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Natural Fiber Polymer


Composites: A Review
D. NABI SAHEB and J. P. JOG
Polymer Engineering Group, Chemical Engineering Division, National Chemical Laboratory,
Pune 411 008, India
Received: May 3, 1999
Accepted: May 19, 1999

ABSTRACT: Natural fiber reinforced composites is an emerging area in


polymer science. These natural fibers are low cost fibers with low density and
high specific properties. These are biodegradable and non-abrasive. The natural
fiber composites offer specific properties comparable to those of conventional
fiber composites. However, in development of these composites, the
incompatibility of the fibers and poor resistance to moisture often reduce the
potential of natural fibers and these draw backs become critical issue. This
review presents the reported work on natural fiber reinforced composites with
special reference to the type of fibers, matrix polymers, treatment of fibers and
fiber-matrix interface. 1999 John Wiley & Sons, Inc. Adv in Polymer Techn
18: 351 363, 1999

Introduction

ver the past few decades, we find that polymers have replaced many of the conventional
metals/materials in various applications. This is
possible because of the advantages polymers offer
over conventional materials. The most important
advantages of using polymers are the ease of processing, productivity, and cost reduction. In most of
these applications, the properties of polymers are
modified using fillers and fibers to suit the high
strength/high modulus requirements. Fiber-reinCorrespondence to: J. P. Jog

Advances in Polymer Technology, Vol. 18, No. 4, 351 363 (1999)


1999 by John Wiley and Sons, Inc.

forced polymers offer advantages over other conventional materials when specific properties are
compared. These composites are finding applications in diverse fields from appliances to spacecrafts.
Natural fibers have recently attracted the attention of scientists and technologists because of the
advantages that these fibers provide over conventional reinforcement materials, and the development of natural fiber composites has been a subject
of interest for the past few years.1 4 These natural
fibers are low-cost fibers with low density and high
specific properties. These are biodegradable and
nonabrasive, unlike other reinforcing fibers. Also,
they are readily available and their specific properties are comparable to those of other fibers used

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for reinforcements. However, certain drawbacks
such as incompatibility with the hydrophobic polymer matrix, the tendency to form aggregates during
processing, and poor resistance to moisture greatly
reduce the potential of natural fibers to be used as
reinforcement in polymers.
In this article, we shall review the reported work
on various aspects of natural fiber reinforced composites and address some of the basic issues in development of such composites.

Natural Fibers
Before discussing the methods of the preparation
of these composites and their performance, we describe the types of natural fibers, their microstructure, and their chemical composition.

TYPES OF NATURAL FIBERS


Natural fibers are grouped into three types: seed
hair, bast fibers, and leaf fibers, depending upon the
source. Some examples are cotton (seed hairs),
ramie, jute, and aflax (bast fibers), and sisal and abaca (leaf fibers). Of these fibers, jute, ramie, flax, and
sisal are the most commonly used fibers for polymer
composites. 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 I.
As can be seen from Table I, the tensile strength
of glass fibers is substantially higher than that of
natural fibers even though the modulus is of the
same order. However, when the specific modulus of
natural fibers (modulus/specific gravity) is considered, the natural fibers show values that are comparable to or better than those of glass fibers. These

higher specific properties are one of the major advantages of using natural fiber composites for applications wherein the desired properties also include weight reduction.

MICROSTRUCTURE OF THE FIBERS


Natural fibers themselves are cellulose fiber reinforced materials as they consist of microfibrils in
an amorphous matrix of lignin and hemicellulose.
These fibers consist of several fibrils that run all
along the length of the fiber. The hydrogen bonds
and other linkages provide the necessary strength
and stiffness to the fibers.

CHEMICAL COMPOSITION OF NATURAL


FIBERS
The chemical composition of natural fibers varies
depending upon the type of fiber. Primarily, fibers
contain cellulose, hemicellulose, pectin, and lignin.
The properties of each constituent contribute to the
overall properties of the fiber. Hemicellulose is responsible for the biodegradation, moisture absorption, and thermal degradation of the fiber as it
shows least resistance whereas lignin is thermally
stable but is responsible for the UV degradation.
The percentage composition of each of these components varies for different fibers. Generally, the fibers contain 60 80% cellulose, 5 20% lignin, and
up to 20% moisture.

