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Chemical Treatments of Natural Fiber for Use

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J Polym Environ (2007) 15:2533
DOI 10.1007/s10924-006-0042-3
ORIGINAL PAPER
Chemical Treatments of Natural Fiber for Use in Natural
Fiber-Reinforced Composites: A Review
Xue Li Lope G. Tabil Satyanarayan Panigrahi
Published online: 4 January 2007

Springer Science+Business Media, LLC 2006
Abstract Studies on the use of natural fibers as
replacement to man-made fiber in fiber-reinforced
composites have increased and opened up further
industrial possibilities. Natural fibers have the advan-
tages of low density, low cost, and biodegradability.
However, the main disadvantages of natural fibers in
composites are the poor compatibility between fiber
and matrix and the relative high moisture sorption.
Therefore, chemical treatments are considered in
modifying the fiber surface properties.
In this paper, the different chemical modifications
on natural fibers for use in natural fiber-reinforced
composites are reviewed. Chemical treatments includ-
ing alkali, silane, acetylation, benzoylation, acrylation,
maleated coupling agents, isocyanates, permanganate
and others are discussed. The chemical treatment of
fiber aimed at improving the adhesion between the
fiber surface and the polymer matrix may not only
modify the fiber surface but also increase fiber
strength. Water absorption of composites is reduced
and their mechanical properties are improved.
Keywords Fiber-reinforced composites
Natural
fiber
Chemical modifications
Chemical coupling
agents
Surface treatments
X. Li
L. G. Tabil (&)
S. Panigrahi
Department of Agricultural and Bioresource Engineering,
University of Saskatchewan, 57 Campus Drive, Saskatoon,
SK, Canada S7N 5A9
e-mail: lope.tabil@usask.ca
X. Li
e-mail: xul214@mail.usask.ca
S. Panigrahi
e-mail: sap382@mail.usask.ca
Introduction
Processing of plastic composites using natural fibers as
reinforcement has increased dramatically in recent
years [15]. Fiber-reinforced composites consist of
fiber as reinforcement and a polymer as matrix. Plastic
polymers including high density polyethylene (HDPE),
low density polyethylene (LDPE), polypropylene (PP),
polyether ether ketone (PEEK), etc. have been
reported as the matrices [19]. Traditional fiber-rein-
forced composites use various types of glass, carbon,
aluminum oxide, and many others as reinforcing
component. Natural fibers, especially bast (bark)
fibers, such as flax, hemp, jute, henequen and many
others were applied by some researchers as fiber
reinforcement for composites in recent years. [15,
911]. Advantages of natural fibers over man-made
fibers include low density, low cost, recyclability and
biodegradablility [1214]. These advantages make
natural fibers potential replacement for glass fibers in
composite materials. Mechanical properties of natural
fibers, especially flax, hemp, jute and sisal, are very
good and may compete with glass fiber in specific
strength and modulus [15, 16]. Table 1 lists the
mechanical properties of some natural and man-made
fibers. Natural fiber-reinforced composites can be
applied in the plastics, automobile and packaging
industries to cut down on material cost [17].
