COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 67 (2007) 1627–1639
www.elsevier.com/locate/compscitech

Short natural-fibre reinforced polyethylene and natural

rubber composites: Effect of silane coupling agents and fibres loading
M. Abdelmouleh a, S. Boufi a,*
, M.N. Belgacem b, A. Dufresne b

a
LMSE, Faculté des sciences de Sfax, BP 802-3018 Sfax, Tunisia
b
LGP2, Ecole Française de Papeterie et des Industries Graphiques (INPG), BP 65, F-38402 St. Martin d’Hères, France

Received 5 February 2006; received in revised form 22 June 2006; accepted 2 July 2006
Available online 1 September 2006

Abstract

Composites materials based on cellulose fibres (raw or chemically modified) as reinforcing elements and thermoplastic matrices were
prepared and characterized, in terms of mechanical performances, thermal properties and water absorbance behaviour. Four different cel-
lulose fibres with different average lengths were used, namely avicel, technical, alfa pulps and pine fibres. Two thermoplastic polymers, i.e.
low density polyethylene and natural rubber, were employed as matrices. Cellulose fibres were incorporated into the matrices, as such or
after chemical surface modification involving three silane coupling agents, namely c-methacryloxypropyltrimethoxy (MPS), c-mercaptop-
royltrimethoxy (MRPS) and hexadecyltrimethoxy-silanes (HDS). As expected, the mechanical properties of the composites increased with
increasing the average fibre length and the composite materials prepared using both matrices and cellulose fibres treated with MPS and
MRPS displayed good mechanical performances. On the other hand with HDS bearing merely aliphatic chain only a modest enhancement
on composite properties is observed which was imputed to the incapacity of HDS to bring about covalent bonding with matrix.
 2006 Elsevier Ltd. All rights reserved.

Keywords: A. Polymer-matrix composites (PMCs); A. Coupling agents; B. Fiber/matrix bond; B. Interface

1. Introduction fibre/polymer compatibility and their interfacial adhesion

Over the past decade there has been a growing interest in
the use of lignocellulosic fibres as reinforcing elements in
polymeric matrix [1–5]. The specific properties of this nat-
ural product, namely low cost, lightweight, renewable char-
acter, high specific strength and modulus, availability in a
variety of forms throughout the word, reactive surface
and the possibility to generate energy, without residue,
after burning at the end of their life-cycle, motivate their
association with organic polymers to elaborate composite
materials. However, it is well known that different surface
properties between the fibre and the matrix, i.e. the former
is highly polar and hydrophilic while the latter is, generally,
non-polar and relatively hydrophobic, impose the surface
modification of the fibres surface, in order to improve the
*
Corresponding author. Tel.: +216 74 274 400; fax: +216 74 274 437.
E-mail address: sami.boufi@fss.rnu.tn (S. Boufi).
[6]. Without such a treatment, natural fibres embedded in
a polymeric matrix generate unstable interfaces and the
stress applied to the fibre/polymer composite is not
efficiently transferred from the matrix to the fibre and the
beneficial reinforcement effect of the fibre remains underex-
ploited. Likewise, the poor ability of the polymer to wet the
fibre hinders the homogenous dispersion of short fibres
within the polymeric matrix [7].
Several strategies of surface modifications aiming at
improving the compatibility between cellulose fibres and
polymer matrices were recently reviewed [8]. The chemical
modification using coupling agents bearing two reactive
groups, one of which being likely to react with the OH
function at the fibre surface, whereas the other one is left
to copolymerize with the matrix, constitutes a highly inter-
esting way allowing the establishment of covalent bonding
between fibres and matrix, thus leading to materials with
high mechanical properties. Many coupling agents have

0266-3538/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.07.003
1628 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639