NATURAL FIBER COMPOSITES


The matrix phase plays a crucial role in the performance of polymer composites. Both thermosets
and thermoplastics are attractive as matrix materials
for composites. In thermoset composites, formulation is complex because a large number of compo-

TABLE I
Mechanical Properties of Natural Fibers
Fiber

Specific Gravity

Tensile Strength
(MPa)

Modulus
(GPa)

Specific
Modulus

Jute
Sisal
Flax
Sunhemp
Pineapple
Glass Fiber-E

1.3
1.3
1.5
1.07
1.56
2.5

393
510
344
389
170
3400

55
28
27
35
62
72

38
22
50
32
40
28

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nents are involved such as base resin, curing agents,
catalysts, flowing agents, and hardeners. These
composite materials are chemically cured to a
highly cross-linked, three-dimensional network
structure. These cross-linked structures are highly
solvent resistant, tough, and creep resistant. The fiber loading can be as high as 80% and because of
the alignment of fibers, the enhancement in the
properties is remarkable.
Thermoplastics offer many advantages over thermoset polymers. One of the advantages of thermoplastic matrix composites is their low processing
costs. Another is design flexibility and ease of molding complex parts. Simple methods such as extrusion and injection molding are used for processing
of these composites. In thermoplastics most of the
work reported so far deals with polymers such as
polyethylene, polypropylene, polystyrene, and
poly(vinyl chloride). This is mainly because the processing temperature is restricted to temperatures below 200C to avoid thermal degradation of the natural fibers. For thermoplastic composites, the
dispersion of the fibers in the composites is also an
important parameter to achieve consistency in the
product. Thermoplastic composites are flexible and
tough and exhibit good mechanical properties.
However, the % loading is limited by the processability of the composite. The fiber orientation in the
composites is random and accordingly the property
modification is not as high as is observed in thermoset composites.
Properties of the fibers, the aspect ratio of the fibers, and the fiber matrix interface govern the
properties of the composites. The surface adhesion
between the fiber and the polymer plays an important role in the transmission of stress from matrix to
the fiber and thus contributes toward the performance of the composite.
Another important aspect is the thermal stability
of these fibers. These fibers are lignocellulosic and
consist of mainly lignin, hemicellulose, and cellulose. The cell walls of the fibers 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 thermoplastics are processed at high temperatures, the thermal stability of
the fibers at processing temperatures is important.
Thus 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.

ADVANCES IN POLYMER TECHNOLOGY

TABLE II
Reported Work on Natural Fiber Composites
Fiber

Matrix Polymer

Wood flour/fiber

PE
PP
PVC
PS
Polyurethane
PP
SBR, nitrile rubber
Epoxy
Polyester
Phenolformaldehyde
PE
Natural rubber
Polyester epoxy
Epoxy
PE, polyester
Polyester, PP
Rubber
PE, PP
Natural rubber
Polyester
PP
PP
Epoxy

Jute

Sisal

Abaca
Pineapple
Sunhemp
Oil palm
Kenaf
Coir
Banana
Flax
Wheat straw
Bamboo

References
5 12
13 28
29 31
32 34
35
36 40
50, 51
41, 42
43 49
52
53 55
58 61
56, 57, 62
72
67 69
76
80
63 66
75
73 74
70 71
70
78

Numerous reports are available on the natural


fiber composites. Table II summarizes the reported
work on natural fiber composites. As can be seen
from the table, the majority of the work is on wood
flour, with a few reports on other fibers such as jute,
sisal, and kenaf.

Major Issues in Development of


Composites
THERMAL STABILITY OF NATURAL
FIBERS
Natural fibers are complex mixtures of organic
materials and as a result, thermal treatment leads to
a variety of physical and chemical changes. The
thermal stability of natural fibers can be studied by
thermogravimetric analysis (TGA). A typical TGA
for jute fibers is shown in Figure 1. As can be seen
from the figure, the natural fibers start degrading at
about 240C. The thermal degradation of lignocellulosic materials has been reviewed by Nguyen

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FIGURE 1. Typical TGA thermogram of cellulose fiber


(jute powder).

