COMPOSITES

SCIENCE AND
TECHNOLOGY
Composites Science and Technology 67 (2007) 16271639
www.elsevier.com/locate/compscitech

Short natural-bre reinforced polyethylene and natural

rubber composites: Eect of silane coupling agents and bres loading
M. Abdelmouleh a, S. Bou
b

a,*

, M.N. Belgacem b, A. Dufresne

a
LMSE, Faculte des sciences de Sfax, BP 802-3018 Sfax, Tunisia
LGP2, Ecole Francaise de Papeterie et des Industries Graphiques (INPG), BP 65, F-38402 St. Martin dHe`res, 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 bres (raw or chemically modied) as reinforcing elements and thermoplastic matrices were
prepared and characterized, in terms of mechanical performances, thermal properties and water absorbance behaviour. Four dierent cellulose bres with dierent average lengths were used, namely avicel, technical, alfa pulps and pine bres. Two thermoplastic polymers, i.e.
low density polyethylene and natural rubber, were employed as matrices. Cellulose bres were incorporated into the matrices, as such or
after chemical surface modication involving three silane coupling agents, namely c-methacryloxypropyltrimethoxy (MPS), c-mercaptoproyltrimethoxy (MRPS) and hexadecyltrimethoxy-silanes (HDS). As expected, the mechanical properties of the composites increased with
increasing the average bre length and the composite materials prepared using both matrices and cellulose bres 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
Over the past decade there has been a growing interest in
the use of lignocellulosic bres as reinforcing elements in
polymeric matrix [15]. The specic properties of this natural product, namely low cost, lightweight, renewable character, high specic 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 dierent surface
properties between the bre 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
modication of the bres surface, in order to improve the
*

Corresponding author. Tel.: +216 74 274 400; fax: +216 74 274 437.
E-mail address: sami.bou@fss.rnu.tn (S. Bou).

0266-3538/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.07.003

bre/polymer compatibility and their interfacial adhesion

[6]. Without such a treatment, natural bres embedded in
a polymeric matrix generate unstable interfaces and the
stress applied to the bre/polymer composite is not
eciently transferred from the matrix to the bre and the
benecial reinforcement eect of the bre remains underexploited. Likewise, the poor ability of the polymer to wet the
bre hinders the homogenous dispersion of short bres
within the polymeric matrix [7].
Several strategies of surface modications aiming at
improving the compatibility between cellulose bres and
polymer matrices were recently reviewed [8]. The chemical
modication using coupling agents bearing two reactive
groups, one of which being likely to react with the OH
function at the bre surface, whereas the other one is left
to copolymerize with the matrix, constitutes a highly interesting way allowing the establishment of covalent bonding
between bres and matrix, thus leading to materials with
high mechanical properties. Many coupling agents have

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M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

been investigated, namely anhydrides, maleated polymer

[911], isocyanates [1214], triazines [15] and alkoxysilanes
[1620], as recently reviewed [8]. Among these dierent
reagents, maleated polypropylene (MaPP) or polyethylene
(MaPE) gave signicant enhancement in tensile and exural strength, ranging from 40% up to 80%, was pointed
out when they are blended with cellulose bres before mixing with matrix [9,11].
Silane coupling chemicals present three main advantages: (i) they are commercially available in a large scale;
(ii) at one end, they bear alkoxysilane groups capable of
reacting with OH-rich surface, and (iii) at the second end,
they have a large number of functional groups which can
be tailored as a function of the matrix to be used. The last
feature ensures, at least, a good compatibility between the
reinforcing element and the polymer matrix or even covalent bonds between them. The reaction of silane coupling
agents with lignocellulose bres (mainly: cellulose and lignin) was found to be quite dierent to compare with that
observed between them and glass surface, in the sense that
with cellulose macromolecules, only prehydrolyzed silanes
underwent the reaction with cellulose surface [21].
Besides the chemical bonding theory which is the most
evident mechanism by which organosilane coupling agents
are acting, other theories have been proposed, such as the
interpenetrating networks theory which states that the
matrix diuse inside the silane interphase to form an entangled network [2225].
Our group has been involved in series of works aiming at
understanding silanecellulose system [2628]. Thus, the
interaction of silane coupling agents with cellulosic bres
and the eect of some parameters, such as the pH, the initial
amount of silane with respect to cellulose and the adsorption contact time, on their anchoring capability onto the
bre surface have been ascertained. Dierent spectroscopic
techniques have been used to evidence the presence of silane
and to quantify its amount on the substrate and to elucidate
the structure of the anchored siloxane network on the bres
surface [27]. Then, using epoxy and unsaturated polyester
resins we have shown that the bre treatment with silane
coupling agents bearing functional group able to react with
the matrix enhanced signicantly the mechanical strength of
the nal composite [28].
In the present study three silane coupling agents, dierent by the functionality of the radical moiety appended to
silicon atoms were used to treat delignied cellulose bres
in order to improve their adhesion to LDPE and NR
matrix. The eect of these treatments on the mechanical
properties of the ensuing composites and on their water
uptake ability was investigated accordingly.