A better understanding of the chemical composition
and surface adhesive bonding of natural fiber is
necessary for developing natural fiber-reinforced com-
posites. The components of natural fibers include
cellulose, hemicellulose, lignin, pectin, waxes and
water soluble substances. The composition of selected
natural fibers is shown in Table 2 [18, 19]. The
123
26 J Polym Environ (2007) 15:2533

Table 1 Mechanical
properties of natural fibers as Fiber Density Elongation Tensile strength Youngs modulus
compared to conventional (g/cm3) (%) (MPa) (GPa)
reinforcing fibers [9, 10, 16] Cotton 1.51.6 3.010.0 287597 5.512.6
Jute 1.31.46 1.51.8 393800 1030
Flax 1.41.5 1.23.2 3451500 27.680
Hemp 1.48 1.6 550900 70
Ramie 1.5 2.03.8 220938 44128
Sisal 1.331.5 2.014 400700 9.038.0
Coir 1.2 15.030.0 175220 4.06.0
Softwood kraft 1.5 1000 40.0
Eglass 2.5 2.53.0 20003500 70.0
Sglass 2.5 2.8 4570 86.0
Aramide (normal) 1.4 3.33.7 30003150 63.067.0
Carbon (standard) 1.4 1.41.8 4000 230.0240.0

Table 2 Chemical
composition of selected Type of fiber Cellulose (%) Lignin (%) Hemicellulose Pectin (%) Ash (%)
common natural fibers [18, (or Pentosan) (%)
19] A. Bast fiber
Fiber flax 71 2.2 18.620.6 2.3
Seed flax 4347 2123 2426 5
Kenaf 3157 1519 21.523 25
Jute 4571.5 1226 13.621 0.2 0.52
Hemp 5777 3.713 1422.4 0.9 0.8
Ramie 68.691 0.60.7 516.7 1.9
B. Core fiber
Kenaf 3749 1521 1824 24
Jute 4148 2124 1822 0.8
C. Leaf fiber
Abaca 5663 79 1517 3
Sisal 4778 711 1024 10 0.61
Henequen 77.6 13.1 48

composition may differ with the growing condition and
test methods even for the same kind of fiber. Cellulose
is a semicrystalline polysaccharide made up of D-
glucopyranose units linked together by b-(1-4)-gluco-
sidic bonds [19]. And the large amount of hydroxyl
group in cellulose gives natural fiber hydrophilic
properties when used to reinforce hydrophobic matri-
ces; the result is a very poor interface and poor
resistance to moisture absorption [20]. Hemicellulose is
strongly bound to cellulose fibrils presumably by
hydrogen bonds. Hemicellulosic polymers are
branched, fully amorphous and have a significantly
lower molecular weight than cellulose. Because of its
open structure containing many hydroxyl and acetyl
groups, hemicellulose is partly soluble in water and
hygroscopic [16]. Lignins are amorphous, highly com-
plex, mainly aromatic, polymers of phenylpropane
units [19] but have the least water sorption of the
natural fiber components [16].
Because the low interfacial properties between fiber
and polymer matrix often reduce their potential as
reinforcing agents due to the hydrophilic nature of
natural fibers, chemical modifications are considered to
optimize the interface of fibers. Chemicals may acti-
vate hydroxyl groups or introduce new moieties that
can effectively interlock with the matrix. The devel-
opment of a definitive theory for the mechanism of
bonding by chemicals in composites is a complex
problem. Generally, chemical coupling agents are
molecules possessing two functions. The first function
is to react with hydroxyl groups of cellulose and the
second is to react with functional groups of the matrix.
Bledzki and Gassan [9] outlined several mechanisms of
coupling in materials, namely: (a) elimination of weak
boundary layers; (b) production of a tough and flexible
layer; (c) development of a highly crosslinked inter-
phase region with a modulus intermediate between
that of substrate and of the polymer; (d) improvement
of the wetting between polymer and substrate; (e)
formation of covalent bonds with both materials; and
(f) alteration of acidity of substrate surface.
Chemical modifications of natural fibers aimed at
improving the adhesion with a polymer matrix were
investigated by a number of researchers [4, 2124].
However, different chemicals were used and very
limited papers [9, 18] took a partial review on the

123
J Polym Environ (2007) 15:2533
mechanism and utilization of chemical treatments in
fiber-reinforced composites.
Chemical Treatments
Alkaline Treatment
Alkaline treatment or mercerization is one of the most
used chemical treatment of natural fibers when used to
reinforce thermoplastics and thermosets. The impor-
tant modification done by alkaline treatment is the
disruption of hydrogen bonding in the network struc-
ture, thereby increasing surface roughness. This treat-
ment removes a certain amount of lignin, wax and oils
covering the external surface of the fiber cell wall,
depolymerizes cellulose and exposes the short length
crystallites [18]. Addition of aqueous sodium hydrox-
ide (NaOH) to natural fiber promotes the ionization of
the hydroxyl group to the alkoxide [25]:
Fiber  OH NaOH ! Fiber  O  Na H2 O 1
Thus, alkaline processing directly influences the
cellulosic fibril, the degree of polymerization and the
extraction of lignin and hemicellulosic compounds [26].
