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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
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
CCC 0730-6679/99/040351-13
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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.
higher specific properties are one of the major advantages of using natural fiber composites for applications wherein the desired properties also include weight reduction.
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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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
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BIODEGRADATION AND
PHOTODEGRADATION OF NATURAL
FIBERS
Natural fibers (lignocellulosics) are degraded by
biological organisms since they can recognize the
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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.
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Functional Group
Vinyl
2
3
Chloropropyl
Epoxy
Applicable Polymera
Chemical Structure
CH2 " CHSiCl3
CH2 " CHSi(OC2H5 )3
ClCH2CH2CH2Si(OCH3 )3
O
CH2CHCH2O(CH2)3Si(OCH3)3
4
Methacryl
Amine
H2N(CH2 )3Si(OC2H5 )3
HN(CH2 )2NH(CH2 )3Si(OCH3 )3
6
7
8
Cationic styryl
Phenyl
Mercapto
All polymers
PS, addition to amine silane
EP, PUR, SBR, EPDM
Phosphate
(titanate)
CH3
CH2 " C 9 COO(CH2)3Si(OCH3)3
C3H7OTi[O 9 P 9 O 9 P(OC8H17)2]3
OH
10
Neoalkoxy
(zirconate)
neoalkoxy-Ti[O 9 P 9 O 9 P(OC8H17)2]3
OH
a
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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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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
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
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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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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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
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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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-
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References
1. Schneider, J. P.; Myers, G. E.; Clemons, C. M.; English,
B. W. Eng Plast 1995, 8 (3), 207.
2. Reinforced Plastics 1997, 41(11), 22.
3. Colberg, M.; Sauerbier, M. Kunstst-Plast Europe 1997, 87
(12), 9.
4. Schloesser, Th.; Knothe, J. Kunstst-Plast Europe 1997, 87 (9),
25.
5. Beshay, A. D.; Kokta, B. V.; Maldas, D.; Daneault, C. Polym
Compos 1985, 6, 261.
6. Maiti, S. N.; Singh, K. J Appl Polym Sci 1986, 32, 4285.
7. Raj, R. G.; Kokta, B. V.; Maldas, D.; Daneault, C. J Appl
Polym Sci 1989, 37, 1089.
8. Raj, R. G.; Kokta, B. V.; Grouleau, G.; Daneault, C. Polym
Plast Technol Eng 1989, 28 (3), 247.
9. Raj, R. G.; Kokta, B. V.; Grouleau, G.; Daneault, C. Polym
Plast Technol Eng 1990, 29 (4), 339.
10. Raj, R. G.; Kokta, B. V.; Daneault, C. J Mater Sci 1990, 25,
1851.
11. Carrasco, F.; Saurina, J.; Arnau, J. J.; Pages, P. 6th European
Conference on Composite Materials, France, 1993, p 483.
12. Berenbrok, P. A.; Liles, B. E. Special Areas Annual Technical
Conference ANTEC, Toronto, Conference Proceedings,
Vol. 3, pp 2931 2933; Society of Plastics Engineers, Brookfield, CT, 1997.
13. Lightsey, G.; Short, P. H.; Klasinsley, K. S.; Mann, L. J Miss
Acad Sci 1979, 24, 76.
14. Dalvag, H.; Klason, C.; Stromvall, H. E. Int J Polym Mater
1985, 11, 9.
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78. Jain, S.; Kumar, R.; Jindal, U. C. Adv Compos Mater 1990,
135, Oxford IBH Publ Comp Pvt Ltd, New Delhi, India.
79. Ismail, H. R.; Rosnah, N. Polymer 1997, 38, 4059.
86. Gonzalez, C.; Myers, G. E. Int J Polym Mater 1993, 23, 67.
88. Takase, S.; Shiraishi, N. J Appl Polym Sci 1989, 37, 645.
89. Rowell, R. M. ACS Proceedings, Polym Mater Sci Eng 1992,
67, 461.
90. Rowell, R. M.; Clemson, C. M. Proceedings of the 26th International Particleboard/Composites Symposium, WA, p
251, 1992.
92. Mohanty, A. K.; Singh, B. C. J Appl Polym Sci 1987, 34, 1325.
93. Muzumdar, P.; Sanyal, S.; Dasgupta, B.; Shaw, S. C.; Guha,
R. Indian J Fibre Technol 1994, 19, 286.
Appendix
I. Macromolecule of Cellulose
HO
H
OH
OH
H
H
O
OH
OH
H
O
H
OH
O
CH2OH
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CH2OH
O
H
OH
CH2OH
O
H
O
OH
O
CH2OH
OH
H
OH
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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.
O
Cell 9 O 9 C RH N
Cell 9 O 9 C R
CH3
CH2
O
HOCl !: H OCl
Cell 9 C 9 O
CH
(b) With H2O2
H2O2 !: HOO H
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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