New lignocellulosic bres-reinforced composite materials: A stepforward

in the valorisation of the Posidonia oceanica balls

Ramzi Khiari
a,b
, Zied Marrakchi
a,b
, Mohamed Naceur Belgacem
a,
, Evelyne Mauret
a
, Farouk Mhenni
b
a
Laboratoire de Gnie des Procds Papetiers, UMR CNRS 5518, Grenoble INP-Pagora, 461, rue de la papeterie, B.P. 65, 38402 Saint Martin dHres Cedex, France
b
Research Unity of Applied Chemistry & Environment, Department of Chemistry, Faculty of Sciences, Monastir 5019, Tunisia
a r t i c l e i n f o
Article history:
Received 23 April 2011
Received in revised form 27 August 2011
Accepted 30 August 2011
Available online 12 September 2011
Keywords:
A. Particle-reinforced composites
D. Dynamic mechanical thermal analysis
(DMTA)
D. Photoelectron spectroscopy (XPS)
E. Extrusion
a b s t r a c t
In this work, new lignocellulosic particles obtained from Posidonia oceanica were studied to reinforce a
commercial biodegradable thermoplastic matrix. First, these reinforcing llers were characterised by
Fourier-transform infrared (FT-IR) and X-ray photoelectron (XPS) spectroscopies. Then, they were used
to prepare several composite lms using BIOPLAST GF 106 matrix. Different P. oceanica fragment load-
ings, namely 0%, 10%, 20% and 30% (w/w with respect to the matrix) were investigated. The morphology
of the ensuing materials was assessed by scanning electron microscopy (SEM), whereas their thermal and
mechanical properties were studied by differential scanning calorimetry (DSC), dynamic mechanical
analysis (DMA) and tensile tests. The obtained results showed that P. oceanica-based particles enhanced
the thermo-mechanical properties of the thermoplastic matrix.
Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved.
1. Introduction
Lignocellulose-based bres or particles are the most widely
used as biodegradable reinforcing elements for composite materi-
als. In the last years, the utilisation of lignocellulosic materials to
process novel composites has attracted growing interest [1,2]. Such
a success is derived by their low-cost and their environmentally
friendly character. Indeed, important industries, such as automo-
tive [3], building [46] and packaging [710], have focussed their
attention to the development of new materials lled with natural
bres or powders. In addition to the above-mentioned advantages,
these materials possess interesting mechanical and physical prop-
erties [1,11,12], which, however, vary according to their botanical
origin. In fact, lignocellulosic bres or particles are available
mainly from wood, but several local annual plants and agricultural
crops as well as industrial residues can also be considered as po-
tential sources of raw materials.
During the last decade, several composites based on lignocellu-
losic materials from worldwide annual plants, such as Cannabis
sativa, kenaf, eucalyptus, rice straw, bagasse and cotton were stud-
ied [11,13]. In most cases, the prepared materials displayed very
promising properties and opened the door for using a renewable
material in the context of polymer-based composites. Unfortu-
nately, one of the major drawbacks associated with the use of these
reinforcing elements is their sensitivity to water release and up-
take, which was partially resolved (or at least improved) by several
surface treatments [14,15]. The increasing demand of lignocellu-
losic materials for traditional uses (mainly paper and textile, but
also for cellulose derivatives) and concerning their potential incor-
poration into new material families imposes looking for new
sources. For this purpose, several studies have tried to valorise var-
ious agricultural or industrial by-products available locally. The
present work ts within this strategy and intends to confer an up-
dated value to a marine residue (Posidonia oceanica balls) largely
available in Tunisia.
