Professional Documents
Culture Documents
1 Azizi Samir Et Al. 2005 - Review of Recent Research Into Cellulose Whiskers, Their Properties and Their Application in Nanocomposite Field
1 Azizi Samir Et Al. 2005 - Review of Recent Research Into Cellulose Whiskers, Their Properties and Their Application in Nanocomposite Field
1 Azizi Samir Et Al. 2005 - Review of Recent Research Into Cellulose Whiskers, Their Properties and Their Application in Nanocomposite Field
Reviews
Review of Recent Research into Cellulosic Whiskers, Their
Properties and Their Application in Nanocomposite Field
My Ahmed Said Azizi Samir,†,‡,⊥ Fannie Alloin,‡ and Alain Dufresne*,§
Centre de Recherches sur les Macromolécules Végétales (CERMAV-CNRS), Université Joseph Fourier,
BP 53, 38041 Grenoble Cedex 9, France, Laboratoire d’Electrochimie et de Physico-chimie des Matériaux
et des Interfaces, (LEPMI-INPG), BP 75, F38402 St Martin d’Hères Cedex, France, and Ecole Française
de Papeterie et des Industries Graphiques (EFPG-INPG), BP 65, F38402 St Martin d’Hères Cedex, France
Received October 6, 2004; Revised Manuscript Received December 6, 2004
There are numerous examples where animals or plants synthesize extracellular high-performance skeletal
biocomposites consisting of a matrix reinforced by fibrous biopolymers. Cellulose, the world’s most abundant
natural, renewable, biodegradable polymer, is a classical example of these reinforcing elements, which occur
as whiskerlike microfibrils that are biosynthesized and deposited in a continuous fashion. In many cases,
this mode of biogenesis leads to crystalline microfibrils that are almost defect-free, with the consequence of
axial physical properties approaching those of perfect crystals. This quite “primitive” polymer can be used
to create high performance nanocomposites presenting outstanding properties. This reinforcing capability
results from the intrinsic chemical nature of cellulose and from its hierarchical structure. Aqueous suspensions
of cellulose crystallites can be prepared by acid hydrolysis of cellulose. The object of this treatment is to
dissolve away regions of low lateral order so that the water-insoluble, highly crystalline residue may be
converted into a stable suspension by subsequent vigorous mechanical shearing action. During the past
decade, many works have been devoted to mimic biocomposites by blending cellulose whiskers from different
sources with polymer matrixes.
to difficulties associated with surface interactions. The As reported above, one of the restrictions in lignocellulosic
inherent polar and hydrophilic nature of polysaccharides and based systems is the difficulty in achieving acceptable
the nonpolar characteristics of most of the thermoplastics dispersion levels of the filler within the polymeric matrix.
result in difficulties in compounding the filler and the matrix An alternative way to palliate this restriction consists of using
and, therefore, in achieving acceptable dispersion levels, a latex, i.e., an aqueous suspension of polymer particles, or
which results in inefficient composites. This hydrogen a water soluble polymer to form the matrix. From the former,
bonding is best exemplified in paper where these secondary it is well-known that emulsion polymerization can lead to
interactions provide the basis of its mechanical strength. materials easily processed, either by film casting techniques
Moreover, the processing temperature of composites is (water evaporation for paint applications for example) or by
restricted to about 200 °C because lignocellulosic materials freeze-drying (or more simply by flocculation) followed by
start to degrade near 230 °C. This limits the type of classical extrusion process. As a matter of fact, different
thermoplastics that can be used in association with polysac- monomers can be statistically copolymerized to adjust the
charide fillers to commodity plastics such as polyethylene, glass-rubber transition temperature at a given value. More
polypropylene, poly(vinyl chloride), and polystyrene. How- generally, it is also possible to mix different types of water
ever, it is worth noting that these lower-price plastics suspensions including some polymer lattices and organic or
constitute about 70% of the total amount of thermoplastics inorganic stabilized suspensions. We will see that, in addition
consumed by the plastics industry. to some practical applications, the study of these systems
can help us to understand some physical properties as
Another drawback of lignocellulosic fillers is their high
moisture absorption and the resulting swelling and decrease geometric and mechanical percolation effects.
in mechanical properties. Moisture absorbance and corre- Whiskers are fibers which have been grown under
sponding dimensional changes can be largely prevented if controlled conditions that lead to the formation of high-purity
the hydrophilic filler is thoroughly encapsulated in a single crystals.8 They constitute a generic class of materials
hydrophobic polymer matrix and there is good adhesion having mechanical strengths equivalent to the binding forces
between both components. However, if the adhesion level of adjacent atoms. The resultant highly ordered structure
between the filler and the matrix is not good enough, a produces not only unusually high strengths but also signifi-
diffusion pathway can preexist or can be created under cant changes in electrical, optical, magnetic, ferromagnetic,
mechanical solicitation. The existence of such a pathway is dielectric, conductive, and even superconductive properties.
also related to the filler connection and therefore to its The tensile strength properties of whiskers are far above those
percolation threshold. of the current high-volume content reinforcements and allow
Stable aqueous suspensions of cellulose monocrystals can the processing of the highest attainable composite strengths.
be prepared by acid hydrolysis of the biomass. Throughout The first references to the existence of definite crystalline
the paper, different descriptors of the cellulosic colloidal zones interposed in the amorphous structure of cellulose
particles will be used, including whiskers, monocrystals, materials were made by Nageli and Schwendener,9 who in
nanocrystals, microcrystalline cellulose, and cellulose crys- 1877 already confirmed the optical anisotropy of vegetable
tallites. Depending on the source, these nanocrystals offer a products both in cell walls and in fibers.
wide variety of aspect ratios (L/d, L being the length and d Commercial forms of microcrystalline cellulose as stable
the diameter), from almost particulate fillers (L/d ) 1) to thixotropic-gel systems involving aqueous colloidal disper-
about 100. These suspensions display a colloidal behavior. sions consist of a hydrolyzed level-off degree of polymer-
They can be used to process nanocomposite materials using ization (DP) at high-solids concentration. They were first
a polymer as the matrix. Nanocomposites are a relatively described by Battista and Smith in a patent10 issued in 1961.
new class of composites that exhibit ultrafine phase dimen- This patent, along with a later publication11 and book,12
sions of 1-1000 nm. Because of the nanometric size effect, described a combination of two characteristic prerequisites
these composites have some unique outstanding properties for producing colloidal phenomena from a fibrous high
with respect to their conventional microcomposite counter- polymer such as cellulose: (i) a controlled chemical pre-
parts. The first study was published in 1990 by researchers treatment to destroy the molecular bonds whereby micro-
at Toyota (Japan) and dealt with montmorillonite clay crystals are hinged together in a network structure and (ii)
reinforced polyamide 6.7 Thermoplastic pellets were obtained an appropriate use of mechanical energy to disperse a
by polymerizing caprolactam with clay. sufficient amount of the unhinged microcrystals in the
As most of the present-day polymers used for preparing aqueous phase to produce the characteristic rheological
nanocomposites are synthetic materials, their processability, behavior and the smooth fat-like spreadability of the resulting
biocompatibility, and biodegradability are much more limited colloidal microcrystalline cellulose gels. It was clearly
than those of natural polymers. Compared to the studies in demonstrated that stable gel systems were obtained only
the field of conventional microcomposites and nanocom- when the mechanical energy was introduced into an aqueous
posites based on synthetic nonbiodegradable materials, only suspension of level-off DP cellulose in which the total solids
limited work has been reported in the area of bionanocom- concentration was of the order of 5% or more and only if
posites. Another advantage of the natural nanofillers is their the mechanical energy was severe enough to liberate a
availability and their resulting lower cost in comparison to minimum number of monocrystals to make a stable gel
synthetic nanofillers. possible.
