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

and electrostatic repulsion forces lead to a stable aqueous
The development and the application of polymeric suspension. Aqueous suspensions of charged whiskers
composite materials filled with nanosized rigid particles display a birefringent character [20] and form a chiral
(essentially inorganic) has attracted both scientific and nematic order phase with the optical characteristics of a
industrial interest. Over the last few years much effort has cholesteric liquid crystal [21,22].
been devoted to the use of nanocrystals obtained from Polymer composites reinforced with tunicin (an animal
polysaccharides, viz. cellulose [1 10], starch [11,12] or cellulose) whiskers display spectacularly enhanced mech-
chitin [13 17] as reinforcing agents in polymeric matrices. anical properties even at a low whiskers content [1,2,5 7].
The advantages of natural fillers are their low density, The first announcement of the use of cellulose whiskers as a
renewable character, high specific strength and biodegrad- reinforcing phase involved an amorphous model matrix
ability associated with the highly specific properties of composed of a copolymer of styrene and butyl acrylate [1].
nanoparticles. Further the nanoscale dimensions of poly- The formation of a rigid network resulting from strong
saccharide crystals enable these nanocomposites to be interactions between adjacent whiskers by hydrogen bond-
transparent in well dispersed composites. ing was proposed to explain the mechanical behavior of
Cellulose can be extract from plant cell walls and some cellulose whiskers reinforced composites [1,2].
sea animals. Cellulose nanocrystals (whiskers) can be The development of new polymer electrolytes is needed
for many kinds of electrochemical applications such as
obtained by the acid hydrolysis of cellulose microfibrils
separators in high energy density lithium battery. Poly
[18]. They consist of highly crystalline rod-like particles
(oxyethylene) (POE) based polymer electrolytes are the most
with a high specific area [19]. When sulfuric acid is used for
commonly studied, due to their cationic solvatation ability.
* Corresponding author. Tel: 33-4-76-82-69-95; fax: 33-4-76-82-69- However, the high degree of crystallinity of POE strongly
33. restricts the ionic conductivity at room temperature. There-
E-mail address: [email protected] (A. Dufresne). fore, POE based electrolytes should be used above their
0032-3861/$ - see front matter q 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2004.03.094
4150 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157

melting temperature Tm to display appropriate conduc- 2.3. Nanocomposites processing

tivity. Unfortunately, the mechanical properties are very
poor in this temperature range. Crystallinity can be reduced The POE powder was first dispersed in a small volume of
or eliminated using several strategies i.e. high degrees of methanol. After addition of water, the solution was stirred
branching, copolymerization or formation of comb during 24 h at room temperature. The solution was protected
branched polymers. The amorphous state and improved against light by an aluminium film. It was mixed with the
mechanical behavior can be usually easily achieved using desired amount of whiskers aqueous suspension. The
cross-linked copolymers [23]. However, suitable mechan- cellulose whiskers content was varied from 0 to 30 wt%
ical properties require a high cross-linking density that depending on the experimental analysis to be performed.
results in a strong reduction of the assisted mobility of the The resulting suspension was stirred again during 24 h and
ionic species, and thus of conductivity. degassed under vacuum in order to remove the remaining
Another way to improve the mechanical properties above air. Solid films were obtained by casting this suspension on
Tm consists in using POE based composite electrolytes. Teflon plates and water evaporation at 40 8C for one week.
However, the reinforcing phase should increase the Drastic drying of the formed films was carried out at 100 8C
mechanical behavior without decreasing significantly the under vacuum for 72 h. 2,2-Dimethoxypropane was used as
ionic mobility. dehydration agent. The final films were around 200 mm
In the present work tunicin whiskers were used as the thick.
reinforcing phase in a POE matrix. The morphology, as well
as the thermal and mechanical behavior of these nanocom-
2.4. Microscopies
posite materials have been investigated. This preliminary
study will be used to understand the properties of similar
A scanning electron microscope (SEM), JEOL JSM-
systems in which a lithium salt has been added. The
6100 instrument, using 7 KV secondary electrons, was used
conductivity of tunicin whiskers reinforced POE based
for the composite morphology investigations. The speci-
electrolytes will be published in the near future.
mens were frozen under liquid nitrogen, then fractured,
mounted, coated with gold/palladium on a JEOL JFC-
1100E ion sputter coater and observed.