P. oceanica is the dominant grass in the Mediterranean Sea.
Important quantities of P. oceanica fragments accumulate on Tuni-
sian coasts each year, requiring the cleaning of the beaches every
summer. In the last few years, P. oceanica has been studied as: (i)
a low-cost adsorbent for removing dyes or phenol [16,17], (ii) a
substrate for papermaking [10] or (iii) a starting material for cellu-
lose derivatives [1820]. However, to the best of our knowledge, no
data has been reported yet regarding the use of these materials as
llers in composite materials. Thus, several composite lms were
prepared using a thermoplastic matrix (BIOPLAST GF 106) and
incorporating different P. oceanica fragment loadings, namely: 0%,
10%, 20%, and 30%. The morphology of the ensuing materials was
examined by scanning electron microscopy (SEM), whereas their
thermal and mechanical properties were studied by differential
scanning calorimetry (DSC), dynamic mechanical analysis (DMA)
and tensile tests.
0266-3538/$ - see front matter Crown Copyright 2011 Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2011.08.022

Corresponding author. Tel.: +33 (0)4 76 82 69 62; fax: +33 (0)4 76 82 69 33.
E-mail address: naceur.belgacem@pagora.grenoble-inp.fr (M.N. Belgacem).
Composites Science and Technology 71 (2011) 18671872
Contents lists available at SciVerse ScienceDirect
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j our nal homepage: www. el sevi er. com/ l ocat e/ compsci t ech
2. Experimental
2.1. Materials
2.1.1. P. oceanica
The P. oceanica balls (Fig. 1) were collected in Monastir. They
were washed and rinsed with distilled water in order to eliminate
the sand and other soil contaminations. They were dried at room
temperature during 1 month. The ensuing materials were milled
and sieved to a granulometry of around 50 lm, and then succes-
sively extracted with hexane, dichloromethane and acetone. The
size distribution of the used fraction was also determined. Each
extraction was carried out at least in duplicate and the experimen-
tal error is around 5%.
2.1.2. Matrix
The thermoplastic matrix used in this study, BIOPLAST GF 106,
was supplied from Biotec., to which we are indebted. This matrix is
made from potato our and a copolyester, typically used for the
production of plastic lms (http://www.biotec-distribution.eu/fr).
2.2. Composite preparation
P. oceanica cellulose-reinforced BIOPLAST GF 106 composites
were prepared by mixing the thermoplastic matrix with P. oceanica
at different loadings, namely 10%, 20% and 30% (w/w with respect
to the matrix), in a Brabender mixing device, working at 50 rpm
and 160 C for 10 min. After mixing, the ensuing materials were
moulded by hot pressing in a hydraulic press (at 150 C, under
10 ton and for 5 min) with a suitable steel mould into rectangular
lms (10 5 cm
2
) of about 0.5 mm thickness. Finally, the mould
was left to cool down, and the composite lms were recovered
when the temperature was about 40 C. All the composite lms
were prepared in triplicate.
2.3. Characterisation methods
Several methods were used to thoroughly characterise the raw
materials and the composite lms.
2.3.1. Particle size distribution
The particle size distribution of P. oceanica fragments was inves-
tigated by laser diffraction using a Mastersizer X Malvern. The
sample was dispersed in aqueous medium under mechanical stir-
ring for 2 min. The test was repeated at least in triplicate and the
difference between the various values obtained was within an
experimental error of 5%.
2.3.2. Spectroscopic analysis: FT-IR and XPS
The FT-IR spectra were recorded in a bio-Rad spectrophotome-
ter. For this purpose, 100 mg of anhydrous KBr and 1 mg of dry P.
oceanica material, obtained after each soxhlet extraction, were
pressed into small pellets using a laboratory press. The acquisition
conditions were 64 scans and 4 cm
1
resolutions. The wave num-
ber scanning was in the range of 5004000 cm
1
.
The X-ray photoelectron spectroscopy (XPS) experiments were
performed with a XR3E2 apparatus (Vacuum Generators, UK)
equipped with a monochromated MgKa X-ray source (1253.6 eV)
and operating at 15 kV under a current of 20 mA. Samples were
placed in an ultrahigh vacuum chamber (10
8
mbar) with electron
collection by a hemispherical analyzer at an angle of 90. The signal
decomposition was realised using SpectrumNT, and the CAHsignal
was used as a reference peak at 285.0 eV. These measurements
were carried at least in triplicate and the difference between the
various values obtained was within an experimental error of 5%.