et al. in detail for modified and unmodified


materials.81,82
The thermal degradation of natural fibers is a
two-stage process, one in the temperature range
220 280C and another in the range 280 300C. The
low-temperature degradation process is associated
with degradation of hemicellulose whereas the
high-temperature process is due to lignin. The apparent activation energies for the two processes are
about 28 and 35 kcal/mol, which correspond to the
degradation of hemicellulose and lignin, respectively. The degradation of natural fibers is a crucial
aspect in the development of natural fiber composites and thus has a bearing on the curing temperature in the case of thermosets and extrusion temperature in thermoplastic composites.
For improvement of thermal stability, attempts
have been made to coat the fibers and/or to graft
the fibers with monomers. Grafting is possible since
the lignin can react with the monomers. Mohanty et
al.83 have reported that grafting of acrylonitrile on
jute improved the thermal stability as evidenced by
the increase in the degradation temperature from
170 to 280C. Sabaa84 has also reported improved
thermal stability for acrylonitrile-grafted sisal fibers
as evidenced by the increased initial degradation
temperature, lowering of the rate of degradation,
and the total weight loss. In another study by Yap
et al.,85 the polymer wood composites were prepared by in situ polymerization of various monomers and it was observed that the maximum rate of
degradation was substantially reduced for phosphonate-treated wood flour.
The degradation of natural fibers leads to poor
organoleptic properties such as odor and color and
also deterioration of their mechanical properties.

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Sridhar et al.43 have studied the thermal stability of


jute fibers at temperatures ranging from 150 to
300C both in air and under vacuum. The degradation was monitored by measuring the weight
loss, change in chemical structure, and mechanical
properties. It was observed that heating under vacuum at 300C for 2 h resulted in 60% decrease in the
tensile strength, which was ascribed to the depolymerization and oxidation of fibers. In actual practice, processing is carried out under atmospheric
conditions and the possibility of thermal degradation leading to inferior mechanical properties cannot be ruled out.
Gonzalez and Myers86 87 have studied the effect
of thermal degradation on the mechanical properties of wood/polymer composites. The temperature
range of study was from 220 to 260C and the exposure time was varied from 4 to 4096 min. It was
observed that although, in general, the mechanical
properties deteriorate, as a result of thermal degradation of wood flour, toughness and bending
strength were more affected. It was also pointed out
that the changes in the surface chemistry might
cause changes in the wood/polymer bonding that
is responsible for the inferior properties of the composites. In another study of PP/wood flour composites, similar loss in properties has been reported
after extrusion at 250C.88
The thermal degradation of the fibers also results
in production of volatiles at processing temperatures 200C. This can lead to porous polymer
products with lower densities and inferior mechanical properties.

MOISTURE CONTENT OF THE FIBERS


Cellulosic fibers are hydrophilic and absorb
moisture. The moisture content of the fibers can
vary between 5 and 10%. This can lead to dimensional variations in composites and also affects the
mechanical properties of the composites. During
processing of composites based on thermoplastics,
the moisture content can lead to poor processability
and porous products. Treatment of natural fibers
with chemicals or grafting of vinyl monomers can
reduce the moisture gain.

BIODEGRADATION AND
PHOTODEGRADATION OF NATURAL
FIBERS
Natural fibers (lignocellulosics) are degraded by
biological organisms since they can recognize the

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carbohydrate polymers in the cell wall. Lignocellulosics exposed outdoors undergo photochemical
degradation caused by ultraviolet light. Resistance
to biodegradation and UV radiation can be improved by bonding chemicals to the cell wall polymers or by adding polymer to the cell matrix.

PROCESSING OF THERMOSET
COMPOSITES
Thermosets are processed by simple processing
techniques such as hand layup and spraying, compression, transfer, resin transfer, injection, compression injection, and pressure bag molding operations.
A few other methods such as centrifugal casting, cold
press molding, continuous laminating, encapsulation, filament winding, pultrusion, reinforced reaction injection molding, rotational molding, and vacuum forming are being used for composites but use
of these methods for natural fiber composites is
hardly reported. In thermoset polymers, the fibers
are used as unidirectional tapes or mats. These are
impregnated with the thermosetting resins and then
exposed to high temperature for curing to take place.

pounding PP/wood composites. It was observed


that tensile strength varied nonlinearly with rpm,
mixing temperature, and time, indicating that fiber
length and dispersion need to be optimum to obtain
enhanced properties.

Dispersion of the Fibers in the Matrix


The incorporation of cellulosic fibers in thermoplastics leads to poor dispersion of the fibers due to
strong interfiber hydrogen bonding, which holds
the fibers together. Treatment of the fibers and/or
use of external processing aids can reduce this problem.
Various processing aids/coupling agents such
as stearic acid, mineral oil, and maleated ethylene
have been used. 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 functions as a lubricant that is adsorbed by the fibers
and this facilitates the disentanglement of individual fibers.