614 Biomacromolecules, Vol. 6, No. 2, 2005 Azizi Samir et al.
low polarity solvents was made possible recently thanks to Cellulose whiskers are interesting model systems for the
coating or chemical modification of the MCC surface. study of shear dynamics of rigid rods in aqueous suspension.
Coating of cotton and tunicin whiskers by a surfactant such Bercea and Navard78 reported the rheological comportment
as Beycostat NA (BNA) was found to lead to stable of tunicin whiskers aqueous suspensions. They distinguished
suspensions in toluene and cyclohexane.67,68 Goussé et al.69 two different behaviors according to whiskers concentration.
stabilized tunicin microcrystals in tetrahydrofuran (THF) by In the isotropic phase (c < 0.8 wt %) where whiskers are
a partial silylation of their surface. Araki et al.64 prepared randomly oriented, the decrease of the viscosity in relation
original sterically stable aqueous and nonaqueous MCC to shear rate increase can be explained by whiskers align-
suspensions by grafting monoamino oligooxyethylene mono- ment. In the anisotropic phases (c > 0.8 wt %), the behavior
methyl ether at the MCC surface using a carboxylation- is similar to that of liquid crystal polymers with a weak shear
amidation procedure. In a recent publication,70 we have thinning region surrounded by two others shear thinning
shown that it is possible to obtain stable whiskers suspensions regions.
in dimethylformamide (DMF) without either addition of a Araki et al.63 studying H2SO4 and HCl-prepared cellulose
surfactant or any chemical modification. This should allow whiskers demonstrated that the charge of the surface is one
avoiding the use of water as the solvent for composites of the main parameter which control the interwhisker
polymer electrolytes processing. interactions and so the rheological behavior of their suspen-
In 1959, Marchessault et al.50 reported the birefringent sions. The suspensions of charged whiskers showed no time
character of acid-treated cellulose and chitin crystallites. The dependence in viscosity. However, the uncharged HCl-
birefringence of MCC aqueous suspensions can be observed prepared whisker suspensions were thixotropic at concentra-
through a pair of cross-nicols. This birefringence results from tions above 0.5 wt % and antithixotropic below 0.3 wt %.
two origins: (i) a structural form anisotropy of cellulose One of the most interesting characteristic of MCC aqueous
(∆n ≈ 0.05) and (ii) a flow anisotropy resulting from suspensions consists of their self-organization into stable
alignment of MCC under flow generally operated before chiral nematic phases. Whiskers align in the same direction
observation. Shear induced alignment of cotton whiskers in to form nematic planes. The later are stacked such that the
colloidal aqueous suspension was studied by Ebeling et al.71 angle of the director in each subsequent plan is offset
using SAXS experiments. They demonstrated that this incrementally. It was suggested that the chiral ordering
alignment is shear rate-dependent, and it is completely origins from geometrical twists in the microcrystals and/or
reversible. They suggest the presence of planar domains of helical distribution of their surface charge.53,79,80 Evidence
randomly oriented microcrystals which align at low shear of the role of the twisted whiskers’ geometry in chirality
rates and are broken up at higher shear rates enabling was reported when the chiral nematic order was obtained
alignment of the individual whiskers. The whiskers appeared for uncharged whiskers sterically stabilizated.64,68 Revol et
to be randomly aligned prior to shearing and are horizontally al.53 observed this chiral ordering of MCC aqueous suspen-
aligned along the shear direction when the shear rate exceeds sions for various cellulose origins such as wood, cotton,
5 s-1. Ordering of diluted suspensions of cellulose whiskers ramie, and bacterial cellulose. They also reported the
was evidenced using static and dynamic light scattering by conservation of this structure after water evaporation. Sugi-
de Souza Lima and Borsali.72 These authors observed yama et al.81 reported the possibility to align cellulosic
numerous peaks in the scattered intensity, which were whiskers and form a highly ordered cellulosic film. It was
interpreted in terms of electrostatic repulsive interactions achieved by drying diluted aqueous suspensions of tunicin
between whiskers. These interactions are of long-range order, whiskers at room temperature under a strong homogeneous
and the arrangement of whiskers was supposed to be in 7T magnetic field. Resulting films were examined using
cylindrical/hexagonal packing. Addition of salt to the polarized optical microscopy and TEM. The microcrystal axis
suspension induces destruction of this order and leads to orientation perpendicular to the magnetic field direction was
whiskers flocculation, demonstrating the role of the electro- confirmed by electron and X-ray diffraction. The anisotropic
static interactions between whiskers to control both stability magnetic susceptibility of the individual C-C, C-O, C-H,
and order. and O-H bonds and their relative orientation in the crystal
As predict by Onsager,73 the cellulose whiskers can were suggested to originate from the magnetic orientation.
undergo an orientational disorder-order phase transition However, a negligible role in alignment was attributed to
from a disordered isotropic phase to an orientationally the ester groups at the whiskers surface that result from the
ordered phase. Whiskers point with equal probability in every sulfuric acid hydrolysis.
direction in the isotropic phase. However, they cluster around Using this process to orient cellulose microcrystals, Revol
a preferred direction in the anisotropic phase. Suspensions et al.82,83 created an important new material with original
divided in isotropic and anisotropic phases when a critical optical properties. Solidified liquid crystals of cellulose with
concentration was reached.74 The phase transition depends the capability to reflect colored light were prepared from
on the geometrical axial ratio of whiskers,73 their surface wood pulp microcrystals suspensions. Optical properties of
charge,74,75 and their length polydispersity.76 Dong et al.77 these materials depend on both the cellulose origin and the
reported an increase in the critical concentration at the phase preparation conditions. The wavelength of reflected light can
transition in the presence of counterions. The latter influence be controlled by adjusting the ionic strength of the suspen-
also the stability of the cellulose whisker suspensions and sion. These new materials have a high application potential
modify the temperature dependence of the phase separation. like those for security papers.
Recent Research into Cellulosic Whiskers Biomacromolecules, Vol. 6, No. 2, 2005 617
4. Cellulosic Whiskers in Nanocomposite Applications to prepare composites films: (i) by casting on Teflon or
Since the first announcement of using cellulose whiskers propylene dishes followed by water evaporation at moderate
as a reinforcing phase by Favier et al.,84 new nanocomposite temperatures, (ii) by freeze-drying and hot-pressing, or (iii)
materials with original properties were obtained by physical by freeze-drying, extruding, and hot-pressing the mixture.
incorporation of cellulose whiskers into a polymeric matrix. Composite films were also obtained by cross-linking in situ
Like for any multiphase materials, the properties of these an unsaturated matrix after solvent casting using a thermal
cellulosic nanocomposites depend on that of the two or photo cross-linking agent.96,99
constituents, namely whiskers and matrix in addition to Experimental Investigation of Nanocomposite Films.
morphological aspects and their interfacial comportments Morphological Characterizations. Simple naked eye exami-
(whiskers/matrix interactions). Both natural and synthetic nation of the film’s surface can prove the existence of
polymers were explored as the matrix. Natural polymers such remaining air bubbles or the inhomogeneous aspect. This is
as poly (β-hydroxyoctanoate) (PHO),85-87 starch,88 silk generally the case when either the degassing was not efficient
fibroin,89 and cellulose acetate butyrate (CAB)90 reinforced or the evaporation temperature was too high. The problem
with cellulose whiskers were reported in the literature. Poly- can be complicated when the matrix is in the latex form.
