, 3, 14, 24, 27, 28, 29, 30, 31, 32, 33, 34, oxidants, 65
35, 36, 37, 38, 39, 40, 41, 43, 46, 47, 48, 53, 54, oxidation, 20, 38, 61, 63
56, 57, 58, 59, 61, 63, 73, 74, 75, 76, 77, 85, 88, oxidative, 63
92, 100, 104, 115, 120, 141, 142, 154, 156, 157, oxide, 23, 30, 61, 62, 68, 78
158, 176, 186 oxygen, 2, 62, 114
natural environment, 34
natural polymers, 30
P
natural resources, 54
neck, 15
packaging, 2, 30, 54, 158
Netherlands, 162
paints, 101
network, 2, 3, 4, 13, 16, 23, 26, 56, 57, 107, 110,
Paraguay, 101
111, 114, 142, 199
parameter, 55, 57, 84, 85, 94, 124, 131, 136, 168
New Jersey, 139
parenchyma, 153
New York, 51, 74, 75, 97, 138
parenchymal, 147
newspapers, 179
Parkinson, 138
niobium, 78
particles, 4, 5, 6, 7, 9, 10, 13, 14, 22, 81, 82, 83, 84,
nitrate, 68, 88
85, 86, 90, 91, 93, 95, 107, 110, 113, 115, 142,
nitrogen, 19, 124, 128
147, 148, 150, 152, 153, 154, 158
NMR, 139
pathways, 188
noise, 112, 158, 171
pectin, 34, 35, 36, 55
non-crystalline, 36
pectins, 35, 56
non-renewable, 42, 157
peptides, 29
non-uniform, 116
percolation, 13, 147
normal, 146, 178, 182, 183, 191, 192, 193
periodic, 123
not-for-profit, 142
permeability, 3, 23, 130, 175, 176, 179, 194
nucleating agent, 58, 129, 137
permeation, 38, 121
nucleation, 58
permit, 144, 198
nutrition, 79
peroxide, 31, 39, 40, 43, 61, 65, 102
nylon, 41
Perth, 175, 180
petrochemical, 79, 99, 100
petroleum, 2, 24, 88, 99, 100, 176
pH, 2, 68, 132, 144
214 Index
pharmaceutical, 101 polymerization, 4, 6, 31, 33, 36, 40, 56, 100, 120,
phase transitions, 58 201
phenol, 43, 57, 155, 202 polymers, 1, 3, 10, 18, 23, 24, 30, 34, 38, 42, 48, 53,
phosphate, 61 57, 58, 74, 76, 79, 86, 87, 88, 94, 99, 100, 106,
physical and mechanical properties, 43, 48, 85, 88, 107, 114, 119, 131, 139, 142, 153, 158, 177, 186,
91, 200 198, 199
physical properties, 2, 19, 31, 56, 77, 201 polypeptides, 2
pinus, 32 polypropylene, 30, 38, 42, 44, 57, 60, 63, 73, 74, 75,
pith, 143, 147, 148, 152, 153, 154 77, 154, 155, 158
planar, 180, 194 polysaccharides, 25, 56
plants, 32, 36, 54, 57, 80, 100 polystyrene, 38, 40, 42, 57, 63, 106, 154, 158
plasma, 38, 63 polystyrene melt, 154
plastic, 1, 2, 24, 26, 32, 45, 48, 65, 67, 76, 87, 88, 91, polyurethane, 41, 99, 100, 106, 107, 109, 110, 112,
92, 96, 132, 141, 142, 143, 146, 148, 150, 156 114, 116, 117
plastic deformation, 45 polyurethane foam, 41, 100
plasticization, 4, 9, 10, 23, 24, 30, 125 polyurethanes, 99, 100, 102, 103, 106, 108, 115, 116
plasticizer, 1, 2, 9, 14, 17, 18, 22, 24, 93 polyvinyl alcohol, 3, 28, 158
plastics, 1, 2, 15, 21, 25, 26, 28, 29, 32, 33, 34, 49, polyvinyl chloride, 42, 155
53, 73, 97, 99, 138, 142, 145, 147 polyvinylchloride, 96
platelets, 179, 190 poor, 5, 18, 36, 53, 59, 141, 151, 154, 155
play, 35, 56, 59 pores, 84, 182, 183
PLLA, 45 porosity, 80, 85, 182, 183, 184
polar groups, 85, 88, 199 porous, 59, 142, 147
polarity, 142 potassium, 89
polarization, 127 poultry, 120, 138
pollution, 3, 36, 176 poverty, 142
poly(methyl methacrylate), 29, 88 powder, 3, 4, 88, 96
poly(vinyl chloride), 57, 84 precipitation, 80
polydispersity, 121 prediction, 13, 110, 177
polyester, 18, 21, 30, 35, 45, 46, 48, 75, 76, 79, 96, predictive models, 158