Commercial microcrystalline bres (Technocel-50

labelled Tech-50) with average length of about 50 lm,
and specic surface, measured by the BET technique
using nitrogen, around 2.5 m2/g.
Technocel-2500 bres (labelled Tech-2500), with average
length of about 2.5 mm.
Alfa bres are bleached soda pulps from the Tunisian
annual plant esparto (alfa tenassissima). They had a specic surface (in a dry state) of 3 m2/g and average length
about 500 lm.
Bleached softwood (pine) bres with average length
about 3.5 mm.
The Avicel bres used in this work were purchased from
Aldrich. The average length of this bre was about
70 lm.
2.2. Silane coupling agent
Three commercial silanes chosen for this study (Table 1)
were kindly provided by OSI-WITCO, to whom we are
indebted.

2.3. Polymer matrix

The low density polyethylene (LDPE) used in this work
has a melting temperature of 107 C and a degree of crystallinity around 2830%, as determined by dierential scanning calorimetry (DSC) with a heating rate of 10 C/min.
Its density at room temperature was 0.9 g/cm3. The natural
rubber (NR) (polyisoprene) was a kind gift of the Technical
Centre, MAPA, Liancourt, France, and was provided as

Table 1
The silane coupling agents used in this work

O
O

Si
O

O
O

-Methacryloxypropyltrimethoxysilane
-MPS
O
Si
O
Hexadecyltrimthoxysilane
HDS

2. Materials and experimental procedures

2.1. Cellulose bres
The dierent types of cellulose bres used in this work
were:

HS

Si

O
-mercaptoproyltrimethoxysilane
-MRPS

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

latex. Its TSC (total solid content), DRC (dry rubber content), 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 bres with 3 wt% of the chosen silane was carried out in 80/20 v/v ethanol/water medium for 2 h. Then, the bres were ltered and dried at room
temperature for 2 days, and heated at 120 C under a nitrogen 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 silanetreated cellulose bres 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. CelluloseNR composites were prepared by mixing the cellulose bres (25 wt%
with respect to full composite) into NR latex emulsion.
The ensuing dispersion was poured in Teon mould and
solid lms were obtained by evaporating the water at 50
60 C for 24 days, until a homogeneous solid lm with
0.8 mm thickness was formed.
2.6. Characterization of modied bres
The FTIR spectra were obtained with a PerkinElmer
Paragon 1000 FT-IR spectrometer working in diuse
reectance mode (DRIFT) with a total of 40 scans and
with a resolution of 4 cm1. 5 mg of bres 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 KubelkaMunk
function.