been investigated, namely anhydrides, maleated polymer • Commercial microcrystalline fibres (Technocel-50
[9–11], isocyanates [12–14], triazines [15] and alkoxysilanes labelled Tech-50) with average length of about 50 lm,
[16–20], as recently reviewed [8]. Among these different and specific surface, measured by the BET technique
reagents, maleated polypropylene (MaPP) or polyethylene using nitrogen, around 2.5 m2/g.
(MaPE) gave significant enhancement in tensile and flex- • Technocel-2500 fibres (labelled Tech-2500), with average
ural strength, ranging from 40% up to 80%, was pointed length of about 2.5 mm.
out when they are blended with cellulose fibres before mix- • Alfa fibres are bleached soda pulps from the Tunisian
ing with matrix [9,11]. annual plant esparto (alfa tenassissima). They had a spe-
Silane coupling chemicals present three main advanta- cific surface (in a dry state) of 3 m2/g and average length
ges: (i) they are commercially available in a large scale; about 500 lm.
(ii) at one end, they bear alkoxysilane groups capable of • Bleached softwood (pine) fibres with average length
reacting with OH-rich surface, and (iii) at the second end, about 3.5 mm.
they have a large number of functional groups which can • The Avicel fibres used in this work were purchased from
be tailored as a function of the matrix to be used. The last Aldrich. The average length of this fibre was about
feature ensures, at least, a good compatibility between the 70 lm.
reinforcing element and the polymer matrix or even cova-
lent bonds between them. The reaction of silane coupling 2.2. Silane coupling agent
agents with lignocellulose fibres (mainly: cellulose and lig-
nin) was found to be quite different to compare with that Three commercial silanes chosen for this study (Table 1)
observed between them and glass surface, in the sense that were kindly provided by OSI-WITCO, to whom we are
with cellulose macromolecules, only prehydrolyzed silanes indebted.
underwent the reaction with cellulose surface [21].
Besides the chemical bonding theory which is the most
evident mechanism by which organosilane coupling agents 2.3. Polymer matrix
are acting, other theories have been proposed, such as the
interpenetrating networks theory which states that the The low density polyethylene (LDPE) used in this work
matrix diffuse inside the silane interphase to form an entan- has a melting temperature of 107 C and a degree of crys-
gled network [22–25]. tallinity around 28–30%, as determined by differential scan-
Our group has been involved in series of works aiming at ning calorimetry (DSC) with a heating rate of 10 C/min.
understanding silane–cellulose system [26–28]. Thus, the Its density at room temperature was 0.9 g/cm3. The natural
interaction of silane coupling agents with cellulosic fibres rubber (NR) (polyisoprene) was a kind gift of the Technical
and the effect of some parameters, such as the pH, the initial Centre, MAPA, Liancourt, France, and was provided as
amount of silane with respect to cellulose and the adsorp-
tion contact time, on their anchoring capability onto the
fibre surface have been ascertained. Different spectroscopic
Table 1
techniques have been used to evidence the presence of silane The silane coupling agents used in this work
and to quantify its amount on the substrate and to elucidate
O
the structure of the anchored siloxane network on the fibre’s
O
surface [27]. Then, using epoxy and unsaturated polyester O Si
resins we have shown that the fibre treatment with silane O O
coupling agents bearing functional group able to react with γ-Methacryloxypropyltrimethoxysilane
the matrix enhanced significantly the mechanical strength of γ-MPS
the final composite [28].
In the present study three silane coupling agents, differ- O
ent by the functionality of the radical moiety appended to Si
O
silicon atoms were used to treat delignified cellulose fibres O
in order to improve their adhesion to LDPE and NR
matrix. The effect of these treatments on the mechanical Hexadecyltriméthoxysilane
HDS
properties of the ensuing composites and on their water
uptake ability was investigated accordingly.
O
2. Materials and experimental procedures HS Si
O
O
2.1. Cellulose fibres

The different types of cellulose fibres used in this work γ-mercaptoproyltrimethoxysilane

were: γ-MRPS
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639
latex. Its TSC (total solid content), DRC (dry rubber con-
tent), and density were 61.58%, 60.1% and 1 g cm3,
respectively. The latex particle size was around 1 lm.
2.4. Fibre treatment
The treatment of cellulosic fibres with 3 wt% of the cho-
sen silane was carried out in 80/20 v/v ethanol/water med-
ium for 2 h. Then, the fibres were filtered and dried at room
temperature for 2 days, and heated at 120 C under a nitro-
gen atmosphere for two hours in order to promote the
actual chemical coupling.
2.5. Composite and specimen preparation
Cellulose reinforced LDPE composites were obtained by
mixing the matrix with each type of untreated and silane-
treated cellulose fibres using a Brabender (FDO 234 H
model) with a rotor speed of 50 rpm and mixing chamber
temperature of 170 C during 10 up to 15 min. The ensuing
cellulose/LDPE materials were then shaped into 0.5 mm
thick sheets by compression moulding at 180 C. The
moulding cycle consisted of 5 min preheating, compression
under a force of 10 ton for 3 min, and air cooling under
load until the mould reached 40 C. Cellulose–NR compos-
ites were prepared by mixing the cellulose fibres (25 wt%
with respect to full composite) into NR latex emulsion.
The ensuing dispersion was poured in Teflon mould and
solid films were obtained by evaporating the water at 50–
60 C for 2–4 days, until a homogeneous solid film with
0.8 mm thickness was formed.
2.6. Characterization of modified fibres
The FTIR spectra were obtained with a Perkin–Elmer
Paragon 1000 FT-IR spectrometer working in diffuse
reflectance mode (DRIFT) with a total of 40 scans and
with a resolution of 4 cm1. 5 mg of fibres was mixed with
200 mg of analytical grade KBr and the resulting mixture
ground and pressed in order to obtain pellets. All DRIFT
spectra were plotted according to the Kubelka–Munk
function.
2.7. Morphological characterization
The average fibre morphology was determined using an
optical microscope equipped with CCD camera and image
analysis software. These measurements gave the fibre
length and particle diameter distribution.
2.8. Characterization of composites
2.8.1. Differential scanning calorimetry
Differential scanning calorimetry (DSC) was performed
with a Perkin–Elmer DSC7 equipment, fitted with a cooler
system using liquid nitrogen. Samples, around 10 mg, were
placed in pressure-tight DSC cells and at least two individ-
1629
ual measurements were carried out to ensure perfect reli-
ability of measurements. Each sample was heated from 0
to +250 C at a heating rate of 10 C/min. The melting
temperature (Tm) was taken as the peak temperature of
the melting endotherm.
2.8.2. Tensile testing
The strength of cellulose fibre reinforced LDPE compos-
ites was determined using an Instron 4301 universal Testing
machine. Tests were carried out according to ASTM stan-
dards D638 using a 100 N load cell and 50 mm/min cross-
head speed. The specimens were thin rectangular strips
(5 · 10 · 0.5 mm of width, length and thickness, respec-
tively). Tensile strength and modulus values correspond
to the average of four samples.
2.8.3. Dynamic mechanical analysis (DMA)
Dynamic mechanical tests were carried out with a RSA2
spectrometer from Rheometrics working in the tensile
mode. The value of 0.05% for the strain magnitude was
chosen in order to fall into the linear domain of viscoelas-
ticity of the material. The samples were thin rectangular
strips with dimensions of about 30 · 5 · 0.5 mm3. Mea-
surements were performed in isochronal conditions at
1 Hz, and the temperature was varied between 120 up
to 120 C at a rate of 3 C/min. This setup measured the
complex tensile modulus E*, i.e. the storage, E 0 , and the
loss, E00 , components, as well as their ratio (E00 /E 0 ), i.e.
tan d.
2.8.4. Scanning electron microscopy (SEM)
The tensile fracture surfaces of the composites, contain-
ing 15% (v/v) of alfa fibres, were examined with a scanning
electron microscope (ABT-55). Fracture surfaces of the
composite samples were coated with gold and then ana-
lysed at 7 keV. Before the fracture, the specimens were fro-
zen into liquid nitrogen to impede the plastic deformation
of the matrix and to get well defined fibre–matrix interface.
2.8.5. Water absorption
The sample dimensions for water absorption experi-
ments were1 · 1 cm · 0.5 mm. A minimum of two samples
were tested for each material. Samples were weighted and
then soaked in distilled water at 25 C. The samples were
removed at specific time intervals, blotted to remove the
excess water on the surface and immediately weighed.
The difference between the mass after a given time of
immersion and the initial mass compared to the initial mass
led to the determination of the water absorption.
3. Results and discussion
3.1. Fibre modification
The optimal conditions ensuring efficient chemical
anchoring of the organosilane coupling agent onto cellu-
lose fibres have been established previously [26]. In this
1630 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639