In alkaline treatment, fibers are immersed in NaOH
solution for a given period of time. Ray et al. [21] and
Mishra et al. [22] treated jute and sisal fibers with 5%
aqueous NaOH solution for 2 h up to 72 h at room
temperature. Similar treatments were attempted by
Morrison et al. [27] to treat flax fiber. Garcia et al. [28]
reported that 2% alkali solution for 90 s at 200C and
1.5 MPa pressure was suitable for degumming and
defibrillation to individual fibers. These researchers
observed that alkali led to an increase in amorphous
cellulose content at the expense of crystalline cellulose.
It is reported that alkaline treatment has two effects
on the fiber: (1) it increases surface roughness resulting
in better mechanical interlocking; and (2) it increases
the amount of cellulose exposed on the fiber surface,
thus increasing the number of possible reaction sites
[29]. Consequently, alkaline treatment has a lasting
effect on the mechanical behavior of flax fibers,
especially on fiber strength and stiffness [26]. Van de
Weyenberg et al. [24] reported that alkaline treatment
gave up to a 30% increase in tensile properties (both
strength and modulus) for flax fiberepoxy composites
and coincided with the removal of pectin. Alkaline
treatment also significantly improved the mechanical,
impact fatigue and dynamic mechanical behaviors of
fiber-reinforced composites [23, 30, 31]. Jacob et al.
[31] examined the effect of NaOH concentration (0.5,
27
1, 2, 4 and 10%) for treating sisal fiber-reinforced
composites and concluded that maximum tensile
strength resulted from the 4% NaOH treatment at
room temperature. Mishra et al. [32] reported that 5%
NaOH treated sisal fiber-reinforced polyester compos-
ite had better tensile strength than 10% NaOH treated
composites. This is because at higher alkali concentra-
tion, excess delignification of natural fiber occurs
resulting in a weaker or damaged fiber. The tensile
strength of the composite decreased drastically after
certain optimum NaOH concentration.
Silane Treatment
Silane is a chemical compound with chemical formula
SiH4. Silanes are used as coupling agents to let glass
fibers adhere to a polymer matrix, stabilizing the
composite material. Silane coupling agents may reduce
the number of cellulose hydroxyl groups in the fiber
matrix interface. In the presence of moisture, hydro-
lyzable alkoxy group leads to the formation of silanols.
The silanol then reacts with the hydroxyl group of the
fiber, forming stable covalent bonds to the cell wall
that are chemisorbed onto the fiber surface [25].
Therefore, the hydrocarbon chains provided by the
application of silane restrain the swelling of the fiber by
creating a crosslinked network due to covalent bonding
between the matrix and the fiber. The reaction schemes
are given as follows [25]:
H2 O
CH2 CHSiOC2 H5 3 ! CH2 CHSiOH3 3C2 H5 OH
2
CH2 CHSiOH3 Fiber  OH
! CH2 CHSi OH2 O  Fiber H2 O 3
Many researchers applied silane treatment in sur-
face modification of glass fiber composites [3336].
Silane coupling agents were also found to be effective
in modifying natural fiberpolymer matrix interface
and increasing the interfacial strength. Three amino-
propyl trimethoxy silane with concentration of 1% in a
solution of acetone and water (50/50 by volume) for
2 h was reportedly used to modify the flax surface [24].
Rong et al. [37] soaked sisal fiber in a solution of 2%
aminosilane in 95% alcohol for 5 min at a pH value of
4.55.5 followed by 30 min air drying for hydrolyzing
the coupling agent. Silane solutions in a water and
ethanol mixture with concentration of 0.033% and 1%
were also carried by Valadez et al. [38] and Agrawal
et al. [25] to treat henequen fibers and oil palm fibers.
123
28
It was verified that the interaction between the silane
coupling agent modified fiber and the matrix was much
stronger than that of alkaline treatment, which led to
composites with higher tensile strength from silane-
treated than alkaline-treated fiber [38]. Thermal sta-
bility of the composites was also improved after silane
treatment [25].
