Composites: Part B 43 (2012) 2883–2892

Contents lists available at SciVerse ScienceDirect

Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

Chemical treatments on plant-based natural fibre reinforced polymer composites:

An overview
M.M. Kabir ⇑, H. Wang, K.T. Lau, F. Cardona
Centre of Excellence in Engineered Fibre Composite (CEEFC), Faculty of Engineering and Surveying, University of Southern Queensland, Toowoomba, Queensland 4350, Australia

a r t i c l e i n f o a b s t r a c t

Article history: This paper provides a comprehensive overview on different surface treatments applied to natural fibres
Received 11 November 2011 for advanced composites applications. In practice, the major drawbacks of using natural fibres are their
Received in revised form 29 December 2011 high degree of moisture absorption and poor dimensional stability. The primary objective of surface
Accepted 5 February 2012
treatments on natural fibres is to maximize the bonding strength so as the stress transferability in the
Available online 14 May 2012
composites. The overall mechanical properties of natural fibre reinforced polymer composites are highly
dependent on the morphology, aspect ratio, hydrophilic tendency and dimensional stability of the fibres
Keywords:
used. The effects of different chemical treatments on cellulosic fibres that are used as reinforcements for
B. Fibre/matrix bond
E. Surface treatments
thermoset and thermoplastics are studied. The chemical sources for the treatments include alkali, silane,
B. Mechanical properties acetylation, benzoylation, acrylation and acrylonitrile grafting, maleated coupling agents, permanganate,
peroxide, isocyanate, stearic acid, sodium chlorite, triazine, fatty acid derivate (oleoyl chloride) and fun-
gal. The significance of chemically-treated natural fibres is seen through the improvement of mechanical
strength and dimensional stability of resultant composites as compared with a pristine sample.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction
Increasing environmental awareness throughout the world has
greatly impacted materials engineering and design. Renewed inter-
est in the utilization of natural materials addresses ecological is-
sues such as recyclability and environmental safety. Currently,
synthetic fibres like glass, carbon and aramid are widely being used
in polymer-based composites because of their high stiffness and
strength properties [1]. However, these fibres have serious draw-
backs in terms of their biodegradability, initial processing costs,
recyclability, energy consumption, machine abrasion, health haz-
ards, etc. [2]. Despite these, most significantly, adverse environ-
mental impacts alter the attention from synthetic fibres to
natural/renewable fibres. The introduction of natural fibres from
annually renewable resources are now popularly used as reinforce-
ments in polymer matrix. These provide benefits to the environ-
ment with respect to the degradability and utilization of natural
materials [1]. The successful use of these fibres is dependent on
their well defined structural and mechanical properties. These
properties are influenced by the locality in which they originate,
climate conditions, age of the plants and the extraction methods
that are used. These parameters determine the characterization
factor for fibres [2–4].
⇑ Corresponding author. Address: P-9, CEEFC, USQ, Darling downs, Toowoomba,
Queensland 4350, Australia. Tel.: +61 413760260.
E-mail address: kabirm@usq.edu.au (M.M. Kabir).
Natural fibres like flax, hemp, jute and sisal have been well rec-
ognized as good potential reinforcements for engineering fibre com-
posites. The advantageous features of these fibres are lightweight,
high specific modulus, non-toxic and easy for processing and
absorbing CO2 during their growth [3,4]. These benchmarking prop-
erties open the wide area of natural fibres in the composite sector
and challenge the replacement of synthetic fibres. However, natural
fibres are not a problem-free alterative and they possess certain
shortfalls in properties. Their structural compositions (cellulose,
hemicelluloses, lignin, pectin and waxy substances) allow moisture
absorption from the environment which leads to poor bonding with
the matrix materials [5]. Additionally, the chemical structures of the
fibres and matrix are different and couplings between these two
phases are challenging. This causes ineffective stress transfer
throughout the interface of the composites. Therefore, certain
chemical treatments on the surface of natural fibres are definitely
needed. These treatments are usually based on the use of reagent
functional groups that are capable of reacting with the fibre struc-
tures and changing their composition. As a result, the tendency of
moisture absorption of the fibres is reduced and this facilitates
greater compatibility with the polymer matrix [3]. For the fabrica-
tion of natural fibre composites, different fibre arrangements such
as short-randomly oriented, long-unidirectional and woven fabrics
were used. These composites were then investigated by several
researchers with respect to their mechanical and thermal proper-
ties. Many academic and industrial research activities are ongoing
to develop better interfacial bonding properties of the composites.

