Polymer 45 (2004) 41494157

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Cellulose nanocrystals reinforced poly(oxyethylene)

My Ahmed Said Azizi Samira,b, Fannie Alloinb, Jean-Yves Sanchezb, Alain Dufresnec,*
a
Centre de Recherches sur les Macromolecules Vegetales (CERMAV-CNRS), Universite Joseph Fourier, BP 53, 38041 Grenoble cedex 9, France
b
Laboratoire dElectrochimie et de Physico-chimie des Materiaux et des Interfaces (LEPMI-INPG), BP 75, F38402 St Martin dHe`res Cedex, France
c
Ecole Francaise de Papeterie et des Industries Graphiques (EFPG-INPG), BP 65, F38402 St Martin dHe`res Cedex, France
Received 18 December 2003; received in revised form 2 March 2004; accepted 24 March 2004

Abstract
Nanocomposite materials were prepared from poly(oxyethylene) (POE) as the matrix and a stable aqueous suspension of cellulose
nanocrystals extracted from tunicate as the reinforcing phase. After dissolving POE in water and mixing with the cellulose nanocrystals
suspension, solid films were obtained by casting and evaporating the preparations. Resulting films were characterized using scanning electron
microscopy, differential scanning calorimetry, thermogravimetric analysis and dynamic mechanical analysis. Favorable interactions between
cellulose and POE were evidenced and assumed to be partially responsible for a decrease of the crystallinity of the matrix. A thermal
stabilization of the nanocomposites for temperatures higher than the melting temperature of POE was reported and ascribed to the formation
of a rigid cellulosic network within the matrix assumed to be governed by a percolation effect. The formation of this percolating network was
not altered by the matrix crystallization process and filler/POE interactions.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Cellulose whiskers; Poly(oxyethylene); Nanocomposite

1. Introduction hydrolysis, cellulose whiskers are charged at their surface

The development and the application of polymeric
composite materials filled with nanosized rigid particles
(essentially inorganic) has attracted both scientific and
industrial interest. Over the last few years much effort has
been devoted to the use of nanocrystals obtained from
polysaccharides, viz. cellulose [1 10], starch [11,12] or
chitin [13 17] as reinforcing agents in polymeric matrices.
The advantages of natural fillers are their low density,
renewable character, high specific strength and biodegrad-
ability associated with the highly specific properties of
nanoparticles. Further the nanoscale dimensions of poly-
saccharide crystals enable these nanocomposites to be
transparent in well dispersed composites.
Cellulose can be extract from plant cell walls and some
sea animals. Cellulose nanocrystals (whiskers) can be
obtained by the acid hydrolysis of cellulose microfibrils
[18]. They consist of highly crystalline rod-like particles
with a high specific area [19]. When sulfuric acid is used for
* Corresponding author. Tel: 33-4-76-82-69-95; fax: 33-4-76-82-69-
33.
E-mail address: alain.dufresne@efpg.inpg.fr (A. Dufresne).
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.03.094
and electrostatic repulsion forces lead to a stable aqueous
suspension. Aqueous suspensions of charged whiskers
display a birefringent character [20] and form a chiral
nematic order phase with the optical characteristics of a
cholesteric liquid crystal [21,22].
Polymer composites reinforced with tunicin (an animal
cellulose) whiskers display spectacularly enhanced mech-
anical properties even at a low whiskers content [1,2,5 7].
The first announcement of the use of cellulose whiskers as a
reinforcing phase involved an amorphous model matrix
composed of a copolymer of styrene and butyl acrylate [1].
The formation of a rigid network resulting from strong
interactions between adjacent whiskers by hydrogen bond-
ing was proposed to explain the mechanical behavior of
cellulose whiskers reinforced composites [1,2].
The development of new polymer electrolytes is needed
for many kinds of electrochemical applications such as
separators in high energy density lithium battery. Poly
(oxyethylene) (POE) based polymer electrolytes are the most
commonly studied, due to their cationic solvatation ability.