97, 158, 175 preservative, 89
polyesters, 3, 15, 26, 158 press, 41, 89, 90, 91, 106, 142, 144, 161, 172, 203
polyethylene, 38, 40, 42, 53, 57, 61, 63, 65, 67, 73, pressure, 3, 4, 41, 53, 87, 88, 143, 144, 168, 169,
74, 75, 76, 77, 78, 93, 141, 155, 158 171, 200, 201
polyhydroxyalcanoates, 158 prices, 33, 96
polymer blends, 18 probability, 148, 177
polymer chains, 36, 125, 177, 199 processing variables, 157, 158, 159, 171
polymer composites, 6, 34, 36, 42, 57, 58, 73, 83, producers, 81
84, 85, 96, 155, 157, 158, 162, 175, 176, 177, 180, production, 2, 24, 32, 33, 34, 41, 43, 57, 63, 74, 76,
181, 186 79, 81, 88, 95, 96, 100, 104, 112, 114, 115, 116,
polymer electrolytes, 28 144, 155, 157, 158, 171, 197, 198
polymer matrix, 8, 40, 41, 53, 54, 59, 61, 64, 67, 79, productivity, 80, 96, 198
82, 83, 87, 88, 92, 94, 113, 127, 131, 134, 180, profit, 142
183, 184, 190 projectiles, 44
polymer molecule, 87, 94, 199, 200 promoter, 41
polymer networks, 30 propagation, 15, 111, 122, 191
polymer systems, 40, 43 propylene, 79, 87, 92, 94
polymeric chains, 58 protection, 80
polymeric composites, 123, 176
polymeric materials, 51, 58, 100, 133
Index 215
protein, 2, 4, 6, 8, 9, 11, 14, 16, 17, 20, 22, 23, 24, relaxation, 1, 107, 108, 111, 113, 126, 127, 178, 199,
25, 26, 27, 28, 29, 30, 34, 79, 86, 87, 88, 89, 90, 200, 201
91, 92, 97, 120 relaxation processes, 107
protein films, 2, 26 renewable resource, 37, 87, 99, 120
proteinase, 21, 132 reparation, 78
proteins, 1, 2, 3, 4, 6, 8, 9, 10, 13, 14, 15, 16, 17, 18, residues, 14, 20, 61, 76, 81, 93, 95
19, 23, 24, 25, 26, 28, 29, 54, 79, 92, 120 resin, 43, 48, 57, 65, 88, 91, 96, 155, 175, 180, 183,
publishers, 154 184, 186, 189, 191, 200
pulp, 32, 44, 54 resins, 25, 34, 42, 45, 79, 100, 102, 176, 179
PVA, 3, 7, 8, 14, 15, 19, 24, 88 resistance, 2, 23, 41, 43, 45, 46, 47, 48, 53, 59, 79,
PVC, 74, 84, 85, 86, 87, 91, 92, 94, 96 82, 85, 88, 90, 91, 92, 94, 95, 97, 103, 111, 116,
PVC matrix, 91, 94 125, 145, 151, 168, 171, 183, 186, 190, 191, 197
pyrolysis, 58 resistivity, 37
resolution, 28
resources, 1, 37, 54, 80, 81, 87, 88, 99, 100, 120,
Q
158, 198
retention, 61, 106, 147
quaternary ammonium, 7, 10
retention volume, 106
rheological properties, 154, 200
R rheology, 26, 28
rice, 158
radiation, 40, 41 rigidity, 45, 57, 108, 111, 113
random, 57, 96, 116, 135, 168, 179 risk, 31, 32, 34
range, 2, 4, 8, 15, 17, 19, 24, 44, 46, 48, 81, 91, 95, rivers, 36
103, 109, 111, 114, 115, 126, 131, 148, 150, 158, room temperature, 5, 23, 44, 63, 89, 92, 108, 110,
163, 198, 200 111, 113, 115, 132, 144, 180, 181
ratio analysis, 134 roughness, 61, 71, 161, 167, 168, 169, 170
raw material, 33, 87, 99, 100, 114, 142, 197, 202 roughness measurements, 161
raw materials, 87, 99, 100, 142 rubber, 8, 48, 195
reactants, 102, 103, 106, 117 rubbery state, 113
reaction rate, 106, 112, 115 Russia, 32
reaction time, 16 rye, 92
reactive groups, 59, 101
reactivity, 26, 29
reagent, 62, 63 S
reasoning, 108
safety, 33
recovery, 39, 73, 199
sample, 19, 68, 83, 91, 115, 122, 126, 130, 131, 135,
recycling, 43, 143
143, 148, 171, 177, 180, 181, 182, 183, 191, 192,
reflection, 68, 153
194
refractory, 42