FIBER MATRIX INTERFACE


PROCESSING OF THERMOPLASTIC
COMPOSITES
The processing of natural fiber thermoplastic
composites involves extrusion of the ingredients at
melt temperatures followed by shaping operations
such as injection molding and thermoforming. Fiber fiber interactions as well as fiber matrix interactions play a crucial role in determining the properties of such composites. Many times, it is observed
that these fibers do not function as an effective reinforcement system due to poor adhesion at the fiber matrix interface. Cellulose fibers also tend to
aggregate and therefore the fibers do not disperse
well in a hydrophobic polymer matrix and thus
pose difficulties in achieving a uniform distribution
of fiber in the matrix. The surface characteristics of
the reinforcing fiber are important in the transferring of stress from the matrix to the fiber. The pretreatment of the fiber with suitable additives prior
to processing leads to good dispersion and significantly improved mechanical properties of the composites.
The properties of the composites are also influenced by the processing parameters in the case of
thermoplastic composites. Takase and Shiraishi88
have reported the effect of processing parameters
such as mixing time, rpm, and temperature in com-

ADVANCES IN POLYMER TECHNOLOGY

The incorporation of hydrophilic natural fibers in


polymers leads to heterogeneous systems whose
properties are inferior due to lack of adhesion between the fibers and the matrix. Thus the treatment
of fibers for improved adhesion is a critical step in
the development of such composites. The treatment
of the fibers may be bleaching, grafting of monomers, acetylation, and so on. In addition to the surface treatment of fibers, use of a compatibilizer or a
coupling agent for effective stress transfer across the
interface can also be explored. The compatibilizer
can be polymers 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. Table III presents the structures,
functional groups, and applications of a few commercial coupling agents. (The coupling mechanism
for the silane coupling agent is illustrated in the Appendix.)

MODIFICATION OF NATURAL FIBERS


Natural fibers are incompatible with the hydrophobic polymer matrix and have a tendency to form
aggregates. These are hydrophilic fibers and thus

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TABLE III
Some Typical Representative Commercial Coupling Agents115
Sl. No.

Functional Group

Vinyl

2
3

Chloropropyl
Epoxy

Applicable Polymera

Chemical Structure
CH2 " CHSiCl3
CH2 " CHSi(OC2H5 )3
ClCH2CH2CH2Si(OCH3 )3
O

Elastomers, polyethylene, silicone elastomers, UP, PE, PP, EPDM, EPR


EP
Elastomers, especially butyl elastomers, epoxy, phenolic and melamine, PC, PVC, UR

CH2CHCH2O(CH2)3Si(OCH3)3
4

Methacryl

Amine

H2N(CH2 )3Si(OC2H5 )3
HN(CH2 )2NH(CH2 )3Si(OCH3 )3

Unsaturated polyesters, PA, PC, PUR, MF,


PF, PI, MPF

6
7
8

Cationic styryl
Phenyl
Mercapto

All polymers
PS, addition to amine silane
EP, PUR, SBR, EPDM

Phosphate
(titanate)

CH2CHC6H4CH2HH2(CH2 )3Si(OCH3 )3Cl


C6H5Si(OCH3 )3
HS(CH2 )3Si(OCH3 )3
HS(CH2 )2Si(OC2H5 )3
O
O

Unsaturated polyesters, PE, PP, EPDA,


EPM

CH3
CH2 " C 9 COO(CH2)3Si(OCH3)3

C3H7OTi[O 9 P 9 O 9 P(OC8H17)2]3

Polyolefins, ABS, phenolics, polyesters,


PVC, polyurethane, styrenics

OH
10

Neoalkoxy
(zirconate)

neoalkoxy-Ti[O 9 P 9 O 9 P(OC8H17)2]3

Polyolefins, ABS, phenolics, polyesters,


PVC, polyurethane, styrenics

OH
a

Abbreviations according to ASTM 1600.