1359-8368/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.compositesb.2012.04.053
2884 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
Experimental parameters were tested by using different chemical
treatments to achieve stronger fibre surface adhesion to surround-
ing matrix.
The objective of this study is to review recent research works
related to different aspects of natural fibres and their composites.
Several critical issues in a fibre matrix adhesion and its influence
to the mechanical properties of natural fibre composites through
different chemical treatments are discussed.
2. Constituents of natural fibre composites
In general, a composite is a material mixture created by a syn-
thetic/natural assembly of two or more physically and chemically
distinct components. The first component is a selected filler or
reinforcing agent (discontinuous phase) whilst the other compo-
nent is a compatible matrix binder (continuous phase). These
two components are combined in order to achieve specific charac-
teristics and properties [2]. Different types of natural fibres, matrix
and processing techniques are used for composite fabrication.
2.1. Natural fibres
Plant based natural fibres are lignocellulosic in nature and are
composed of cellulose, hemicelluloses, lignin, pectin and waxy
substances. The structural composition of fibres are presented in
Table 1. Cellulose is considered the major framework component
of the fibre structure. It provides strength, stiffness and structural
stability of the fibre. The chemical structure of cellulose (Fig. 1a)
consists of three hydroxyl groups (OH). Two of them form hydro-
gen bonds within the cellulose macromolecules (intramolecular)
whilst the rest of the group forms hydrogen bond with other cellu-
lose molecules (intermolecular) [6]. Hemicellulose occurs mainly
in the primary cell wall and has branched polymers containing five
and six carbon sugars (Fig. 1b) of varied chemical structures. Lignin
is amorphous and has an aromatic structure (Fig. 1c) [7]. Pectin
comprises of complex polysaccharides. Their side chains are
cross-linked with the calcium ions and arabinose sugars. Addition-
ally, small amounts of organic (extractives) and inorganic (ash)
components are present in the fibre structure. Organic extractives
are responsible for color, odor and decay resistance whilst inor-
ganic constituents enhance the abrasive nature of the fibre.
Fig. 2 shows a schematic structure of a natural fibre and Fig. 3
presents the model of the structural organization of the three
major structural constituents of the fibre cell wall [8]. In accor-
dance with a specific type of fibre, cellulose microfibrils have their
own cell geometry which is a factor responsible for the properties
of the fibre [2]. Each fibre cell wall consists of primary and second-
ary layers of cellulose microfibrils. The fibre structure develops in
the primary cell wall and is deposited during its growth. The sec-
ondary wall consists of three layers and each layer has a long chain
of helical cellulose microfibrils [9]. The cellulose content increases
Table 1
Structural compositions of natural fibres [10,12].
Name of the fibres Cellulose (wt.%) Lignin (wt.%) Hemicellulose (wt.%)
Bast fibres
Jute 61–71.5 12–13 13.6–20.4
Flax 71 2.2 18.6–20.6
Hemp 70.2–74.4 3.7–5.7 17.9–22.4
Ramie 68.6–76.2 0.6–0.7 13.1–16.7
Leaf Fibres
Sisal 67–78 8.0–11.0 10.0–14.2
PALF 70–82 5–12 – –
Seed fibres.
Cotton 82.7 0.7–1.6 5.7
steadily from primary to secondary layers and the hemicelluloses
amount are similar in each layer. However, lignin content de-
creases in this sequence. Hemicellulose molecules are hydrogen
bonded with cellulose fibrils and they form cementing materials
for the fibre structure. Lignin and pectin are coupled with the cel-
lulose–hemicellulose network and provides an adhesive quality to
hold the molecules together. This adhesive quality is the cause for
the strength and stiffness properties of the fibre. Secondary thick
layer (s2) determines the mechanical properties of the fibre.
Generally, fibres with a higher cellulose content and a lower micro-
fibrillar angle (the angle between the fibre axis and cellulose
microfibrils) have better strength properties [10,11]. Mechanical
properties of natural fibre over synthetic fibre are presented in
Table 2. Although natural fibres have relatively lower strength
properties compared to the synthetic fibres, the specific modulus
and elongation at break signifies the potentiality of these fibres
to replace synthetic fibres in engineering polymer composites.
2.2. Matrix
A matrix is a binder material that is used to hold fibres in position
and transfer external loads to internal reinforcements. In natural
fibre reinforced polymer composites, both thermoset and thermo-
plastic matrices such as unsaturated polyesters, epoxies and
phenolics, and polypropylenes, polyethylenes and elastomers,
respectively are widely used for composites applications [14,15].
These matrices have different chemical structures and undergo
different reactivities with the surface molecules of fibres in
composites. Table 3 stands for the comparison of thermoset and
thermoplastic matrices.
2.3. Processing techniques
In principle, processing techniques of natural fibre composites
are similar to those utilized in processing synthetic fibres. Depend-
ing on the length, orientation and type of the fibre, randomly ori-
ented (short), unidirectional (raw and carded) and woven fabrics
are used as reinforcements in thermoset and thermoplastic matri-
ces. For thermoset composites, the basic fabrication method is
known as ‘‘hand layup’’. This is a manual mixing procedure be-
tween the fibre and matrix. In this process, the uniformity of the
composite in terms of thickness, fibre to matrix ratio and void con-
tent throughout the sample depends on the workmanship skill.
Conversely, in vacuum assisted resin transfer moulding (VARTM),
resin is pulled inside under vacuum pressure and mixed with the
fibres/fibre mats. Under this condition, the resin impregnation
quality in a composite is much better than that fabricated by the
hand layup technique and the void content can be kept as minimal.
This method provides precise fibre spacing and dimension of the
composite. Another method known as pultrusion, is used for both
thermosets and thermoplastics. The composite profile is produced
by pulling the reinforcement through a heated die which is then
Pectin (wt.%) Wax (wt.%) Micro-fibrillar/spiral angle (°) Moisture content (wt.%)
0.2 0.5 8.0 12.6
2.3 1.7 10.0 10.0
0.9 0.8 6.2 10.8
1.9 0.3 7.5 8.0
10.0 2.0 20.0 11.0
– 14.0 11.8
– 0.6 – 33–34
 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892 2885

OH OCH3
OH
HO O
O O
O O H2C – C – OH
O
HO OH OH
CH2
n

OCH3
O

(a) (c)

O H H OH
CH3–C–O H
H O
H H O
O
H
O H O
H
H
HO H OH
H
(b)
Fig. 1. Chemical structure of (a) cellulose (b) hemicelluloses and (c) lignin [2].

Table 2
Secondary wall S3 Comparative properties of natural fibres with conventional manmade fibres
[10,12,13].

Name Density Tensile Young’s Specific Specific Elongation

of (g/cm3) strength modulus strength modulus at break
Secondary wall S2
fibres (MPa) (GPa) (GPa/ (GPa/ (%)
g/cm3) g/cm3)
Microfibril angle
Jute 1.3–1.4 393–773 13–26.5 0.3–0.5 10–18.3 1.16–1.5
Cellulose crystalline Flax 1.50 345– 27.6 0.2–0.7 18.4 2.7–3.2
microfibrils 1100
Hemp 1.14 690 30–60 0.6 26.3– 1.6
Secondary wall S1 52.6
Ramie 1.50 400–938 61.4–128 0.3–0.6 40.9– 1.2–3.8
85.3
Cellulose amorphous Sisal 1.45 468–640 9.4–22.0 0.3–0.4 6.4–15.2 3–7
microfibrils (consists PALF 1.52 413– 34.5– 0.3–1.1 22.7– 1.6
of lignin and Primary wall 1627 82.51 54.3
hemicelluloses) Cotton 1.5–1.6 287–800 5.5–12.6 0.2–0.5 3.7–7.8 7.0–8.0
E-glass 2.5 2000– 70 0.8–1.4 28 2.5
3500
S-glass 2.5 4570 86 1.8 34.4 2.8
Aramid 1.4 3000– 63–67 2.1–2.2 45–47.8 3.3–3.7
3150

Fig. 2. Structure of natural fibre.