2. Experimental
A Zeiss polarizing optical microscope was used to
observe and follow the growth of the POE spherulites. The
2.1. Polymeric matrix
microscope was connected to a Mettler FP82HT hotstage
and a Metller FP90 as temperature controller. Micrographs
Poly(oxyethylene) (POE) with a high molecular weight
were recorded with a color View 12 camera. Numerical
Mw 5 106 g mol21 was purchased as a white powder
acquisition and analysis were achieved using the Analysis
from Aldrich. The polymer was used as received.
3.2 software. Samples were melted at 90 8C for 5 min and
then cooled to the crystallization temperature T 56:3 8C:
2.2. Tunicin whiskers
More than 150 microphotographs were taken every two
seconds between the appearance of the first nucleus and the
Cellulose nanocrystals were extracted from tunicate (a
end of growth. Average radiuses of spherulites were
sea animal). The preparation of cellulose whiskers was
largely described elsewhere [1,2]. Small fragments of the measured assuming a circular geometry. The average radial
external wall of tunicate were first deproteinized by three growth rate was calculated as the slope of the straight lines
successive bleaching treatments as described by Wise et al. representing the plot of the spherulites radius as a function
[18] and disintegrated in water with a warning blender. The of time.
resulting aqueous tunicin (purified cellulose from tunicate)
suspension was mixed with sulfuric acid and hydrolysis 2.5. Differential scanning calorimetry (DSC)
conditions were 65 8C for 30 min under strong stirring. The
suspension was washed with water until neutrality was Differential scanning calorimetry (DSC) was performed
reached and sonicated with a Branson Sonifier. It did not using a DSC2920 CE modulated differential scanning
sediment or flocculate as a consequence of surface sulfate calorimeter from TA. Around 20 mg of samples were
groups created during the sulfuric acid treatment [20]. It is placed in a DSC cell in glove box. Each sample was heated
made up of individual cellulose fragments consisting of from 2 100 to 110 8C at a heating rate of 10 8C min21.
slender parallelepiped rods that have a broad distribution in The glass transition temperature Tg was taken as the
size [1,2,8]. These fragments have a length ranging from inflection point of the specific heat increment at the glass
500 nm up to 1 2 mm and they are almost 15 nm in width. rubber transition while the melting temperature Tm was
The average aspect ratio (L=d; L being the length and d the taken as the peak temperature of the melting endotherm.
diameter) and the specific area of these whiskers was For the crystallization study, the sample was first heated
estimated to be close to 70 and 170 m2 g21 [7], respectively. to 110 8C and kept at this temperature for 5 min to ensure
 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157 4151

complete melting of POE. It was then cooled down to 0 8C The fractured surface of nanocomposite films displays a
at a cooling rate of 10 8C min21. similar non-uniform aspect. By comparing the micrograph
showing the surface of fracture of unfilled POE (panel a) and
2.6. Thermogravimetric analysis of composites (panels b and c), it is easy to identify cellulose
whiskers. They appear like white dots, whose concentration
Thermogravimetric measurements were carried out with is a direct function of the cellulose content in the composite.
a Netzsch STA409 thermal analyzer. Few milligrams of the These shiny dots correspond to the transverse sections of the
sample were heated from room temperature up to 500 8C at cellulose whiskers. Their diameter, around 60 nm, is much
10 8C min21 under nitrogen flow. higher than the whiskers diameter. This results from a
charge concentration effect due to the emergence of tunicin
2.7. Dynamic mechanical analysis (DMA) whiskers from the observed surface. It is worth noting that
the filler is more or less evenly distributed within the
Dynamic mechanical measurements were carried out polymeric matrix but some whiskers are not fully indivi-
with a spectrometer RSA2 from rheometrics working in the dualized and form small aggregates (indicate by arrows).