Acetylation of Natural Fibers
Acetylation describes a reaction introducing an acetyl
functional group (CH3COO) into an organic com-
pound. Acetylation of natural fibers is a well-known
esterification method causing plasticization of cellu-
losic fibers. The reaction involves the generation of
acetic acid (CH3COOH) as by-product which must be
removed from the lignocellulosic material before the
fiber is used. Chemical modification with acetic anhy-
dride (CH3-C(=O)-O-C(=O)-CH3) substitutes the
polymer hydroxyl groups of the cell wall with acetyl
groups, modifying the properties of these polymers so
that they become hydrophobic [39]. The reaction of
acetic anhydride with fiber is shown as [39]:
Fiber  OH CH3  C O  O  C O  CH3
! Fiber  OCOCH3 CH3 COOH
4 sion, thereby considerably increasing the strength of
Acetylation can reduce the hygroscopic nature of
natural fibers and increases the dimensional stability of
composites. Acetylation was used in surface treatments of
fiber for use in fiber-reinforced composites [10, 37, 39, 40].
Acetylation treatment of sisal fiber was reported to
improve the fibermatrix adhesion. The procedure
included an alkaline treatment initially, followed by
acetylation. Mishra et al. [32] investigated the acetyla-
tion of sisal fibers. Dewaxed sisal fiber was immersed in
5 and 10% NaOH solution for 1 h at 30C; the
alkaline-treated fiber was soaked in glacial acetic acid
for 1 h at 30C; it was decanted and soaked in acetic
anhydride containing one drop of concentrated H2SO4
for 5 min. Nair et al. [41] treated raw sisal fiber in 18%
NaOH solution, then in glacial acetic acid and finally in
acetic anhydride containing two drops of concentrated
H2SO4 for a period of 1 h. The treated surface of sisal
fiber reportedly became very rough and had a number
of voids that provided better mechanical interlocking
with the polystyrene (PS) matrix. A hypothetical
model of interface between the sisal fiber and PS
composites has been postulated. Meanwhile, the
thermal stability of treated fiber composites was found
to be higher than that of untreated fiber composite
123
J Polym Environ (2007) 15:2533
because of better thermal stability of treated fibers and
improved fibermatrix interactions in treated fiber
composites [41]. It was also reported that acetylated
natural fiber-reinforced polyester composites exhibited
higher bio-resistance and less tensile strength loss
compared to composites with silane treated fiber in
biological tests [42].
Benzoylation Treatment
Benzoylation is an important transformation in organic
synthesis [43]. Benzoyl chloride is most often used in
fiber treatment. Benzoyl chloride includes benzoyl
(C6H5C=O) which is attributed to the decreased
hydrophilic nature of the treated fiber and improved
interaction with the hydrophobic PS matrix. The
reaction between the cellulosic hydroxyl group of the
fiber and benzoyl chloride is shown in Eqs. 5 and 6 [44].
Fiber  OH NaOH ! Fiber  O Na H2 O 5
Benzoylation of fiber improves fiber matrix adhe-
composite, decreasing its water absorption and improv-
ing its thermal stability. Joseph et al. [44] and Nair
et al. [41] used NaOH and benzoyl chloride
(C6H5COCl) solution for surface treatment of sisal
fibers. A hypothetical model of the interface of PS-
benzoylated sisal fiber composite has been postulated
by Nair et al. [41]. It was observed that the thermal
stability of treated composites were higher than that of
untreated fiber composites. A similar method was also
applied by Wang [45] to improve the interfacial
adhesion of flax fiber and polyethylene (PE) matrix.
The fiber was initially alkaline pre-treated in order to
activate the hydroxyl groups of the cellulose and lignin
in the fiber; then the fiber was suspended in 10%
NaOH and benzoyl chloride solution for 15 min. The
isolated fibers were then soaked in ethanol for 1 h to
remove the benzoyl chloride and finally was washed
with water and dried in the oven at 80C for 24 h.