2.3.3. Scanning electron microscopy
Scanning electron microscopy (SEM) was used to investigate
the morphology of the different composite lms. The micrographs
were recorded with a ZEISS-ULTRA55 SEM device, operating at
10 kV. Prior to the analysis, each sample was frozen under liquid
nitrogen during 5 min and then fractured. The fractured surface
was then coated with a gold/palladium layer before analyses.
2.3.4. Differential scanning calorimetry
Differential scanning calorimetry (DSC) experiments were per-
formed using a DSC Q100 device from TA instrument. For each
composite, about 10 mg of the sample was placed in a DSC cell
and then heated from 90 to 250 C, under a heating rate of
10 C min
1
. These measurements were carried out at least in
duplicate.
2.3.5. Tensile tests
The mechanical behaviour of the composite lms, cut into probe
samples with dimensions of 30 5 0.4 mm
3
, was tested using a
RSA 2 mechanical analyzer system from Rheometrics, working in
tensile mode. The elongation, stress at break, as well as the Youngs
modulus were determined. All the samples were conditioned for
24 h in conditioned room, under controlled temperature (23 C)
and relative humidity (50%). These measurements were performed
ve times and the difference between the various values obtained
was within an experimental error of 5%.
2.3.6. Dynamic mechanical analysis
The dynamic mechanical analysis (DMA) of the composite lms
was performed using a RSA 3 DMA apparatus from Rheometrics,
working in the tensile mode. For this analysis, the samples were
cut into thin rectangular strips with dimensions 30 5
0.4 mm
3
. The measurements were carriedout under isochronal con-
ditions at 1 Hz, and the temperature scanning interval varied from
100 to 250 C, with a heating rate of 2 C min
1
. The samples were
previously conditioned for 24 h under controlled temperature
(23 C) and relative humidity (50%), before being tested. These mea-
surements were also carried out at least in duplicate.
3. Results and discussion
3.1. Preparation and characterisation of P. oceanica fragments
After the milling of the P. oceanica balls and subsequent sieving,
the ensuing fragments were soxhlet extracted with organic sol-
vents possessing increasing polarities, i.e.: hexane, dichlorometh-
ane and acetone. The amount of extractives obtained with each
solvent was found to be around 2.9%, 6.5% and 1.3%, for hexane,
dichloromethane and acetone respectively, which yield a quite
signicant global value, reaching about 10% by weight. This Fig. 1. Posidonia oceanica balls.
1868 R. Khiari et al. / Composites Science and Technology 71 (2011) 18671872
apparently high number is comparable to those obtained for other
annual plants or agricultural crops [7,8,10,2125].
The particle size distribution of P. oceanica fragments is pre-
sented in Fig. 2, which shows that a large distribution prole is ob-
tained. Even if the distribution is centred around 50 lm, particles
with much smaller (1 lm) or bigger (400 lm) sizes are present.
The FTIR spectra of the P. oceanica fragments (not shown here),
before and after extractions with the three organic solvents (hex-
ane, dichloromethane and acetone) were established. The obtained
spectra present similar proles, depicting essentially the typical IR
bands of cellulose. In particular, several characteristic peaks are
observed namely: (i) at 3340, 1150 and 950 cm
1
, ascribed to the
vibration and elongation of the hydroxyl AOAH linkages, (ii) in
the region of 950850 cm
1
, the presence of the peak characteristic
of glucosidic units is detected, (iii) the shape of the rst OH peak
(at 3340 cm
1
) shows clearly the presence of strong intermolecular
hydrogen bonds between cellulose macromolecules, and (iv) nal-
ly, a band at 2920 cm
1
is characteristic of the elongation of the
methylene (ACH
2
A) groups.
As expected, the peaks associated with hemicelluloses, lignin
and extractives was not detected by this technique, since the asso-
ciated bands are mostly overlapped with those of cellulose. Never-
theless, the extraction efciency cannot be evidenced by FTIR,
since no changes in the obtained spectra were observed.