1629

ual measurements were carried out to ensure perfect reliability 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 bre reinforced LDPE composites was determined using an Instron 4301 universal Testing
machine. Tests were carried out according to ASTM standards D638 using a 100 N load cell and 50 mm/min crosshead speed. The specimens were thin rectangular strips
(5 10 0.5 mm of width, length and thickness, respectively). 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 viscoelasticity of the material. The samples were thin rectangular
strips with dimensions of about 30 5 0.5 mm3. Measurements 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, containing 15% (v/v) of alfa bres, were examined with a scanning
electron microscope (ABT-55). Fracture surfaces of the
composite samples were coated with gold and then analysed at 7 keV. Before the fracture, the specimens were frozen into liquid nitrogen to impede the plastic deformation
of the matrix and to get well dened brematrix interface.

The average bre morphology was determined using an

optical microscope equipped with CCD camera and image
analysis software. These measurements gave the bre
length and particle diameter distribution.

2.8.5. Water absorption

The sample dimensions for water absorption experiments 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 specic time intervals, blotted to remove the
excess water on the surface and immediately weighed.
The dierence 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.

2.8. Characterization of composites

3. Results and discussion

2.8.1. Dierential scanning calorimetry

Dierential scanning calorimetry (DSC) was performed
with a PerkinElmer DSC7 equipment, tted with a cooler
system using liquid nitrogen. Samples, around 10 mg, were
placed in pressure-tight DSC cells and at least two individ-

3.1. Fibre modication

2.7. Morphological characterization

The optimal conditions ensuring ecient chemical

anchoring of the organosilane coupling agent onto cellulose bres have been established previously [26]. In this

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M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

study, the grafting of the coupling agent was performed

through a physical adsorption of the hydrolyzed silane followed by a curing process at 120 C under inert atmosphere. 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 cellulose samples (Tech-50) treated with MPS, before and
after heat treatment. In both cases, the spectrum corresponding to untreated cellulose was deduced, in order to
emphasize the band issuing from the silane moiety. The
two spectra show dierent 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
SiOCellulose and SiOSi 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 SiOH groups were substantially enhanced. The peaks near 1100 and 1080 cm1 are
related to residual unhydrolyzed SiOCH3 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 SiOH groups. This
band disappeared after the heat treatment and was
replaced by a wide band around 1040 cm1, characteristic
of SiOSi 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 rst part of our study relatively long bre Tech2500 were used to prepare LDPE-based composites by
thorough mixing of the bres with the polymer followed
by a compression moulding step to form a composite lm
with uniform thickness. By this method homogenous composites can be obtained up to 50 wt% bre loading.
0.180

C=O

0.17
0.16
0.15

1713.72
1701.27

0.14

C=C

0.13
0.12

Si-O-Si + Si-O-Cellulose

0.11
0.10

K-M

1201.79

1181.43

1636.36

0.09
0.08

Si-O-Si

0.07
0.06
0.05

1134.76

0.04
0.03
0.02

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

1130.62

1204.05

Si-O-Si

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-modied bres (Tech-50) (a) before and (b) after heat treatment (9001250 cm1 region). Inset:
18501550 cm1 region after heat treatment.

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

The evolution of tensile stress vs strain curves at dierent bre contents is shown in Fig. 2. All the curves display
a linear Hookean range at low strain (<20%) followed by a
softening region which continue up to 40%. Then the plastic deformation under roughly constant stress is maintained until the failure occurs. With the increase of the
bres content, both the modulus and the tensile strength
increase, while the elongation at break decreases. These different eects are better depicted in Fig. 3. One can notice
that the modulus did not increase linearly with the bres
fraction and a discontinuity occurred at about 15 vol%,
composition above which a much faster increase is
observed. A similar discontinuity was noted for the elongation at break and the tensile strength. In these cases, this
phenomenon took place at around 15 and 25 vol%, respectively. This discontinuity could be attributed to the onset of
the geometric percolation of the bres. Indeed, thanks to
the numerous hydroxyl groups on the bres surface, a three
dimensional connected network could be formed through
15

Tensile stress (Mpa)

10%
19.5%

12

37%
50%
0%

0
0

50

100

150

200

250

Strain (in %)
Fig. 2. Typical tensile stress vs. strain (DL/L0) curves for LDPE-based
composites lled with untreated Tech-2500 cellulose bres at 25 C and for
a crosshead speed of 10 mm min1. The bre contents are indicated in the
gure.