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. These structures
contain reactive functional groups that are capable of bonding to the reactive groups in the matrix
polymer, e.g., the carboxyl group of the polyester
resin. Thus modification of natural fibers is attempted to make the fibers hydrophobic and to improve interfacial adhesion between the fiber and the
matrix polymer.89 103 Chemical treatments such as
dewaxing (defatting), delignification, bleaching,
acetylation, and chemical grafting are used for modifying the surface properties of the fibers and for
enhancing its performance. (The mechanisms of
these reactions are discussed in detail in the Appendix.)
Chemical modification of natural fibers has been
reviewed by Rowell.90 Table IV summarizes the various chemical treatments and coupling agents used
so far for the modification of the fiber surface.
Delignification (dewaxing) is generally carried

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out by extracting with alcohol or benzene and treatment with NaOH followed by drying at room
temperature.93 Many oxidative bleaching agents
such as alkaline calcium or sodium hypochlorite
and hydrogen peroxide are commercially used.
Bleaching generally results in loss of weight and
tensile strength.94 These losses are mainly attributed
to the action of the bleaching agent or alkali or alkaline reagent on the noncellulosic constituents of
fibers such as hemicellulose and lignin.
Acetylation of jute is reported to impart resistance to fungal attack and hydrophobicity. The
change in properties is attributed to the decrease in
moisture sorption in the cell walls and blocking of
the hydroxyl group of the wall components in such
a way that enzymes of the wood-degrading microorganisms cannot recognize them as attachable substrates. Acetylated jute is considerably more hydrophobic than unmodified jute.95 The acetylated jute
shrinks much less than unmodified jute when exposed to water and thus exhibits improved dimensional stability.

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TABLE IV
Chemical Treatments Used for Modification of Natural Fibers
Fiber

Chemical Treatments

Coupling Agents/Compatibilizers

Wood flour

Succinic acid, EHMA, styrene, ureaformaldehyde, m-phenylene bismaleimide, acetic anhydride, maleic anhydride, itaconic
anhydride, polyisocyanate, linoleic acid, abietic acid, oxalic acid,
rosin
Phenol formaldehyde, malemineformaldehyde, cardanol
formaldehyde
NaOH, isocyanate, sodium alginate, N-substituted methacrylamide
p-phenylene diamine
Sodium alginate
Sodium alginate, sodium carbonate

Maleated PP, acrylic acid grafted


PP, Silane A-174, Epolene C-18,
Silane A-172, A-174, and A-1100,
PMPPIC, zirconates, titanates

Jute
Sisal
Pineapple
Banana
Coir

Chemical modification through graft copolymerization provides a potential route for significantly
altering their physical and mechanical properties.
Chemical grafting involves attaching to the surface
of a fiber/filler a suitable polymer with a solubility
parameter similar to that of the polymer matrix,
which acts as an interfacial agent and improves the
bonding between the fiber and the matrix. Graft copolymerization of vinyl monomers such as methyl
methacrylate, acrylamide, and acrylonitrile onto cellulose, cellulose derivatives, and lignocellulosic fibers has been well established and has been extensively studied over the past few decades.96 98
Impregnation with monomer followed by its polymerization has also been one of the most common
methods used for treatment of fibers. Samal and coworkers99 have reviewed various methods of graft
copolymerization onto cellulose fibers. Graft copolymerization onto cellulose takes place through an
initiation reaction involving attack by macrocellulosic radicals on the monomer to be grafted. The
generation of the macrocellulosic radicals is accomplished by a variety of methods such as (1) diazotization, (2) chain transfer reactions, (3) redox reactions, (4) photochemical initiation, and (5)
radiation-induced synthesis.
The effect of treatments with other chemicals, for
instance, sodium alginate and sodium hydroxide,
has been reported for coir, banana, and sisal fibers
by Mani and Satyanarayan.100 The treatment resulted in an increase in debonding stress and thus
improved the ultimate tensile strength up to 30%.
Basak et al.39 have reported that treatment of jute
with polycondensates such as phenol formaldehyde, malemine formaldehyde, and cashew nut

ADVANCES IN POLYMER TECHNOLOGY

shell liquid formaldehyde improved the wettability of jute fibers and reduced the water regain properties. Treatment with cardanol formaldehyde
was also found to reduce water absorption and improved the mechanical properties of a jute/polyolefin composite.37 The chemical treatment of jute fibers
with ethylenediamine and hydrazine results in formation of complexes with the hydroxyl group of the
cellulose and thus reduces the moisture absorption
of the fiber.46,47
Samal and Ray102 have studied the chemical modification of pineapple leaf fiber using alkali treatment, diazo coupling with aniline, and cross-linking
with formaldehyde and p-phenylenediamine. These
chemical treatments resulted in significant improvements in mechanical properties, chemical resistance,
and reduced moisture regain. A study by Yap et
al.103 has shown that the treatment of wood with
vinyl monomers improved termite and funogal resistance and they also imparted flame retardancy to
polymer wood composites.