saturated fat, 23
regular, 114
saturated fatty acids, 23
rehabilitation, 80
saturation, 135
reinforcement, 4, 8, 9, 10, 11, 14, 29, 31, 32, 34, 38,
savings, 37
41, 42, 44, 45, 48, 53, 57, 59, 63, 70, 71, 76, 81,
sawdust, 79
83, 87, 106, 107, 109, 115, 116, 117, 119, 120,
scaffolding, 81
121, 155, 179, 194
scaling, 4
reinforcing fibers, 45, 88, 131
scanning calorimetry, 128
relationship, 4, 12, 85, 92, 136, 181, 197, 201
Scanning electron, 6, 7, 47, 91, 107, 116, 193, 194
relationships, 89, 158, 159, 171
scanning electron microscopy, 46, 68, 71, 84, 119,
122, 169
216 Index
scanning electronic microscopy (SEM), 107 sodium, 16, 24, 29, 41, 48, 63, 68, 86, 88, 91, 92, 96,
scarcity, 120 132, 141, 143
scattering, 35, 68, 162 sodium dodecyl sulfate (SDS), 91
scholarships, 195 sodium hydroxide, 24, 68, 88, 92, 141, 143
sclerenchyma, 54 soil, 21, 27, 80, 84, 159
Scots pine, 203 sol-gel, 6, 28
SDS, 91 solid-state, 28
search, 42 solubility, 16, 23, 26
seawater, 175, 176, 181, 189, 194 solvent, 57, 62, 64, 65, 92, 106
seed, 37, 54 solvents, 47, 57
SEED, 35 sorbitol, 2, 25, 28
seeding, 36 sorption, 48, 155, 175, 176, 194, 200
seeds, 25, 32 sorption kinetics, 48
selecting, 159, 160 South America, 101
SEM, 5, 6, 7, 46, 48, 66, 68, 71, 73, 84, 91, 92, 111, soy, 1, 2, 22, 25, 26, 27, 29, 88, 89, 90, 91, 97
119, 121, 122, 123, 132, 133, 134, 147, 150, 152, soybean, 24, 79, 86, 88
153, 154, 162, 170, 195 SPA, 87, 88, 90
SEM micrographs, 71, 162, 170 species, 55, 80, 88, 102, 105, 106, 198, 200, 202
semi-natural, 80 specific gravity, 54
sensitivity, 9, 22, 23, 96 spectroscopy, 48
separation, 6, 10, 11, 31, 36, 41, 44, 57, 107 spectrum, 68, 104, 105
series, 55, 114, 177 speed, 3, 4, 5, 7, 67, 94, 122, 144, 158, 161, 162,
serine, 120 163, 164, 165, 166, 182
sewage, 159, 161, 167, 171 spherulite, 5, 6
shape, 84, 114, 121, 122, 124, 127, 131, 200 stability, 19, 43, 46, 58, 61, 91, 94, 95, 109, 119, 120,
shaping, 59 129, 130, 131, 132, 137, 159
shear, 125, 178, 202 stabilization, 91
shores, 80 stages, 130, 144, 145, 171
shortage, 100 standard deviation, 147
shoulder, 16 standard error, 162, 163
sign, 147, 160 Standards, 196
signaling, 153 starch, 2, 14, 28, 29, 75, 93, 158, 159
signs, 160 statistical analysis, 157
silane, 23, 31, 39, 43, 60, 61, 64, 65, 77, 94, 97, 141, steel, 44, 144, 182
142, 146, 153, 155 steel plate, 44
silanol groups, 13, 94 steric, 115
silica, 3, 6, 7, 10, 11, 13, 14, 17, 18, 22, 27, 28, 29, 87 stiffness, 2, 39, 56, 58, 91, 115, 123, 124, 178, 198,
silicate, 7, 28, 29, 32, 86, 92 201, 202
silicon, 60, storage, 4, 8, 11, 108, 110, 113, 119, 124, 125, 137
silk, 54, 120 strain, 2, 11, 12, 13, 14, 15, 16, 45, 82, 114, 115,
silver, 68 124, 146, 175, 197, 199, 200, 201
sites, 32, 40, 58, 67, 84, 111 strains, 11, 114
skeleton, 114 streams, 32, 36
Slovenia, 197 stress, 11, 12, 14, 15, 43, 45, 59, 60, 61, 63, 67, 116,
sludge, 159, 161, 167, 169, 171 122, 125, 142, 146, 151, 152, 191, 197, 200, 201
SME, 3, 4 stretching, 11, 63
smoke, 46 strong interaction, 99, 100, 112
smoothness, 167 styrene, 44
social context, 142 sub-Saharan Africa, 80
substances, 34, 79, 88, 94, 95, 142, 148
Index 217
substitution, 33, 87 Thailand, 96