Acrylation and Acrylonitrile Grafting
Acrylation reaction is initiated by free radicals of the
cellulose molecule. Cellulose can be treated with high
energy radiation to generate radicals together with
chain scission [9].
J Polym Environ (2007) 15:2533
Acrylic acid (CH2=CHCOOH) can be graft poly-
merized to modify glass fibers [46, 47]. Sreekala et al.
[48, 49] used acrylic acid in natural fiber surface
modification. Oil palm fibers were mixed with 10%
NaOH for about 30 min and then treated with a
solution of acrylic acid at 50C for 1 h at various
concentrations. The fibers were washed with aqueous
alcohol solution and dried. The tensile strength of oil
palm fiberPE composites did not increase. Other
chemical treatments on oil palm fibers were also
investigated, including alkaline, acetylation, peroxide,
permanganate, silane and acrylation. Treatments like
silane and acrylation led to strong covalent bond
formation and thereby, the tensile strength and
Youngs modulus of treated fibers were improved
marginally. However, it was reported by Li et al. [50]
that the tensile strength of acrylic acid treated flax
fiberHDPE composites was improved and water
absorption of composites was decreased.
Acrylonitrile (AN, (CH2=CHC N)) is also used
to modify fibers. The reaction of AN with fiber
hydroxyl group occurs in the following manner [18]:
Fiber  OH CH2 CHCN ! Fiber  OCH2 CH2 CN
7 modify fiber surface but also the PP matrix to achieve
Graft copolymerization of AN on sisal fibers was
studied by Mishra et al. [22] using a combination of
NaIO4 and CuSO4 as initiator in an aqueous medium
at temperatures between 50 and 70C. Reaction
medium, treatment time, initiator, AN concentration
and even fiber loading influenced the graft effect. It
was found that untreated fibers absorbed the most
Fig. 1 The reaction of
cellulose fibers with hot
MAPP copolymers [58]
29
water and 25% AN-grafted sisal fibers absorbed the
least water, suggesting that changes in chemistry of the
fiber surface reduced the affinity of fibers to moisture.
It was also found that grafting of chemically modified
fibers with 5% AN brought a higher increase in tensile
strength and Youngs modulus of fibers than grafting
with 10 and 25% AN. The explanation for this was that
grafting at low concentration of AN may create orderly
arrangement of polyacrylonitrile units. Mishra et al.
[22] also concluded that optimum graft yield was
obtained for treatment duration of 3 h.
Sreekala et al. [49] treated oil palm fiber with AN in
1% H2SO4 solution after alkali and KMnO4 oxidized
pretreatment. However, the expected increase in fiber
matrix adhesion and reduction in water sorption on
fiber reinforced phenol formaldehyde (PF) composites
after treatment was not observed.
Maleated Coupling Gents
Maleated coupling agents are widely used to strength-
en composites containing fillers and fiber reinforce-
ments [5154]. The difference with other chemical
treatments is that maleic anhydride is not only used to
better interfacial bonding and mechanical properties in
composites [5557]. The PP chain permits maleic
anhydride to be cohesive and produce maleic anhy-
dride grafted polypropylene (MAPP). Then the treat-
ment of cellulose fibers with hot MAPP copolymers
provides covalent bonds across the interface (Fig. 1).
The mechanism of reaction of maleic anhydride with
PP and fiber can be explained as the activation of the
123
30
copolymer by heating (170C) before fiber treatment
and then the esterification of cellulose fiber [58]. After
this treatment, the surface energy of cellulose fibers is
increased to a level much closer to the surface energy
of the matrix. This results in better wettability and
higher interfacial adhesion of the fiber.
Mohanty et al. [59] used MAPP as coupling agent
for the surface modification of jute fibers. It has been
found that a 30% fiber loading with 0.5% MAPP
concentration in toluene and 5 min impregnation time
with 6 mm average fiber lengths gave the best results.
A 72.3% increase in flexural strength was observed
with the treated composites. In addition to PP matrix,
Mishra et al. [60] reported that maleic anhydride
treatment reduced the water absorption to a great
extent in banana, hemp and sisal fiber-reinforced
novolac composites. Mechanical properties like
Youngs modulus, flexural modulus, hardness and
impact strength of plant fiber-reinforced composites
increased after maleic anhydride treatment.