16

350
Elongation at break %
Elastic modulus (MPa)
Tensile strength (MPa)

14
12

250

hydrogen bonding interaction between the bres contact

areas. These connected zones enhance the strength and
the modulus of the composite.
The degree of crystallinity (Xc) of Tech-2500/LDPE
composites, calculated using the heat of fusion, as determined by DSC measurements, is reported in Table 2 for
both unlled PE and reinforced composites with 50 wt%
Tech-2500. Both the extent of crystallinity and the melting
temperature seems not, within the experimental accuracy to
evolve signicantly after the bres incorporation within
LDPE matrix, even after treatment with the dierent
silane. The degree of crystallinity and the melting temperature of the polymeric matrix remained close to 2225% and
to 107 C, respectively.
The eect of surface modication on the nonlinear
mechanical behaviour of LDPE composites was investigated at room temperature for composites containing
50 wt% of Tech-2500 cellulose bres, as shown in Fig. 4.
It reveals that both the modulus and tensile strength are
enhanced by the bre treatment. However, this evolution
depended on the silane structure. Thus, the tensile strength
and the modulus increased by 26% and 17%, respectively,
for MPS and by only 12% and 6%, respectively, for MRPS.
On the other hand, only a modest rise in tensile strength
(about 6%) was observed after treatment with HDS silane.
The mechanical behaviour of lignocellulosic bres reinforced LDPE was also investigated in the linear range using
dynamic mechanical analysis (DMA) to investigate the
properties of the interface and the impact of the bres
treatment on brematrix adhesion. The macroscopic
behaviour of heterogeneous materials depends on four
main parameters, viz. (i) the behaviour of each phase, (ii)
the volume fraction of each phase, (iii) the spatial arrangement of the phase or morphology, and (iv) the interface
properties. The latter mainly depends on the degree of
interaction between the phases, i.e. the bre treatment for
bre-lled composites.
In this experiment, composite samples were subjected to
a controlled sinusoidal stress and the resultant displacement was measured. The evolution of the logarithm of
the storage tensile modulus log E 0 and loss factor (tan d)
at 1 Hz vs temperature for unlled LDPE, and both
untreated and treated Tech-2500 reinforced LDPE composites are displayed in Fig. 5. The tan d curve (Fig. 5b)

10
200
8
150
6
100

E (MPa)

(MPa), r (%)

300

1631

50

0
0

10

20

30

40

50

60

Fibres weight fraction (%)

Table 2
Heat of fusion (DHm) and degree of crystallinity (Xc) of Tech-2500/LDPE
composites reinforced with dierent silane treated bres at 50% weight
fraction
Sample

DHm (J/g)

Xc (%)a

Tm (C)

LDPE
Tech-LDPE
Tech-MPS-LDPE
Tech-MRPS-LDPE
Tech-HDS-LDPE

75.7
43.4
51.5
52.5
44.4

27
22
26
26
22

107
107.8
108.3
107.5
106.5

Fig. 3. Evolution of the Youngs modulus (E), tensile strength (r), and
elongation at break (er) vs cellulose bres content for LDPE-based
composites reinforced with untreated Tech-2500 cellulose bres.

m
X c w DH
, where DH 0m 285 J g1 is the heat of fusion for 100%
DH 0
F

crystalline PE and wF is the weight fraction of polymeric matrix material

in the composite [41].