However, the high degree of crystallinity of POE strongly
restricts the ionic conductivity at room temperature. There-
fore, POE based electrolytes should be used above their
4150 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157
melting temperature Tm to display appropriate conduc-
tivity. Unfortunately, the mechanical properties are very
poor in this temperature range. Crystallinity can be reduced
or eliminated using several strategies i.e. high degrees of
branching, copolymerization or formation of comb
branched polymers. The amorphous state and improved
mechanical behavior can be usually easily achieved using
cross-linked copolymers [23]. However, suitable mechan-
ical properties require a high cross-linking density that
results in a strong reduction of the assisted mobility of the
ionic species, and thus of conductivity.
Another way to improve the mechanical properties above
Tm consists in using POE based composite electrolytes.
However, the reinforcing phase should increase the
mechanical behavior without decreasing significantly the
ionic mobility.
In the present work tunicin whiskers were used as the
reinforcing phase in a POE matrix. The morphology, as well
as the thermal and mechanical behavior of these nanocom-
posite materials have been investigated. This preliminary
study will be used to understand the properties of similar
systems in which a lithium salt has been added. The
conductivity of tunicin whiskers reinforced POE based
electrolytes will be published in the near future.
2. Experimental
2.1. Polymeric matrix
Poly(oxyethylene) (POE) with a high molecular weight
Mw 5 106 g mol21 was purchased as a white powder
from Aldrich. The polymer was used as received.
2.2. Tunicin whiskers
Cellulose nanocrystals were extracted from tunicate (a
sea animal). The preparation of cellulose whiskers was
largely described elsewhere [1,2]. Small fragments of the
external wall of tunicate were first deproteinized by three
successive bleaching treatments as described by Wise et al.
[18] and disintegrated in water with a warning blender. The
resulting aqueous tunicin (purified cellulose from tunicate)
suspension was mixed with sulfuric acid and hydrolysis
conditions were 65 8C for 30 min under strong stirring. The
suspension was washed with water until neutrality was
reached and sonicated with a Branson Sonifier. It did not
sediment or flocculate as a consequence of surface sulfate
groups created during the sulfuric acid treatment [20]. It is
made up of individual cellulose fragments consisting of
slender parallelepiped rods that have a broad distribution in
size [1,2,8]. These fragments have a length ranging from
500 nm up to 1 2 mm and they are almost 15 nm in width.
The average aspect ratio (L=d; L being the length and d the
diameter) and the specific area of these whiskers was
estimated to be close to 70 and 170 m2 g21 [7], respectively.
2.3. Nanocomposites processing
The POE powder was first dispersed in a small volume of
methanol. After addition of water, the solution was stirred
during 24 h at room temperature. The solution was protected
against light by an aluminium film. It was mixed with the
desired amount of whiskers aqueous suspension. The
cellulose whiskers content was varied from 0 to 30 wt%
depending on the experimental analysis to be performed.
The resulting suspension was stirred again during 24 h and
degassed under vacuum in order to remove the remaining
air. Solid films were obtained by casting this suspension on
Teflon plates and water evaporation at 40 8C for one week.
Drastic drying of the formed films was carried out at 100 8C
under vacuum for 72 h. 2,2-Dimethoxypropane was used as
dehydration agent. The final films were around 200 mm
thick.
2.4. Microscopies
A scanning electron microscope (SEM), JEOL JSM-
6100 instrument, using 7 KV secondary electrons, was used
for the composite morphology investigations. The speci-
mens were frozen under liquid nitrogen, then fractured,
mounted, coated with gold/palladium on a JEOL JFC-
1100E ion sputter coater and observed.
A Zeiss polarizing optical microscope was used to
observe and follow the growth of the POE spherulites. The
microscope was connected to a Mettler FP82HT hotstage
and a Metller FP90 as temperature controller. Micrographs
were recorded with a color View 12 camera. Numerical
acquisition and analysis were achieved using the Analysis
3.2 software. Samples were melted at 90 8C for 5 min and
then cooled to the crystallization temperature T 56:3 8C:
More than 150 microphotographs were taken every two
seconds between the appearance of the first nucleus and the
end of growth. Average radiuses of spherulites were
measured assuming a circular geometry. The average radial
growth rate was calculated as the slope of the straight lines
representing the plot of the spherulites radius as a function
of time.