Permanganate Treatment
Permanganate is a compound that contains permanga-
nate group MnO4. Permanganate treatment leads to the
formation of cellulose radical through MnO3 ion forma-
tion. Then, highly reactive Mn3+ ions are responsible for
initiating graft copolymerization as shown below [16]:
Most permanganate treatments are conducted by
using potassium permanganate (KMnO4) solution (in
acetone) in different concentrations with soaking
duration from 1 to 3 min after alkaline pre-treatment
[10, 23, 48, 49, 54]. Paul et al. [10] dipped alkaline-
treated sisal fibers in permanganate solution at con-
centrations of 0.033, 0.0625 and 0.125% in acetone for
1 min. As a result of permanganate treatment, the
hydrophilic tendency of the fibers was reduced, and
thus, the water absorption of fiber-reinforced composite
decreased. The hydrophilic tendency of fiber decreased
as the KMnO4 concentrations increased. But at higher
KMnO4 concentrations of 1%, degradation of cellulosic
123
J Polym Environ (2007) 15:2533
fiber occurred which resulted in the formation of polar
groups between fiber and matrix.
Peroxide Treatment
In organic chemistry, peroxide is a specific functional
group or a molecule with the functional group ROOR
containing the divalent ion OO. Organic peroxides
tend to decompose easily to free radicals of the form
RO
; RO
then reacts with the hydrogen group of the
matrix and cellulose fibers. For example, the peroxide
initiated free radical reaction between PE matrix and
cellulose fibers is shown by the following [10, 23]:
RO  OR!2RO
10
RO
PE  H!ROH PE 11
RO
Cellulose  H!ROH Cellulose
12
PE Cellulose
!PE  Cellulose 13
Benzoyl peroxide (BP, ((C6H5CO)2O2) and dicumyl
peroxide (DCP, (C6H5C(CH3)2O)2) are chemicals in
the organic peroxide family that are used in natural
fiber surface modifications. In peroxide treatment,
fibers are coated with BP or DCP in acetone solution
for about 30 min after alkali pre-treatment [10, 48, 49].
Peroxide solution concentration was 6% [10] and
saturated solutions of peroxide in acetone were used
[48, 49]. Sreekala et al. [48] observed that high
temperature was favored for the decomposition of
the peroxide; peroxide-treated oil palm fiber-rein-
forced PF composites could withstand tensile stress to
a higher strain level. Joseph and Thomas [23] investi-
gated BP and DCP treatment on short sisal fiber-
reinforced PE composites. The tensile strength values
of composites increased with the increase in concen-
tration of peroxide up to a certain level (4% for DCP
and 6% for BP) and then remained constant. As a
result of peroxide treatment, the hydrophilicity of the
fibers decreased [10] and the tensile properties
increased [23].
Isocyanate Treatment
An isocyanate is a compound containing the isocyanate
functional group N=C=O, which is highly susceptible
to reaction with the hydroxyl groups of cellulose and
J Polym Environ (2007) 15:2533
Fig. 2 The reaction pathway for the preparation of urethane
derivative of cardanol [23]
lignin in fibers. Isocyanate is reported to work as a
coupling agent used in fiber-reinforced composites [10,
23, 40]. The reaction between fiber and isocyanate
coupling agent is shown below [16]:
where R could be different chemical groups (such as
alkyl). Wu et al. [61] investigated the grafting of
isocyanate-terminated elastomers onto the surfaces of
carbon fibers (CF). The reaction between phenyl
isocyanate (C6H5NCO) and surface carboxyl and
phenolic functions is given as Eq. 15.
