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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. 䉷 1999 John Wiley & Sons, Inc. Adv in Polymer Techn
18: 351 – 363, 1999

forced polymers offer advantages over other con-

Introduction
O ver the past few decades, we find that poly-
mers 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 pro-
cessing, 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-rein-
Correspondence to: J. P. Jog
ventional materials when specific properties are
compared. These composites are finding applica-
tions in diverse fields from appliances to space-
crafts.
Natural fibers have recently attracted the atten-
tion of scientists and technologists because of the
advantages that these fibers provide over conven-
tional reinforcement materials, and the develop-
ment 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 prop- short
erties are comparable to those of other fibers used standard

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

䊚 1999 by John Wiley and Sons, Inc. CCC 0730-6679/99/040351-13
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NATURAL FIBER POLYMER COMPOSITES

for reinforcements. However, certain drawbacks
such as incompatibility with the hydrophobic poly-
mer 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 com-
posites and address some of the basic issues in de-
velopment of such composites.
Natural Fibers
higher specific properties are one of the major ad-
vantages of using natural fiber composites for ap-
plications wherein the desired properties also in-
clude weight reduction.
MICROSTRUCTURE OF THE FIBERS
Natural fibers themselves are cellulose fiber re-
inforced 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.

Before discussing the methods of the preparation CHEMICAL COMPOSITION OF NATURAL

of these composites and their performance, we de-
scribe the types of natural fibers, their microstruc-
ture, 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 ab-
aca (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 consid-
ered, the natural fibers show values that are com-
parable to or better than those of glass fibers. These
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 re-
sponsible for the biodegradation, moisture absorp-
tion, 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 com-
ponents varies for different fibers. Generally, the fi-
bers contain 60 – 80% cellulose, 5 – 20% lignin, and
up to 20% moisture.
NATURAL FIBER COMPOSITES
The matrix phase plays a crucial role in the per-
formance of polymer composites. Both thermosets
and thermoplastics are attractive as matrix materials
for composites. In thermoset composites, formula-
tion is complex because a large number of compo-

TABLE I
Mechanical Properties of Natural Fibers
Tensile Strength Modulus Specific
Fiber Specific Gravity (MPa) (GPa) Modulus

Jute 1.3 393 55 38

Sisal 1.3 510 28 22
Flax 1.5 344 27 50
Sunhemp 1.07 389 35 32
Pineapple 1.56 170 62 40
short
Glass Fiber-E 2.5 3400 72 28
standard

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NATURAL FIBER POLYMER COMPOSITES