2.5. Differential scanning calorimetry (DSC)
Differential scanning calorimetry (DSC) was performed
using a DSC2920 CE modulated differential scanning
calorimeter from TA. Around 20 mg of samples were
placed in a DSC cell in glove box. Each sample was heated
from 2 100 to 110 8C at a heating rate of 10 8C min21.
The glass transition temperature Tg was taken as the
inflection point of the specific heat increment at the glass
rubber transition while the melting temperature Tm was
taken as the peak temperature of the melting endotherm.
For the crystallization study, the sample was first heated
to 110 8C and kept at this temperature for 5 min to ensure
 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157
complete melting of POE. It was then cooled down to 0 8C
at a cooling rate of 10 8C min21.
2.6. Thermogravimetric analysis
Thermogravimetric measurements were carried out with
a Netzsch STA409 thermal analyzer. Few milligrams of the
sample were heated from room temperature up to 500 8C at
10 8C min21 under nitrogen flow.
2.7. Dynamic mechanical analysis (DMA)
Dynamic mechanical measurements were carried out
with a spectrometer RSA2 from rheometrics working in the
tensile mode. The strain amplitude was fixed at 0.05% so as
to be in the domain of the linear viscoelasticity of the
material. The samples were thin rectangular strips with
dimensions about 20 7 0.2 mm3. Measurements were
performed in isochronal condition at 1 Hz and the
temperature was varied between 150 and 450 K by steps
of 2 K.
2.8. Heat flow microcalorimetry
The calorimetric measurements (Setaram - C 80 micro-
calorimeter) were performed in a two-compartment cell: a
lower compartment, where 5 mg of whiskers were placed
and an upper compartment where typically 500 mg of the
different solvents were introduced. A PTFE membrane
separated the two compartments. A reference cell of the
same type was used, the upper compartment containing also
500 mg of the same solvent and the lower compartment
being empty. The two cells were placed in the apparatus for
temperature equilibration until the relative heat flow was
below 50 mW. The PTFE membranes of the two cells were
then pierced simultaneously by a movable steel needle. For
each measurement the temperature was fixed at 40 8C and
the experiment was performed twice.
3. Results and discussion
3.1. Morphology of films
The morphology of the composites was characterized by
SEM. Fig. 1 shows the fractured surface of the unfilled POE
matrix (panel a) and nanocomposite films reinforced with 3
(panel b) and 6 wt% of whiskers (panel c), just after
fracture. The freshly fractured surface of the unfilled POE
film (Fig. 1(a)) is not uniform and both fibrillar zones and
holes are observed. The fibrillar aspect is most probably due
to the brittle fracture procedure under liquid nitrogen and
from the semi-crystalline nature of POE. The presence of
holes at the fractured surface could result from entrapped air
within the film during the water evaporation step despite
degassing of the suspension.
4151
The fractured surface of nanocomposite films displays a
similar non-uniform aspect. By comparing the micrograph
showing the surface of fracture of unfilled POE (panel a) and
of composites (panels b and c), it is easy to identify cellulose
whiskers. They appear like white dots, whose concentration
is a direct function of the cellulose content in the composite.
These shiny dots correspond to the transverse sections of the
cellulose whiskers. Their diameter, around 60 nm, is much
higher than the whiskers diameter. This results from a
charge concentration effect due to the emergence of tunicin
whiskers from the observed surface. It is worth noting that
the filler is more or less evenly distributed within the
polymeric matrix but some whiskers are not fully indivi-
dualized and form small aggregates (indicate by arrows).
3.2. Thermal behavior and crystallization of POE
DSC measurements were performed on the POE matrix
and related tunicin whiskers composites. Scans were
performed at least two weeks after film formation and
storage in a glove box to ensure stabilization of the degree of
crystallinity and perfect reliability of measurements. The
values of the glass rubber transition temperature Tg ;
melting temperature Tm and corresponding heat of fusion
DHm are collected in Table 1. No significant influence of
the cellulose whiskers content on Tg is reported and its value
is around 2 60 8C. The melting temperature is also found to
be roughly constant for low whiskers content, up to 10 wt%.