XPS was also used to analyze the surface of the untreated and
treated P. oceanica samples, as shown in Fig. 3 and Tables 1 and
2. Table 1 summarises the data deduced from the XPS low-resolu-
tion spectra corresponding to the four samples studied here. These
results show that the main atoms present at the surface of the
investigated samples are C, O, N, Al, Si and Ca. As expected from lig-
nocellulosic chemical structures, the dominant atoms are C and O.
The presence of inorganic atoms witnesses about the presence of
naturally occurring contaminations, such as alluminosilicates and
calcium salts (most probably carbonates). The extraction of the P.
oceanica substrates did not induce any change in the atomic com-
position of the surface (even if up to 10% of extractive compounds
were removed). The O/C ratios for these surfaces were also found
to be roughly the same (ca. 0.7), which is very common for ligno-
cellulosic substrates [26,27].
Fig. 3 displays the high-resolution deconvolution of the C1s
peak for the virgin and extracted samples. Again, similar results
are observed for all the soxhlet extracted samples (Fig. 4bd).
These data disagree with those reported in the literature for other
lignocellulosic materials, in which it was systematically demon-
strated that the extraction with organic solvents decreases signi-
cantly the intensity of C1 peak, as a result of removing several
surfactant type structures (vegetal oils and rosins) and phenolic
fragments (tannins and lignin) [26,27]. In our case, the suggested
relative good stability of the C1 signal intensity could be attributed
to the fact that the aliphatic- and aromatic-type structures present
at the P. oceanica surface are chemically bonded to the molecular
architecture of the bulk material.
From the FT-IR and XPS results, it is clear that despite the elim-
ination of some extractives, the extraction procedure, on the
whole, did not alter signicantly the surface composition of the
investigated materials. For this reason, we decided to use the virgin
P. oceanica fragments (without any further purication) for the
preparation of the composite lms.
3.2. Preparation and characterisation of the composite lms
The P. oceanica particles were introduced into the matrix up to a
maximumloading of 30 wt.%, without any signicant change in the
aspect of the ensuing lms. In fact, the particles agglomeration was
apparently avoided.
3.2.1. Morphology
The SEM micrographs obtained from the fractured cross sec-
tions of the composite lms are illustrated in Fig. 4, which shows
that the cellulose particles are quite homogeneously distributed
within the thermoplastic matrix, even for a high reinforcing level
(as high as 30%, see Fig. 4d).
These gures also show that the ller/matrix interface is inti-
mately linked, which suggests that a good interfacial adhesion with
the matrix will be yielded, as emphasised by Fig. 4d and e. Thus,
the absence of holes and the apparent intimate contact between -
bres and matrix (good apparent wetting and absence of space be-
tween the particle and the matrix) suggests that the two phases
display a rather good compatibility.
3.2.2. Thermal properties
The thermal properties of the matrix as well as those of all the
other composite lms prepared in this work were studied. The DSC
tracings of the composite lms are very similar (results not shown)
to that of the matrix. In fact, in all the cases, a glass transition tem-
perature (T
g
) very close to that of the matrix (about to 0 C) was de-
tected, suggesting that the introduction of the lignocellulosic llers
did not affected the T
g
of the matrix. This feature is quite interest-
ing and very useful in practice because the produced lms keep
their exibility even for the highest ller loading investigated here.
3.2.3. Mechanical properties
3.2.3.1. Tensile tests. The mechanical properties (Youngs modulus,
strength and elongation at break) were also investigated at room
temperature (25 C) and the results are summarised in Table 3.
As expected, the elongation at break decreased signicantly with
increasing bre loading, due to the stiffening effect induced by
lignocellulosic llers [11], while the stress at break remained fairly
unchanged (about 17 MPa). Besides, the Youngs modulus en-
hanced with increasing the llers loading. For example, the
Youngs modulus of the composite containing 30 wt.% of P. ocea-
nica particles is three times higher than that of the unlled matrix.
These data conrm that the P. oceanica fragments played a real
reinforcing effect for the thermoplastic matrix (Table 3), as previ-
ously reported for other cellulose bres from other sources and
other polymeric matrices [11].