study, the grafting of the coupling agent was performed
through a physical adsorption of the hydrolyzed silane fol-
lowed by a curing process at 120 C under inert atmo-
sphere. This treatment guaranteed irreversible chemical
bonding of the silane onto the cellulose surface, as deduced
from FTIR and ESCA spectroscopy as well as contact
angle and IGC measurements.
Fig. 1 presents DRIFT spectra corresponding to the cel-
lulose samples (Tech-50) treated with MPS, before and
after heat treatment. In both cases, the spectrum corre-
sponding to untreated cellulose was deduced, in order to
emphasize the band issuing from the silane moiety. The
two spectra show different bands at 1712 and 1637 cm1,
which are associated with the stretching vibrations of the
C@O and C@C groups of the acrylic moiety, respectively.
The broad shape of the C@O peak suggests that this group
is in interaction with the surface through hydrogen bonds
with the hydroxyl groups. The broad intense bands around
1200 and 1135 cm1 were assigned to the stretching of the –
Si–O–Cellulose and –Si–O–Si– bonds, respectively [1,29].
The strong increase in the intensity of these bands after
the heat treatment suggested that the grafting of silane
onto cellulose as well as the intermolecular condensation
between adjacent adsorbed –Si–OH groups were substan-
tially enhanced. The peaks near 1100 and 1080 cm1 are
related to residual unhydrolyzed Si–OCH3 groups and their
small intensity indicates that most of the silane adsorbed
under these conditions was actually hydrolyzed. The large
band around 1015 cm1, present in the spectrum of the
uncured sample, was attributed to –Si–OH groups. This
band disappeared after the heat treatment and was
replaced by a wide band around 1040 cm1, characteristic
of –Si–O–Si– moieties. These peak assignments are in
agreement with those reported in other studies dealing with
glass surfaces treated with the same coupling agents [29].
3.2. LDPE matrix
In the first part of our study relatively long fibre Tech-
2500 were used to prepare LDPE-based composites by
thorough mixing of the fibres with the polymer followed
by a compression moulding step to form a composite film
with uniform thickness. By this method homogenous com-
posites can be obtained up to 50 wt% fibre loading.

0.180

0.17
C=O
0.16

0.15 1713.72
1701.27
0.14

0.13 C=C
0.12

Si-O-Si + Si-O-Cellulose 0.11

0.10
K-M 1636.36
0.09

1201.79 1181.43 0.08

Si-O-Si 0.07

0.06

0.05

1134.76 0.04

0.03

0.02
b 0.014
1850.0 1820 1800 1780 1760 1740 1720 1700 1680 1660 1640 1620 1600 1580 1560 1537.4
-1
cm

968.69
1181.83
K-M
1204.05 1130.62

Si-O-Si
a
1001.08
1099.36
1038.74
968.32
1083.93

1013.88

Si-OCH3 1051.92
1036.85

Si-OH

1250.0 1220 1200 1180 1160 1140 1120 1100 1080 1060 1040 1020 1000 980 960 940 920 900.2
cm-1
Fig. 1. DRIFT substraction spectra of cellulose MPS-modified fibres (Tech-50) (a) before and (b) after heat treatment (900–1250 cm1 region). Inset:
1850–1550 cm1 region after heat treatment.
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639 1631