(styrene-co-butyl acrylate) (poly(S-co-BuA)),91,92 poly(vinyl Great intention must be made for the choice of both time
chloride) (PVC),93 polypropylene,94 waterborne epoxy,95 and and temperature conditions during water evaporation with
poly(oxyethylene)96 were used as synthetic matrixes. respect to the latex particles coalescence process.
Processing techniques have an important incidence on the Scanning electron microscopy (SEM) is generally em-
final properties of the composites. These techniques are ployed for the more extensive morphological inspection. It
conditioned by both intrinsic properties of whiskers and consists of the observation of fractured surface films at liquid
polymeric matrix (solubility, dispersibility, and degradation) nitrogen temperature. This technique allows for conclusions
and the desired final properties such as geometrical shape. about the homogeneity of the composite, presence of voids,
Water is the preferred processing medium because of the dispersion level of the whiskers within the continuous matrix,
high stability of aqueous cellulose whisker dispersions and presence of aggregates, sedimentation, and possible orienta-
the expected high level of dispersion of the filler within the tion of whiskers. By comparing the micrographs showing
host matrix in the resulting composite film. Therefore, this the surface of fracture of the unfilled matrix and of
restricts the choice of the matrix to hydrosoluble polymers. composites, cellulose whiskers can be easily identified. In
The use of aqueous dispersed polymers, i.e., latexes, is a fact, they appear like white dots. Their concentration is a
first alternative, which allows the use of hydrophobic direct function of the cellulose composition in the composite.
polymers as a matrix and ensures a good level of dispersion These shiny dots correspond to the transversal sections of
of the filler indispensable for homogeneous composites the cellulose whiskers. Their diameter determined by SEM
processing. A second alternative consists of dispersing microscopy is much higher than the whiskers diameter. This
cellulose whiskers in an adequate (with regard to matrix) results from a charge concentration effect due to the
organic medium. This was made possible by the coating emergence of cellulose whiskers from the observed surface.
whiskers surface with a surfactant67 or by chemically The topological dispersion of whiskers in the nanocom-
modifying their surface.64,69,97 The use of a surfactant is the posite film strongly depends on the processing technique and
simplest method. However, the high amount of surfactant conditions. A SEM comparison between either cast and
required to coat this high specific surface filler (four times evaporated or freeze-dried and subsequently hot-pressed
higher than that of whiskers68) prohibits the use of this composites based on a copolymer of styrene and butyl
technique in composite applications. The surface chemical acrylate (poly(S-co-BuA)) matrix filled with wheat straw
modification of cellulose whiskers is another way to disperse whiskers92 demonstrated that the former were less homoge-
cellulose whiskers in organic solvents. It generally involves neous and displayed a gradient of whiskers concentration
reactive hydroxyl groups from the surface of the whis- between the upper and lower faces of the composite film.
kers.59,64,69 However, the mechanical performances of the This sedimentation phenomenon was confirmed using WAXS
resulting composites were found to strongly decrease after by comparing the diffracted X-ray beams by the two faces.
chemical modification as reported for chitin whiskers from It was suggested that this observation was most probably
crab shell.98 Recently, it was shown70 that tunicin whiskers induced by the processing technique itself. Favier100 reported
could be dispersed in DMF without additives or any surface a large exploration of processing effects on the morphology
modifications. This result opens the way for using some of tunicin whiskers filled poly(S-co-BuA) composites. She
hydrophobic polymers as a matrix in addition to allowing used different techniques such as SEM, WAXS, MET, and
additional possible chemical modifications of whiskers polarized light microscopy. The latter technique showed
especially those incompatible with the presence of water. homogeneity of the birefringent character of cast/evaporated
The first step in composites processing consists of mixing films and the existence of different colored domains in hot-
the aqueous whiskers suspension and the dispersed or pressed and extruded/hot-pressed composites. From the
solubilized polymer matrix. Homogeneous suspensions were different experimental techniques, it was concluded that the
obtained by classical magnetic stirring at room temperature casting/evaporation technique results in the more homoge-
or by using an autoclave reactor for mixing at high neous films, where the whiskers have a tendency to orient
temperatures. The suspensions were generally degassed under randomly into horizontal plans. Heterogeneous composites
vacuum to remove air. Three different techniques were used with numerous locally oriented domains of whiskers were
618 Biomacromolecules, Vol. 6, No. 2, 2005 Azizi Samir et al.
obtained by the other techniques. Small angle neutron It was reported that Tm values were nearly independent of
scattering (SANS) is another way to check the dispersion of the filler content in plasticized starch88,103 and in poly-
the whiskers into the matrix. This technique was used by (oxyethylene) (POE)104 filled with tunicin whiskers. The
Chazeau101 to conclude that there was an isotropic dispersion same observation was reported for CAB reinforced with
of tunicate whiskers in plasticized poly(vinyl chloride) and native bacterial cellulose whiskers.90 For the CAB matrix,
a lack of any aggregates. Tm values were found to increase when the amount of
Thermal Properties. The glass-rubber transition temper- trimethylsilylated whiskers arises. The authors ascribed this
ature, Tg, of cellulose whisker filled polymer composites is difference to the stronger filler-matrix interaction in the case
an important parameter, which controls different properties of chemically modified whiskers.
of the resulting composite such as its mechanical behavior, A significant increase in crystallinity of sorbitol plasticized
matrix chains dynamics, and swelling behavior. Differential starch103 was reported when the tunicin whiskers content was
scanning calorimetry (DSC) and dynamic mechanical analy- increased. This phenomenon was ascribed to an anchoring
sis (DMA) can be used to evaluate Tg of polymers and effect of the cellulosic filler, probably acting as a nucleating
composites. In DSC experiments, Tg is generally taken as agent. The same effect was reported for POE based com-
the inflection point of the specific heat increment at the posites104 and isotactic polypropylene (iPP) filled with
glass-rubber transition. From DMA tests, not a transition cellulosic whiskers coated with a surfactant.94 In these
but a relaxation process is evidenced in this temperature systems, the nucleating effect was supported by optical
range. The temperature position of this relaxation process polarized light observations of composites during their
(TR) depends on both Tg and the frequency of the measure- isothermal crystallization.
ment. Its value can be taken as the temperature at the When whiskers are coated with surfactant, they are very
maximum peak of the internal friction factor (tan δ ) good nucleating agents for iPP. On the contrary, untreated
E′′/E′) or the loss modulus (E′′), where E′ corresponds to whiskers do not modify the crystallization of iPP. When
the storage tensile modulus. In shear solicitation, E′ and E′′ whiskers are grafted by maleated iPP, cellulose acts like an
are replaced by the storage shear modulus, G′, and the loss antinucleating agent.94
shear modulus, G′′, respectively. It seems that the nucleating effect of cellulosic whiskers
For tunicin whisker filled composites, no modification of is mainly governed by surface chemical considerations.