Table 3
Comparison of thermoplastic and thermoset matrix [14].
Lignin
Hemicelluloses Advantages Disadvantages
Thermoset
Cellulose – Low resin viscosity – Brittle
– Good fibre wetting – Non-recyclable via
– Excellent thermal stability – Standard techniques
Fig. 3. Structural organization of the three major constituents in the fibre cell wall. once polymerised
– Chemically resistant – Not post-formable
Thermoplastic
mixed with matrix. For the thermoplastic matrix, compression – Recyclable – Poor melt flow
molding (reinforcement is mixed with matrix and pressed with a – Easy to repair by welding – Need to be heated above the melting point
heated plate) and injection molding (fibre–resin is added as granu- and solvent bonding for processing purposes
– Post formable
late to the machine and melted into fluid mass, then injected under
– Tough
high pressure into the form) are used for composite fabrication [16].
2886 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
These processes involved high temperature (over 200 °C) and pres-
sure (5 MPa) for complete reaction between fibre and matrix.
3. Factors affecting the composite properties
3.1. Plant fibre structure
The cellulose structure of the fibres is distinguished through
crystalline and amorphous regions. Large numbers of strong in-
tra-molecular hydrogen bonds are formed in the crystallite region.
This creates cellulose block and makes it difficult for other chemi-
cal penetrations. However, dyes and resins are absorbed easily by
the amorphous region. The hydrophilic hydroxyl groups present
in this region are combined with water molecules from the atmo-
sphere. Hemicellulose, lignin, pectin and waxy substances do nor-
mally hold these water molecules. This makes the fibre hydrophilic
and polar in character which lowers the compatibility with the
non-polar/hydrophobic matrix [3,6,11]. For the distension of the
crystalline region, the elimination of the hydrophilic hydroxyl
groups and the removal of surface impurities (waxy substances),
natural fibre requires to be chemically modified. Chemical treat-
ments such as mercerization, acetylation, benzoylation, peroxide
and coupling agents with or without heat are widely being applied
to modify fibre surface and structure.
3.2. Thermal stability of fibres
Natural fibre generally starts degrading at about 240 °C. Struc-
tural constituents of the fibre (cellulose, hemicelluloses, lignin,
etc) are sensitive with different range of temperatures. It was re-
ported that, lignin starts degrading at a temperature around
200 °C and hemicelluloses and cellulosic constituents degraded at
higher temperatures [14]. Thermal stability of the fibre can be en-
hanced by removing certain proportion of hemicelluloses and
lignin constituents by different chemical treatments. The degrada-
tion of natural fibres is an important issue in the development of
composites in both manufacturing (curing, extrusion or injection
moulding) and materials in service [17,18].
3.3. Fibre length, loading and orientation
The mechanical properties of the composites are depended on
several factors such as fibre length, loading and orientation in
the matrix. When a load is applied to the matrix, stress transfer oc-
curs by shear at the interface along the fibre length and ends of the
fibre. The extent of load transfer is a function of the critical fibre
length (aspect ratio), the direction and orientation of fibre and
the compatibility between fibre–matrix interfaces. Depending on
the fibre orientation at the matrix, three types of composite are
prepared. Firstly, longitudinally aligned fibre composites generally
have higher tensile strength but lower compressive strength (due
to fibre buckling). Secondly, transversely directed fibres undergo
very low tensile strength, which is lower than the matrix strength.
Finally, randomly orientated short fibre composites have different
mechanical properties. This is due to the complexities of load dis-
tribution at different direction along the interfaces, consistent
mechanical properties of these composites are far more difficult.
By controlling factors such as the aspect ratio, the dispersion and
orientation of fibres, considerable improvements in the properties
can be accomplished [10,11,14].
3.4. Presence of voids
During the insertion of fibre into the matrix, air or other volatile
substances may be trapped inside the composites. After the curing
process micro-voids are formed along the individual fibre tows and
in the matrix rich regions. This causes sudden failure of the com-
posites and shows poor mechanical properties. The curing and
cooling rate of the composites are also responsible for the void for-
mation [14]. High void content (over 20% by volume) is responsible
for lower fatigue resistance, greater affinity to water diffusion and
increase variation (scatter) in mechanical properties [19,20]. Com-
posites at higher fibre content display more risk for void formation
[20].
3.5. Moisture absorption of fibres
The lignocellulosic fibres are hydrophilic and absorb moisture.
Many hydrogen bonds (hydroxyl groups AOH) are present be-
tween the macromolecules in the fibre cell wall. When moisture
from the atmosphere comes in contact with the fibre, the hydrogen
bond breaks and hydroxyl groups form new hydrogen bonds with
water molecules. The cross section of the fibre becomes the main
access of water penetration. The interaction between hydrophilic
fibre and hydrophobic matrix causes fibre swelling within in the
matrix. This results weakening the bonding strength at the inter-
face, which leads to dimensional instability, matrix cracking and
poor mechanical properties of the composites [21]. Therefore, the
removal of moisture from fibres is an essential step for the prepa-
ration of composites. The moisture absorption of fibres can be re-
duced by eliminating hydrophilic hydroxyl groups from the fibre
structure through different chemical treatments [22].
4. Surface modification of natural fibres
The fibre–matrix interface is a diffusion or reaction zone, in
which two phases are chemically and/or mechanically combined.
Interfacial adhesion plays a predominant part to characterize the
mechanical properties of the composites. If there is poor adhesion
across the phase boundary, then relatively weak dispersion of force
occurs and results in poor mechanical properties [22]. For rein-
forcement of natural fibre into the matrix, several problems occur
along the interface due to the presence of hydrophilic hydroxyl
groups. This hydrophilic nature hinders the effective reaction with
the matrix. In addition to this, pectin and waxy substances cover
the reactive functional groups of the fibre and act as a barrier to
interlock with the matrix. To enhance the effectiveness of interfa-
cial bonding, fibre surface needs to be modified with different
chemical treatments, reactive additives and coupling agents.
Chemical treatments expose more reactive groups on the fibre sur-
face and thus facilitates efficient coupling with the matrix. As a re-
sult, better mechanical properties of the composites can be
achieved [23].
4.1. Chemical methods
The major problem of natural fibre composites originate from
the hydrophilic nature of the fibre and hydrophobic nature of the
matrix. The inherent incompatibility between these two phases re-
sults weakening bonding at the interface. Chemical treatments on
reinforcing fibre can reduce its hydrophilic tendency and thus im-
prove compatibility with the matrix [24,25]. Several research activ-
ities have been conducted to improve fibre adhesion properties
with the matrix through chemical treatments. The followings are
the reviews of different chemical treatments on the fibre and their
effects on composite properties.
4.1.1. Alkaline treatment
The treatment on natural fibres by sodium hydroxide (NaOH) is
widely being used to modify the cellulosic molecular structure. It
 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
Fibre-cell-OH + NaOH Fibre cell-O-Na+ + H2O + impurities
Scheme 1.
Wax & Oil
Cellulose
Lignin
(i) (ii)
Fig. 4. Typical structure of (i) untreated and (ii) alkalized cellulose fibre [6].
changes the orientation of highly packed crystalline cellulose order
and forming an amorphous region. This provides more access to
penetrate chemicals. In the amorphous region, cellulose micro-
molecules are separated at large distances and the spaces are filled
by water molecules. Alkali sensitive hydroxyl (OH) groups present
among the molecules are broken down, which then react with
water molecules (HAOH) and move out from the fibre structure.
The remaining reactive molecules form fibre–cell–O–Na groups be-
tween the cellulose molecular chains [9]. Due to this, hydrophilic
hydroxyl groups are reduced and increase the fibres moisture
resistance property. It also takes out a certain portion of hemicel-
luloses, lignin, pectin, wax and oil covering materials [26–28]. As
a result, the fibre surface becomes clean. In other words, the fibre
surface becomes more uniform due to the elimination of microv-
oids and thus the stress transfer capacity between the ultimate
cells improves. In addition to this, it reduces fibre diameter and
thereby increases the aspect ratio (length/diameter). This increases
effective fibre surface area for good adhesion with the matrix [14].