The evolution of tensile stress vs strain curves at differ- hydrogen bonding interaction between the fibres contact
ent fibre contents is shown in Fig. 2. All the curves display areas. These connected zones enhance the strength and
a linear Hookean range at low strain (<20%) followed by a the modulus of the composite.
softening region which continue up to 40%. Then the plas- The degree of crystallinity (Xc) of Tech-2500/LDPE
tic deformation under roughly constant stress is main- composites, calculated using the heat of fusion, as deter-
tained until the failure occurs. With the increase of the mined by DSC measurements, is reported in Table 2 for
fibres content, both the modulus and the tensile strength both unfilled PE and reinforced composites with 50 wt%
increase, while the elongation at break decreases. These dif- Tech-2500. Both the extent of crystallinity and the melting
ferent effects are better depicted in Fig. 3. One can notice temperature seems not, within the experimental accuracy to
that the modulus did not increase linearly with the fibres evolve significantly after the fibres incorporation within
fraction and a discontinuity occurred at about 15 vol%, LDPE matrix, even after treatment with the different
composition above which a much faster increase is silane. The degree of crystallinity and the melting tempera-
observed. A similar discontinuity was noted for the elonga- ture of the polymeric matrix remained close to 22–25% and
tion at break and the tensile strength. In these cases, this to 107 C, respectively.
phenomenon took place at around 15 and 25 vol%, respec- The effect of surface modification on the nonlinear
tively. This discontinuity could be attributed to the onset of mechanical behaviour of LDPE composites was investi-
the geometric percolation of the fibres. Indeed, thanks to gated at room temperature for composites containing
the numerous hydroxyl groups on the fibres surface, a three 50 wt% of Tech-2500 cellulose fibres, as shown in Fig. 4.
dimensional connected network could be formed through It reveals that both the modulus and tensile strength are
enhanced by the fibre treatment. However, this evolution
depended on the silane structure. Thus, the tensile strength
15
10% and the modulus increased by 26% and 17%, respectively,
19.5% for MPS and by only 12% and 6%, respectively, for MRPS.
12
Tensile stress (Mpa)

37%
On the other hand, only a modest rise in tensile strength
50%
0% (about 6%) was observed after treatment with HDS silane.
9 The mechanical behaviour of lignocellulosic fibres rein-
forced LDPE was also investigated in the linear range using
6 dynamic mechanical analysis (DMA) to investigate the
properties of the interface and the impact of the fibres
3 treatment on fibre–matrix adhesion. The macroscopic
behaviour of heterogeneous materials depends on four
0 main parameters, viz. (i) the behaviour of each phase, (ii)
0 50 100 150 200 250 the volume fraction of each phase, (iii) the spatial arrange-
Strain (in %) ment of the phase or morphology, and (iv) the interface
Fig. 2. Typical tensile stress vs. strain (DL/L0) curves for LDPE-based properties. The latter mainly depends on the degree of
composites filled with untreated Tech-2500 cellulose fibres at 25 C and for interaction between the phases, i.e. the fibre treatment for
a crosshead speed of 10 mm min1. The fibre contents are indicated in the fibre-filled composites.
figure. In this experiment, composite samples were subjected to
a controlled sinusoidal stress and the resultant displace-
ment was measured. The evolution of the logarithm of
350 16
Elongation at break %
the storage tensile modulus log E 0 and loss factor (tan d)
300
Elastic modulus (MPa) 14 at 1 Hz vs temperature for unfilled LDPE, and both
Tensile strength (MPa)
untreated and treated Tech-2500 reinforced LDPE com-
12
250 posites are displayed in Fig. 5. The tan d curve (Fig. 5b)
σ (MPa), ε r (%)

10
200 Table 2
E (MPa)

8 Heat of fusion (DHm) and degree of crystallinity (Xc) of Tech-2500/LDPE

150 composites reinforced with different silane treated fibres at 50% weight
6 fraction
100
4 Sample DHm (J/g) Xc (%)a Tm (C)
50 2 LDPE 75.7 27 107
Tech-LDPE 43.4 22 107.8
0 0 Tech-MPS-LDPE 51.5 26 108.3
0 10 20 30 40 50 60 Tech-MRPS-LDPE 52.5 26 107.5
Fibres weight fraction (%) Tech-HDS-LDPE 44.4 22 106.5
a
X c ¼ w DH m
DH 0
, where DH 0m ¼ 285 J g1 is the heat of fusion for 100%
Fig. 3. Evolution of the Young’s modulus (E), tensile strength (r), and F m

elongation at break (er) vs cellulose fibres content for LDPE-based crystalline PE and wF is the weight fraction of polymeric matrix material
composites reinforced with untreated Tech-2500 cellulose fibres. in the composite [41].
1632 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639

400 18 ation to a relaxation process occurring in the partially-

Modulus
16 ordered interface between the lamellae and the amorphous
350 Strength
region and can be defined as the glass transition of the ste-
14
rically hindered interfacial region. The storage modulus E 0
Modulus (MPa)