tensile mode. The strain amplitude was fixed at 0.05% so as
to be in the domain of the linear viscoelasticity of the 3.2. Thermal behavior and crystallization of POE
material. The samples were thin rectangular strips with
dimensions about 20 7 0.2 mm3. Measurements were DSC measurements were performed on the POE matrix
performed in isochronal condition at 1 Hz and the and related tunicin whiskers composites. Scans were
temperature was varied between 150 and 450 K by steps performed at least two weeks after film formation and
of 2 K. storage in a glove box to ensure stabilization of the degree of
crystallinity and perfect reliability of measurements. The
2.8. Heat flow microcalorimetry values of the glass rubber transition temperature Tg ;
melting temperature Tm and corresponding heat of fusion
The calorimetric measurements (Setaram - C 80 micro- DHm are collected in Table 1. No significant influence of
calorimeter) were performed in a two-compartment cell: a the cellulose whiskers content on Tg is reported and its value
lower compartment, where 5 mg of whiskers were placed is around 2 60 8C. The melting temperature is also found to
and an upper compartment where typically 500 mg of the be roughly constant for low whiskers content, up to 10 wt%.
different solvents were introduced. A PTFE membrane However, for higher filler loading the Tm value decreases
separated the two compartments. A reference cell of the significantly. A similar effect was reported by Nishio et al.
same type was used, the upper compartment containing also [24] and Guo and Liang [25] for POE/cellulose blends. This
500 mg of the same solvent and the lower compartment decrease of Tm could be ascribed to two effects. The first one
being empty. The two cells were placed in the apparatus for is a morphological phenomenon and could be related to a
temperature equilibration until the relative heat flow was decrease of the POE crystallites size due to the formation of
below 50 mW. The PTFE membranes of the two cells were a close cellulose network within the matrix, mainly for high
then pierced simultaneously by a movable steel needle. For filler content. The POE spherulites growth could be
each measurement the temperature was fixed at 40 8C and therefore restricted. The second effect could originate
the experiment was performed twice. 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,
3. Results and discussion

3.1. Morphology of films Table 1

Temperatures of the calorimetric transitions of tunicin whiskers filled POE
using data obtained from the DSC curves: glass rubber transition
The morphology of the composites was characterized by
temperature Tg ; melting temperature Tm , associated heat of fusion
SEM. Fig. 1 shows the fractured surface of the unfilled POE DHm and degree of crystallinity (xc and xp)
matrix (panel a) and nanocomposite films reinforced with 3
(panel b) and 6 wt% of whiskers (panel c), just after Whiskers content (wt%) Tg (8C) Tm (8C) DHm (J/g) x ca xpa
fracture. The freshly fractured surface of the unfilled POE
0 260.8 66.6 124.7 0.61 0.61
film (Fig. 1(a)) is not uniform and both fibrillar zones and 6 261.2 66.9 116.0 0.56 0.59
holes are observed. The fibrillar aspect is most probably due 10 258.7 67 114.3 0.55 0.61
to the brittle fracture procedure under liquid nitrogen and 15 259.7 65.7 98.0 0.47 0.55
from the semi-crystalline nature of POE. The presence of 30 259.7 63.4 72.6 0.35 0.46
holes at the fractured surface could result from entrapped air a DHm
xc DH and xp xwc ; where DHm 8 205 J g21 is the heat of fusion
m8
within the film during the water evaporation step despite for 100% crystalline POE [27] and w is the weight fraction of polymeric
degassing of the suspension. 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 Fig. 4. Polarized optical micrographs obtained after 100 s isothermal
time t to the total area. The reference time was fixed at the crystallization at 53.6 8C for a POE based film filled with (a) 0 and (b)
beginning of the crystallization process. All the curves 10 wt% tunicin whiskers.
display the same shape, an early fast primary crystallization
birefringent spherulites are clearly identified through the
and a slower secondary crystallization, and superimpose
characteristic Maltese cross pattern indicating a spherical
regardless of the tunicin whiskers content.