However, for higher filler loading the Tm value decreases
significantly. A similar effect was reported by Nishio et al.
[24] and Guo and Liang [25] for POE/cellulose blends. This
decrease of Tm could be ascribed to two effects. The first one
is a morphological phenomenon and could be related to a
decrease of the POE crystallites size due to the formation of
a close cellulose network within the matrix, mainly for high
filler content. The POE spherulites growth could be
therefore restricted. The second effect could originate
from the expected strong interactions between ether oxygen
groups of POE and hydroxyl groups of cellulose whiskers
[26]. Owing to the high specific area of tunicin whiskers,
Table 1
Temperatures of the calorimetric transitions of tunicin whiskers filled POE
using data obtained from the DSC curves: glass rubber transition
temperature Tg ; melting temperature Tm , associated heat of fusion
DHm and degree of crystallinity (xc and xp)
Whiskers content (wt%) Tg (8C) Tm (8C) DHm (J/g) x ca xpa
0 260.8 66.6 124.7 0.61 0.61
6 261.2 66.9 116.0 0.56 0.59
10 258.7 67 114.3 0.55 0.61
15 259.7 65.7 98.0 0.47 0.55
30 259.7 63.4 72.6 0.35 0.46
a DHm
xc DH and xp xwc ; where DHm 8 205 J g21 is the heat of fusion
m8
for 100% crystalline POE [27] and w is the weight fraction of polymeric
matrix material in the composite.
4152 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157

Fig. 1. Scanning electron micrographs from the fractured surfaces of (a) unfilled POE matrix and related composites filled with (b) 3 wt% and (c) 6 wt% tunicin
whiskers.

significant interactions can be established mainly at high increases. It could be ascribed to an anti nucleation effect of
loading level. the filler. Theoretically, the nucleation rate is the product of
The degree of crystallinity of tunicin whiskers/POE films mass transport and nucleation parameters [28]. The
was calculated using the heat of fusion determined from transport factor is related to chains self-diffusion. Two
DSC measurements and the one corresponding to a 100% phenomena could explain the anti nucleation effect of
crystalline POE reported by Vidotto et al. [27]. These values cellulose whiskers.
are reported in Table 1. xc corresponds to the apparent
degree of crystallinity of the films calculated from the
enthalpy of fusion per gram of composite, whereas xp was
obtained from the heat of fusion per gram of POE in the
composite. For low whiskers content, up to 10 wt%, the xp
value is quite constant, but it is found to decrease for higher
loading level. It could be ascribed to a steric phenomenon,
POE spherulites growing in the presence of a close
cellulosic network as the dispersed phase in agreement
with the decrease of Tm already observed.
Fig. 2 shows DSC thermograms of the dynamic cooling
crystallization of the unfilled POE matrix and 10 and
30 wt% tunicin whiskers based composites. Both the
crystallization temperature corresponding to the peak
temperature of the crystallization exotherm and the Fig. 2. DSC thermograms showing the non-isothermal crystallization at
temperature associated with the beginning of the crystal- 10 8C min21 for POE based composites filled with 0 (W), 10 (A) and
lization process decrease as the cellulose whiskers content 30 wt% (V) of tunicin whiskers.
 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157 4153

(i) The first one is due to the likely strong affinity of POE
molecules with the reactive cellulose surface. This
coupling effect should result in a restricted molecular
mobility of POE chains in contact with the whiskers
surface. Owing to the very high specific area of tunicin
whiskers, this hindered mobility could be strong
enough to affect the global chain self-diffusion of the
matrix. However, no shift of Tg was reported from DSC
measurements.
(ii) The second explanation could be the expected increase
of the viscosity of the polymer melt ascribed to the
presence of whiskers. This increased viscosity may
induce an increase of the activation energy of diffusion
of the chains.