Mechanical and thermal behaviors of the composite are improved
significantly by this treatment. If the alkali concentration is higher
than the optimum condition, the excess delignification of the fibre
can take place, which results in weakening or damaging the fibres
[22,26]. The chemical reaction of the fibre–cell and NaOH is repre-
sented in Scheme 1. Fig. 4 presents the schematic view of the cel-
lulose fibre structure, before and after an alkali treatment. Treated
fibres have lower lignin content, partial removal of wax and oil
cover materials and distension of crystalline cellulose order. Table
4 summarizes the recent results on the effect of alkali treatments
on the mechanical and thermal properties of composites.
Table 4
Recent works on alkali treated fibre reinforced polymer composites.
Fibre matrix composites Applied treatment methods
Flax–epoxy Alkali treatment
Sisal–polyester 0.5%, 1%, 2%, 4%, 10% NaOH
treatment at room temperature
Hemp non-woven mat 0.16% NaOH for 48 h
with euphorbia resin
Jute–vinylester 5% NaOH for 4, 6 and 8 h
Sisal–polycaprolactone 10% NaOH for 1, 3, 24 and 48 h
composite
Hemp fibre 8% NaOH treatment
Coir–polyester 5% NaOH treatment for 72 h
2887
4.1.2. Silane treatment
Silane is a multifunctional molecule which is used as a coupling
agent to modify fibre surfaces. The composition of silane forms a
chemical link between the fibre surface and the matrix through a
siloxane bridge. It undergoes several stages of hydrolysis, conden-
sation and bond formation during the treatment process of the fi-
bre. Silanols form in the presence of moisture and hydrolysable
alkoxy groups (hydrolysis, see Scheme 2a [36]). During condensa-
tion process, one end of silanol reacts with the cellulose hydroxyl
group (Si–O–cellulose, see Scheme 2b [36]) and other end reacts
(bond formation) with the matrix (Si-Matrix) functional group.
This co-reactivity provides molecular continuity across the inter-
face of the composite. It also provides the hydrocarbon chain that
restrains the fibre swelling into the matrix [22,32]. As a result, fibre
matrix adhesion improves and stabilizes the composite properties
[26]. Natural fibres exhibit micro-pores on their surface and silane
coupling agents act as a surface coating. This penetrates into the
pores and develops mechanically interlocked coatings on fibre sur-
face. Silane treated fibre composites provide better tensile strength
properties than the alkali treated fibre composites [33]. Seki [34]
investigated the effect of alkali (5% NaOH for 2 h) and silane (1%
oligomeric siloxane with 96% alcohol solution for 1 h) treatments
on flexural properties of jute epoxy and jute polyester composites.
For jute epoxy composites silane over alkali treatments showed
about 12% and 7% higher strength and modulus properties com-
pared to the alkali treatment alone. Similar treatments reported
around 20% and 8% improvement for jute polyester composites. Se-
ver et al. [35] applied different concentrations of (0.1%, 0.3% and
0.5%) silane (c-Methacryloxy-propyl-trimethoxy-silane) treat-
ments on jute fabrics polyester composites. Tensile, flexural and
interlaminar shear strength properties were investigated and com-
pared with the untreated fibre composites. The results for 0.3% si-
lane treated composites showed around 40%, 30% and 55%
improvement in tensile, flexural and interlaminar shear strength
respectively.
4.1.3. Acetylation treatment
Acetylation treatment is known as esterification method for
plasticizing of natural fibres. Acetyl group (CH3CO) reacts with
the hydrophilic hydroxyl groups (OH) of the fibre and takes out
the existed moisture. As a result, hydrophilic nature of the fibre
is decreased and improves dimensional stability of the composites
[36]. Moreover, this treatment provides rough surface topography
with less number of void contents that give better mechanical
interlocking with the matrix [4,26]. Fibres are acetylated with
and without an acid catalyst to graft acetyl groups onto the cellu-
lose structure. In general, acetic acid and acetic anhydride individ-
ually does not react sufficiently with the fibres. To accelerate the
reaction, fibres are initially soaked in acetic acid and consequently
treated with acetic anhydride between the time periods of 1–3 h
Results on mechanical and thermal properties References
30% increased in tensile strength and modulus with the removal of pectin [26]
4% alkali treatment reported maximum tensile strength properties [26]
Tensile strength was increased by 30% and doubled the shear strength properties [27]
was found compared to the untreated fibre composites
4 h alkali treated composite accounted 20% and 19% increased in flexural strength [28]
and interlaminar shear strength properties
Increased in elastic modulus with the increased with reaction time [29]
Thermal stability was increased by 4% [30]
Flexural and impact strength was increased by 40% with respect to the untreated [31]
fibre composites
2888 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
Scheme 2a.
Scheme 2b.
with higher temperature. Acetylation reaction with and without
acid catalyst on fibre are given in Scheme 3 [40]. Rowell et al.
[37] investigated acetic anhydride treatment on different types of
natural fibres to analyze the effects of equilibrium moisture con-
tent and reported, improved moisture resistance properties. This
was due to the removal of hemicellulose and lignin constituents
from the treated fibre. Mishra et al. [38] used acetic anhydride
treatment (with glacial acetic acid and sulphuric acid) on alkali
pre-treated (5% and 10% NaOH solution for 1 h at 300 °C) dewaxed
sisal fibre and reported, improved fibre matrix adhesion character-
istics of the composites. Bledzki et al. [39] studied different con-
centration of acetylation treatment on flax fibre and reported
50% higher thermal properties. Moreover, 18% acetylated flax fibre
polypropylene composites showed 25% higher tensile and flexural
properties compared to the untreated fibre composites.
Acetylation with acid catalyst
(CH3CO)2O
Fibre-OH + CH3COOH
Conc. H2SO4
Acetylation without acid catalyst
O O
Fibre-OH + CH3 – C – O – C – CH3
Scheme 3.
4.1.4. Benzoylation treatment
Benzoylation treatment uses benzoyl chloride to decrease
hydrophilic nature of the fibre and improves interfacial adhesion,
thereby increasing strength of the composite. It also enhances
thermal stability of the fibre [26,41]. During benzoylation treat-
ment alkali pre-treatment is used. At this stage, extractable mate-
rials such as lignin, waxes and oil covering materials are removed
and more reactive hydroxyl (OH) groups are exposed on the fibre
surface. Then the fibres are treated with benzoyl chloride. OH
groups of the fibre are further replaced by benzoyl group and it at-
tached on the cellulose backbone. This results more hydrophobic
nature of the fibre and improves adhesion with the matrix. Joseph
et al. [42] implied benzoyl chloride treatment on alkali pre-treated
sisal fibre and reported higher thermal stability compared to the
untreated fibre composites. Similar treatment was carried out on
flax fibre reinforced in low density polyethylene composites by
Wang et al. [22]. The reported result was 6% and 33% higher tensile
strength and moisture resistance properties. The reaction between
the cellulosic AOH group of fibre and benzoyl chloride is given in
Scheme 4 [14].
4.1.5. Peroxide treatment
Interface properties of fibre and matrix can be improved by per-
oxide treatment. The peroxide-induced grafting of polyethylene
adheres onto the fibre surface. Additionally, peroxide initiated free
radicals react with the hydroxyl group of the fibre and with the
matrix. As a result, good fibre matrix adhesion along the interface
occurs. This treatment also reduced moisture absorption tendency
by the fibre and improves thermal stability [22,43]. Sapieha et al.
[44] reported pre-treatment on fibre by benzoyl or dicumyl perox-
ide and showed higher mechanical properties of the composites.
The mechanism of peroxide treatment involves alkali pre-treat-
ment on the fibre then coated with benzoyl peroxide or dicumyl
peroxide (around 6% concentration) in acetone solution for 30
mins. Complete decomposition of peroxide can be achieved by
heating the solution at higher temperature [26,43]. Joseph et al.
[42] investigated optimum concentration of benzoyl peroxide
(6%) and dicumyl peroxide (4%) treatments on short sisal fibre-
reinforced polyethylene composites and reported improved tensile
strength properties. The reaction between the cellulosic AOH
group of the fibre and decomposition of the peroxides is given in
Scheme 5 [36].
4.1.6. Maleated coupling agents
Maleated coupling agents provide efficient interaction with the
functional surface of the fibre and matrix. During grafting, maleic
anhydride reacts with the hydroxyl groups (OH) in the amorphous
region of cellulose structure and removes it (OH groups) from the
fibre cells. This produces brush like long chain polymer coating on
the fibre surface and reduce hydrophilic tendency. Therefore, mal-
eated coupler forms carbonAcarbon bond to the polymer chain
O
Fibre – O – C – CH3 + H2O
O O
Fibre – O – C – CH3 + CH3C - OH
 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892 2889