Fig. 4 shows polarized optical micrographs of POE symmetry. For the 10 wt% tunicin whiskers reinforced
based films. The films were first heated at 90 8C for material the supermolecular structure is quite different
5 min and rapidly cooled down to 53.6 8C. The (panel b). The spherulites exhibit a less birefringent
micrographs were obtained after 100 s isothermal crystal- character, most probably due to a weakly organized
lization at 53.6 8C. For the unfilled POE matrix (panel a), 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
Fig. 3. Evolution of the conversion fraction determined from DSC
thermograms in Fig. 2 vs. time for POE based composites filled with 0 possible transcrystallization phenomenon was observed.
(W), 10 (A) and 30 wt% (V) of tunicin whiskers. 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 hydrophilic cellulose whiskers in presence of a highly
disagree with this hypothesis for POE based composites. hydrophobic solvent and evaluate the contribution of the
From the polarized optical microscopic observations the alkane part of POE to the global interactions. Results are
growth rate of the POE spherulites was determined. It was reported in Table 2. The heat of immersion is directly
calculated from the determination of the time evolution of related to the interaction between cellulosic whiskers and
the spherulitic radius during isothermal crystallization. the solvent and it can be used to determine contact angles
Crystallization conditions were similar to those chosen in [30]. The highest value of Dho was obtained for water due to
Fig. 4 and consist in melting the polymer at 90 8C for 5 min the strong hydrophilic character of cellulose. On the
and cooling it down to 53.6 8C. Fig. 5 shows the evolution of contrary and as expected, dodecane displays the weakest
the POE spherulites radius vs. time during isothermal interactions.
crystallization at 53.6 8C for the unfilled matrix (filled For oligoethers, intermediate values were obtained. The
symbols) and 10 wt% filled composite (open symbols). Its highest value reported for a,b-dihydroxy oligo(oxyethy-
value is systematically lower for the composite compared to lene) (PEG200) compared to polyethylene glycol dimethy-
the unfilled matrix in agreement with our previous optical lether (PEGDME500) and tetra(ethylene glycol) dimethyl
microscopic and DSC observations. A linear dependence is ether (tetraglymea low molecular weight PEGDM)
observed and the growth rate was calculated from the slope suggests a stronger affinity of the cellulose whiskers surface
of the linear fit of the curves. Its value is 0.27 mm s21 for the with hydroxyl end groups of POE than its ether oxygen
unfilled POE and 0.28 mm s21 for the composite. Therefore, groups. However, the difference in Dho observed between
surprisingly the presence of the tunicin whiskers within the the tetraglyme and the PEGDME500 indicates significant
polymeric matrix does not affect the spherulitic growth rate
interactions between ether oxygen groups and the cellulose
of POE during its crystallization. This observation could be
whiskers.
ascribed to the composition-independence of the POE POE
Kondo and Sawatari [26] have shown the influence of the
interactions during the crystallization process. Polymer
hydroxyl regiochemistry in cellulose on hydrogen bonds
chains located in the vicinity of the cellulose/POE interface
formation in cellulose/POE blends. IR spectroscopy
could most probably strongly interact with the cellulosic
measurements support that primary hydroxyl groups at the
surface and coat the cellulose whiskers with a polymeric
position C6 of the glucose unit of cellulose interact
shell of restricted mobility. On the contrary, bulk POE
predominantly with ether oxygen in POE in comparison to
chains mainly responsible for the crystallization process
display a crystallization rate similar to the one of the unfilled the cellulose hydroxyl groups in position C2 and C3.
matrix.