Though the two mentioned explanations could be

involved simultaneously in the observed anti nucleation
effect of tunicin whiskers, similar results reported for
cellulose whiskers reinforced isotactic polypropylene [29]
support the latter.
The non-isothermal crystallization kinetics of tunicin
whiskers/POE composites are plotted in Fig. 3. It displays
the evolution of the conversion fraction as a function of time
for the unfilled POE matrix and 10 and 30 wt% whiskers
based composites. The conversion fraction was determined
as the ratio of the area under the crystallization exotherm at
time t to the total area. The reference time was fixed at the
beginning of the crystallization process. All the curves
display the same shape, an early fast primary crystallization
and a slower secondary crystallization, and superimpose
regardless of the tunicin whiskers content.
Fig. 4 shows polarized optical micrographs of POE
based films. The films were first heated at 90 8C for
5 min and rapidly cooled down to 53.6 8C. The
micrographs were obtained after 100 s isothermal crystal-
lization at 53.6 8C. For the unfilled POE matrix (panel a),
Fig. 3. Evolution of the conversion fraction determined from DSC
thermograms in Fig. 2 vs. time for POE based composites filled with 0
(W), 10 (A) and 30 wt% (V) of tunicin whiskers.
Fig. 4. Polarized optical micrographs obtained after 100 s isothermal
crystallization at 53.6 8C for a POE based film filled with (a) 0 and (b)
10 wt% tunicin whiskers.
birefringent spherulites are clearly identified through the
characteristic Maltese cross pattern indicating a spherical
symmetry. For the 10 wt% tunicin whiskers reinforced
material the supermolecular structure is quite different
(panel b). The spherulites exhibit a less birefringent
character, most probably due to a weakly organized
structure. The cellulosic filler most probably interferes
with the spherulite growth and it is possible that during
growth the whiskers are ejected and then occluded in
interspherulitic regions. The high viscosity of the filled
medium most probably restricts this phenomenon and
limit the size of the spherulites as observed in Fig. 4(b).
This observation agrees with Tm values and dynamic
cooling crystallization experiments. The ejection of the
tunicin whiskers during the spherulite growth could be
partly responsible for the small filler aggregates observed
by SEM.
By comparing Fig. 4(a) and (b), it is also worth noting
that the number of nuclei after 100 s isothermal crystal-
lization at 53.6 8C seems to be higher in the composite than
in the unfilled matrix. It could be ascribed to a nucleating
effect of whiskers as reported for a semi-crystalline
poly(hydroxyoctanoate) [6] or a thermoplastic starch [8]
matrix reinforced with tunicin whiskers, for which a
possible transcrystallization phenomenon was observed.
However, the decrease of the temperature for which the
4154 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157
non-isothermal crystallization process begins seems to
disagree with this hypothesis for POE based composites.
From the polarized optical microscopic observations the
growth rate of the POE spherulites was determined. It was
calculated from the determination of the time evolution of
the spherulitic radius during isothermal crystallization.
Crystallization conditions were similar to those chosen in
Fig. 4 and consist in melting the polymer at 90 8C for 5 min
and cooling it down to 53.6 8C. Fig. 5 shows the evolution of
the POE spherulites radius vs. time during isothermal
crystallization at 53.6 8C for the unfilled matrix (filled
symbols) and 10 wt% filled composite (open symbols). Its
value is systematically lower for the composite compared to
the unfilled matrix in agreement with our previous optical
microscopic and DSC observations. A linear dependence is
observed and the growth rate was calculated from the slope
of the linear fit of the curves. Its value is 0.27 mm s21 for the
unfilled POE and 0.28 mm s21 for the composite. Therefore,
surprisingly the presence of the tunicin whiskers within the
polymeric matrix does not affect the spherulitic growth rate
of POE during its crystallization. This observation could be
ascribed to the composition-independence of the POE POE
interactions during the crystallization process. Polymer
chains located in the vicinity of the cellulose/POE interface
could most probably strongly interact with the cellulosic
surface and coat the cellulose whiskers with a polymeric
shell of restricted mobility. On the contrary, bulk POE
chains mainly responsible for the crystallization process
display a crystallization rate similar to the one of the unfilled
matrix.