Mechanical Properties of
Natural Fiber Composites
The properties of natural fiber reinforced composites depend on a number of parameters such as
volume fraction of the fibers, fiber aspect ratio, fiber matrix adhesion, stress transfer at the interface,
and orientation. Most of the studies on natural fiber
composites involve study of mechanical properties
as a function of fiber content, effect of various treat-

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ments of fibers, and the use of external coupling
agents.104 108 Other aspects include the prediction of
modulus and strength using some well-established
models for two-phase systems and comparison with
experimental data.104
Both the matrix and fiber properties are important in improving mechanical properties of the 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 for determining
the fracture properties. In short-fiber-reinforced
composites, there exists a critical fiber length that is
required to develop its full stressed condition in the
polymer matrix. Fiber lengths shorter than this critical length lead to failure due to debonding 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, good 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-fiber-filled composite.105 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 fiber, probably due to lack of wetting of the fiber surface by
the polymer.

THERMOSET COMPOSITES
For thermoset composites, the fibers are combined with phenolic, epoxy, and polyester resins to
form composite materials. These thermoset polymers contain reactive groups, which aid the interface development. The reported work on thermoset
composites covers the effect of process parameters
such as curing temperature and various treatments
on the properties of composites.
For jute/polyester composites, an increase in
modulus and strength was reported up to a volume
fraction of 0.6 followed by a decrease. Further increase in volume fraction resulted in a decrease in
the properties, which was attributed to insufficient
wetting of the fiber.44 In another study of jute/poly-

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ester composites, it was noted that the mechanical


properties were dependent on the secondary chemical bonding between jute fiber and polyester.45 Sanadi et al.76 have studied the mechanical properties
of sunhemp fiber reinforced polyester. The tensile
strength and modulus increased linearly with increasing fiber content following the rule of mixtures.
The improved toughness was ascribed to the fiber
pullout mechanism in the composite. In banana/
polyester composites, the improvement in the properties was observed only when the fiber weight fraction was more than 19%. At 30% fiber content, the
flexural strength was 97 MPa and elastic modulus
was 6.5 GPa.73 Jain et al.78 have studied bamboo/
epoxy composites up to a volume fraction of 0.85. It
was noted that the composites with banana fiber exhibited better tensile, impact, and flexural strength
compared with the properties of other natural fiber
composites.
Ismail and Rosnah79 have studied the curing
characteristics of oil/palm fiber reinforced rubber
composites. It was noted that the presence of bonding agents prolonged the curing time; however, the
mechanical properties were better due to improved
interfacial bonding as evidenced by SEM studies.
Tobias and Ibarra74 have studied the effect of cure
temperature on flexural strength of polyester-based
composites. The flexural strength increased with increasing cure temperature and maximum strength
was obtained for abaca/polyester composites compared to banana/polyester and rice hull/polyester
composites. The incorporation of pineapple leaf fibers in polyester resulted in an increase of 2.3 times
in the specific flexural stiffness at 30 wt% content of
the fiber.68 The use of Silane A-172 further improved
the properties of the composites.
For sisal/polyester composites, the effect of treatments of fibers with silane, titanate, and zirconate
coupling agents and N-substituted methacrylamide
was investigated by Singh et al.56 The treatments resulted in improved strength retention properties of
the composites and thereby the composites exhibited better properties in humid as well as dry conditions. Similar improved moisture resistance was
reported by Bisinda et al.62
For natural rubber composites with sisal fibers,
treatment with resorcinol and hexamethylenetetramine resulted in a better storage modulus. The relaxation process for the composites was altered and
the composites exhibited a two-stage relaxation process corresponding to the matrix and the interface.
The process was sensitive to the type of bonding
agent used.60,61