Joseph and Thomas [23] studied the chemical
treatment of cardanol derivative of toluene diisocya-
Fig. 3 A possible reaction
between the free isocyanate
groups in CTDIC and
cellulosic sisal fiber [23]
31
nate (CTDIC) in sisal fiberLDPE composites. CTDIC
was prepared by cardanol and toluene-2,4-diisocyanate
(TDIC) and formed one free isocyanate group for
further reaction (Fig. 2). It was demonstrated that
CTDIC reduced the hydrophilic nature of the sisal
fiber (Fig. 3), thereby enhancing the tensile properties
of the sisal fiberLDPE composites.
George et al. [62] treated pineapple leaf fiber with
polymethylene-polyphenyl-isocyanate (C15H10N2O2)
solution at 50C for 30 min to improve the fiber
matrix interfacial adhesion. Comparing silane and
isocyanate-treated wood fiberPS composites, it was
reported that isocyanate treatment was more effective
than silane treatment in enhancing the mechanical
properties of cellulose fiberPS composites [63]. Sree-
kala et al. [48] reported that TDIC-treated oil palm
fiberPF composites had lower tensile strength and
Youngs modulus than permanganate-, peroxide-and
alkaline-treated fiberPF composites, but had higher
tensile strength and similar Youngs modulus with
silane-and acrylic acid-treated fiberPF composites.
Other chemical treatments
Stearic acid (CH3(CH2)16COOH) in ethyl alcohol
solution was investigated in fiber treatment by Paul
et al. [10] and Zafeiropoulos [64]. It was reported that
this treatment removed non-crystalline constituents of
the fibers, thus altering the fiber surface topography.
Zafeiropoulos [64] also observed that treated flax fibers
were more crystalline than the untreated ones and
stearation decreased the fiber surface free energy.
Sodium chlorite (NaClO2) usually is used in
bleaching fibers; however, it could delignify ligno-
cellulosics. Studies have been conducted wherein it
was used in fiber surface treatment for composites.
Mishra et al. [65] dipped untreated sisal fiber, for use
in sisalPS biocomposites, in sodium chlorite
123
32
solution with a liquor ratio of 25:1 at 75C for 2 h.
Tensile strength of bleached sisal fiberPS composite
was less than other chemical treated fiber composites
which may be due to the fact that delignification of
the fiber lowered its tensile strength [65]. But it was
reported that flexural strength was better for
bleached fiber composite because of lower stiffness
and more flexible character of fibers after delignifi-
cation. After delignification, the polymer replaces
the role of lignin in fibers and makes composites
more hydrophobic and tougher [65]. Similar result on
tensile strength of bleached composites using sodium
chlorite was also reported by Li et al. [50] on flax
fiberPE composites.
It was also reported that triazine (C3H3N3) deriva-
tives (eg. C3N3Cl3) could form covalent bonds with
cellulose fibers. Therefore, these can be used in the
modification of vegetable fiber for natural fiber com-
posites to reduce the number of cellulose hydroxyl
groups which are available for water uptake [58].
Conclusion
Natural fibers are considered as potential replacement
for man-made fibers in composite materials. Although
natural fibers have advantages of being low cost and
low density, they are not totally free of problems. A
serious problem of natural fibers is their strong polar
character which creates incompatibility with most
polymer matrices. Surface treatments, although having
a negative impact on economics, are potentially able to
overcome the problem of incompatibility. Chemical
treatments can increase the interface adhesion be-
tween the fiber and matrix, and decrease the water
absorption of fibers. Therefore, chemical treatments
can be considered in modifying the properties of
natural fibers. Some compounds are known to promote
adhesion by chemically coupling the adhesive to the
material, such as sodium hydroxide, silane, acetic acid,
acrylic acid, maleated coupling agents, isocyanates,
potassium permanganate, peroxide, etc. Fiber modifi-
cation methods discussed in this paper have different
efficacy in causing adhesion between the matrix and
the fiber. Yet most chemical treatments have achieved
various levels of success in improving fiber strength,
fiber fitness and fibermatrix adhesion in natural fiber-
reinforced composites.
Acknowledgments The authors would like to acknowledge the
financial support from the Natural Sciences & Engineering
Research Council (NSERC) of Canada, Agriculture and Agri-
Food Canada and the Saskatchewan Flax Development Board.
123
J Polym Environ (2007) 15:2533
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