1632

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

18

400
Modulus

350

16

Strength

12

250

10

200

Strength (MPa)

Modulus (MPa)

14

300

150
4

100

2
0

50
LDPE

Tech

Tech-MPS

Tech-MRPS

Tech-HDS

Fig. 4. Youngs modulus and tensile strength of LDPE-based composites

reinforced with 50 wt% Tech-2500 cellulosic bres submitted to dierent
bre surface treatments.

exhibits two relaxation processes located around 20 C

(labelled a) and 6065 C (labelled ac). They are associated
with the chain segment mobility of the polymer branches
and to molecular motion within the crystalline phase,
respectively. Nitta and Tanaka [30] attributed the ac relax-

LDPE
Tech-2500
Tech-2500/M PS
Tech-2500/M RPS
Tech-2500/HDS

9.5
9

log (E')

8.5
9

8
7.5

8.5

7
8

6.5

10

20

30

40

50

6
-100

-80

-60

-40

-20

20

40

60

80

100

120

Temperature C

0.25
Tech-2500
Tech-2500/MPS

0.2

transition

20

Tech-2500/MRPS
Tech-2500/HDS
LDPE

0.15

Tang

transition

0.1

0.05

0
-100

-80

-60

-40

-20

40

60

80

100

Temperature C
Fig. 5. 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 LDPE-based
composites reinforced with 50 wt% Tech-2500 cellulosic bres submitted
to dierent bre surface treatments. The inset is an expanded view of
log E 0 vs temperature curves.

ation to a relaxation process occurring in the partiallyordered interface between the lamellae and the amorphous
region and can be dened as the glass transition of the sterically hindered interfacial region. The storage modulus E 0
(Fig. 5a) decreases by a factor 10 and 100 across the a and
ac relaxation zones, respectively. Around 110 C an abrupt
drop in E 0 occurred as a result of the melting of the crystalline phase. The incorporation of Tech-2500 bres results in
an appreciable rise in E 0 , particularly above the a relaxation temperature range conrming the reinforcing eect
of Tech-2500 bres. Thus, at 20 C, E 0 was multiplied by
a factor two compared to the unlled matrix. The a relaxation did not exhibit any change in its temperature position
(Fig. 5b), whereas the ac relaxation was shifted from 60 to
67 C after the bres addition which could be attributed to
segmental immobilization of the polymer chain at the bre
surface.
Depending on the silane structure, the bre treatment
aected both E 0 and tan d curves, as depicted in Figs. 5a
and b, respectively. To analyse this eect, the relative modulus E0r and the relative loss factor tan dr were evaluated
using Eq. (1) for each treatment
E0r

E0c
E0m

and

tan dr

tan dc
;
tan dm

where E0c and E0m are the storage modulus of the composite
and unlled matrix, respectively, estimated at the same
temperature, and tan dc and tan dm the corresponding magnitude of the ac relaxation process. Figs. 6 and 7 show the
values of E0r and tan dr, respectively, for both untreated and
silane-treated cellulose bres (Technocel-50, Technocel2500 and alfa bres) reinforced LDPE composites (bre
content = 50 wt%). The relative storage tensile modulus
was estimated at T = 20 C.
By comparing the eect of untreated cellulosic bres, we
observed that the relative reinforcing eect is signicantly
higher for Tech-2500 than for Tech-50. This eect is
ascribed to the average length of the bres, which is well
known to aect the mechanical performances of composites. At the same time, the relative magnitude of the ac
relaxation process decreases. It is well known that its value
depends on both the number of mobile units participating
to the relaxation process and to the magnitude of the modulus drop through the relaxation. The behaviour of
untreated alfa bres reinforced LDPE is intermediate
between Tech-50 and Tech-2500.
For treated bres reinforced LDPE, it can be seen that
only MPS and MRPS enhanced the storage modulus,
except for Tech-50 reinforced composites for which no signicant reinforcing eect was observed. The increase in E 0
at 20 C is about 15% and 35% for MPS and MRPS,
respectively, in presence of Tech-2500 and about 12%
and 20% with alfa bres. This improvement could be
attributed to the increase in the interfacial work of adhesion between bres and matrix through the interface. As
a consequence, the relative damping properties decrease.
One can ask about the possible mechanism of interaction

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

1633

3
2.5

E'r

2
1.5
1
Tech-2500
Alfa
Tech-50

0.5
0
LDPE

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
bres submitted to dierent bre surface treatments. LDPE refers to the unlled matrix and 0 to untreated bres-based composite.