Tg values was reported when increasing the amount of Indeed, Bonini94 did not observe any nucleating effect of
whiskers, regardless the nature of the polymeric ma- the iPP matrix when using either untreated or grafted with
trix.84,88,93,100,102 Similar results were reported for bacterial90 anhydride maleic iPP tunicin whiskers. Grunert and Winter90
and wheat straw92 cellulose whisker based composites. Hajji assumed from DSC measurements that native bacterial fillers
et al.102 demonstrated that in addition to their independence impede the crystallization of the CAB matrix, whereas
on the filler content, Tg’s of tunicin whiskers/poly(S-co-BuA) silylated ones help to nucleate the crystallization.
composites are independent of the processing conditions. In A transcrystallization phenomenon was reported for tunicin
glycerol plasticized starch (amylopectin) based composites, whiskers filled semicrystalline matrixes such as PHO86 and
Anglès and Dufresne88 reported peculiar effects of tunicin glycerol plasticized starch.88 It consists on a preferential
whiskers on the Tg of the amylopectin-rich fraction depending crystallization of the amorphous polymeric matrix chains
on moisture conditions. For a low loading level (up to 3.2 during cooling at the surface of the whiskers. For glycerol
wt %), a classical plasticization effect of water was reported. plasticized starch based systems, the formation of the
However, an antiplasticization phenomenon was observed transcrystalline zone around the whiskers was assumed to
for higher whiskers content (6.2 wt % and up). These be due to the accumulation of plasticizer in the cellulose/
observations were discussed according to the possible amylopectin interfacial zones improving the ability of
interactions between hydroxyl groups on the cellulosic amylopectin chains to crystallize. These specific crystalliza-
surface and amylopectin, the selective partitioning of glycerol tion conditions were evidenced at high moisture content and
and water in the bulk amylopectin matrix or at the whiskers high whiskers content (>16.7 wt %) by DSC and WAXS. It
surface, and the restriction of amorphous amylopectin chains was displayed through a shoulder on the low-temperature
mobility in the vicinity of the amylopectin crystallite coated side of the melting endotherm and the observation of a new
filler surface. For tunicin whiskers/sorbitol plasticized starch,103 peak in the X-ray diffraction pattern. This transcrystalline
Tg’s were found to increase slightly up to about 15 wt % zone could originate from a glycerol-starch V structure. In
whiskers and to decrease for higher whiskers loading. addition, the inherent restricted mobility of amylopectin
Crystallization of amylopectin chains upon whiskers addition chains was put forward to explain the lower water uptake of
and migration of sorbitol molecules to the amorphous cellulose/starch composites for increasing filler content.
domains were proposed to explain the observed modifica- Noishiki et al.89 studied silk fibroin/tunicin whisker
tions. composites using IR spectroscopy. The silk fibroin was
In semicrystalline matrix based nanocomposites, the melt- prepared from silk cocoon dissolved in LiSCN and com-
ing temperature (Tm) and heat of fusion (∆Hm) of the posites were obtained by solution casting. The authors
thermoplastic matrix were determined from DSC measure- reported a conformational change of fibroin chains from a
ments. X-ray diffraction was also used as a technique to random coil to an ordered structure. This change seems
elucidate the eventual modifications in the crystalline to be related to the highly ordered surface of cellulosic
structure of the matrix after the addition of the whiskers. whiskers.
Recent Research into Cellulosic Whiskers Biomacromolecules, Vol. 6, No. 2, 2005 619
( )
(ii) The second step is the estimation of the modulus of VR - VRc b
the percolating filler network. It is obviously different from ψ ) VR for VR > VRc (10)
the one of individual whiskers and depends on the origin of 1 - VRc
the cellulose, preparation procedure of the whiskers, and
where b ) 0.4124,125 for a 3D network.
obviously the nature and strength of interwhisker interactions.
This percolation approach was found to fit satisfactory
This modulus can be assumed to be that of a paper sheet for
the experimental data, especially for high filler load-
which the hydrogen bonding forces provide the basis of its
ing.84-86,100,102,108 At high temperatures when the polymeric
stiffness. Experimental tensile tests were performed on films
matrix could be assumed to have a negligible stiffness, the
prepared from the evaporation of a suspension of cellulose
calculated stiffness of the composites is simply the product
whiskers in a Teflon mold. For tunicin91,100 and wheat straw
of that of the percolating fillers network by the volume
cellulose whiskers,92 the tensile modulus was around 15 and
fraction of percolating fillers phase
6 GPa, respectively. The apparent tensile modulus of a
cellulose whisker network can be calculated by a 3-D finite Ec ) ψER (11)
elements simulation.118,121 The linking elements were con-
sidered as beams with adjustable stiffness. All of the Figure 7 shows the comparison between experimental and
calculated values were lower than 1 GPa. For link modulus predicted data from both the Halpin-Kardos model and the
values below 1 GPa, the network modulus was found to percolation approach. In this figure, the logarithm of the
increase with increasing whisker concentration and seemed relative storage tensile modulus measured at Tg + 50 K
to increase linearly with the link modulus. For a higher (log E′CTg+50K/E′mTg+50K, where E′CTg+50K and E′mTg+50K
622 Biomacromolecules, Vol. 6, No. 2, 2005 Azizi Samir et al.
during the first stretching cycles indicated the progressive reinforcing agents for low-thickness polymer electrolytes for
damaging of the percolating network, which was initially lithium batteries application.96,99,135-137 For the latter, it is
present. worth noting that the filler content is generally relatively low,
Interfacial Phenomena. DMA experiments can provide below 10 wt%, avoiding significant decrease of the ionic
additional information on the microstructure of heterogeneous conductivity.
materials from the characteristics of the relaxation process
associated to the modulus drop at the glass-rubber transition. 5. Conclusions
It is displayed through the concomitant energy dissipation The present contribution, reporting 10 years worth of work
process giving rise to a maximum of the mechanical loss performed on the processing and behavior of new nanocom-
factor, tan δ, and loss modulus, E′′. In particular, in posite materials of thermoplastic polymers reinforced by
nanocomposite materials, interfacial phenomena are expected polysaccharide microcrystals, can be considered as an effort
to be important owing to the high specific area of the aimed at providing further knowledge to a research area
involved fillers. For tunicin whiskers, the geometrical specific presenting yet a variety of pending issues. It was shown that
area is around 170 m2 g-1, and for a 6 wt % filled composite, the use of high aspect ratio cellulose whiskers induces a
they are of the order of 100 000 cm2 of surfaces per cm3 of mechanical percolation phenomenon leading to outstanding
material.87 Studying tunicin whiskers reinforced PVC com- and unusual mechanical properties through the formation of
posites, Chazeau et al.101,132 claimed the presence of an a rigid filler network. In addition to some practical applica-
immobilized polymeric matrix layer in the vicinity of the tions, the study of such model systems can help to understand
filler. The changes in the shear loss modulus induced by the some physical properties as geometric and mechanical
cellulosic filler were discussed using a mean field approach percolation effects.
and assuming a three-phase system. Cellulose can also be used as a microfibrillar filler, which
Noishiki et al.89 investigated nanocomposite films based is more accessible in terms of available amounts and
on silk fibroin reinforced with tunicin whiskers. It was preparation. The mechanical behavior is then very sensitive
observed that the cellulose surface caused morphological to the cellulose purification level and cellulose microfibrils
modifications of silk fibroin chains. The highly ordered individualization state.
tunicin whiskers surface induced the silk crystallization at The subject generates substantial interests, and the variety
the filler-matrix interface. of possible sources of cellulose for preparing nanocrystals
For tunicin whiskers and PHO based composites, signifi- is broad. Polysaccharide nanocrystals can also be obtained
cant differences were observed depending on the nature of from other abundant renewable resources such as chitin and
the matrix.133 When a semicrystalline PHO was used as the starch by acid hydrolysis. For the former, they appear as
matrix, the molecular mobility of amorphous macromolecular rodlike particles with an aspect ratio related to the origin of
chains was reported to be only slightly affected by the the chitin, whereas for the latter, the nanoparticles consist
presence of cellulose whiskers, owing to a possible trans- of platelets with nanometer scale dimensions. Practical
crystallization phenomenon leading to a coating of the filler applications of such fillers and transition into industrial
with the crystalline phase. In contrast, the flexibility of chains technology require a favorable ratio between the expected
in the surface layer was lowered by the conformational performances of the composite material and its cost. There
restrictions imposed by the cellulose surface, when an are still significant scientific and technological challenges
amorphous PHO was used as the matrix. This phenomenon to take up.
resulted in a broader interphase and in a broadening of the
relaxation process associated to the glass-rubber transition. Acknowledgment. The authors thank the Région Rhône-
A physical model based on a percolation approach, suitable Alpes for financial support.
for the prediction of the reinforcing effect of cellulose
References and Notes
whiskers, was used to predict the mechanical loss angle. The
ratio of the experimental and predicted magnitude of the main (1) Eichhorn, S. J.; Baillie, C. A.; Zafeiropoulos, N.; Mwaikambo, L.