3.3. Cellulose/POE interactions
The possibility of cellulose whiskers/POE interactions
has been suggested several times in this study and used as a
potential hypothesis to explain some observations. They
were quantified using heat flow microcalorimetry. The heat
of immersion, Dho ; was directly measured by mixing tunicin
whiskers with water, dodecane and oligoethers. Dodecane
was used for comparison to display the behavior of
Fig. 5. Evolution of the spherulitic radius determined from polarized optical
microscopy vs. time for POE based composites filled with 0 (V) and
10 wt% (A) of tunicin whiskers during isothermal crystallization at 53.6 8C.
hydrophilic cellulose whiskers in presence of a highly
hydrophobic solvent and evaluate the contribution of the
alkane part of POE to the global interactions. Results are
reported in Table 2. The heat of immersion is directly
related to the interaction between cellulosic whiskers and
the solvent and it can be used to determine contact angles
[30]. The highest value of Dho was obtained for water due to
the strong hydrophilic character of cellulose. On the
contrary and as expected, dodecane displays the weakest
interactions.
For oligoethers, intermediate values were obtained. The
highest value reported for a,b-dihydroxy oligo(oxyethy-
lene) (PEG200) compared to polyethylene glycol dimethy-
lether (PEGDME500) and tetra(ethylene glycol) dimethyl
ether (tetraglymea low molecular weight PEGDM)
suggests a stronger affinity of the cellulose whiskers surface
with hydroxyl end groups of POE than its ether oxygen
groups. However, the difference in Dho observed between
the tetraglyme and the PEGDME500 indicates significant
interactions between ether oxygen groups and the cellulose
whiskers.
Kondo and Sawatari [26] have shown the influence of the
hydroxyl regiochemistry in cellulose on hydrogen bonds
formation in cellulose/POE blends. IR spectroscopy
measurements support that primary hydroxyl groups at the
position C6 of the glucose unit of cellulose interact
predominantly with ether oxygen in POE in comparison to
the cellulose hydroxyl groups in position C2 and C3.
3.4. Thermogravimetric analysis
The potential use of tunicin whiskers/POE composites as
a matrix in electrolyte polymer applications requires
thermal stability. Unfilled POE and related composites
filled with various whiskers contents were tested using
thermogravimetric analysis (TGA) (Fig. 6). Thermal
degradation phenomena of POE have been reported [31]
and a complex mechanism of POE degradation was
proposed. The weakening of C O bonds may accelerate
the thermal degradation as observed in POE/metallic cation
complexes [32,33].
Fig. 6 shows that the degradation of POE starts around
300 8C. No significant influence of the presence of cellulose
whiskers on the thermal stability was reported despite strong
cellulose/POE interactions.
Table 2
Heat of immersion Dho measured at 40 8C for tunicin whiskers with water,
dodecane, polyethylene glycol 200 (PEG200), polyethylene glycol
dimethylether 500 (PEGDME500) and tetra(ethylene glycol) dimethyl
ether (tetraglyme)
Water PEG200 PEGDME500 Tetraglyme Dodecane
Dho (J/g) 252.2 236.2 229.2 220.1 21.1
 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157
Fig. 6. TGA curves under nitrogen for unfilled POE matrix and related
composites. The tunicin whiskers contents are indicated in the figure.
3.5. Mechanical behavior
Fig. 7 shows the temperature dependence of the storage
tensile modulus E0 of the unfilled POE matrix and related
composites. As it is well known, the exact determination of
the glassy modulus depends on the precise knowledge of the
sample dimensions. In order to minimize this influence, the
glassy elastic tensile modulus, E0 at 2 100 8C was normal-
ized at 4.8 GPa for all the samples. It corresponds to the
observed average value regardless the composition. The
unfilled POE displays a typical behavior of semi-crystalline
polymer with three distinct zones. In the glassy state T ,
210 K; the tensile storage modulus E0 remains roughly
constant. Around 213 K, the modulus drop is associated to
the glass rubber transition of the POE amorphous phase.