3.2.3.2. DMA. The dynamic mechanical analysis of the composite
lms was also performed. The results on the evolution of the stor-
age modulus (logE
0
) and of the loss factor (tand) was ascertained as
a function of temperature, in isochronal conditions at a constant
frequency of 1 Hz, as presented in Figs. 5a and 5b.
The obtained curve associated to the storage modulus (E
0
) for
the unlled BIOPLAST matrix (Fig. 5a) displays a typical behaviour
as that of fully amorphous thermoplastic polymers. Below the T
g
,
i.e., 0 C, the BIOPLAST matrix is in its glassy state with a storage
Particle size (m)
V
o
l
u
m
e

(
%
)

Fig. 2. Particles size distribution of Posidonia oceanica fragments.
R. Khiari et al. / Composites Science and Technology 71 (2011) 18671872 1869
modulus of about 1 GPa. It starts to decrease slightly with temper-
ature, but remains roughly constant. An abrupt and signicant de-
crease is observed around 0 C (T
g
), corresponding to the relaxation
behaviour associated with the transition of the matrix from glassy
to rubbery states. This observation is consistent with the region of
glass transition temperature, as determined by DSC measurements.
For temperatures higher than the T
g
of the matrix, the storage
modulus attained a plateau-like stage around 1 MPa, which corre-
sponds to a rubbery state. Finally, the E
0
dropped down to zero at
temperatures higher than 40 C, indicating that the owing process
of the matrix occurs.
The logE
0
curves of the composite lms (Fig. 5a) were norma-
lised with respect to that of the matrix at the glassy plateau. Below
the T
g
there is no difference between the modulus values of the
matrix and those of the lled lms. However, above the T
g
, the
presence of P. oceanica llers induced a signicant mechanical
reinforcement. Indeed, at room temperature (25 C), the storage
modulus of the composite materials containing 10, 20 and
30 wt.% of P. oceanica particles (Table 4) were 59, 97 and
119 MPa, respectively. Such increase is relatively signicant when
compared to that of the pure matrix (7.8 MPa). Again, this behav-
iour can be attributed to the incorporation of the P. oceanica llers,
which reinforced the matrix yielding homogeneous and continu-
ous structure of the nal composite lms. Fig. 5a also shows that
above the T
g
, the llers extended slightly the rubbery plateau of
the lms, as conrmed by the increase of the temperature at which
the composites owed. Thus, this parameter increased from 40 C
for virgin matrix, to around 70, 75 and 85 C for the composites
lled with 10, 20 and 30 wt.%, respectively.
Fig. 5b shows the evolution of the tan(d) vs temperature at 1 Hz
for the different BIOPLAST-based composites. Even if the values of
T
g
deduced from these graphs do not reect the real phenomenon,
279 281 283 285 287 289
CPS
C-C
C-O
O-C-O
O-C=O
279 281 283 285 287 289
CPS
C-C
C-O
O-C-O
O-C=O
279 281 283 285 287 289
CPS
C-C
C-O
O-C-O
O-C=O
279 281 283 285 287 289
CPS
C-C
C-O
O-C-O
O-C=O
a
c
d
b
Fig. 3. XPS results of the untreated and treated Posidonia oceanica samples.
Table 1
Atomic composition of Posidonia oceanica surface, as determined from low resolution XPS spectra.
Samples C N O Al Si Ca
Virgin 55.99 0.85 2.50 0.33 36.78 0.76 1.18 0.24 3.47 0.44 0.50 0.33
Hexane-extracted 56.07 0.65 2.56 0.56 36.68 0.44 1.19 0.36 2.96 0.07 0.54 0.05
Dichloromethane-extracted 55.38 0.42 2.61 0.09 36.31 0.34 1.34 0.01 3.91 0.51 0.41 0.14
Acetone-extracted 53.99 1.00 2.48 0.20 37.74 0.77 1.34 0.34 3.85 0.28 0.60 0.18
Table 2
C1s deconvolution XPS data of Posidonia oceanica surface.