Fibre – OH + NaOH Fibre- O-Na+ + H2O the fibre. After delignification, fibres become more flexible and
O O
have lower stiffness properties [26]. Li et al. [49] studied the effects
of sodium chlorite (sodium chlorite:water 1:25, at 700 °C for 24 h)
treatment on alkali pre-treated (5% NaOH for 1 h) sisal fibre and
Fibre- O-Na+ + C1C Fibre- O – C + NaCl
found a higher tensile strength and a lower moisture absorption
rate. Similar results were reported by Mishra et al. [50] on sisal fi-
Scheme 4.
bre reinforced polyester biocomposites.

RO OR 2RO 4.1.8. Acrylation and acrylonitrile grafting

RO + Cellulose – H R – OH + Cellulose
R= peroxide functional group
Scheme 5.
with the matrix [32]. This covalent bonding between the hydroxyl
groups of the fibre and the anhydride groups of the maleic anhy-
dride provide balanced properties to make bridge interface for effi-
cient interlocking [45].
The reaction mechanism of maleic anhydride, polypropylene
(MAPP) and the cellulose fibre are presented in Scheme 6. MAPP
copolymer is activated at a temperature of 1700 °C and then the
esterification of the cellulose fibres is carrying out. This treatment
results better wettability of the fibre and enhance interfacial adhe-
sion [26,45].
Mohanty et al. [46] used jute fibre (30% fibre loading, 6 mm on
fibre length) treated with 0.5% MAPP concentration in toluene for
5 min and reinforced in PP matrix. The composite showed around
72% higher flexural strength properties compared to the untreated
fibre composites. Water absorption tendency by the treated fibre
composite was also reduced. Similar studies was performed by
Mohanty et al. [47] and reported, 1%MAPP treated sisal fibre–PP
composite exhibited around 50%, 30% and 58% higher tensile, flex-
ural and impact strength properties respectively.
4.1.7. Sodium chlorite treatment
Sodium chlorite (NaClO2) is used for the bleaching of fibres in
acid solution. NaClO2 is acidified and liberates choleric acid
(HClO2), which undergoes an oxidation reaction and forms chlorine
dioxide (ClO2). ClO2 reacts with lignin constituents and lignin is re-
moved from the fibre. It also reacts with the hydrophilic hydroxyl
groups of hemicelluloses [48]. These combined effects remove
moisture from the fibre and enhance the hydrophobic nature of
PP chain
Acrylic acid (CH2@CHCOOH) is used to enhance interfacial
bonding between the fibre and matrix (polypropylene). CH2@
CHCOOH reacts with the cellulosic hydroxyl groups of the fibre
and provides more access of reactive cellulose macroradicals to
the polymerization medium. The carboxylic acids from coupling
agents form ester linkages with the cellulose hydroxyl groups. It
reduces hydrophilic hydroxyl groups from the fibre structure and
improves moisture resistance properties. Therefore, the grafting
with acrylic acid on to the matrix is initiated by peroxide radicals.
Peroxide provides oxygenAoxygen bonds to extract hydrogen
atoms from the tertiary carbon of the polymer chain. This coupling
mechanism between the fibre and matrix by acrylic acid enhances
the stress transfer capacity at the interface and thus improves
composite properties [26,51,52].
The treatment process involves alkali pre-treated fibres being
immersed with different concentrations of acrylic acid at higher
temperatures for 1 h, followed by washing with an aqueous alcohol
solution and oven dried [26]. The reactions between fibre AOH
groups and acrylic acid are given in Scheme 7.
Li et al. [53] reported higher tensile strength properties for ac-
rylic acid treated flax fibre HDPE composites. It also reduced
hydrophilic tendency of the fibre. Patel et al. [54] studied acryla-
tion on an alkali pre-treated jute fibre reinforced in epoxy-phenolic
matrix and reported increased composites tensile and flexural
strength by 42.2% and 13.9% respectively.
Grafting on the fibre by acrylonitrile (AN (CH2@CHAC„N)) is an
effective method of surface modification. AN (CH2@CHAC„N) ini-
tiates free radicals to react with cellulose molecules by dehydroge-
nation and oxidation. Then the activated free radical sites interact
with the monomer of the matrix. The resulting copolymer process
between the fibre and matrix enhances the interlocking efficiency
at the interface [55]. This treatment on sisal fibre resulted in a 25%
less water absorption tendency, higher tensile strength and modu-
lus properties of the composite [26]. The reaction between fibre
AOH groups and acrylonitrile is presented in Scheme 8.
Mishra et al. [56] studied the effects of acrylonitrile treatment
on sisal fibre reinforced in polyesteramide (BAK) composites and
reported 13% and 11% higher in tensile and flexural strength

PP chain

O H H O H H properties.
HO – C – C C–C
O + H2O
HO – C – C – C C–C– C 4.1.9. Isocyanate treatment
O H O H Isocyanate works as a coupling agent for fibre surface modifica-
tion. The functional group (AN@C@O) of isocyanate reacts with the
O H H
hydroxyl groups of cellulose and lignin constituents of the fibres
and therefore a urethane linkage is formed. This chemical linkage
Fibre

O C–C
provides strong covalent bonds between the fibre and matrix. In
O C–C– C addition to this, isocyanate also reacts with the moisture present
PP chain

O H H O H
OH C–C
Fibre + O Fibre – OH + C2H3COOH Fibre – OOC2H3 + H2O
OH C–C– C
O H H
O H Scheme 7.
Fibre