1.1

Tan r

0.9

0.7
Tech-2500
Alfa
Tech-50

0.5
LDPE

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 bres submitted to dierent
bre surface treatments. LDPE refers to the unlled matrix and 0 to untreated bres-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 bres and the matrix which enhance the interfacial 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 processing temperature and the kneading time on the Brabender
are relatively low, i.e; 170 C and 15 min, respectively, the
presence of cellulose bres is cited to promote the thermal
degradation of the composite [31,32]. The signicant yellowing of the lled sample after mixing and compression
moulding support this hypothesis. Espert et al. [32] showed
that the addition of cellulose bres to PP matrix aected

appreciably the thermo-oxidative stability and reduced

the oxidation temperature from 205 C for unlled 2.5 %
ethyl vinyl acetate modied-PP to about 175 C for composite containing 40% w/w kraft pulp bres.
Despite the presence of a long aliphatic chain on HDS,
which imparts hydrophobic character to the bre surface,
lowers its surface energy and increases its wettability and
dispersion within the non-polar matrix, no signicant evolution is noted for E0r . This eect 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 bres 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 bres 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 interaction depicted in Scheme 1.

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M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

Cellulosic
fiber

MPS
modified fiber

PE
Matrix

Interface

Scheme 1. Schematic illustration of the interfacial zone in LDPE-based composites containing MPS-modied cellulose bres. Note that the relative size of
the bres 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 bres surface induced by the chemical bridging through the interface. It is worth noting that, independently of the silane structure, ac transition did not exhibit
any shift in its position after bre 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 bres were
also carried out to investigate the brematrix interface
and compare their aspect after silane treatment. The surface of fracture for untreated bres-based composite is
shown in Fig. 8a for two dierent magnications. It is clear
that the interfacial adhesion between the bres and the
matrix is poor. Indeed, the bres 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 bres are broken o
near the surface and do not leave any voids on the fractured surface. Likewise no discontinuity is reported
between the two phases and the bres seem to be totally
layered by the matrix. This observation gives direct evidence about the adhesion improvement at the interface in
the presence of reactive silane. Compared to untreated
bres, the treatment with HDS (Fig. 8c) did not improve
the adhesion in the interfacial region as indicated by the
considerable pulling-out of the bres 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 formulated from DMA experiments.
3.3. Natural rubber matrix
Natural rubber (NR) is one of the most important elastomers, widely used in dierent industrial sectors. NR is
often reinforced by the incorporation of ller such as carbon black silica and short bres. The use of natural bres

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 bres in the
NR latex. The presence of water makes easier the dispersion of the bres within the matrix without prerequisite
heating. However, with such a procedure the bres 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 unlled NR
matrix, and both unmodied and modied Tech-2500 reinforced 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 glassrubber transition of the
elastomer. This relaxation phenomenon involves cooperative motions of long chain sequences which induce dissipation 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
bres 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 bres incorporation which act as a nucleating agent.
The crystalline regions behaving as ller particles due to
their nite size, which would increase the modulus substantially. 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 bres does not increase
signicantly the composite modulus below Tg. This eect
may be ascribed to the fact that in its glassy state the dierence between the modulus of the matrix (2 GPa) and the
one of the bres (1015 GPa) is not high enough to generate a remarkable reinforcement eect 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 bres with silane coupling agents
greatly aects the rubbery plateau modulus (Fig. 9a). From
3.6 MPa for the untreated bres-based composite, it jumps
to 10, 12.6 and 6.3 MPa for the MPS, MRPS and HDS
treated bres, respectively. Likewise, the magnitude of
the tan d peak decreases signicantly upon the addition