Samples C groups concentration and their corresponding binding energy (eV)
O/C CAC CAO C@O OAC@O
282 284 286 287
Virgin 0.65 47.08 0.54 38.11 0.98 11.04 0.29 3.77 0.37
Hexane-extracted 0.65 44.67 1.36 39.67 0.45 10.96 0.70 4.71 0.29
Dichloromethane-extracted 0.65 46.19 2.13 38.78 0.84 11.00 0.77 4.05 0.52
Acetone-extracted 0.69 44.22 0.30 41.09 0.27 11.07 0.16 3.63 0.19
1870 R. Khiari et al. / Composites Science and Technology 71 (2011) 18671872
it, nevertheless, retrieves a good idea of the temperature at which
this thermal event takes place (around 18 C). Additionally, it can
be noticed that the incorporation of the llers induced a decrease
in the relaxation amplitude. This phenomenon can be attributed
to a corresponding decrease of the entities participating in the
relaxation mechanism. It is worth to note that the behaviour of
the composite lm with 10 wt.% of llers was somehow out of
the observed trend. Thus, it is worth noting that DSC showed no
impact of the ller on the T
g
of the polymer matrix, whereas the
tan delta in the DMA seems to show some changes with the 10%
reinforced composite. This apparent disagreement could be ex-
plained by the different nature of the two tests. DSC is a static mea-
surement while DMA is carried out under dynamic conditions. In
fact, the sample is under tension which could induce particle
Fig. 4. SEM micrographs of the fractured cross-sections of the composite lms with (a) 0, (b and d) 20 and (c and e) 30 wt.% of bre loadings.
7
7,5
8
8,5
9
9,5
-100 -75 -50 -25 0 25 50 75 100
Temperature (C)
L
o
g

E
'
0% 10%
20% 30%
Fig. 5a. Evolution of the storage modulus logarithm (logE
0
) against temperature for
the prepared BIOPLAST-based composites.
0
0,1
0,2
0,3
Temperature (C)
T
a
n
g

D
e
l
t
a
0% 10%
20% 30%
-50 -40 -30 -20 -10 0 10 20 30
Fig. 5b. Evolution of the tan(d) against temperature at for the prepared BIOPLAST-
based composites.
Table 4
DMA results of the composite lms prepared with different ller loadings (wt.%).
Samples Posidonia/BIOPLAST (weight
fractions)
E
0
C25
(MPa)
T
f
(C)
E
0
C25normalised
(MPa)
0/100 7.83 42.45 7.83
10/90 163 60.32 58.9
20/80 294 69.65 96.9
30/70 295 81.57 119
Table 3
Mechanical properties of composite lms prepared with different ller loadings
(wt.%).
wt.% Elongation at break
(%)
Stress at break
(MPa)
Youngs modulus
(MPa)
0 407.1 17.5 67.52
10 80.4 16.8 109.8
20 42.2 16.4 144.7
30 27.7 18.2 180.5
R. Khiari et al. / Composites Science and Technology 71 (2011) 18671872 1871
reorganisation and/or deformation and matrix stretching. These
values were conrmed and no rational explanation could be given
at this stage. Additional studies are under investigation in order to
better explain such a feature.
4. Conclusions
Composite lms possessing different Posidonia oceanica frag-
ment loadings (0, 10, 20, 30 wt.%) were prepared and characterised
by thermal and mechanical analyses. The processing conditions of
the composites prepared here did not show any difculty and the
obtained results demonstrated that they own both good thermal
and mechanical properties (specically concerning the Youngs
modulus). The improvement of the mechanical properties and
the easy processing conditions allow extrapolating the incorpora-
tion of these llers to other polymeric matrices and open a rational
way of valorising Posidonia oceanica residue.
Acknowledgments
The authors would like to thank IFC (Institut de Coopration
Franais de l.ambassade de France en Tunisie) and MIR (Mobilit
Internationale de la Rgion Rhne-Alpe) for their nancial support.
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