O C–C
O O C–C– C
H-H O H
Fibre – OH + CH2=CHCN Fibre – OCH2CH2CN

Scheme 6. Scheme 8.
2890 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
on the fibre surface and forms urea which can further react with
the hydroxyl groups of the celluloses [32]. This secondary reaction
results in higher moisture resistance properties of the fibre and
provides better bonding with the matrix to enhance composite
properties [55]. The reaction between the fibre and isocyanate cou-
pling agent is shown in Scheme 9, where R could be different
chemical groups.
George et al. [57] used isocyanate with dimethyl formamide
(DMF) solvent to treat flax fibre. The DMF solvent has a higher boil-
ing point and better solubility with isocyanates and the fibre. Due
to this, thermal stability of the fibre was increased. The resultant
treated (flax-epoxy) fibre composite showed 12.5% and 17.7% high-
er tensile strength and modulus properties respectively, compared
to the untreated fibre composite.
4.1.10. Stearic acid treatment
Stearic acid (CH3(CH2)16COOH) in ethyl alcohol solution is used
to modify the fibre surfaces. The carboxyl group of stearic acid re-
acts with the hydrophilic hydroxyl groups of the fibre and im-
proves water resistance properties. This treatment removes non-
crystalline (pectin, wax oil covering materials, etc.) constituents
from the fibre structure. As a result, fibre bundles are breaking
down and more fibrillation occurs [58,59]. Fibre dispersion into
the matrix facilitates better bonding at the interface and provides
improved properties of the composites. Kalaprasad et al. [43] used
stearic acid treatment on sisal fibre in ethyl alcohol solution and
showed higher tensile strength and modulus properties. Torres
et al. [60] used 3% stearic acid treated sisal fibre reinforced in poly-
ethylene composites and reported 23% higher shear strength prop-
erties compared to the untreated fibre composites. The reaction
between fibre and stearic acid is presented in Scheme 10.
4.1.11. Permanganate treatment
Permanganate treatment on natural fibres is conducted by
potassium permanganate (KMnO4) in acetone solution. This treat-
ment forms highly reactive permanganate (Mn3+) ions to reacts
with the cellulose hydroxyl groups and forms cellulose–manganate
for initiating graft copolymerization. This treatment enhances
chemical interlocking at the interface and provides better adhesion
with the matrix [61]. Formation of cellulose–manganate is respon-
sible for higher thermal stability of the fibre. It also reacts with the
lignin (hydrophilic AOH groups) constituents and separates from
the fibre cell wall. It reduces the hydrophilic nature of the fibre.
Higher concentrations of KMnO4 (more than 1%) cause excess del-
ignification (removal of cementing materials) within the cellulosic
structure and degrade fibre properties [59,26].
Paul et al. [59] reported that, during an oxidation reaction,
KMnO4 etches the fibre surface and makes it physically rougher
to improve mechanical interlocking with the matrix. Flexural
strength and modulus properties were increased by 5% and 10%
for the treated banana fibre polypropylene composites. Li et al.
[53] applied 0.2% potassium permanganate (KMnO4) solution (in
2% acetone) on alkali (2% NaOH for 1 h) pre-treated flax fibre and
reported treated fibre-LLDPE and HDPE composites had higher ten-
sile strength properties compared to the untreated fibre compos-
O H
Fibre – OH + R – N = C = O Fibre – O – C – N – R
Scheme 9.
Fibre-OH + CH3(CH2)16COOH CH3(CH2)16COO-O-Fibre + H2O
Scheme 10.
ites. The reaction between fibre–OH group and potassium
permanganate is given in Scheme 11.
4.1.12. Triazine treatment
Triazine treatment is used for surface modification of the natu-
ral fibres. A triazine (C3H3N3) derivative (e.g. C3H3N3Cl3) has mul-
tifunctional groups in its structure. The reactive chlorines are
presented in the heterocyclic ring reacts with the hydroxyl groups
of the fibre by esterification and provide linkage between the cel-
lulose phase and coupling agent. The carbonAcarbon double bonds
(C@C) form covalent bonds with the matrix by grafting. It also pro-
vides a secondary reaction with the hydrophilic hydroxyl groups of
cellulose and lignin that provides better moisture resistance prop-
erties [26,55,62]. This modification provides crosslinking between
the cellulose (through hydrogen bond) and matrix. This results
strong adhesion at the interface and improves composite proper-
ties [2]. The possible reaction between triazine derivative and fi-
bre–OH groups are given in Scheme 12.
Zadorecki et al. [63] used trichloro-s-triazine based different
coupling agents to treat cellulose fibres and were reinforced in
unsaturated polyester resin. Improved fibre matrix adhesion and
higher moisture resistance properties were reported for the treated
fibre composites.
4.1.13. Fatty acid derivate (oleoyl chloride) treatment
Fatty acid derivative is used as a coupling agent to modify fibre
surface to improve wettability and interfacial adhesion characteris-
tics. Oleoyl chloride is a fatty acid derivate which reacts with the
hydroxyl groups (esterification) and grafted on the cellulose back-
bone of the fibre. During esterification, the molecules are penetrat-
ing inside the cellulose structure and reacts with the hydroxyl
groups of the fibre and the matrix. Additionally, hydrophilic hydro-
xyl groups present on the external surface are removed by this
treatment and make the fibre more hydrophobic. This improves
the wetting and adhesion of fibre surface into the matrix and pro-
vides improved composite properties. Modification on jute fibre
with dichloromethane and pyridine solvent under a dry nitrogen
atmosphere results in more hydrophobic characteristics and in-
creases composite properties [64].
O
Fibre - OH + KMnO4 Fibre – O – H – O – Mn – OK+
O
Scheme 11.
R
Cl HN
N N H2 NR N N + HCL
Cl N Cl Cl N Cl
R R
HN HN
Fibre-OH + N N N N + HCL
N Cl
Cl N Cl O
Fibre
Scheme 12.
 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
4.1.14. Fungal treatment
Fungal treatment has been recently considered as a promising
alternative for surface modification of natural fibres. This biological
treatment is environment friendly and efficient. Fungi treatment is
used to remove non-cellulosic components (such as wax) from the
fibre surface by the action of specific enzymes. White rot fungi pro-
duces extracellular oxidases enzymes that reacts with lignin con-
stituents (lignin peroxidase). This causes the removal of lignin
from the fibre. It also increases hemicelluloses solubility and thus