300
12
(Fig. 5a) decreases by a factor 10 and 100 across the a and

Strength (MPa)
250 10 ac relaxation zones, respectively. Around 110 C an abrupt
8
drop in E 0 occurred as a result of the melting of the crystal-
200
line phase. The incorporation of Tech-2500 fibres results in
6
150 an appreciable rise in E 0 , particularly above the a relaxa-
4 tion temperature range confirming the reinforcing effect
100 2 of Tech-2500 fibres. Thus, at 20 C, E 0 was multiplied by
a factor two compared to the unfilled matrix. The a relax-
50 0
LDPE Tech Tech-MPS Tech-MRPS Tech-HDS ation did not exhibit any change in its temperature position
(Fig. 5b), whereas the ac relaxation was shifted from 60 to
Fig. 4. Young’s modulus and tensile strength of LDPE-based composites
67 C after the fibres addition which could be attributed to
reinforced with 50 wt% Tech-2500 cellulosic fibres submitted to different
fibre surface treatments. segmental immobilization of the polymer chain at the fibre
surface.
exhibits two relaxation processes located around 20 C Depending on the silane structure, the fibre treatment
(labelled a) and 60–65 C (labelled ac). They are associated affected both E 0 and tan d curves, as depicted in Figs. 5a
with the chain segment mobility of the polymer branches and b, respectively. To analyse this effect, the relative mod-
and to molecular motion within the crystalline phase, ulus E0r and the relative loss factor tan dr were evaluated
respectively. Nitta and Tanaka [30] attributed the ac relax- using Eq. (1) for each treatment
E0c tan dc
E0r ¼ and tan dr ¼ ; ð1Þ
a 9.5
LDPE
Tech-2500 E0m tan dm
Tech-2500/M PS
9 Tech-2500/M RPS where E0c and E0m are the storage modulus of the composite
Tech-2500/HDS
and unfilled matrix, respectively, estimated at the same
8.5
temperature, and tan dc and tan dm the corresponding mag-
log (E')

8 9 nitude of the ac relaxation process. Figs. 6 and 7 show the

values of E0r and tan dr, respectively, for both untreated and
7.5
8.5 silane-treated cellulose fibres (Technocel-50, Technocel-
7 2500 and alfa fibres) reinforced LDPE composites (fibre
8 content = 50 wt%). The relative storage tensile modulus
6.5 0 10 20 30 40 50
was estimated at T = 20 C.
6 By comparing the effect of untreated cellulosic fibres, we
-100 -80 -60 -40 -20 0 20 40 60 80 100 120 observed that the relative reinforcing effect is significantly
Temperature ˚C higher for Tech-2500 than for Tech-50. This effect is
ascribed to the average length of the fibres, which is well
b 0.25
Tech-2500 known to affect the mechanical performances of compos-
c transition
Tech-2500/MPS ites. At the same time, the relative magnitude of the ac
0.2 Tech-2500/MRPS relaxation process decreases. It is well known that its value
Tech-2500/HDS
LDPE
depends on both the number of mobile units participating
0.15 to the relaxation process and to the magnitude of the mod-
transition
ulus drop through the relaxation. The behaviour of
Tang

untreated alfa fibres reinforced LDPE is intermediate

0.1
between Tech-50 and Tech-2500.
For treated fibres reinforced LDPE, it can be seen that
0.05 only MPS and MRPS enhanced the storage modulus,
except for Tech-50 reinforced composites for which no sig-
0
nificant reinforcing effect was observed. The increase in E 0
-100 -80 -60 -40 -20 0 20 40 60 80 100 at 20 C is about 15% and 35% for MPS and MRPS,
Temperature ˚ C respectively, in presence of Tech-2500 and about 12%
and 20% with alfa fibres. This improvement could be
Fig. 5. Evolution of the (a) logarithm of the storage tensile modulus E 0 , attributed to the increase in the interfacial work of adhe-
and (b) loss angle tangent tan d vs temperature at 1 Hz for LDPE-based
sion between fibres and matrix through the interface. As
composites reinforced with 50 wt% Tech-2500 cellulosic fibres submitted
to different fibre surface treatments. The inset is an expanded view of a consequence, the relative damping properties decrease.
log E 0 vs temperature curves. One can ask about the possible mechanism of interaction
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639 1633

2.5

2
E'r 1.5

0.5 Tech-2500
Alfa
Tech-50
0
LDPE 0 MPS MRPS HDS

E0r
Fig. 6. Relative storage tensile modulus estimated at 20 C for LDPE-based composites reinforced with 50 wt% Techn-50, Alfa or Tech-2500 cellulosic
fibres submitted to different fibre surface treatments. ‘‘LDPE’’ refers to the unfilled matrix and ‘‘0’’ to untreated fibres-based composite.

1.1

0.9
Tan δr

0.7
Tech-2500
Alfa
Tech-50
0.5
LDPE 0 MPS MRPS HDS

Fig. 7. Relative loss factor tan dr for LDPE-based composites reinforced with 50 wt% Tech-50, Alfa or Tech-2500 cellulosic fibres submitted to different
fibre surface treatments. ‘‘LDPE’’ refers to the unfilled matrix and ‘‘0’’ to untreated fibres-based composite.