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

1635

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

of the ller and its treatment emphasizes this eect. However, 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 modulus 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 bres and the matrix through the interface, thus enhancing the adhesion between the two phases.
Evidence of a better enhancement of the breNR adhesion is also conrmed by SEM observation of frozen frac-

tured surface of specimen (Fig. 10) which reveals that the

bres 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 bres are treated with
non-reactive HDS.
Scheme 2 gives a schematic representation of the dierent possible reactions occurring in presence of MPS and
MRPS silanes which are promoted by radical grafting reaction 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) 16271639

9.5
Tech-2.5/NR
Tech-2.5/HDS-NR
Tech-2.5/M PS-NR

log (E')

8.5

Tech-2.5/M RPS-NR
NR

8
7.5
7
6.5
6
-80

-60

-40

-20

20

40

Temperature C

1.2
Tech-2.5/-NR

Tech-2.5/-HDS-NR
Tech-2.5/M PS-NR

Tang

0.8

Tech-2.5/M RPS-NR

0.6
0.4
0.2
0
-100

-80

-60

-40

-20

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 bres submitted
to dierent bre surface treatments.

formed during the evaporation period. These results conrm again that reactive silane coupling agents are suitable
for the modication of cellulose bres, as reinforcing elements for non-polar thermoplastic polymeric matrices.

3.4. Eect of the bre length

One of the most important parameters controlling the
mechanical properties of short bres composite besides
the interfacial shear strength (determined by the interfacial
adhesion) is the bre 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 natural bres and deserves some attention. With this aim in
view, cellulose bres with dierent lengths were used, as
such or after silane-treatment, to prepare LDPE and NRbased composites. For the former, the amount of bres
was xed to 50 wt%, whereas for the latter, only 25 wt%
of reinforcing elements was incorporated.
Tech-50, avicel, alfa, Tech-2500 and pine bres having
an average length around 0.05, 0.07, 0.5, 2.5 and 3.5 mm,

respectively, have been used to prepare LDPE and NRbased composites. The relative modulus E0r at 20 C and
loss angle tangent magnitude tan dr were determined from
Eq. (1) for untreated bres-based composites. Results are
shown in Figs. 11 and 12, respectively. It is observed that
for LDPE-based composites reinforced Tech-50, avicel
and alfa bres whose average length is lower than
0.5 mm, the modulus is raised by a factor 150% with
respect to the unlled matrix, whereas in the presence of
longer bres (2.5 and 3.5 mm), this factor is multiplied by
200% and 300%, respectively. NR-based composites prepared using avicel and Tech-2500 were also investigated
(Figs. 11 and 12). Again, higher stiness of the composite
was reported for longer bres. For a given bre type, the
relative reinforcing eect is higher for NR-based composites than for LDPE-based materials despite the higher ller
content for the latter. This is ascribed to the crystallinity of
LDPE.
This trend is quite expected for short bre reinforced
composites, as predicted by Cox model which correlated
the modulus to the bre volume fraction and length, as follows [40]:


tanhbl=2
E c E f /f 1 
2
Em /m ;
bl=2

1=2
2  Gm
;
3
b
Ef  r2f LnR=rf
r  rmax
f
;
4
lc
s
where Ef, and Em and correspond to the bre and the matrix modulus, respectively; /f, /m to their respective volume fraction. l, r, rmax
and s are the bre length, the
f
bre radius, the tensile strength of the bre and the shear
strength of the brematrix interface, respectively. Gm
and R are the bres shear modulus and the interval among
the bres. 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 bres. Below lc the reinforcing eect is low
and the bres are under-exploited. Even though, Cox approach makes the assumption of parallel bres, the dependence of the modulus as a function of the length follows the
same trend with bres having dierent orientations. It
should also be noted that the bres radius remained
roughly constant (about 57 lm), as conrmed 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 bres and should not reect the coupling eciency. This discrepancy could be rationalized if
we assume that treatment with reactive silanes improved
the bre matrix adhesion and therefore led, according to
the expression of lc (Eq. (4)), to a decrease in the bres critical length lc. Hence, for the same bres length Ec will be
higher for the composite with lower lc.