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THERMOPLASTIC COMPOSITES
Polyethylene-Based Composites
The mechanical properties of thermoplastic composites can be improved by improving the compatibility between the fiber and matrix. Compatibilizers such as maleated ethylene, maleated propylene,
and a few acrylic-grafted linear polymers are reported to enhance the adhesion between the fiber
and polymer matrix.5 12 For HDPE/cellulose fiber
composites (at 10 and 30% fiber concentration), the
best improvement in tensile strength and tensile
modulus was achieved with maleated ethylene. The
enhancement in the properties was attributed to the
coupling reaction (ester linkage) between the maleated ethylene and the hydroxyl group of cellulose,
which improves the bonding between the fiber and
matrix.7
Mechanical properties of HDPE/wood fiber
composites have been studied by Carrasco et al.11
Two types of coupling agents Epolene C-18 and
Silane 174 were evaluated. Use of silane coupling
agents resulted in composites with better properties
than those of Epolene-treated and untreated wood
fiber. The influence of coupling agents on the mechanical properties of HDPE/wood fibers has also
been studied by Raj et al.4,5 It has been observed that
incorporation of wood fibers in HDPE resulted in
an increase in the stiffness and decrease in tensile
strength for untreated wood fibers. Treatment of
wood fibers with silane coupling agent and polyisocyanate resulted in an increase in tensile strength.
Raj et al.7 have compared the tensile and impact
properties of LLDPE/wood fiber composites with
mica and glass fiber composites and have shown
that the potential advantage of using wood fibers as
reinforcement is in terms of material cost and specific properties. Pretreated wood fiber produced a
significant improvement in tensile strength and
modulus. Grafting of aspen chemithermomechanical pulp was found to improve the mechanical
properties of LLDPE composites as noted by Beshay
et al.5
The influence of various chemical treatments on
the properties of sisal/PE composites has been investigated by Joseph et al.55 The chemical treatments
included treatments with sodium hydroxide, isocyanate, and peroxide. The enhancement in the
properties was ascribed to the bonding between sisal fiber and the PE matrix. Treatment with the cardanol derivative of toluene isocyanate was found to
be better than other treatments as evidenced by the

ADVANCES IN POLYMER TECHNOLOGY

decrease in the hydrophilic nature of the composite.


The composites exhibited better dimensional stability and retention of properties even after aging,
which was ascribed to the improved moisture
resistance.54

PP-Based Composites
A systematic study of the effect of surface treatments on the properties of PP/cellulose fiber has
been carried out by Bataille et al.16 The results indicated an increase in modulus with increase in the
fiber content. The addition of coupling agents and/
or maleic anhydride PP improved the interfacial adhesion, thereby leading to improved properties.
Sain et al.21 have reported that the properties of PP/
wood fiber composites were very poor due to the
absence of interface modifiers. However, it was
noted that use of maleated PP, itaconic anhydride, and bismaleimide-modified PP resulted in a
stable surface and thus improved tensile strength.
An increase in tensile and impact strength was reported when rosin was used in PP/wood flour
composites.13
Sun and Hawke24 have studied the performance
of wood fiber composites using polyisocyanate as a
bonding material. Sain et al.20 have demonstrated
the use of bismaleimide modification for improving
the properties of PP/wood fiber composites. Write
and Mathias18 have reported synergistic reinforcement of balsa wood composites using ethyl--(hydroxy methyl)acrylate (EHMA) and styrene. The
significant improvements in the properties were ascribed to the strong interaction between the fiber
and the matrix polymer, confirmed by solid-state
NMR and SEM. The composite also exhibited improved dimensional stability. Tibor23 has reported
that the properties of electron beam processed PP/
wood fiber composites were significantly better
than those of conventionally processed composites.
The improvement in the performance was explained on the basis of creation of active sites in the
polymer as well as the fibers, which resulted in improved adhesion.
Significant improvement in the properties was
observed for PP/kenaf fiber composites when maleated PP was used for modifying the fiber matrix
interface.64 66 Dalvag et al.14 used maleic anhydride
modified propylene to improve the strength and
ductility of PP/wood fiber and PP/cellulose flour
composites. Hydrolytic pretreatment of cellulose fibers with oxalic acid was found to improve the homogeneity and mechanical properties of PP, HDPE,