3.4. Thermogravimetric analysis
3.3. Cellulose/POE interactions

The possibility of cellulose whiskers/POE interactions The potential use of tunicin whiskers/POE composites as
has been suggested several times in this study and used as a a matrix in electrolyte polymer applications requires
potential hypothesis to explain some observations. They thermal stability. Unfilled POE and related composites
were quantified using heat flow microcalorimetry. The heat filled with various whiskers contents were tested using
of immersion, Dho ; was directly measured by mixing tunicin thermogravimetric analysis (TGA) (Fig. 6). Thermal
whiskers with water, dodecane and oligoethers. Dodecane degradation phenomena of POE have been reported [31]
was used for comparison to display the behavior of 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

Fig. 5. Evolution of the spherulitic radius determined from polarized optical
microscopy vs. time for POE based composites filled with 0 (V) and Dho (J/g) 252.2 236.2 229.2 220.1 21.1
10 wt% (A) of tunicin whiskers during isothermal crystallization at 53.6 8C.
 M.A.S. Azizi Samir et al. / Polymer 45 (2004) 41494157 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
Fig. 6. TGA curves under nitrogen for unfilled POE matrix and related formulations. However, DSC measurements show that the
composites. The tunicin whiskers contents are indicated in the figure. degree of crystallinity of POE was composition-indepen-
dent up to about 10 wt% tunicin whiskers and then
3.5. Mechanical behavior
decreases for higher whiskers content. Therefore, the
increase of the relaxed modulus should be ascribed to a
Fig. 7 shows the temperature dependence of the storage
reinforcing effect of cellulose whiskers. A similar obser-
tensile modulus E0 of the unfilled POE matrix and related
vation was reported for semi-crystalline poly(caprolactone)
composites. As it is well known, the exact determination of
reinforced with high aspect ratio chitin whiskers obtained
the glassy modulus depends on the precise knowledge of the
from Riftia tubes [14].
sample dimensions. In order to minimize this influence, the
The main effect of tunicin whiskers on the mechanical
glassy elastic tensile modulus, E0 at 2 100 8C was normal-
behavior of POE is observed at high temperature, above the
ized at 4.8 GPa for all the samples. It corresponds to the
melting temperature of the matrix. Whereas the storage
observed average value regardless the composition. The
tensile modulus of the unfilled matrix drops irremediably
unfilled POE displays a typical behavior of semi-crystalline
with the melting of the crystalline POE domains, whiskers
polymer with three distinct zones. In the glassy state T ,
bring a thermal stabilization effect. The modulus of
210 K; the tensile storage modulus E0 remains roughly
composites remains constant up to temperatures higher
constant. Around 213 K, the modulus drop is associated to
than 400 K. The first studies performed on tunicin whiskers
the glass rubber transition of the POE amorphous phase.
filled nanocomposites used an amorphous polymeric matrix
The magnitude of this modulus drop is weak because of the
composed of a copolymer of styrene and butyl acrylate [1,
high degree of crystallinity of the material. In the
2]. A thermal stabilization of the modulus was observed
temperature range 210 320 K, the storage tensile modulus
above Tg of the matrix, up to 500 K, a temperature at which
slowly decreases but remains around 1 GPa. In this
cellulose starts to degrade. It was ascribed to the formation
temperature range, amorphous rubbery domains coexist
of a rigid percolating cellulose whiskers network. This
with crystalline domains, which play the role of both filler
network, assumed to be formed through strong whisker/
particles and physical cross-links. At higher temperatures
whisker hydrogen bonds interactions, was observed for
the modulus drops sharply and irremediably due to the
whiskers content higher than the percolation threshold,
melting of the crystalline zones of POE around 330 K. For
around 1 vol%, i.e. 1.25 wt%, for tunicin whiskers/POE
high molecular weight POE, temporary entanglements
composites. The percolation threshold strongly depends on
between macromolecular chains may normally act as
the aspect ratio of the rod-like reinforcing particles [4].