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

1637

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

peroxyde

radical

Cellulosic
fiber

MPS
modified fiber

NR
Matrix

Interface

Scheme 2. Schematic illustration of the interfacial zone in NR-based composites containing MPS-modied cellulose bres. Note that the relative size of
the bres and of the chemical species are not on scale.

1638

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

4

3.5

3.5

Water uptake (%)

E'r

2.5
2
1.5

2.5
2
1.5

Tech2500 + MPS
Tech2500 + MRPS

Tech2500 + HDS

Tech2500

0.5

PE

0.5

0
0

Tech50

Avicel

Alfa

Tech2500

Pine

Avicel

NR-matrix

LDPE-matrix

Tech2500

Fig. 11. Relative storage tensile modulus E0r estimated at 20 C for LDPEand NR-based composites reinforced with 50 wt% and 25 wt%, respectively, untreated cellulose bres presenting dierent average lengths.

10

12

14

16

18

20

Time (days)
Fig. 13. Water uptake versus immersion time at 25 C for LDPE-based
composites reinforced with 50 wt% alfa bres submitted to dierent bre
surface treatments. The lines serve to guide the eye.

3.5. Water absorption properties

1
0.9
0.8

Ta n r

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
Te ch50

Avice l

Alfa

LDPE-matrix

Te ch 2500

Pine

Avice l

Te ch2500

NR-matrix

Fig. 12. Relative loss factor tan dr for LDPE- and NR-based composites
reinforced with 50 wt% and 25 wt%, respectively, untreated cellulose bres
presenting dierent average lengths.

The eect of the silane treatment on the mechanical performances of the LDPE-based composites in presence of
bres with dierent length was investigated and the relative
storage modulus E0r at 20 C for both unmodied and modied bres was determined. A similar trend as the one
reported in Figs. 6 and 7 was observed provided that the
bres average length was higher than 0.5 mm. For shorter
bres, the improvement induced by the silane treatment
was modest. Thus, the treatment of the cellulosic ller with
MRPS results in an increase of the modulus by a factor of
250% for Tech-2500 and only 25% for Tech-50 in LDPEmatrix at 50 wt%. The same behaviour was reported for
Tech-2500 and avicel reinforced NR composites. As the
bres length is lower than lc, the reinforcing action is modest and any improvement in the interfacial adhesion would
not provoke noticeable eect on E 0 .

The most serious handicap related to the use of lignocellulosic bres in composite materials is their extreme sensitivity to water, which reduces dramatically their
mechanical performances in a damp atmosphere. The evolution of the water absorption as a function of the immersion time is shown in Fig. 13 for LDPE-based composites
reinforced with 50 wt% alfa bres submitted to dierent
bre surface treatments. For all composites, the water
absorption was found to increase with immersion time
reaching a plateau after about 6 days. For unlled LDPE
the water absorption is very low due to the apolar nature
of this polymer. For composites, the equilibrium water
uptake was found to depend on the treatment of the bres.
Thus, the LDPE composites containing untreated bres
absorbed 3.5% of water, whereas the composites based
on HDS-, MPS- and MRPS-treated bres absorbed 2.2%,
2.6% and 3% of water, respectively. The treatment of the
bres with HDS did not bring about signicant reduction
in water absorption compared to MPS or MRPS, despite
the marked hydrophobic character of the ensuing modied
bre. It seems therefore that the covalent bonding between
the bres 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 bres structure, than chemical linkage between the bres and the
matrix will inevitably reduce the expansion possibility of
the bres which in turn reduces the water uptake by the
composite material.
4. Conclusion
This work clearly shows that cellulose bres can be eectively used as reinforcing elements in thermoplastic LDPE
and NR matrices. It constitutes a good alternative to glass
inorganic bres commonly used as a reinforcing material.
This approach became successful thanks to coupling agents

M. Abdelmouleh et al. / Composites Science and Technology 67 (2007) 16271639

from silane family. It can be believed that from the combination of adequate bres (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 eectively enhance
the interfacial adhesion in the presence of polypropylene
matrix.
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