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and PS that contained various amounts of bleached
pulp.15
Improvement in the mechanical strength of wood
fiber filled thermoplastic composites has been
achieved with the use of coupling agents. Cellulose
fibers treated with vinyl chloride, plasticizers, and
an isocyanate produced better adhesion with silane
coupling agents A-172 and A-174, and A-1100 exhibited better bonding between the fibers and PVC
matrix.29 31
The physical properties of silane-treated wood/
PMMA composites were studied by Elvy et al.109 As
a result of treatment, the compressive strength was
found to increase from 180 to 210% for treated wood
fiber composites. The increased values of stress are
attributed to the incorporation of polymer into the
void spaces in the wood fiber.
As discussed earlier, reports on wood fiber composites with engineering polymers are scarce. This
is mainly because of the high processing temperature ( 250C) required for processing of engineering polymers. The influence of the use of jute fibers
on the mechanical properties of ABS has been studied by Bawadekar and Jog.110 It has been observed
that the ABS/jute fiber composites show remarkable improvement in the flexural modulus from
2000 to 3500 MPa at 30% jute fiber content. The
composites showed marginal changes in the tensile
strength values whereas tensile modulus increased
with increase in jute fiber content. Surface treatment
of jute using coupling agents was found to result in
further improvement in the modulus.111

Recent Developments
A natural fiber composite with an outstanding
combination of properties is not a dream today. Use
of proper processing techniques, fiber treatments,
and compatibilizers/coupling agents can lead to
composites with optimum properties for a particular application.
Recently, there has been increasing interest in
commercialization of natural fiber composites and
their use, especially for interior paneling in the automobile industry. These composites with density
around 0.9 g/cm3, stiffness around 3000 MPa, impact strength of 25 kJ/m2, and good sound absorption characteristics are being used by a number of
leading companies.112 Composites based on polyole-

360

fins are now commercially available. It is reported


that these composites offer advantages of 20% reduction in processing temperature and 25% reduction in cycle time in addition to a weight reduction
of about 30%.113 The composites provide woodlike
appearance without requiring the maintenance. The
extruded profiles can be used as a wood substitute
in various applications such as window systems and
decking.114
These developments are confined to polymer
composites based on PE, PP, PS, and PVC, for which
the processing temperature is about 200C. The real
challenge for the scientist is to improve the thermal
stability of these fibers so that they can be used with
engineering polymers and further the advantage of
both the polymers and the fibers. Thus improved
thermal stability of natural fibers and modification
of fibers for better performance are still an indispensable task for the scientist. Such attempts can
widen the applications of natural fiber composites

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Appendix
I. Macromolecule of Cellulose

HO
H

OH

OH
H

H
O

OH

OH
H

O
H
OH

O
CH2OH

362

CH2OH

O
H

OH

CH2OH
O

H
O

OH

O
CH2OH

OH

H
OH

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II. Bleaching Process

Two macrocellulosic radicals might couple to


yield a dimerized product

In industry, the most common process of bleaching the cellulose/jute uses oxidizing agents such as
sodium hypochlorite, calcium hypochlorite, or hydrogen peroxide. In the reaction process, nascent
oxygen is also reported.93 The nature of the coloring
matter and the reaction mechanism have not been
reported so far.

2CellD !: dimerized polymer


(c) Grafting of monomer on acetylated cellulose92
O

O
Cell 9 O 9 C RH N

Cell 9 O 9 C R

(a) With sodium hypochlorite

CH3

NaOCl H2O !: NaOH HOCl

CH2
O

HOCl !: H OCl

Cell 9 C 9 O

HOCl H Cl !: Cl2 H2O

CH
(b) With H2O2

H2O2 !: HOO H

III. Grafting of Monomer on Cellulose


Macromolecule95
(a) Formation of the macromolecule radical
Cell 9 H RD !: CellD R 9 H;
RD OHD or SO4D

IV. Coupling Agents


Most of the silane/titanate/zirconate coupling
agents can be represented as R 9 (CH2 ) 9 X(OR)n ,
where X Si, Ti, or Zr, n 0 3, OR is the hydrolyzable alkoxy group, and R and R are the functional organic groups (Table III). For example, for
triazine coupling agents, triazine derivatives form a
covalent bond with cellulose fibers, schematically
represented as91

(b) Grafting the monomer


Initiation

Cl
N

CellD M !: Cell 9 MD
Cl

N
N

H2Np

Cl

Propagation
Cell 9 M M
Cell 9 M n1 M

cellulose fiber

Cell 9 M2
Cell 9 Mn

Termination
Cell 9 MDn Cell 9 MnD !:

HN

HN

N
graft
copolymer

Dimerization

Cl

N
N

N
Cl

N
N

Cl

cellulose fiber

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