substrates, 38, 63 thermal analysis, 46, 123
sucrose, 2, 25 thermal decomposition, 16
sugar, 56 thermal degradation, 2, 20, 46, 57, 58, 75, 130, 147,
sugarcane, 63, 68, 70, 74, 77, 78 148, 200
sulfate, 24, 91 thermal energy, 4
sulfonamides, 92 thermal expansion, 131
sulfuric acid, 68 thermal properties, 25, 30, 58, 64, 74, , 81, 94, 121
sulphate, 16, 61, 78 thermal resistance, 46
summer, 159, 161, 168, 169, 170, 171 thermal stability, 19, 46, 58, 61, 91, 94, 109, 119,
Sun, 28, 30, 74, 97 130, 131, 132, 137
sunflower, 100 thermal treatment, 16, 29, 30, 83
surface area, 61, 80, 132, 152 thermograms, 129
surface chemistry, 47, 48 thermogravimetric, 20, 61, 109, 119, 121
surface energy, 38, 41, 63 thermogravimetry, 109
surface layer, 202 thermo-mechanical, 137
surface modification, 31, 38, 39, 41, 53, 63 thermoplastic, 1, 11, 15, 23, 25, 26, 29, 31, 38, 42,
surface properties, 25, 38, 63, 201, 202 43, 57, 58, 59, 64, 71, 75, 77, 87, 120, 176
surface roughness, 61, 161, 167, 168, 169, 170 thermoplastic composites, 38, 43, 57, 58, 59, 64
surface tension, 48 thermoplastics, 27, 38, 57, 58, 59, 76, 142
surface treatment, 26, 31, 47, 48, 60, 64, 66, 75, 76, thermoset polymers, 57
77, 81, 86, 91, 92, 96, 97 thermosets, 57
surfactant, 112, 115 thermosetting, 29, 31, 38, 43, 44, 176
surfactants, 33 thermosetting polymer, 38, 43
sustainability, 73 three-dimensional, 2, 57
swelling, 23, 47, 48, 80, 82, 84, 89, 90, 91, 142, 184 threshold, 46
switching, 43 timber, 198, 202
Switzerland, 32 time frame, 170
symbols, 5, 22, 160, 163, 167 tissue, 147
synthesis, 49, 99, 100, 103 titanium, 60, 78
synthetic fiber, 36, 38, 42, 176 Titanium, 77
synthetic polymers, 3, 158 titanium dioxide, 78
TMA, 119, 121, 131
toluene, 39, 67
T
torque, 4
total energy, 45, 111
talc, 60, 176
total product, 42, 81
tannins, 34
toughness, 1, 14, 19, 23, 24, 111, 114, 117, 120, 175,
teflon, 167
176, 181, 182, 183, 189, 191
Teflon, 143, 144, 167, 168
toxic, 21
TEM, 7, 19
toxic products, 21
tensile, 1, 4, 5, 6, 7, 11, 12, 13, 14, 16, 17, 24, 29, 30,
toxicity, 176
37, 38, 39, 41, 44, 47, 54, 56, 61, 63, 70, 71, 74,
trajectory, 191
80, 81, 84, 85, 88, 89, 91, 93, 94, 97, 110, 111,
transesterification, 102
116, 119, 120, 121, 122, 123, 137, 141, 142, 143,
transfer, 43, 45, 59, 60, 61, 63, 142, 200
146, 147, 152, 153, 154, 161, 163, 164
transformations, 158
tension, 45, 48
transglutaminase, 10, 29
tetrahydrofurane, 106
transition, 1, 2, 8, 10, 15, 16, 17, 18, 19, 21, 23, 24,
textile, 32, 36
26, 28, 29, 57, 82, 87, 107, 121, 124, 125, 126,
textiles, 36, 53
197, 198, 199, 200
TGA, 19, 20, 46, 119, 121, 129, 130, 131
218 Index
transition temperature, 1, 2, 8, 10, 24, 82, 87, 121,