Y.; Ansell, M. P.; Dufresne A.; Entwistle, K. M.; Herrera-Franco,
relaxation process of the composite was used to calculate P. J.; Escamilla, G. C.; Groom, L.; Hugues, M.; Hill, C.; Rials, T.
the thickness of the interphase. G.; Wild, P. M. Review: current international research into cellulosic
Possible Applications. Cellulose crystallites in the form fibres and composites. J. Mater. Sci. 2001, 36, 2107-2131.
(2) Hill, S. Cars that grow on trees. New Scientist. February 1997, 36-
of microcrystalline cellulose are currently utilized widely 39.
industrially. Novel applications in a diverse range of fields (3) Kozlowski, R.; Mieleniak, B. New trends in the utilisation of
were recently presented,134 from iridescent pigments to byproducts of fibre crops residue in pulp and paper industry, building
engineering, automotive industry and interior furnishing. In Proceed-
biomolecular NMR studies. In the nanocomposite field, up ings of the 3rd International Symposium on Natural Polymers and
to now, cellulose whiskers were only used as geometrically Composites (ISNaPol 2000); Mattoso, L., Leao, A., Frollini, E., Eds.;
and structurally well-defined model cellulosic filler and no May 14-17th 2000, Sao Pedro, Brazil; pp 504-510.
practical industrial application was envisaged. This is mainly (4) Leao, A. L.; Rowell, R.; Tavares, N. Application of natural fibers in
automotive industry in Brazil - Thermoforming process. Prasad, P.
ascribed to the duration of the preparation technique. N., Mark, J. E., Kandil, S., Kafafi, Z. H., Eds.; In Science and
However, two important applications may be cited. The first technology of polymers and adVanced materials. Plenum Press: New
one concerns the solidified liquid crystals for optical ap- York, 1998; pp 755-760.
(5) Dahlke, B.; Larbig, H.; Scherzer, H. D.; Poltrock, R. Natural fiber
plications like in security paper (refs 82 and 83). The second reinforced foams based on renewable resources for automotive interior
is related to the use of these whiskers as mechanical applications. J. Cellular Plast. 1998, 34 (4), 361-379.
624 Biomacromolecules, Vol. 6, No. 2, 2005 Azizi Samir et al.
(6) Herrmann, A. S.; Nickel, J.; Riedel, U. Construction materials based (34) Wada, M.; Okano, T.; Sugiyama, J. Synchrotron-radiated X-ray and
upon biologically renewable resources - from components to finished neutron diffraction study of native cellulose. Cellulose 1997, 4 (3),
parts. Polym. Degrad. Stab. 1998, 59 (1-3), 251-261. 221-232.
(7) Okada, A.; Kawasumi, M.; Usuki, A.; Kojima, Y.; Kurauchi, T.; (35) Yamamoto, H.; Horii, F. CPMAS carbon-13 NMR analysis of the
Kamigaito, O. Nylon 6-clay hybrid. Mater. Res. Symp. Proc. 1990, crystal transformation induced for Valonia cellulose by annealing at
171, 45-50. high temperatures. Macromolecules 1993, 26 (6), 1313-1317.
(8) Milewski, J. V. Whiskers. In Concise encyclopedia of composite (36) Sugiyama, J.; Okano, T.; Yamamoto, H.; Horii, F. Transformation
materials; Kelly, A., Ed.; Pergamon: New York, 1994; pp 311- of Valonia cellulose crystals by an alkaline hydrothermal treatment.
314. Macromolecules 1990, 23 (12), 3196-3198.
(9) Nageli, C.; Schwendener, S. Das Mikroscop/Theorie und anwendung (37) Earl, W. L.; VanderHart, D. L. Observations by high-resolution
desselben. 2. Verbesserte auflage. Verlag von Wilheelm Engel- carbon-13 nuclear magnetic resonance of cellulose I related to
mann: Leipzig, 1877. morphology and crystal structure. Macromolecules 1981, 14 (3),
(10) Battista, O. A.; Smith, P. A. U.S. Patent 2,978,446. 570-574.
(11) Battista, O. A.; Smith, P. A. Microcrystalline cellulose. J. Ind. Eng. (38) Ishikawa, A.; Okano, T.; Sugiyama, J. Fine structure and tensile
Chem. 1962, 54 (9), 20-29. properties of ramie fibres in the crystalline form of cellulose I, II,
(12) Battista, O. A. Microcrystal Polymer Science; McGraw-Hill Inc.: IIII and IVI. Polymer 1997, 38 (2), 463-468.
New York, 1975. (39) Fink, H. P.; Philipp, B.; Paul, D.; Serimaa, R.; Paakkari, T. The
(13) De Souza Lima, M. M.; Borsali, R. Rodlike cellulose microcrystals: structure of amorphous cellulose as revealed by wide-angle X-ray
structure, properties and applications. Macromol. Rapid Comm. 2004, scattering. Polymer 1987, 28 (8), 1265-1270.
25, 771-787. (40) Grigoriew, H.; Chmielewski, A. G. Capabilities of X-ray methods
(14) Hon, D. N. S. Cellulose: a random walk along its historical path. in studies of processes of permeation through dense membranes. J.
Cellulose 1994, 1 (1), 1-25. Membr. Sci. 1998, 142 (1), 87-95.
(15) Sjoström, E. Wood chemistry fundamentals and applications; Aca- (41) Sakurada, I.; Nukushina, Y. Experimental determination of the elastic
demic Press: New York, 1993. modulus of crystalline regions in oriented polymers. J. Polym. Sci.
(16) O’Sullivan, A. C. Cellulose: the structure slowly unravels. Cellulose 1962, 57, 651-660.
1997, 4, 173-207. (42) Sarko, A.; Marchessault, R H. Supramolecular structure of polysac-
(17) Meyer, K. H.; Misch, L. L. Positions des atomes dans le nouveau charides. J. Polym. Sci. Polym. Symp. 1969, 28, 317-331.
modèle spatial de la cellulose. HelV. Chim. Acta 1937, 20, 232- (43) Muller, M.; Czihak, C.; Vogl, G.; Fratzl, P.; Schober, H.; Riekel, C.
245. Direct observation of microfibril arrangement in a single native
cellulose fiber by microbeam small-angle X-ray scattering. Macro-
(18) Honjo, G.; Watanabe, M. Examination of cellulose fiber by the low-
molecules 1998, 31 (12), 3953-3957.
temperature specimen method of electron diffraction and electron
(44) Muller, M.; Czihak, C.; Schober, H.; Nishiyama, Y.; Vogl, G. All
microscopy. Nature 1958, 181, 326-328.
disordered regions of native cellulose show common low-frequency
(19) Sarko, A.; Muggli, R. Packing analysis of carbohydrates and
dynamics. Macromolecules 2000, 33 (5), 1834-1840.
polysaccharides. III. Valonia cellulose and cellulose II. Macromol-
(45) Mazeau, K.; Heux, L. Molecular dynamics simulations of bulk native
ecules 1974, 7 (4), 486-494.
crystalline and amorphous structures cellulose. J. Phys. Chem. B 2003,
(20) Gardner, K. H.; Blackwell, J. The structure of native cellulose.
107 (10), 2394-2404.
Biopolymers 1974, 13, 1975-2001.