nents are involved such as base resin, curing agents, TABLE II

catalysts, flowing agents, and hardeners. These Reported Work on Natural Fiber Composites
composite materials are chemically cured to a Fiber Matrix Polymer References
highly cross-linked, three-dimensional network
structure. These cross-linked structures are highly Wood flour/fiber PE 5– 12
solvent resistant, tough, and creep resistant. The fi- PP 13– 28
ber loading can be as high as 80% and because of PVC 29– 31
the alignment of fibers, the enhancement in the PS 32– 34
Polyurethane 35
properties is remarkable.
Thermoplastics offer many advantages over ther- Jute PP 36– 40
SBR, nitrile rubber 50, 51
moset polymers. One of the advantages of thermo-
Epoxy 41, 42
plastic matrix composites is their low processing Polyester 43– 49
costs. Another is design flexibility and ease of mold- Phenol–formaldehyde 52
ing complex parts. Simple methods such as extru- Sisal PE 53– 55
sion and injection molding are used for processing Natural rubber 58– 61
of these composites. In thermoplastics most of the Polyester epoxy 56, 57, 62
work reported so far deals with polymers such as Abaca Epoxy 72
polyethylene, polypropylene, polystyrene, and Pineapple PE, polyester 67– 69
poly(vinyl chloride). This is mainly because the pro-
Sunhemp Polyester, PP 76
cessing temperature is restricted to temperatures be-
Oil palm Rubber 80
low 200⬚C to avoid thermal degradation of the nat-
ural fibers. For thermoplastic composites, the Kenaf PE, PP 63– 66
dispersion of the fibers in the composites is also an Coir Natural rubber 75
important parameter to achieve consistency in the Banana Polyester 73– 74
product. Thermoplastic composites are flexible and Flax PP 70– 71
tough and exhibit good mechanical properties. Wheat straw PP 70
However, the % loading is limited by the process- Bamboo Epoxy 78
ability of the composite. The fiber orientation in the
composites is random and accordingly the property
modification is not as high as is observed in ther- Numerous reports are available on the natural
moset composites. fiber composites. Table II summarizes the reported
Properties of the fibers, the aspect ratio of the fi- work on natural fiber composites. As can be seen
bers, and the fiber – matrix interface govern the from the table, the majority of the work is on wood
properties of the composites. The surface adhesion flour, with a few reports on other fibers such as jute,
between the fiber and the polymer plays an impor- sisal, and kenaf.
tant role in the transmission of stress from matrix to
the fiber and thus contributes toward the perform-
ance of the composite.
Another important aspect is the thermal stability Major Issues in Development of
of these fibers. These fibers are lignocellulosic and Composites
consist of mainly lignin, hemicellulose, and cellu-
lose. The cell walls of the fibers undergo pyrolysis
THERMAL STABILITY OF NATURAL
with increasing processing temperature and con-
FIBERS
tribute to char formation. These charred layers help
to insulate the lignocellulosic from further thermal Natural fibers are complex mixtures of organic
degradation. Since most thermoplastics are pro- materials and as a result, thermal treatment leads to
cessed at high temperatures, the thermal stability of a variety of physical and chemical changes. The
the fibers at processing temperatures is important. thermal stability of natural fibers can be studied by
Thus the key issues in development of natural re- thermogravimetric analysis (TGA). A typical TGA
inforced composites are (i) thermal stability of the for jute fibers is shown in Figure 1. As can be seen
fibers, (ii) surface adhesion characteristics of the fi- from the figure, the natural fibers start degrading at
bers, and (iii) dispersion of the fibers in the case of about 240⬚C. The thermal degradation of lignocel- short
thermoplastic composites. lulosic materials has been reviewed by Nguyen standard