between these agents and LDPE matrix, which gave rise to
the improvement of the interfacial adhesion in this system.
Both MPS and MRPS contain functional groups which can
react with radical species to generate a covalent bond;
either by an addition reaction with the p-bond (for MPS)
or through a transfer reaction with the mercapto moiety.
The radical species may be generated through peroxide
decomposition which arises from the thermal oxidation
likely to occur during the processing of the composite.
The resulting reaction gives rise to chemical bonding
between the fibres and the matrix which enhance the inter-
facial adhesion. Scheme 1 depicts possible reactions
between MPS grafts and LDPE matrix where the radical
species result from thermal degradation during the mixing
and compressing process. Indeed, even though the process-
ing temperature and the kneading time on the Brabender
are relatively low, i.e; 170 C and 15 min, respectively, the
presence of cellulose fibres is cited to promote the thermal
degradation of the composite [31,32]. The significant yel-
lowing of the filled sample after mixing and compression
moulding support this hypothesis. Espert et al. [32] showed
that the addition of cellulose fibres to PP matrix affected
appreciably the thermo-oxidative stability and reduced
the oxidation temperature from 205 C for unfilled 2.5 %
ethyl vinyl acetate modified-PP to about 175 C for com-
posite containing 40% w/w kraft pulp fibres.
Despite the presence of a long aliphatic chain on HDS,
which imparts hydrophobic character to the fibre surface,
lowers its surface energy and increases its wettability and
dispersion within the non-polar matrix, no significant evo-
lution is noted for E0r . This effect may be ascribed to the fact
that the only van der Waals type interactions could be
established with the polymer matrix, leading to a modest
enhancement of adhesion between the fibres and the
matrix. Soxhlet extractions of LDPE or NR matrices using
xylene for LDPE and a mixture THF/xylene for NR were
carried out in order to establish if there are any continuous
bonding between the fibres and the matrix. No traces of
dissolution after several days extraction have occurred with
LDPE, and some part of NR has been extracted leaving a
high amount of the matrix as a swelled gel, indicating the
occurrence of cross-linking of polyisoprene chains. These
experiments corroborate the proposed mechanism of inter-
action depicted in Scheme 1.
1634 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639
Cellulosic
fiber
MPS
modified fiber
Scheme 1. Schematic illustration of the interfacial zone in LDPE-based composites containing MPS-modified cellulose fibres. Note that the relative size of
the fibres and of the chemical species are not on scale.
The tan dr values undergo an opposite trend than E0r ,
since it decreased after treatment with reactive MPS and
MRPS silane and remained unchanged in presence of
HDS. Given the fact that tan d (tan d = E00 /E 0 ) provides
an indication of the fractional energy lost in the system
by the deformation, the decrease in tan dr could be ascribed
to the movement restriction of the polymer chain in the
vicinity of the fibres surface induced by the chemical bridg-
ing through the interface. It is worth noting that, indepen-
dently of the silane structure, ac transition did not exhibit
any shift in its position after fibre treatment. This result
is in disagreement with other reactive reagents which
induce a small shift of a transition in presence of PE matrix
[33].
SEM observations of fractured surface for LDPE-based
composite reinforced with 50 wt% Tech-2500 fibres were
also carried out to investigate the fibre–matrix interface
and compare their aspect after silane treatment. The sur-
face of fracture for untreated fibres-based composite is
shown in Fig. 8a for two different magnifications. It is clear
that the interfacial adhesion between the fibres and the
matrix is poor. Indeed, the fibres are pulled out from the
matrix giving rise to holes and their surface seems to be
clean, intact and free from any adhering polymer. When
using MPS treatment (Fig. 8b), the fibres are broken off
near the surface and do not leave any voids on the frac-
tured surface. Likewise no discontinuity is reported
between the two phases and the fibres seem to be totally
layered by the matrix. This observation gives direct evi-
dence about the adhesion improvement at the interface in
the presence of reactive silane. Compared to untreated
fibres, the treatment with HDS (Fig. 8c) did not improve
the adhesion in the interfacial region as indicated by the
considerable pulling-out of the fibres from the surface
and by the absence of any physical contact between both
components. These observations are in agreement with
the previous results and support further the hypothesis for-
mulated from DMA experiments.
3.3. Natural rubber matrix
Natural rubber (NR) is one of the most important elas-
tomers, widely used in different industrial sectors. NR is
often reinforced by the incorporation of filler such as car-
bon black silica and short fibres. The use of natural fibres
PE Interface
Matrix
to reinforce rubber was the subject of many reports [34–
38]. As reported in Section 2, NR-based composites were
prepared by direct dispersion of cellulosic fibres in the
NR latex. The presence of water makes easier the disper-
sion of the fibres within the matrix without prerequisite
heating. However, with such a procedure the fibres loading
cannot exceed 27 wt%.
The plot of the logarithm of the storage tensile modulus
log E 0 and tan d at 1 Hz vs temperature for unfilled NR
matrix, and both unmodified and modified Tech-2500 rein-
forced composites are shown in Fig. 9a and b, respectively.
At low temperatures, the NR matrix is in the glassy state
and E 0 remains roughly constant around 2 GPa. Then at
ca. 60 C a sharp drop in E 0 , by more than 2 decades
occurs, associated with the glass–rubber transition of the
elastomer. This relaxation phenomenon involves coopera-
tive motions of long chain sequences which induce dissipa-
tion energy revealed by a maximum in tan d (Fig. 9b).
Beyond this relaxation process, a rubbery plateau is
attained for which the modulus slightly decreases when
fibres are incorporated in the matrix and then remains
roughly constant above 0 C over a wide temperature
range. This relaxation was attributed to the melting of
the low amount of crystalline regions of NR generated by
the fibres incorporation which act as a nucleating agent.
The crystalline regions behaving as filler particles due to
their finite size, which would increase the modulus substan-
tially. In a previous study [39], we have shown that the
modulus drop around 0 C was attributed to the melting
of the low amount of crystalline regions of NR during
the temperature scan.
The incorporation of cellulose fibres does not increase
significantly the composite modulus below Tg. This effect
may be ascribed to the fact that in its glassy state the differ-
ence between the modulus of the matrix (2 GPa) and the
one of the fibres (10–15 GPa) is not high enough to gener-
ate a remarkable reinforcement effect at 25 wt% loading.
However, above Tg, a higher increase in the modulus is
observed, i.e. it shifts from 0.9 to 3.6 MPa at 20 C. The
surface treatment of the fibres with silane coupling agents
greatly affects the rubbery plateau modulus (Fig. 9a). From
3.6 MPa for the untreated fibres-based composite, it jumps
to 10, 12.6 and 6.3 MPa for the MPS, MRPS and HDS
treated fibres, respectively. Likewise, the magnitude of
the tan d peak decreases significantly upon the addition
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639 1635