(46) Battista, O. A.; Coppick, S.; Howsmon, J. A.; Morehead, F. F.; Sisson,
(21) Okano, T.; Koyanagi, A. Structural variation of native cellulose W. A. Level-off degree of polymerization: relation to polyphase
related to its source. Biopolymers 1986, 25 (5), 851-861. structure of cellulose fibers. Ind. Eng. Chem. 1956, 48, 333-335.
(22) Wellard, H. J. Variation in the lattice spacing of cellulose. J. Polym. (47) Marchessault, R. H.; Morehead, F. F.; Koch, J. M. Hydrodynamics
Sci. 1954, 13 (71), 471-476. properties of neutral suspensions of cellulose crystallites as related
(23) Atalla, R. H.; VanderHart, D. L. Native cellulose. A composite of to size and shape. J. Colloid Sci. 1961, 16, 327-344.
two distinct crystalline forms. Science 1984, 223 (4), 283-285. (48) Ranby, B. G. The colloidal properties of cellulose micelles, Discus-
(24) VanderHart, D. L.; Atalla, R. H. Studies of microstructure in native sions Faraday Soc. 1951, 11, 158-164.
celluloses using solid state 13C NMR. Macromolecules 1984, 17 (8), (49) Wise, L. E.; Murphy, M.; D’Addiecco, A. A. Chlorite holocellulose,
1465-1472. its fractionation and bearing on summative wood analysis and on
(25) Sugiyama, J.; Vuong, R.; Chanzy, H. Electron diffraction study of studies on hemicelluloses. Paper Trade J. 1946, 122, 35-43.
the two crystalline phases occurring in native celluloses from an algal (50) Marchessault, R. H.; Morehead, F. F.; Walter, N. M. Liquid crystal
cell wall. Macromolecules 1991, 24 (14), 4168-4175. systems from fibrillar polysaccharides. Nature 1959, 184, 632-633.
(26) Vietor, R. J.; Mazeau, K.; Lakin, M.; Perez, S. A priori crystal (51) Sugiyama, J.; Chanzy, H.; Revol, J. F. On the polarity of cellulose
structure prediction of native cellulose. Biopolymers 2000, 54 (5), in the cell wall of Valonia. Planta 1994, 193, 260-265.
342-354. (52) Revol, J. F.; Godbout, L.; Dong, X. M.; Gray, D. G.; Chanzy, H.;
(27) Belton, P. S.; Tanner, S. F.; Cartier, N.; Chanzy, H. High-resolution Maret, G. Chiral nematic suspensions of cellulose crystallites phase
solid-state carbon-13 nuclear magnetic resonance spectroscopy of separation and magnetic field orientation. Liq. Cryst. 1994, 16 (1),
tunicin, an animal cellulose. Macromolecules 1989, 22 (4), 1615- 127-134.
1617. (53) Revol, J. F.; Bradford, H.; Giasson, J.; Marchessault, R. H.; Gray,
(28) Kono, H.; Yunoki, S.; Shikano, T.; Fujiwara, M.; Erata, T.; Takai, D. G. helicoidal self-ordering of cellulose microfibrils in aqueous
M. CP/MAS 13C NMR study of cellulose and cellulose derivatives. suspension. Int. J. Biol. Macromol. 1992, 14 (3), 170-172.
1. Complete assignment of the CP/MAS 13C NMR spectrum of the (54) Heux, L.; Dinand, E.; Vignon, M. R. Structural Aspects in Ultrathin
native cellulose. J. Am. Chem. Soc. 2002, 124 (25), 7506-7511. Cellulose Microfibrils followed by 13C CP-MAS NMR. Carbohydr.
(29) Nishiyama, Y.; Sugiyama, J.; Chanzy, H.; Langan, P. Crystal structure Polym. 1999, 40 (2), 115-124.
and hydrogen bonding system in cellulose IR from synchrotron X-ray (55) Azizi Samir, M. A. S.; Alloin, F.; Paillet, M.; Dufresne, A. Tangling
and neutron fiber diffraction. J. Am. Chem. Soc. 2003, 125 (47), effect in fibrillated cellulose reinforced nanocomposites. Macromol-
14300-14306. ecules 2004, 37 (11), 4313-4316.
(30) Nishiyama, Y.; Langann, P.; Chanzy, H. Crystal structure and (56) Terech, P.; Chazeau, L.; Cavaillé, J.-Y. A Small-Angle Scattering
hydrogen-bonding system in cellulose Iβ×e2 from synchrotron X-ray Study of Cellulose Whiskers in Aqueous Suspensions. Macromol-
and neutron fiber diffraction. J. Am. Chem. Soc. 2002, 124 (31), ecules 1999, 32 (6), 1872-1875.
9074-9082. (57) Dong, X. M.; Revol, J. F.; Gray, D. G. Effect of microcrystallite
(31) Sugiyama, J.; Persson, J.; Chanzy, H. Combined infrared and electron preparation conditions on the formation of colloid crystals of
diffraction study of the polymorphism of native celluloses. Macro- cellulose. Cellulose 1998, 5 (1), 19-32.
molecules 1991, 24 (9), 2461-2466. (58) Sassi, J. F. Etude ultrastructurale de l’acétylation de la cellulose.
(32) Debzi, E. M.; Chanzy, H.; Sugiyama, J.; Tekely, P.; Excoffier, G. Application à la préparation de nanocomposites. Ph.D. Thesis, Joseph
The IR fIβ transformation of highly crystalline cellulose by Fourier University, Grenoble, France, 1995.
annealing in various mediums. Macromolecules 1991, 24 (26), 6816- (59) Sassi, J. F.; Chanzy, H. Ultrastructural aspects of the acetylation of
6822. cellulose. Cellulose 1995, 2 (2), 111-127.
(33) Horii, F.; Hirai, A.; Kitamura, R. CP/MAS 13C NMR spectra of the (60) Nishiyama, Y.; Langan, P.; Chanzy, H. Preparation of tunicin
crystalline components of native celluloses. Macromolecules 1987, cellulose I-beta samples for X-ray and neutron diffraction. Fibre
20 (9), 2117-2120. Diffract. ReV. 2003, 11, 75-78.
Recent Research into Cellulosic Whiskers Biomacromolecules, Vol. 6, No. 2, 2005 625
(61) Backer, A. A.; Helbert, W.; Sugiyama, J.; Miles, M. J. New Insight (88) Anglès, M. N.; Dufresne, A. Plasticized starch/tunicin whiskers
into Cellulose Structure by Atomic Force Microscopy Shows the IR nanocomposites: 1. Structural analysis. Macromolecules 2000, 33
Crystal Phase at Near-Atomic Resolution. Biophys. J. 2000, 79 (2), (22), 8344-8353.
1139-1145. (89) Noshiki, Y.; Nishiyama, Y.; Wada, M.; Kuga, S.; Magoshi, J.
(62) Baker, A. A.; Helbert, W.; Sugiyama, J.; Miles, M. J. Surface structure Mechanical properties of silk fibroin-microcrystalline cellulose
of native cellulose microcrystals by AFM. Appl. Phys. A 1998, A66, composite films. J. Appl. Polym. Sci. 2002, 86 (13), 3425-3429.
S559-S563. (90) Grunert, M.; Winter, W. T. Nanocomposites of cellulose acetate
(63) Araki, J.; Wada, M.; Kuga, S.; Okano, T. Flow properties of butyrate reinforced with cellulose nanocrystals. J. Polym. EnViron.
microcrystalline cellulose suspension prepared by acid treatment of 2002, 10 (1-2), 27-30.
native cellulose. Colloids Surf. A 1998, 142 (1), 75-82. (91) Favier, F.; Chanzy, H.; Cavaillé, J.-Y. Polymer nanocomposites
(64) Araki, J.; Wada, M.; Kuga, S. Steric stabilization of a cellulose reinforced by cellulose whiskers. Macromolecules 1995, 28 (18),
microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 6365-6367.