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NATURAL FIBER POLYMER COMPOSITES
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 – 280⬚C and another in the range 280 – 300⬚C. The
low-temperature degradation process is associated
with degradation of hemicellulose whereas the
high-temperature process is due to lignin. The ap-
parent activation energies for the two processes are
about 28 and 35 kcal/mol, which correspond to the
degradation of hemicellulose and lignin, respec-
tively. The degradation of natural fibers is a crucial
aspect in the development of natural fiber compos-
ites and thus has a bearing on the curing tempera-
ture in the case of thermosets and extrusion tem-
perature 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 280⬚C. 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 pre-
pared by in situ polymerization of various mono-
mers and it was observed that the maximum rate of
degradation was substantially reduced for phos-
phonate-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.
354
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Sridhar et al.43 have studied the thermal stability of
jute fibers at temperatures ranging from 150 to
300⬚C both in air and under vacuum. The degra-
dation was monitored by measuring the weight
loss, change in chemical structure, and mechanical
properties. It was observed that heating under vac-
uum at 300⬚C for 2 h resulted in 60% decrease in the
tensile strength, which was ascribed to the depoly-
merization and oxidation of fibers. In actual prac-
tice, processing is carried out under atmospheric
conditions and the possibility of thermal degrada-
tion leading to inferior mechanical properties can-
not be ruled out.
Gonzalez and Myers86 – 87 have studied the effect
of thermal degradation on the mechanical proper-
ties of wood/polymer composites. The temperature
range of study was from 220 to 260⬚C and the ex-
posure time was varied from 4 to 4096 min. It was
observed that although, in general, the mechanical
properties deteriorate, as a result of thermal degra-
dation 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 com-
posites. In another study of PP/wood flour com-
posites, similar loss in properties has been reported
after extrusion at 250⬚C.88
The thermal degradation of the fibers also results
in production of volatiles at processing tempera-
tures ⬎ 200⬚C. This can lead to porous polymer
products with lower densities and inferior mechan-
ical 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 dimen-
sional 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 short
biological organisms since they can recognize the standard
VOL. 18, NO. 4
ADV WILEY
carbohydrate polymers in the cell wall. Lignocellu-
losics exposed outdoors undergo photochemical
degradation caused by ultraviolet light. Resistance
to biodegradation and UV radiation can be im-
proved by bonding chemicals to the cell wall poly-
mers 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, com-
pression, transfer, resin transfer, injection, compres-
sion injection, and pressure bag molding operations.
A few other methods such as centrifugal casting, cold
press molding, continuous laminating, encapsula-
tion, filament winding, pultrusion, reinforced reac-
tion injection molding, rotational molding, and vac-
uum 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.
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. Fi-
ber – fiber interactions as well as fiber – matrix inter-
actions play a crucial role in determining the prop-
erties of such composites. Many times, it is observed
that these fibers do not function as an effective re-
inforcement system due to poor adhesion at the fi-
ber – 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 transfer-
ring of stress from the matrix to the fiber. The pre-
treatment of the fiber with suitable additives prior
to processing leads to good dispersion and signifi-
cantly improved mechanical properties of the com-
posites.
The properties of the composites are also influ-
enced 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
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NATURAL FIBER POLYMER COMPOSITES
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 thermo-
plastics 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 prob-
lem.
Various processing aids/coupling agents such
as stearic acid, mineral oil, and maleated ethylene
have been used. The concentration of the addi-
tive is approximately 1% by weight of fibers. The
stearic acid is highly effective in dispersing, re-
ducing fiber to fiber interaction. Mineral oil func-
tions as a lubricant that is adsorbed by the fibers
and this facilitates the disentanglement of individ-
ual fibers.
FIBER – MATRIX INTERFACE
The incorporation of hydrophilic natural fibers in
polymers leads to heterogeneous systems whose
properties are inferior due to lack of adhesion be-
tween 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 mono-
mers, acetylation, and so on. In addition to the sur-
face 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 com-
mercial coupling agents. (The coupling mechanism
for the silane coupling agent is illustrated in the Ap-
pendix.)
MODIFICATION OF NATURAL FIBERS
Natural fibers are incompatible with the hydro-
phobic polymer matrix and have a tendency to form short
aggregates. These are hydrophilic fibers and thus standard
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TABLE III
Some Typical Representative Commercial Coupling Agents115
Sl. No. Functional Group Chemical Structure Applicable Polymera

1 Vinyl CH2 " CHSiCl3 Elastomers, polyethylene, silicone elasto-

2 Chloropropyl
3 Epoxy
4 Methacryl
5 Amine
6 Cationic styryl
7 Phenyl
8 Mercapto
9 Phosphate
(titanate)
10 Neoalkoxy
(zirconate)
a Abbreviations according to ASTM 1600.
CH2 " CHSi(OC2H5 )3 mers, UP, PE, PP, EPDM, EPR
ClCH2CH2CH2Si(OCH3 )3 EP
O Elastomers, especially butyl elastomers, ep-
oxy, phenolic and melamine, PC, PVC, UR
CH2CHCH2O(CH2)3Si(OCH3)3
CH3 Unsaturated polyesters, PE, PP, EPDA,
EPM
CH2 " C 9 COO(CH2)3Si(OCH3)3
H2N(CH2 )3Si(OC2H5 )3 Unsaturated polyesters, PA, PC, PUR, MF,
HN(CH2 )2NH(CH2 )3Si(OCH3 )3 PF, PI, MPF
CH2CHC6H4CH2H⫹H2(CH2 )3Si(OCH3 )3Cl⫺ All polymers
C6H5Si(OCH3 )3 PS, addition to amine silane
HS(CH2 )3Si(OCH3 )3 EP, PUR, SBR, EPDM
HS(CH2 )2Si(OC2H5 )3
O O Polyolefins, ABS, phenolics, polyesters,
PVC, polyurethane, styrenics
C3H7OTi[O 9 P 9 O 9 P(OC8H17)2]3
OH
O O Polyolefins, ABS, phenolics, polyesters,
PVC, polyurethane, styrenics
neoalkoxy-Ti[O 9 P 9 O 9 P(OC8H17)2]3
OH