The magnitude of this modulus drop is weak because of the
high degree of crystallinity of the material. In the
temperature range 210 320 K, the storage tensile modulus
slowly decreases but remains around 1 GPa. In this
temperature range, amorphous rubbery domains coexist
with crystalline domains, which play the role of both filler
particles and physical cross-links. At higher temperatures
the modulus drops sharply and irremediably due to the
melting of the crystalline zones of POE around 330 K. For
high molecular weight POE, temporary entanglements
between macromolecular chains may normally act as
effective cross-links and ensure temporary modulus stabil-
ization above melting temperature [34]. This phenomenon
Fig. 7. Storage tensile modulus E0 vs. temperature at 1 Hz for POE based
composites filled with (A) 0, (W) 3, ( ) 6 and (S) 10 wt% of tunicin
whiskers.
4155
was not observed in our experiments, probably because of
the frequency value (1 Hz) in our DMA tests.
Tunicin whiskers filled nanocomposites display a similar
behavior and a weak modulus drop is observed around
210 K. However, compared to the unfilled POE matrix, the
magnitude of this modulus drop is lower. The temperature
position of this relaxation process does not vary with the
cellulose content in agreement with DSC measurements.
The highest rubbery modulus for composites could result
from a highest degree of crystallinity of POE in composite
formulations. However, DSC measurements show that the
degree of crystallinity of POE was composition-indepen-
dent up to about 10 wt% tunicin whiskers and then
decreases for higher whiskers content. Therefore, the
increase of the relaxed modulus should be ascribed to a
reinforcing effect of cellulose whiskers. A similar obser-
vation was reported for semi-crystalline poly(caprolactone)
reinforced with high aspect ratio chitin whiskers obtained
from Riftia tubes [14].
The main effect of tunicin whiskers on the mechanical
behavior of POE is observed at high temperature, above the
melting temperature of the matrix. Whereas the storage
tensile modulus of the unfilled matrix drops irremediably
with the melting of the crystalline POE domains, whiskers
bring a thermal stabilization effect. The modulus of
composites remains constant up to temperatures higher
than 400 K. The first studies performed on tunicin whiskers
filled nanocomposites used an amorphous polymeric matrix
composed of a copolymer of styrene and butyl acrylate [1,
2]. A thermal stabilization of the modulus was observed
above Tg of the matrix, up to 500 K, a temperature at which
cellulose starts to degrade. It was ascribed to the formation
of a rigid percolating cellulose whiskers network. This
network, assumed to be formed through strong whisker/
whisker hydrogen bonds interactions, was observed for
whiskers content higher than the percolation threshold,
around 1 vol%, i.e. 1.25 wt%, for tunicin whiskers/POE
composites. The percolation threshold strongly depends on
the aspect ratio of the rod-like reinforcing particles [4].
The value of the high temperature storage modulus
increases with increasing the filler content in agreement
with the increasing whisker/whisker interaction probability
and density of the cellulosic network. The modulus is
around 18, 45 and 235 MPa for composites filled with 3, 6
and 10 wt%, respectively. After melting of the crystalline
domains of the polymeric matrix around 65 8C, the
mechanical stabilization of tunicin whiskers reinforced
POE is supposed to be mainly provided by the percolating
cellulosic network. Previous studies [1,2,5 7] have shown
that the high reinforcing effect of tunicin whiskers
reinforced amorphous thermoplastic can be well predicted
following the adaptation of the percolation concept to the
classical phenomenological series-parallel model of
Takayanagi et al. [35]. The main advantage of this approach
was to account for interactions between the fillers and for
the hydrogen-bonding forces that hold the percolating
4156 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157
cellulose whiskers network. Details of the calculation can be
found elsewhere [1,2,4 7]. When the filler modulus is far
higher than the one of the matrix, i.e. above Tm in our case,
the predicted composite modulus, Ec ; is simply given by
Ref. [5]:
Ec c E R
where c and ER correspond to the volume fraction and
modulus of the stiff percolating network, respectively. c can
be written as:
c0 for vR , vRc
 b
vR 2 vRc
c vR for vR $ vRc
1 2 vRc
where vR ; vRc and b correspond to the volume fraction of
filler, the critical volume fraction at the percolation
threshold and the corresponding critical exponent, respect-
ively. It means that all the stiffness of the material results
from infinite aggregates of tunicin whiskers.