W
125, 197, 198, 199, 200
transitions, 8, 9, 10, 139
wastes, 79, 81, 83, 95
transmission, 36
water absorption, 14, 47, 48, 59, 78, 80, 84, 85, 86,
transmission electron microscopy, 36
92, 134, 135, 137, 142, 144, 146, 147, 148, 154,
transparent, 87
155, 159, 176, 182, 185, 190
transport, 177
water diffusion, 176
transportation, 176, 202
water permeability, 3, 175, 176, 194
transverse section, 147
water resources, 80
treatment methods, 31
water sorption, 200
triglyceride, 100, 101, 102, 104, 106, 112, 114
water vapor, 3, 23, 30, 48
triglycerides, 104
water-soluble, 32, 56
waxes, 34, 35, 56, 101
U weak interaction, 163
weakness, 91
uniform, 59, 67, 115, 116, 179 wear, 197
United States, 80, 101, 120, 180 weight loss, 2, 19, 20, 21, 63, 65, 66, 109, 132, 134,
urea, 24, 43, 88 136, 137, 159, 161, 167, 168, 169, 170
urethane, 109 weight ratio, 67, 86, 122
weight reduction, 54
western countries, 36
V
wetting, 61, 63, 64, 107, 112
wheat, 1, 2, 15, 23, 24, 25, 26, 27, 28, 29, 30, 92,
vacuum, 3, 44, 67, 68, 132, 144, 180
141, 142, 143, 144, 147, 148, 150, 155
validation, 161
winter, 159, 161, 167, 168, 169, 170
validity, 158, 160
wood, 3, 27, 38, 41, 43, 54, 60, 63, 76, 77, 79, 87,
values, 4, 9, 10, 21, 33, 46, 54, 68, 75, 89, 91, 93,
91, 93, 96, 97, 99, 100, 101, 106, 107, 108, 109,
103, 104, 106, 112, 115, 116, 125, 126, 130, 132,
110, 111, 112, 113, 115, 116, 117, 154, 155, 157,
148, 150, 157, 159, 160, 162, 166, 168, 169, 171,
158, 159, 161, 162, 170, 171, 197, 198, 199, 200,
183, 184, 202
201, 202, 203, 204
Van der Waals, 95, 120
wood density, 200
vapor, 3, 23, 30, 77, 200
wood products, 96
variables, 25, 43, 56, 89, 158, 159, 160, 161, 162,
wood species, 198
163, 165, 171, 177
woods, 80, 81
variance, 160, 162
wool, 54, 120
variation, 8, 13, 17, 71, 89, 126, 131, 137, 201
workers, 157, 158
vegetable oil, 99, 100, 102, 103, 104, 114, 116, 117
vehicles, 176
velocity, 188 X
versatility, 53
vinyl chloride, 79, 87, 91 X-ray diffraction, 68
vinyl monomers, 59
viscoelastic properties, 125
Y
viscosity, 4, 38, 63, 82, 103, 104, 106, 107, 115, 147,
177, 183
yarn, 3, 16, 88
visible, 7
yield, 1, 14, 36, 37, 115, 198
voids, 14, 107, 142, 170, 186, 188
vulcanizates, 96
Z
zirconium, 60, 63, 68, 70