exhibit poor resistance to moisture. To eliminate the
problems related to high water absorption, treat-
ment of fibers with hydrophobic aliphatic and cyclic
structures has been attempted. These structures
contain reactive functional groups that are cap-
able 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 at-
tempted to make the fibers hydrophobic and to im-
prove 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 mod-
ifying the surface properties of the fibers and for
enhancing its performance. (The mechanisms of
these reactions are discussed in detail in the Appen-
dix.)
Chemical modification of natural fibers has been
reviewed by Rowell.90 Table IV summarizes the var-
ious chemical treatments and coupling agents used
so far for the modification of the fiber surface.
Delignification (dewaxing) is generally carried
out by extracting with alcohol or benzene and treat-
ment 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 al-
kaline reagent on the noncellulosic constituents of
fibers such as hemicellulose and lignin.
Acetylation of jute is reported to impart resist-
ance 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 micro-
organisms cannot recognize them as attachable sub-
strates. Acetylated jute is considerably more hydro-
phobic than unmodified jute.95 The acetylated jute
shrinks much less than unmodified jute when ex-
posed to water and thus exhibits improved dimen- short
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356 VOL. 18, NO. 4

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TABLE IV
Chemical Treatments Used for Modification of Natural Fibers
Fiber Chemical Treatments
Wood flour Succinic acid, EHMA, styrene, urea–formaldehyde, m-phenyl-
ene bismaleimide, acetic anhydride, maleic anhydride, itaconic
anhydride, polyisocyanate, linoleic acid, abietic acid, oxalic acid,
rosin
Jute Phenol– formaldehyde, malemine–formaldehyde, cardanol–
formaldehyde
Sisal NaOH, isocyanate, sodium alginate, N-substituted methacrylam-
ide
Pineapple p-phenylene diamine
Banana Sodium alginate
Coir Sodium alginate, sodium carbonate
Chemical modification through graft copolymer-
ization 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 co-
polymerization of vinyl monomers such as methyl
methacrylate, acrylamide, and acrylonitrile onto cel-
lulose, cellulose derivatives, and lignocellulosic fi-
bers has been well established and has been exten-
sively studied over the past few decades.96 – 98
Impregnation with monomer followed by its po-
lymerization has also been one of the most common
methods used for treatment of fibers. Samal and co-
workers99 have reviewed various methods of graft
copolymerization onto cellulose fibers. Graft copo-
lymerization onto cellulose takes place through an
initiation reaction involving attack by macrocellu-
losic radicals on the monomer to be grafted. The
generation of the macrocellulosic radicals is accom-
plished by a variety of methods such as (1) diazo-
tization, (2) chain transfer reactions, (3) redox reac-
tions, (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 re-
sulted 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 – formalde-
hyde, malemine – formaldehyde, and cashew nut
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Coupling Agents/Compatibilizers
Maleated PP, acrylic acid grafted
PP, Silane A-174, Epolene C-18,
Silane A-172, A-174, and A-1100,
PMPPIC, zirconates, titanates
—
—
—
—
—
shell liquid – formaldehyde improved the wettabil-
ity of jute fibers and reduced the water regain prop-
erties. Treatment with cardanol – formaldehyde
was also found to reduce water absorption and im-
proved the mechanical properties of a jute/polyole-
fin composite.37 The chemical treatment of jute fibers
with ethylenediamine and hydrazine results in for-
mation 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 mod-
ification of pineapple leaf fiber using alkali treat-
ment, diazo coupling with aniline, and cross-linking
with formaldehyde and p-phenylenediamine. These
chemical treatments resulted in significant improve-
ments 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 re-
sistance and they also imparted flame retardancy to
polymer wood composites.
Mechanical Properties of
Natural Fiber Composites
The properties of natural fiber reinforced com-
posites depend on a number of parameters such as
volume fraction of the fibers, fiber aspect ratio, fi-
ber – matrix adhesion, stress transfer at the interface,
and orientation. Most of the studies on natural fiber
composites involve study of mechanical properties short
as a function of fiber content, effect of various treat- standard
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NATURAL FIBER POLYMER COMPOSITES
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 impor-
tant in improving mechanical properties of the com-
posites. The tensile strength is more sensitive to the
matrix properties, whereas the modulus is depen-
dent on the fiber properties. To improve the tensile
strength, a strong interface, low stress concentra-
tion, fiber orientation is required whereas fiber con-
centration, 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 crit-
ical 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 im-
pact strength of a short-fiber-filled composite.105 The
properties mostly vary with composition as per the
rule of mixtures and increase linearly with compo-
sition. However, it has been observed that this linear
dependence on percentage of fiber content does not
hold at high percentage (⬎ 80%) of the fiber, prob-
ably due to lack of wetting of the fiber surface by
the polymer.
THERMOSET COMPOSITES
For thermoset composites, the fibers are com-
bined with phenolic, epoxy, and polyester resins to
form composite materials. These thermoset poly-
mers contain reactive groups, which aid the inter-
face 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 in-
crease 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-
358
LEFT INTERACTIVE
ester composites, it was noted that the mechanical
properties were dependent on the secondary chem-
ical bonding between jute fiber and polyester.45 San-