2001, 17 (1), 21-27. (92) Helbert, W.; Cavaillé, J.-Y.; Dufresne, A. Thermoplastic nanocom-
(65) Isogai, A.; Kato, Y. Preparation of Polyuronic Acid from Cellulose posites filled with wheat straw cellulose whiskers. Part I: processing
by TEMPO-mediated Oxidation. Cellulose 1998, 5 (3), 153-164. and mechanical behavior. Polym. Compos. 1996, 17 (4), 604-611.
(66) Araki, J.; Wada, M.; Kuga, S.; Okano, T. Influence of surface charges (93) Chazeau, L.; Cavaillé, J. Y.; Canova, G.; Dendievel, R.; Boutherin,
on viscosity behavior of cellulose microcrystal suspension. J. Wood B. Viscoelastic properties of plasticized PVC reinforced with cellulose
Sci. 1999, 45 (3), 258-261. whiskers. J. Appl. Polym. Sci. 1999, 71 (11), 1797-1808.
(67) Bonini, C.; Heux, L. French Patent FR 99.07493. (94) Bonini, C. Mise en évidence du role des interactions fibre/fibre et
(68) Heux, L.; Chauve, G.; Bonini, C. Nonflocculating and chiral-nematic fibre/matrice dans des nanocomposites à renfort cellulosique et
self-ordering of cellulose microcrystals suspensions in nonpolar matrice apolaire (atactique et isotactique). Ph.D. Thesis, Joseph
solvents. Langmuir 2000, 16 (21), 8210-8212. Fourier University, Grenoble, France, 2000.
(69) Goussé, C.; Chanzy, H.; Exoffier, G.; Soubeyand, L.; Fleury, E. Stable (95) Matos Ruiz, M.; Cavaillé, J.-Y.; Dufresne, A.; Graillat, C.; Gérard,
suspensions of partially silylated cellulose whiskers dispersed in J.-F. New waterborne epoxy coatings based on cellulose nanofillers.
ordanic solvents. Polymer 2002, 43 (9), 2645-2651. Macromol. Symp. 2001, 169, 211-222.
(70) Azizi Samir, M. A. S.; Alloin, F.; Sanchez, J.-Y.; El Kissi, N.; (96) Cavaillé, J. Y.; Dufresne, A.; Paillet, M.; Azizi Samir, M. A. S.;
Dufresne, A. Preparation of cellulose whiskers reinforced nanocom- Alloin, F.; Sanchez, J. Y. French Patent FR2841255.
posites from an organic medium suspension. Macromolecules 2004, (97) Grunert, M.; Winter, W. T. Cellulose nanocrystal reinforced acetate
37 (4), 1386-1393. butyrate nanocomposites. Polym. Mater. Sci. Eng. 2002, 86, 367-
(71) Ebeling, T.; Paillet, M.; Borsali, R.; Diat, O.; Dufresne, A.; Cavaillé, 368.
J.-Y.; Chanzy, H. Shear-induced orientation phenomena in suspen- (98) Gopalan, Nair K.; Dufresne, A.; Gandini, A.; Belgacem, M. N. Crab
sions of cellulose microcrystals, revealed by small-angle X-ray shells chitin whiskers reinforced natural rubber nanocomposites. 3.
scattering. Langmuir 1999, 15 (19), 6123-6126. Effect of chemical modification of chitin whiskers. Biomacromol-
(72) de Souza Lima, M. M.; Borsali, R. Static and dynamic light scattering ecules 2003, 4 (6), 1835-1842.
from polyelectrolyte microcrystal cellulose. Langmuir 2002, 18 (4), (99) Azizi Samir, M. A. S.; Alloin, F.; Sanchez, J.-Y.; Dufresne, A. Cross-
992-996. linked nanocomposite polymer electrolytes reinforced with cellulose
whiskers. Macromolecules 2004, 37 (13), 4839-4844.
(73) Onsager, L. The effects of shapes on the interaction of colloidal
(100) Favier, V. Etude de nouveaux matériaux composites obtenus à partir
particles. Ann. N. Y. Acad Sci 1949, 51, 627-659.
de latex filmogènes et de whiskers de cellulose: effet de percolation
(74) Dong, X. M.; Kimura, T.; Revol, J. F.; Gray, D. G. Effects of ionic
mécanique. Ph.D. Thesis, Joseph Fourier University, Grenoble,
strength on the isotropic-chiral nematic phase transition of suspensions
France, 1995.
of cellulose crystallites. Langmuir 1996, 12 (8), 2076-2082.
(101) Chazeau, L.; Etude de nanocomposites à renfort cellulosique et
(75) Stroobants, A.; Lekkerkerker, H. N. W.; Odijk, T. Effect of
matrice poly(chlorure de vinyle): mise en œuvre, étude structurale,
electrostatic interaction on the liquid crystal phase transition in
comportement mécanique. Ph.D. Thesis, Joseph Fourier University,
solutions of rodlike polyelectrolytes. Macromolecules 1986, 19 (8),
Grenoble, France, 1998.
2232-2238.
(102) Hajji, P.; Cavaillé, J. Y.; Favier, V.; Gauthier, C.; Vigier, G. Tensile
(76) Speranza, A.; Sollich, P. Simplified Onsager theory for isotropic- behavior of nanocomposites from latex and cellulose whiskers. Polym
nematic phase equilibria of length polydisperse hard rods. J. Chem. Compos. 1996, 17 (4), 612-619.
Phys. 2002, 117 (11), 5421-5436. (103) Mathew, A. P.; Dufresne, A. Morphological investigation of nano-
(77) Dong, X. M.; Gray, D. G. Effect of counterions on ordered phase composites from sorbitol plasticized starch and tunicin whiskers.
formation in suspensions of charged rodlike cellulose crystallites. Biomacromolecules 2002, 3 (3), 609-617.
Langmuir 1997, 13 (8), 2404-2409. (104) Azizi Samir, M. A. S.; Alloin, F.; Sanchez, J.-Y.; Dufresne, A.
(78) Bercea, M.; Navard, P. Shear dynamics of aqueous suspensions of Cellulose nanocrystals reinforced poly(oxyethylene). Polymer 2004,
cellulose whiskers. Macromolecules 2000, 33 (16), 6011-6016. 45 (12), 4033-4041.
(79) Orts, W. J.; Godbout, L.; Marchessault, R. H.; Revol, J. F. Enhanced (105) Anglès, M. N.; Dufresne, A. Plasticized starch/tunicin whiskers
ordering of liquid crystalline suspensions of cellulose microfibrils: nanocomposites: 2. Mechanical behavior. Macromolecules 2001, 34
a small angle neutron scattering study. Macromolecules 1998, 31 (9), 2921-2931.
(17), 5717-5725. (106) Chazeau, L.; Cavaillé, J. Y.; Terech, P. Mechanical behavior above
(80) Revol, J. F.; Marchessault, R. H. In vitro chiral nematic ordering of Tg of a plasticized PVC reinforced with cellulose whiskers, a SANS
chitin crystallites. Int. J. Biol. Macromol. 1993, 15 (6), 329-335. structural study. Polymer 1999, 40 (19), 5333-5344.
(81) Sugiyama, J.; Chanzy, H.; Maret, G. Orientation of cellulose (107) Eichhorn, S. J.; Young, R. J. The Young’s modulus of a microcrys-
microcrystals by strong magnetic fields. Macromolecules 1992, 25 talline cellulose. Cellulose 2001, 8 (3), 197-207.