effective cross-links and ensure temporary modulus stabil-
The value of the high temperature storage modulus
ization above melting temperature [34]. This phenomenon
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
Fig. 7. Storage tensile modulus E0 vs. temperature at 1 Hz for POE based
Takayanagi et al. [35]. The main advantage of this approach
composites filled with (A) 0, (W) 3, ( ) 6 and (S) 10 wt% of tunicin was to account for interactions between the fillers and for
whiskers. 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 calculated and the experimental data at lower filler content
found elsewhere [1,2,4 7]. When the filler modulus is far (3 and 6 wt%) is probably due to the fact that the prediction
higher than the one of the matrix, i.e. above Tm in our case, does not account for the distribution of the whiskers lengths.
the predicted composite modulus, Ec ; is simply given by Another possible cause of discrepancy could be also the
Ref. [5]: presence of aggregates observed by SEM.
Ec c E R 1
where c and ER correspond to the volume fraction and 4. Conclusions
modulus of the stiff percolating network, respectively. c can
be written as: Nanocomposite materials were prepared from an aqu-
c0 for vR , vRc eous suspension of high aspect ratio rod-like cellulosic
 b particles composed of tunicin whiskers and a poly(oxyethy-
vR 2 vRc 2 lene) (POE) aqueous solution. After casting and water
c vR for vR $ vRc
1 2 vRc evaporation a solid composite film was obtained and
scanning electron microscopic observations revealed an
where vR ; vRc and b correspond to the volume fraction of
evenly dispersed cellulosic phase within the POE matrix.
filler, the critical volume fraction at the percolation
The glass rubber transition temperature of POE was not
threshold and the corresponding critical exponent, respect-
influenced by the cellulosic filler, contrarily to the melting
ively. It means that all the stiffness of the material results
temperature and degree of crystallinity which were found to
from infinite aggregates of tunicin whiskers.
decrease for highly filled (10 wt% and above) materials.
It is now of interest to compare the performances of
This restricted crystallinity was confirm by dynamic cooling
tunicin whiskers/POE nanocomposites to the data predicted
crystallization experiments and polarized optical micro-
from this model based on the percolation concept. The
scopic observations. It was ascribed to both strong
volume fraction c was calculated using the parameters
interactions between the POE chains and cellulosic surface
already used in our previous studies: vRC 1 vol% for the
and increased viscosity of the melt composite. Cellulose/
percolation threshold and b 0:4 for the critical exponent
POE interactions were quantified using heat flow micro-
in a three-dimensional problem according to the percolation
theory [1,2,4 7]. The densities of crystalline cellulose and calorimetry measurements. The mechanical behavior of
POE were taken as 1.5 and 1.2 g cm23, respectively. The tunicin whiskers/POE nanocomposites was evaluated in the
tensile modulus, ER ; of a film of cellulose whiskers was linear range over a broad temperature range from dynamic
measured from a tensile test performed on a film prepared mechanical analysis. The main effect of the filler was a
by water evaporation of a tunicin whiskers suspension thermal stabilization of the storage modulus for the
ER 8 GPa: Literature reports values ranging between 5 composites above the melting temperature of the POE
and 15 GPa depending on the source of cellulose [1,2,4]. matrix. This phenomenon was well predicted from a model
The calculated moduli are 35, 106 and 255 MPa for the based on the percolation concept. It was shown that the
composites filled with 3, 6 and 10 wt% of tunicin whiskers, formation of the cellulosic network through inter-whiskers
respectively. The order of magnitude of the predicted data hydrogen bonds, assumed to be responsible for the high
agrees with the experimental ones. It is a good indication mechanical properties of the composites, was not affected
that the cellulose whiskers percolation phenomenon is by the matrix crystallization process and filler/POE
almost not affected by the crystallization process of the interactions.
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 Acknowledgements
values obtained for tunicin whiskers reinforced cross-linked
unsaturated polyether, which were around 25 and 70 MPa The authors thank the Region Rhone-Alpes for financial
for 3 and 6 wt% filled composites, respectively [36]. support, and Mrs D. Dupeyre and M.M. Paillet for helping
However, these experimental data could be affected by in SEM study and tunicin whiskers preparation,
the low temperature storage modulus normalization. The respectively.
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
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