adi et al.76 have studied the mechanical properties
of sunhemp fiber reinforced polyester. The tensile
strength and modulus increased linearly with in-
creasing 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 prop-
erties was observed only when the fiber weight frac-
tion 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 ex-
hibited 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 bond-
ing 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 in-
creasing cure temperature and maximum strength
was obtained for abaca/polyester composites com-
pared to banana/polyester and rice hull/polyester
composites. The incorporation of pineapple leaf fi-
bers 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 treat-
ments of fibers with silane, titanate, and zirconate
coupling agents and N-substituted methacrylamide
was investigated by Singh et al.56 The treatments re-
sulted in improved strength retention properties of
the composites and thereby the composites exhib-
ited better properties in humid as well as dry con-
ditions. Similar improved moisture resistance was
reported by Bisinda et al.62
For natural rubber composites with sisal fibers,
treatment with resorcinol and hexamethylenetetra-
mine resulted in a better storage modulus. The re-
laxation process for the composites was altered and
the composites exhibited a two-stage relaxation pro-
cess corresponding to the matrix and the interface.
The process was sensitive to the type of bonding short
agent used.60,61 standard
VOL. 18, NO. 4
ADV WILEY
THERMOPLASTIC COMPOSITES
Polyethylene-Based Composites
The mechanical properties of thermoplastic com-
posites can be improved by improving the compat-
ibility between the fiber and matrix. Compatibiliz-
ers such as maleated ethylene, maleated propylene,
and a few acrylic-grafted linear polymers are re-
ported 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 ma-
leated 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 me-
chanical 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 polyi-
socyanate 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 spe-
cific properties. Pretreated wood fiber produced a
significant improvement in tensile strength and
modulus. Grafting of aspen chemithermomechani-
cal 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 in-
vestigated by Joseph et al.55 The chemical treatments
included treatments with sodium hydroxide, iso-
cyanate, and peroxide. The enhancement in the
properties was ascribed to the bonding between si-
sal fiber and the PE matrix. Treatment with the car-
danol derivative of toluene isocyanate was found to
be better than other treatments as evidenced by the
ADVANCES IN POLYMER TECHNOLOGY
RIGHT INTERACTIVE
NATURAL FIBER POLYMER COMPOSITES
decrease in the hydrophilic nature of the composite.
The composites exhibited better dimensional stabil-
ity 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 treat-
ments on the properties of PP/cellulose fiber has
been carried out by Bataille et al.16 The results in-
dicated an increase in modulus with increase in the
fiber content. The addition of coupling agents and/
or maleic anhydride PP improved the interfacial ad-
hesion, 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 anhy-
dride, and bismaleimide-modified PP resulted in a
stable surface and thus improved tensile strength.
An increase in tensile and impact strength was re-
ported 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 reinforce-
ment of balsa wood composites using ethyl-␣-(hy-
droxy methyl)acrylate (EHMA) and styrene. The
significant improvements in the properties were as-
cribed to the strong interaction between the fiber
and the matrix polymer, confirmed by solid-state
NMR and SEM. The composite also exhibited im-
proved 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 ex-
plained on the basis of creation of active sites in the
polymer as well as the fibers, which resulted in im-
proved adhesion.
Significant improvement in the properties was
observed for PP/kenaf fiber composites when ma-
leated 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 fi-
bers with oxalic acid was found to improve the ho- short
mogeneity and mechanical properties of PP, HDPE, standard
359
ADV WILEY
NATURAL FIBER POLYMER COMPOSITES
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 ex-
hibited 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 com-
posites with engineering polymers are scarce. This
is mainly because of the high processing tempera-
ture (⬎ 250⬚C) required for processing of engineer-
ing polymers. The influence of the use of jute fibers
on the mechanical properties of ABS has been stud-
ied by Bawadekar and Jog.110 It has been observed
that the ABS/jute fiber composites show remark-
able 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 particu-
lar application.
Recently, there has been increasing interest in
commercialization of natural fiber composites and
their use, especially for interior paneling in the au-
tomobile industry. These composites with density
around 0.9 g/cm3, stiffness around 3000 MPa, im-
pact strength of 25 kJ/m2, and good sound absorp-
tion characteristics are being used by a number of
leading companies.112 Composites based on polyole-
360
LEFT INTERACTIVE
fins are now commercially available. It is reported
that these composites offer advantages of 20% re-
duction in processing temperature and 25% reduc-
tion 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 200⬚C. 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 indis-
pensable task for the scientist. Such attempts can
widen the applications of natural fiber composites
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Appendix
I. Macromolecule of Cellulose
H OH CH2OH
O O
HO H H
OH H H
H O OH H H
H H
O O
CH2OH H OH
362
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115. Information collected from Union Carbide and Kenrich
company data sheets.
H OH CH2OH
O H OH
OH H H
O OH H
H H
CH2OH H OH
n short
standard
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ADV WILEY RIGHT INTERACTIVE