Fig. 8. SEM micrographs of freshly fractured surfaces of LDPE-based composites reinforced with 50 wt% Tech-2500 cellulosic fibres: (a) untreated,
(b) MPS-, and (c) HDS-treated fibres.

of the filler and its treatment emphasizes this effect. How-
ever, the temperature position of the relaxation did not
undergo any appreciable evolution. As in the case of the
LDPE matrix, the appreciable improvement of the modu-
lus in presence of reactive MPS and MRPS reactive silane
is related to their ability to react with the matrix during the
curing process and their capacity to establish covalent
bonds between the fibres and the matrix through the inter-
face, thus enhancing the adhesion between the two phases.
Evidence of a better enhancement of the fibre–NR adhe-
sion is also confirmed by SEM observation of frozen frac-
tured surface of specimen (Fig. 10) which reveals that the
fibres are totally fractured under at the surface level when
they are treated with MPS or MRPS. On the other hand
some pulling out occurs when the fibres are treated with
non-reactive HDS.
Scheme 2 gives a schematic representation of the differ-
ent possible reactions occurring in presence of MPS and
MRPS silanes which are promoted by radical grafting reac-
tion between the –C@C– unsaturations of NR and terminal
–acrylic moieties of MPS or –SH groups of MRPS . The
radical species could be generated from peroxy (or similar)
1636 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639

respectively, have been used to prepare LDPE and NR-

a 9.5
based composites. The relative modulus E0r at 20 C and
9 Tech-2.5/NR loss angle tangent magnitude tan dr were determined from
Tech-2.5/HDS-NR
Tech-2.5/M PS-NR Eq. (1) for untreated fibres-based composites. Results are
8.5
Tech-2.5/M RPS-NR shown in Figs. 11 and 12, respectively. It is observed that
log (E')

NR
8 for LDPE-based composites reinforced Tech-50, avicel
and alfa fibres whose average length is lower than
7.5 0.5 mm, the modulus is raised by a factor 150% with
7
respect to the unfilled matrix, whereas in the presence of
longer fibres (2.5 and 3.5 mm), this factor is multiplied by
6.5 200% and 300%, respectively. NR-based composites pre-
pared using avicel and Tech-2500 were also investigated
6
-80 -60 -40 -20 0 20 40
(Figs. 11 and 12). Again, higher stiffness of the composite
Temperature ˚C was reported for longer fibres. For a given fibre type, the
relative reinforcing effect is higher for NR-based compos-
b 1.2 ites than for LDPE-based materials despite the higher filler
Tech-2.5/-NR
content for the latter. This is ascribed to the crystallinity of
1 LDPE.
Tech-2.5/-HDS-NR
Tech-2.5/M PS-NR This trend is quite expected for short fibre reinforced
0.8 Tech-2.5/M RPS-NR
composites, as predicted by Cox model which correlated
the modulus to the fibre volume fraction and length, as fol-
Tang

0.6 lows [40]:

0.4
0.2
0
-100 -80 -60 -40 -20 0 20
Temperature (˚C)
Fig. 9. Evolution of the (a) logarithm of the storage tensile modulus E 0 ,
and (b) loss angle tangent tan d vs temperature at 1 Hz for NR-based
composites reinforced with 25 wt% Tech-2500 cellulosic fibres submitted
to different fibre surface treatments.
formed during the evaporation period. These results con-
firm again that reactive silane coupling agents are suitable
for the modification of cellulose fibres, as reinforcing ele-
ments for non-polar thermoplastic polymeric matrices.
3.4. Effect of the fibre length
One of the most important parameters controlling the
mechanical properties of short fibres composite besides
the interfacial shear strength (determined by the interfacial
adhesion) is the fibre length or more precisely its aspect
ratio, viz. the ratio between its length and diameter. This
parameter has not been much explored in the case of natu-
ral fibres and deserves some attention. With this aim in
view, cellulose fibres with different lengths were used, as
such or after silane-treatment, to prepare LDPE and NR-
based composites. For the former, the amount of fibres
was fixed to 50 wt%, whereas for the latter, only 25 wt%
of reinforcing elements was incorporated.
Tech-50, avicel, alfa, Tech-2500 and pine fibres having
an average length around 0.05, 0.07, 0.5, 2.5 and 3.5 mm,
 
tanhðbl=2Þ
E c ¼ E f /f 1  þ Em /m ; ð2Þ
bl=2
 1=2
2  Gm
b¼ ; ð3Þ
Ef  r2f LnðR=rf Þ
r  rmax
f
lc ¼ ; ð4Þ
s
where Ef, and Em and correspond to the fibre and the ma-
trix modulus, respectively; /f, /m to their respective vol-
ume fraction. l, r, rmax
f and s are the fibre length, the
fibre radius, the tensile strength of the fibre and the shear
strength of the fibre–matrix interface, respectively. Gm
and R are the fibres shear modulus and the interval among
the fibres. According to Cox model (Eq. (2)), the modulus
of the composite remains roughly constant up to a critical
length lc, above which it grows rapidly. Then it reaches a
second plateau whose value is close to that of a composite
with continuous fibres. Below lc the reinforcing effect is low
and the fibres are under-exploited. Even though, Cox ap-
proach makes the assumption of parallel fibres, the depen-
dence of the modulus as a function of the length follows the
same trend with fibres having different orientations. It
should also be noted that the fibres radius remained
roughly constant (about 5–7 lm), as confirmed by SEM
observations.
Referring to Cox approach, one could ask how Ec could
evolve after the silane treatment, since it depends only on
the aspect ratio of the fibres and should not reflect the cou-
pling efficiency. This discrepancy could be rationalized if
we assume that treatment with reactive silanes improved
the fibre matrix adhesion and therefore led, according to
the expression of lc (Eq. (4)), to a decrease in the fibre’s crit-
ical length lc. Hence, for the same fibres length Ec will be
higher for the composite with lower lc.
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639 1637