reduce hydrophobic tendency of the fibre. In addition to this, fungi
produce hyphane that creates fine holes on the fibre surface and pro-
duces a rough interface for better interlocking with the matrix
[15,65].
The treatment process involves sterilization of the fibres in an
autoclave for 15 min with 120 °C. Afterwards, fungi are added pro-
portionally with the fibre and incubate for 2 weeks at 27 °C. Fibres
are then sterilized, washed and oven dried. Pickering et al. [15] stud-
ied fungal treatment on hemp fibre and reported that a 22% higher
composite strength was achieved in comparison to the untreated
one. Moreover, for hemp polypropylene thermoplastics, fungi over
alkali treatment showed a 32% improvement in composite strength.
5. Conclusions
Natural fibres are gaining interest to be used as reinforcement
in polymer composites due to its potential mechanical properties,
processing advantages and environmental benefits. However,
hydrophilic nature of the fibres lowers the compatibility with the
matrix. This incompatibility results poor mechanical properties of
the composites. Chemical treatment is an essential processing
parameter to reduce hydrophilic nature of the fibres and thus im-
proves adhesion with the matrix. Pre-treatments of fibre change its
structure and surface morphology. Hydrophilic hydroxyl groups
are removed from the fibre by the action of different chemicals.
More reactive hydroxyl groups make an effective coupling with
the matrix. Significant improvements in the mechanical properties
of the composites are reported by using different chemical treat-
ment processes on the reinforcing fibre.
Acknowledgements
The authors gratefully acknowledge to Dr. Mainul Islam and Ali
Naim Khurshid for providing helpful suggestions regarding this
study. This project was supported by the funding from the Univer-
sity of Southern Queensland and The Hong Kong Polytechnic
University.
References
[1] Rout J, Misra M, Tripathy S, Nayak SK, Mohanty AK. The influence of fibre
treatment on the performance of coir-polyester composites. Compos Sci
Technol 2001;61(9):1303–10.
[2] Bledzki AK, Gassan J. Composites reinforced with cellulose based fibres. Prog
Polym Sci 1999;24(2):221–74.
[3] Abdelmouleh M, Boufis S, Belgacem MN, Dufresne A. Short natural-fibre
reinforced polyethylene and natural rubber composites: effect of silane
coupling agents and fibre loading. Compos Sci Technol 2007;67(7–8):1627–39.
[4] Tserki V, Zafeiropoulos NE, Simon F, Panayiotou C. A study of the effect of
acetylation and propionylation surface treatments on natural fibres. Compos
Part A – Appl Sci Manuf 2005;36(8):1110–8.
[5] Doan TTL, Gao SL, Mader E. Jute/polypropylene composites I. Effect of matrix
modification. Compos Sci Technol 2006;66(7–8):952–63.
[6] Leonard YM, Martin PA. Chemical modification of hemp, sisal, jute and kapok
fibres by alkalisation. Appl Polym Sci 2002;84(12):2222–34.
[7] Saheb DN, Jog JP. Natural fibre polymer composites: a review. Adv Polym Tech
1999;18(4):351–63.
[8] Madsen B. Properties of plant fibre yarn polymer composites. PhD thesis, BYG-
DTU, Technical University of Denmark; 2004, ISBN: 87-7877-145-5.
[9] John MJ, Anandjiwala RD. Recent developments in chemical modification and
characterization of natural fibre-reinforced composites. Polym Compos
2008;29(2):187–207.
2891
[10] Fakirov S, Bhattacharyya D, editors. Engineering biopolymers: homopolymers,
blends and composites. Munich Hanser Publishers; 2007, ISBN: 978-1-56990-
405-3.
[11] Mwaikambo YM, Ansell MP. The effect of chemical treatment on the properties
of hemp, sisal, jute and kapok fibres for composite reinforcement. Angew
Makromol Chem 1999;272:108–16.
[12] Mohanty AK, Misra M, Hinrichsen G. Biofibres, biodegradable polymers and
biocomposites: an overview. Macromol Mater Eng 2000;266–277(1):1–24.
[13] Dhakal HN, Zhang ZY, Richardson MOW. Effect of water absorption on the
mechanical properties of hemp fibre reinforced unsaturated polyester
composites. Compos Sci Technol 2007;67(7–8):1674–83.
[14] Joseph PV, Joseph K, Thomas S, Pillai CKS, Prasad VS, Groeninckx G, et al. The
thermal and crystallisation studies of short sisal fibre reinforced polypropylene
composites. Compos Part A – Appl Sci Manuf 2003;34(3):253–66.
[15] Pickering KL, Li Y, Farrell RL, Lay M. Interfacial modification of hemp fibre
reinforced composites using fungal and alkali treatment. J Biobased Mater
Bioenergy 2007;1(1):109–17.
[16] Adekunle K, Akesson D, Skrifvars M. Biobased composites prepared by
compression molding with a novel thermoset resin from soybean oil and a
natural-fiber reinforcement. J Appl Polym Sci 2010;116(3):1759–65.
[17] Sgriccia N, Hawley MC, Misra M. Characterization of natural fibre surfaces and
natural fibre composites. Compos Part A – Appl Sci Manuf 2008;39(10):1632–7.
[18] Taj S, Ali M, Khan S. Review: natural fibre reinforced polymer composites. Proc
Pak Acad Sci 2007;44(2):129–44.
[19] Bowles KJ, Frimpong S. Void effects on the interlaminar shear strength of
unidirectional graphite–fiber-reinforced composites. J Compos Mater
1992;26(10):1487–509.
[20] Vaxman A, Narkis M, Siegmann A, Kenig S. Void formation in short-fiber
thermoplastic composites. Polym Compos 2004;10(6):449–53.
[21] Zakaria S, Poh LK. Polystyrene-benzoylated EFB reinforced composites. Polym
Plast Technol Eng 2002;41(5):951–62.
[22] Wang B, Panigrahi S, Tabil L, Crerar W. Pre-treatment of flax fibres for use in
rotationally molded biocomposites. J Reinf Plast Compos 2007;26(5):447–63.
[23] Dash BN, Rana AK, Mishra SC, Mishra HK, Nayak SK, Tripathy SS. Novel low-
cost jute–polyester composite. II. SEM observation of the fracture surfaces.
Polym Plast Technol Eng 2000;39(2):333–50.
[24] Stana-Kleinschek K, Ribitsch V, Kreze T, Sfiligoj-Smole M, Persin Z. Correlation
of regenerated cellulose fibres morphology and surface free energy
components. Lenzinger Berichte 2003;82:83–95.
[25] Abdelmouleh M, Boufi S, Belgacem MN, Duarte AP, Salah AB, Gandini A.
Modification of cellulosic fibres with functionalized silanes: development of
surface properties. Int J Adhes Adhes 2004;24(1):43–54.
[26] Li X, Tabil LG, Panigrahi S. Chemical treatment of natural fibre for use in
natural fibre-reinforced composites: a review. Polym Environ
2007;15(1):25–33.
[27] Mwaikambo LY, Tucker N, Clark AJ. Mechanical properties of hemp fibre
reinforced euphorbia composites. Macromol Mater Eng 2007;292(9):
993–1000.
[28] Ray D, Sarkar BK, Rana AK, Bose NR. Effect of alkali treated jute fibres on
composite properties. Bull Mater Sci 2001;24(2):129–35.
[29] Cyras VP, Vallo C, Kenny JM, Vazquez A. Effect of chemical treatment on the