It is now of interest to compare the performances of
tunicin whiskers/POE nanocomposites to the data predicted
from this model based on the percolation concept. The
volume fraction c was calculated using the parameters
already used in our previous studies: vRC 1 vol% for the
percolation threshold and b 0:4 for the critical exponent
in a three-dimensional problem according to the percolation
theory [1,2,4 7]. The densities of crystalline cellulose and
POE were taken as 1.5 and 1.2 g cm23, respectively. The
tensile modulus, ER ; of a film of cellulose whiskers was
measured from a tensile test performed on a film prepared
by water evaporation of a tunicin whiskers suspension
ER 8 GPa: Literature reports values ranging between 5
and 15 GPa depending on the source of cellulose [1,2,4].
The calculated moduli are 35, 106 and 255 MPa for the
composites filled with 3, 6 and 10 wt% of tunicin whiskers,
respectively. The order of magnitude of the predicted data
agrees with the experimental ones. It is a good indication
that the cellulose whiskers percolation phenomenon is
almost not affected by the crystallization process of the
matrix and filler/POE interactions. The cellulose-cellulose
interactions seems to be higher than cellulose/POE ones.
This is also supported by the high temperature modulus
values obtained for tunicin whiskers reinforced cross-linked
unsaturated polyether, which were around 25 and 70 MPa
for 3 and 6 wt% filled composites, respectively [36].
However, these experimental data could be affected by
the low temperature storage modulus normalization. The
good agreement between experimental and predicted data
for the highly filled material (10 wt%) could be ascribed to
the high sensibility of the calculated modulus value near the
percolation threshold and its stabilization for higher filler
content. However, the good prediction of this asymptotic
value for compositions far above the percolation threshold
proves the validity of the model based on the percolation
concept. In addition, the discrepancy observed between the
calculated and the experimental data at lower filler content
(3 and 6 wt%) is probably due to the fact that the prediction
does not account for the distribution of the whiskers lengths.
Another possible cause of discrepancy could be also the
presence of aggregates observed by SEM.
1
4. Conclusions
Nanocomposite materials were prepared from an aqu-
eous suspension of high aspect ratio rod-like cellulosic
particles composed of tunicin whiskers and a poly(oxyethy-
2 lene) (POE) aqueous solution. After casting and water
evaporation a solid composite film was obtained and
scanning electron microscopic observations revealed an
evenly dispersed cellulosic phase within the POE matrix.
The glass rubber transition temperature of POE was not
influenced by the cellulosic filler, contrarily to the melting
temperature and degree of crystallinity which were found to
decrease for highly filled (10 wt% and above) materials.
This restricted crystallinity was confirm by dynamic cooling
crystallization experiments and polarized optical micro-
scopic observations. It was ascribed to both strong
interactions between the POE chains and cellulosic surface
and increased viscosity of the melt composite. Cellulose/
POE interactions were quantified using heat flow micro-
calorimetry measurements. The mechanical behavior of
tunicin whiskers/POE nanocomposites was evaluated in the
linear range over a broad temperature range from dynamic
mechanical analysis. The main effect of the filler was a
thermal stabilization of the storage modulus for the
composites above the melting temperature of the POE
matrix. This phenomenon was well predicted from a model
based on the percolation concept. It was shown that the
formation of the cellulosic network through inter-whiskers
hydrogen bonds, assumed to be responsible for the high
mechanical properties of the composites, was not affected
by the matrix crystallization process and filler/POE
interactions.
Acknowledgements
The authors thank the Region Rhone-Alpes for financial
support, and Mrs D. Dupeyre and M.M. Paillet for helping
in SEM study and tunicin whiskers preparation,
respectively.
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