Fig. 10. SEM of fractured surfaces, frozen under liquid nitrogen, of natural latex composites based on long viscose fibres: before treatment (a) and after
treatment with MPS (b), and HDS (c).

peroxyde radical

Cellulosic
fiber

MPS NR Interface
modified fiber Matrix

Scheme 2. Schematic illustration of the interfacial zone in NR-based composites containing MPS-modified cellulose fibres. Note that the relative size of
the fibres and of the chemical species are not on scale.
1638 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639

4 4

3.5 3.5

3 3

Water uptake (%)

2.5
2.5

2
E'r

1.5
1.5 Tech2500 + MPS
Tech2500 + MRPS
1
1 Tech2500 + HDS
Tech2500
0.5
PE
0.5
0
0 0 2 4 6 8 10 12 14 16 18 20
Tech50 Avicel Alfa Tech2500 Pine Avicel Tech2500
Time (days)
LDPE-matrix NR-matrix
Fig. 13. Water uptake versus immersion time at 25 C for LDPE-based
Fig. 11. Relative storage tensile modulus E0r estimated at 20 C for LDPE- composites reinforced with 50 wt% alfa fibres submitted to different fibre
and NR-based composites reinforced with 50 wt% and 25 wt%, respec- surface treatments. The lines serve to guide the eye.
tively, untreated cellulose fibres presenting different average lengths.
3.5. Water absorption properties
1
The most serious handicap related to the use of lignocel-
0.9
lulosic fibres in composite materials is their extreme sensi-
0.8 tivity to water, which reduces dramatically their
0.7 mechanical performances in a damp atmosphere. The evo-
0.6
lution of the water absorption as a function of the immer-
Ta n δr

sion time is shown in Fig. 13 for LDPE-based composites

0.5
0.4
0.3
0.2
0.1
0 uptake was found to depend on the treatment of the fibres.
Te ch50 Avice l Alfa Te ch 2500 Pine
LDPE-matrix
Fig. 12. Relative loss factor tan dr for LDPE- and NR-based composites
reinforced with 50 wt% and 25 wt%, respectively, untreated cellulose fibres
presenting different average lengths.
The effect of the silane treatment on the mechanical per-
formances of the LDPE-based composites in presence of
fibres with different length was investigated and the relative
storage modulus E0r at 20 C for both unmodified and mod-
ified fibres was determined. A similar trend as the one
reported in Figs. 6 and 7 was observed provided that the
fibres average length was higher than 0.5 mm. For shorter
fibres, the improvement induced by the silane treatment
was modest. Thus, the treatment of the cellulosic filler with
MRPS results in an increase of the modulus by a factor of
250% for Tech-2500 and only 25% for Tech-50 in LDPE-
matrix at 50 wt%. The same behaviour was reported for
Tech-2500 and avicel reinforced NR composites. As the
fibres length is lower than lc, the reinforcing action is mod-
est and any improvement in the interfacial adhesion would
not provoke noticeable effect on E 0 .
reinforced with 50 wt% alfa fibres submitted to different
fibre surface treatments. For all composites, the water
absorption was found to increase with immersion time
reaching a plateau after about 6 days. For unfilled LDPE
the water absorption is very low due to the apolar nature
of this polymer. For composites, the equilibrium water
Avice l Te ch2500
Thus, the LDPE composites containing untreated fibres
NR-matrix absorbed 3.5% of water, whereas the composites based
on HDS-, MPS- and MRPS-treated fibres absorbed 2.2%,
2.6% and 3% of water, respectively. The treatment of the
fibres with HDS did not bring about significant reduction
in water absorption compared to MPS or MRPS, despite
the marked hydrophobic character of the ensuing modified
fibre. It seems therefore that the covalent bonding between
the fibres and the matrix is also necessary to reduce the
water absorption by the composite. If one considers that
water molecules will be accumulated within the fibres struc-
ture, than chemical linkage between the fibres and the
matrix will inevitably reduce the expansion possibility of
the fibres which in turn reduces the water uptake by the
composite material.
4. Conclusion
This work clearly shows that cellulose fibres can be effec-
tively used as reinforcing elements in thermoplastic LDPE
and NR matrices. It constitutes a good alternative to glass
inorganic fibres commonly used as a reinforcing material.
This approach became successful thanks to coupling agents
 M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 1627–1639
from silane family. It can be believed that from the combi-
nation of adequate fibres (especially in terms of aspect
ratio) and optimal grafting agents and reaction conditions,
one can succeed in the preparation of good performance
composite materials containing renewable natural
resources. Works are under progress to verify whether
reactive silane coupling agents could effectively enhance
the interfacial adhesion in the presence of polypropylene
matrix.
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