(16), 4232-4234. (108) Dufresne, A.; Cavaillé, J.-Y.; Helbert, W. Thermoplastic nanocom-
(82) Revol, J. F.; Godbout, L.; Gray, D. Solid films of cellulose with posites filled with wheat straw cellulose whiskers. Part II: effect of
chiral nematic order and optically variable properties. PPR 1331 processing and modeling. Polym. Compos. 1997, 18 (2), 198-210.
report, 1998. (109) Morin, A.; Dufresne, A. Nanocomposites of chitin whiskers from
(83) Revol, J. F.; Godbout, L.; Gray, D. U.S. Patent 5,629,055. Riftia tubes and poly(caprolactone). Macromolecules 2002, 35 (6),
(84) Favier, V.; Canova, G. R.; Cavaillé, J.-Y.; Chanzy, H.; Dufresne, 2190-2199.
A.; Gauthier, C. Nanocomposites materials from latex and cellulose (110) Gopalan Nair, K.; Dufresne, A. Crab shells chitin whiskers reinforced
whiskers. Polym. AdV. Technol. 1995, 6, 351-355. natural rubber nanocomposites. 1. Processing and swelling behavior.
(85) Dubief, D.; Samain, E.; Dufresne, A. Polysaccharide microcrystals Biomacromolecules 2003, 4 (3), 657-665.
reinforced amorphous poly(β-hydroxyoctanoate) nanocomposite ma- (111) Halpin, J C.; Kardos, J. L. Moduli of crystalline polymers employing
terials. Macromolecules 1999, 32 (18), 5765-5771. composite theory. J. Appl. Phys. 1972, 43 (5), 2235-2241.
(86) Dufresne, A.; Kellerhals, M. B.; Witholt, B. Transcrystallization in (112) Tsai, S. W.; Halpin, J. C.; Pagano, N. J. Composite materials
mcl-PHAs/cellulose whiskers composites. Macromolecules 1999, 32 workshop. Technomic Publishing Co.: New York, 1968; pp 233-
(22), 7396-7401. 253.
(87) Dufresne A. Interfacial phenomena in nanocomposites based on (113) Berglund, L. Private communication.
polysaccharide nanocrystals. Compos. Interfaces 2003, 10 (4-5), (114) Hammersley, J. M. percolation processes II The connective constant.
369-388. Proc. Cambridge Philos. Soc. 1957, 53, 642-645.
626 Biomacromolecules, Vol. 6, No. 2, 2005 Azizi Samir et al.
(115) Balberg, I.; Binenbaum, M. Computer study of the percolation (127) Nishino, T.; Akano, K.; Nakamae, K. Elastic modulus of the
threshold in a two-dimensional anisotropic system of conducting crystalline regions of cellulose polymorphs. J. Polym. Sci., B: Polym.
sticks. Phys. ReV. B 1983, 28 (7), 3799-3812. Phys. 1995, 33 (11), 1647-1651.
(116) Balberg, I.; Binenbaum, M. Percolation thresholds in the three- (128) Tashiro, K.; Kobayashi, M. Calculation of crystallite modulus of
dimensional sticks system. Phys. ReV. Lett. 1984, 52 (17), 1465- native cellulose. Polym. Bull. 1985, 14, 213-218.
1468. (129) Kroon-Batenburg, L. M. J.; Kroon, J.; Northolt, M. G. Chain modulus
(117) de Gennes, P. G. On a relaxation between percolation theory and and intramolecular hydrogen bonding in native and regenerated
the eleasticity of gels. J. Phys. Lett. 1976, 37, L1-2. cellulose fibers. Polym. Commun. 1986, 27 (10), 290-292.
(118) Favier, V.; Dendievel, R.; Canova, G.; Cavaillé, J. Y.; Gilormini, P. (130) Tashiro, K.; Kobayashi, M. Theoretical evaluation of three-
Simulation and modelling of 3D percolating structures: case of latex dimensional elastic constants of native and regenerated celluloses:
matrix reinforced by a network of cellulose fibers. Acta Mater. 1997, role of hydrogen bonds. Polymer 1991, 32 (8), 1516-1526.
45 (4), 1557-1565. (131) Gopalan Nair, K.; Dufresne, A. Crab shells chitin whiskers reinforced
(119) Flandin, L.; Bidan, G.; Brechet, Y.; Cavaillé, J. Y. New nanocom- natural rubber nanocomposites. 2. Mechanical behavior. Biomacro-
posite materials made of an insulating matrix and conducting fillers: molecules 2003, 4 (3), 666-674.
processing and properties. Polym. Compos. 2000, 21 (2), 165- (132) Chazeau, L.; Paillet, M.; Cavaillé, J. Y. Plasticized PVC reinforced
174. with cellulose whiskers: 1- linear viscoelastic behavior analyzed
(120) Nan, C. W. Physics of inhomogeneous inorganic materials. Prog. through the quasi point defect′ theory. J. Polym. Sci., B: Polym.
Mater. Sci. 1993, 37 (1), 1-116. Phys. 1999, 37 (16), 2151-2164.
(121) Bréchet, Y.; Cavaillé, J. Y.; Chabert, E.; Chazeau, L.; Dendievel, (133) Dufresne, A. Dynamic mechanical analysis of the interphase in
R.; Flandin, L.; Gauthier, C. Polymer Based Nanocomposites: Effect bacterial polyester/cellulose whiskers natural composites. Compos.
of Filler-Filler and Filler-Matrix Interactions. AdV. Eng. Mater. 2001, Interfaces 2000, 7 (1), 53-67.
3 (8), 571-577. (134) Fleming, K.; Gray, D. G.; Matthews, S. Cellulose crystallites. Chem.
(122) Ouali, N.; Cavaillé, J.-Y.; Pérez, J. Elastic, viscoelastic and plastic Eur. J. 2001, 7 (9), 1831-1835.
behavior of multiphase polymer blends. Plast. Rubber Compos. (135) Azizi Samir, M. A. S.; Alloin, F.; Gorecki, W.; Sanchez, J.-Y.;
Process Appl. 1991, 16 (1), 55-60. Dufresne, A. Nanocomposite polymer electrolytes based on poly-
(123) Takayanagi, M.; Uemura, S.; Minami, S. Application of equivalent (oxyethylene) and cellulose nanocrystals. J. Phys. Chem. B 2004,
model method to dynamic rheo-optical properties of crystalline 108 (30), 10845-10852.
polymer. J. Polym. Sci. C 1964, 5, 113-122. (136) Azizi Samir, M. A. S.; Montero Mateos, A.; Alloin, F.; Sanchez,
(124) Stauffer, D. Introduction to Percolation Theory; Taylor and Fran- J.-Y.; Dufresne, A. Plasticized nanocomposite polymer electrolytes
cis: London, 1985. based on poly(oxyethylene) and cellulose whiskers. Electrochem. Acta
(125) De Gennes, P.-G. Scaling Concepts in Polymer Physics; Cornell 2004, 49, 4667-4677.
University Press: Ithaca, NY, 1979. (137) Schroers, M.; Kokil, A.; Weder, C. Solid polymer electrolytes based
(126) Matsuo, M.; Sawatari, C.; Iwai, Y.; Ozaki, F. Effect of orientation on nanocomposites of ethylene oxide-epichlorohydrin copolymers
distribution and crystallinity on the measurement by X-ray diffraction and cellulose whiskers. J. Appl. Polym. Sci. 2004, 93, 2883-2888.
of the crystal lattice moduli of cellulose I and II. Macromolecules
1990, 23 (13), 3266-3275. BM0493685