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CHEMICAL ENGINEERING METHODS AND TECHNOLOGY SERIES

Treatment of Tannery Effluents by Membrane

Handbook of Hydrogels: Properties,

Handbook of Hydrogels: Properties,

Handbook of Membrane Research: Properties,

Chromatography: Types, Techniques and Methods

Green Composites: Properties,

Nova Science Publishers, Inc.

NOTICE TO THE READER

LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Published by Nova Science Publishers, Inc.  New York

Chapter 8 Green Composites Based on Biodegradable

STRUCTURE AND PROPERTIES OF GREEN

Yihu Song and Qiang Zheng

Twin extruder is frequently used to make unplasticized WG blends continuously [52].

WG nanocomposites have been produced by dispersing Cloisite-30B nanoclay into the

Figure 6. Transmission electron microscopy (TEM) images of 3 wt % methyl tallow bis-2-hydroxyethyl

DYNAMIC MECHANICAL AND GLASS TRANSITION BEHAVIORS

Table 1. Influence of HEC content on glass transition temperatures and corresponding

HEC content / wt % Tg1 / C tan at Tg1 Tg2 / C tan at Tg2

Figure 10. Influence of MC content on stress-strain ( - ) relationship of the 25 wt % glycerol

Filler content (wt %) WG/silica composites WG/calcium carbonate composites

Composites using WG/starch/glycerol as matrix and natural fibers as reinforcement have

dramatically to less than 100 % at 50 wt % WG. There is a particle-induced transition from an

INFLUENCE OF PROCESSING CONDITION

INFLUENCE OF PLASTICIZER CONTENT

Glycerol Mechanical properties Glass transition behavior

Table 4. Influence of glycerol content on mechanical properties and moisture absorption

Glycerol content (wt %) Mechanical properties MA / %

Filler content (wt %) WG/silica composites WG/calcium carbonate

Otherwise, addition of a secondary hydrophobic component for lowering the moisture

[18] Hernandez-Munoz, P; Villalobos, R; Chiralt, A. Effect of cross-linking using aldehydes

[68] Coradin, T; Durupthy, O; Livage, J. Interactions of amino-containing peptides with

FLAX AS POTENTIAL FIBER FOR REINFORCEMENT

A. S. Singha and Vijay Kumar Thakur*

TECHNICAL APPLICATIONS OF FLAX FIBER

Homogenization of the fiber‘s properties;

Table.1 Production of plant fiber compared to production of glass-fiber [8].

Fiber Price in comparison to glass-fibers Production (1000t)

I. The natural fibers are very important renewable raw material.

CHEMICAL COMPOSITION OF FLAX FIBER

Table II. Chemical composition and structural parameters

Table III. Chemical composition of different natural fiber [15].

Cotton Jute Flax Ramie Sisal

MECHANICAL PROCESS FOR SEPARATION OF FLAX FIBER

PROPERTIES OF FLAX FIBER

Table IV. Comparative properties of natural fibers and conventional man-made

Fiber Density Diameter Tensile Young‘s Elongation at

SURFACE MODIFICATION OF FLAX FIBER

modifications of natural fibers such as mercerization, isocyanate treatment, acrylation, latex

Fiber-OH + NaOH Fiber-O--Na+ + H2O

Figure 1 Alkali treatments of cellulosic fibers.

Figure 2. Silane treatments of cellulosic fibers [47].

Figure 3. Reaction Between cellulosic-OH groups and benzoyl chloride [48].

Figure 4. Decomposition Reaction of Peroxide [49].

DEVELOPMENT OF NATURAL FIBER COMPOSITES

Thermoplastic polymers constitute an important class of materials with an extensive

Thermosetting polymers also constitute an important class of materials with an extensive

Mechanical Properties of Composites

The mechanical properties of natural fibers reinforced composite depend on many

Tensile Properties of Composites

Natural fiber-reinforced composites often show enhancement in tensile properties upon

Impact Properties of Composites

Table V. Time to ignition of the composites with modar matrix [87].