mechanical properties of starch-based blends reinforced with sisal fibre. J
Compos Mater 2004;38(16):1387–99.
[30] Ouajai S, Shanks RA. Composition, structure and thermal degradation of hemp
cellulose after chemical treatment. Polym Degrad Stab 2005;89(2):327–35.
[31] Prasad SV, Pavithran C, Rohatgi PK. Alkali treatment of coir fibres for coir–
polyester composites. J Mater Sci 1983;18(5):1443–54.
[32] George J, Sreekala MS, Thomas S. A review of interface modification and
characterisation of natural fibre reinforced plastic composites. Polym Eng Sci
2001;41(9):1471–85.
[33] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Chemical
modification of henequen fibres with an organosilane coupling agent. Compos
Part B – Eng 1999;30(3):321–31.
[34] Seki Y. Innovative multifunctional siloxane treatment of jute fibre surface and
its effect on the mechanical properties of jute/thermoset composites. Mater Sci
Eng A 2009;508(1–2):247–52.
[35] Sever K, Sarikanat M, Seki Y, Erkan G, Erdogan UH. The mechanical properties
of c-methacryloxypropyltrimethoxy silane-treated jute/polyester composites.
J Compos Mater 2010;44(15):1913–24.
[36] Sreekala MS, Kumaran MG, Joseph S, Jacob M. Oil palm fibers reinforced phenol
formaldehyde composites: influence of fibers surface modifications on the
mechanical performance. Appl Compos Mater 2000;7(5–6):295–329.
[37] Rowell RM, Young RA, Rowell J. Paper and composites from agro-based
resources. Taylor & Francis Ltd., CRC Press; 1996, ISBN 9781566702355.
[38] Mishra S, Mohanty AK, Drzal LT, Misra M, Parija S, Nayak SK, et al. Studies on
mechanical performance of biofiber/glass reinforced polyester hybrid
composites. Compos Sci Technol 2003;63(10):1377–85.
[39] Bledzki AK, Mamun AA, Lucka-Gabor M, Gutowski VS. The effects of
acetylation on properties of flax fibre and its polypropylene composites.
Express Polym Lett 2008;2(6):413–22.
[40] Mwaikambo LY, Ansell MP. The effect of chemical treatment on the properties
of hemp, sisal, jute and kapok fibres for composite reinforcement. Macromol
Mater Eng 1999;272(1):108–16.
[41] Nair KCM, Thomas S, Groeninckx G. Thermal and dynamic mechanical analysis
of polystyrene composites reinforced with short sisal fibres. Compos Sci
Technol 2001;61(16):2519–29.
2892 M.M. Kabir et al. / Composites: Part B 43 (2012) 2883–2892
[42] Joseph K, Thomas S, Pavithran C. Effect of chemical treatment on the tensile
properties of short sisal fibre-reinforced polyethylene composites. Polymer
1996;37(23):5139–49.
[43] Kalaprasad G, Francis B, Thomas S, Kumar CR, Pavithran C, Groeninckx G, et al.
Effect of fibre length and chemical modifications on the tensile properties of
intimately mixed short sisal/glass hybrid fibre reinforced low density
polyethylene composites. Polym Int 2004;53(11):1624–38.
[44] Sapieha S, Allard P, Zang YH. Dicumyl peroxide-modified cellulose/LLDPE
composites. J Appl Polym Sci 1990;41(9–10):2039–48.
[45] Keener TJ, Stuart RK, Brown TK. Maleated coupling agents for natural fibre
composites. Compos: Part A – Appl Sci Manuf 2004;35(3):357–62.
[46] Mohanty S, Nayak SK, Verma SK, Tripathy SS. Effect of MAPP as a coupling
agent on the performance of jute–PP composites. J Reinf Plast Compos
2004;23(6):625–37.
[47] Mohanty S, Verma SK, Nayak SK, Tripathy SS. Influence of fibre treatment on
the performance of sisal–polypropylene composites. J Appl Polym Sci
2004;94(3):1336–45.
[48] Chattopadhyay H, Sarkar PB. A new method for the estimation of cellulose.
Proc Natl Inst Sci India 1946;12(1):23–46.
[49] Li X, Panigrahi S, Tabil LG. A study of flax fibre-reinforced polyethylene
biocomposites. Appl Eng Agric 2009;25(4):525–31.
[50] Mishra S, Misra M, Tripathy SS, Nayak SK, Mohanty AK. The influence of
chemical surface modification on performance of sisal–polyester
biocomposites. Polym Compos 2002;23(2):164–70.
[51] Bogoeva-Gaceva G, Avella M, Malinconico M, Buzarovska A, Grozdanov A,
Gentile G, et al. Natural fibre eco-composites. Polym Compos 2007;28(1):
98–107.
[52] Zahran MK, Rehan MF. Grafting of acrylic acid onto flax fibres using Mn(IV)-
citric redox system. J Appl Polym Sci 2006;102(3):3028–36.
[53] Li X, Panigrahi S, Tabil LG, Crerar WJ. Flax fibre reinforced composites and the
effect of chemical treatments on their properties. In: Proc CSAE/ASAE annual
intersectional meeting, Winnipeg, 24–25 September, Canada; 2004.
[54] Patel VA, Parsania PH. Performance evaluation of alkali and acrylic acid
treated-untreated jute composites of mixed epoxy-phenolic resins. J Reinf
Plast Compos 2010;29(5):725–30.
[55] Kaliaa S, Kaith BS, Kaur I. Pretreatments of natural fibres and their application
as reinforcing material in polymer composites – a review. Polym Eng Sci
2009;49(7):1253–72.
[56] Mishra S, Tripathy SS, Misra M, Mohanty AK, Nayak SK. Novel eco-friendly
biocomposites: biofibre reinforced biodegradable polyester amide
composites-fabrication and properties evaluation. J Reinf Plast Compos
2002;21(1):55–70.
[57] George J, Ivens J, Verpoest I. Mechanical properties of flax fibre reinforced
epoxy composites. Macromol Mater Eng 1999;272(1):41–5.
[58] Paul SA, Oommen C, Joseph K, Mathew G, Thomas S. The role of interface
modification on thermal degradation and crystallization behavior of
composites from commingled polypropylene fibre and banana fibre. Polym
Compos 2010;31(6):1113–23.
[59] Paul SA, Joseph K, Mathew G, Pothen LA, Thomas S. Influence of polarity
parameters on the mechanical properties of composites from polypropylene
fibre and short banana fibre. Compos: Part A – Appl Sci Manuf 2010;41(10):
1380–7.
[60] Torres FG, Ubillas ML. Study of the interfacial properties of natural fibre
reinforced polyethylene. Polym Test 2005;24(6):694–8.
[61] Rahman MM, Mallik AK, Khan MA. Influences of various surface pretreatments
on the mechanical and degradable properties of photografted oil palm fibers. J
Appl Polym Sci 2007;105(5):3077–86.
[62] Mengeloglu F, Karakus K. Thermal degradation, mechanical properties and
morphology of wheat straw flour filled recycled thermoplastic composites.
Sensors 2008;8(1):500–19.
[63] Zadorecki P, Flodin P. Surface modification of cellulose fibres, II. The effect of
cellulose fibre treatment on the performance of cellulose–polyester
composites. J Appl Polym Sci 1985;30(10):3971–83.
[64] Corrales F, Vilaseca F, Llop M, Girones J, Mendez JA, Mutje P. Chemical
modification of jute fibres for the production of green composites. J Hazard
Mater 2007;144(3):730–5.
[65] Jafari MA, Nikkhah A, Sadeghi AA, Chamani M. The effect of Pleurotus spp.
Fungi on chemical composition and in vitro digestibility of rice straw. Pak J
Biol Sci 2007;10(15):2460–4.