NATURAL FIBER POLYMER COMPOSITES

II. Bleaching Process Two macrocellulosic radicals might couple to

yield a dimerized product
In industry, the most common process of bleach-
ing the cellulose/jute uses oxidizing agents such as 2CellD !: dimerized polymer
sodium hypochlorite, calcium hypochlorite, or hy-
drogen peroxide. In the reaction process, nascent
(c) Grafting of monomer on acetylated cellu-
oxygen is also reported.93 The nature of the coloring
lose92
matter and the reaction mechanism have not been
reported so far.
O O
(a) With sodium hypochlorite Cell 9 O 9 C ⫹ R Cell 9 O 9 C ⫹ RH ⫹ N
CH3 CH2
NaOCl ⫹ H2O !: NaOH ⫹ HOCl
O
HOCl !: H⫹ ⫹ OCl⫺
Cell 9 C 9 O
HOCl ⫹ H⫹ ⫹ Cl⫺ !: Cl2 ⫹ H2O
CH
(b) With H2O2 M

H2O2 !: HOO⫺ ⫹ H⫹
IV. Coupling Agents

III. Grafting of Monomer on Cellulose Most of the silane/titanate/zirconate coupling

Macromolecule95 agents can be represented as R 9 (CH2 ) 9 X(OR⬘)n ,
where X ⫽ Si, Ti, or Zr, n ⫽ 0 – 3, OR is the hydro-
(a) Formation of the macromolecule radical lyzable alkoxy group, and R and R⬘ are the func-
tional organic groups (Table III). For example, for
Cell 9 H ⫹ RD !: CellD ⫹ R 9 H; triazine coupling agents, triazine derivatives form a
covalent bond with cellulose fibers, schematically
RD ⫽ OHD or SO4D represented as91

(b) Grafting the monomer Cl

Initiation
N N H2Np
CellD ⫹ M !: Cell 9 MD
Cl N Cl
Propagation cellulose fiber

Cell 9 M ⫹ M Cell 9 M2 R R
Cell 9 M n⫺1 ⫹ M Cell 9 Mn HN HN

Termination N N N N

graft Cl N Cl O N Cl
Cell 9 MDn ⫹ Cell 9 MnD !:
copolymer

Dimerization cellulose fiber

short
standard

ADVANCES IN POLYMER TECHNOLOGY 363