612 Biomacromolecules 2005, 6, 612-626

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.

1. Introduction • renewable nature

Natural fibers are pervasive throughout the world in plants
such as grasses, reeds, stalks, and woody vegetation. They
are also referred to as cellulosic fibers, related to the main
chemical component cellulose, or as lignocellulosic fibers,
since the fibers usually often also contain a natural polyphe-
nolic polymer, lignin, in their structure. Results suggest that
these agro-based fibers are a viable alternative to inorganic/
mineral based reinforcing fibers in commodity fiber-
thermoplastic composite materials as long as the right
processing conditions are used and for applications where
higher water absorption may be not so critical. The use of
lignocellulosic fibers derived from annually renewable
resources as a reinforcing phase in polymeric matrix
composites provides positive environmental benefits with
respect to ultimate disposability and raw material use.1
Compared to inorganic fillers, the main advantages of
lignocellulosics are listed below:
* To whom correspondence should be addressed. E-mail: Alain.Dufresne@
efpg.inpg.fr. Fax: 33 (4) 76 82 69 33. Tel: 33 (4) 76 82 69 95.
† CERMAV-CNRS.
‡ LEPMI-INPG.
§ EFPG-INPG.
⊥ Present address: Division of Lightweight Structures, Department of
Aeronautical and Vehicle Engineering, Royal Institute of Technology,
SE-10044 Stockholm, Sweden.
10.1021/bm0493685 CCC: $30.25
Published on Web 01/21/2005
• wide variety of fillers available throughout the world
• nonfood agricultural based economy
• low energy consumption
• low cost
• low density
• high specific strength and modulus
• high sound attenuation of lignocellulosic based com-
posites
• comparatively easy processability due to their nonabra-
sive nature, which allows high filling levels, resulting in
significant cost savings
• relatively reactive surface, which can be used for grafting
specific groups.
In addition, the recycling by combustion of lignocellulosics
filled composites is easier in comparison with inorganic
fillers systems. Therefore, the possibility of using lignocel-
lulosic fillers in the plastic industry has received considerable
interest. Automotive applications display strong promise for
natural fiber reinforcements.2-5 Potential applications of agro-
fiber based composites in railways, aircraft, irrigation
systems, furniture industries, and sports and leisure items
are currently being researched.6
Despite these attractive properties, lignocellulosic fillers
are used only to a limited extent in industrial practice due
© 2005 American Chemical Society
Recent Research into Cellulosic Whiskers
to difficulties associated with surface interactions. The
inherent polar and hydrophilic nature of polysaccharides and
the nonpolar characteristics of most of the thermoplastics
result in difficulties in compounding the filler and the matrix
and, therefore, in achieving acceptable dispersion levels,
which results in inefficient composites. This hydrogen
bonding is best exemplified in paper where these secondary
interactions provide the basis of its mechanical strength.
Moreover, the processing temperature of composites is
restricted to about 200 °C because lignocellulosic materials
start to degrade near 230 °C. This limits the type of
thermoplastics that can be used in association with polysac-
charide fillers to commodity plastics such as polyethylene,
polypropylene, poly(vinyl chloride), and polystyrene. How-
ever, it is worth noting that these lower-price plastics
constitute about 70% of the total amount of thermoplastics
consumed by the plastics industry.
Another drawback of lignocellulosic fillers is their high
moisture absorption and the resulting swelling and decrease
in mechanical properties. Moisture absorbance and corre-
sponding dimensional changes can be largely prevented if
the hydrophilic filler is thoroughly encapsulated in a
hydrophobic polymer matrix and there is good adhesion
between both components. However, if the adhesion level
between the filler and the matrix is not good enough, a
diffusion pathway can preexist or can be created under
mechanical solicitation. The existence of such a pathway is
also related to the filler connection and therefore to its
percolation threshold.
Stable aqueous suspensions of cellulose monocrystals can
be prepared by acid hydrolysis of the biomass. Throughout
the paper, different descriptors of the cellulosic colloidal
particles will be used, including whiskers, monocrystals,
nanocrystals, microcrystalline cellulose, and cellulose crys-
tallites. Depending on the source, these nanocrystals offer a
wide variety of aspect ratios (L/d, L being the length and d
the diameter), from almost particulate fillers (L/d ) 1) to
about 100. These suspensions display a colloidal behavior.
They can be used to process nanocomposite materials using
a polymer as the matrix. Nanocomposites are a relatively
new class of composites that exhibit ultrafine phase dimen-
sions of 1-1000 nm. Because of the nanometric size effect,
these composites have some unique outstanding properties
with respect to their conventional microcomposite counter-
parts. The first study was published in 1990 by researchers
at Toyota (Japan) and dealt with montmorillonite clay
reinforced polyamide 6.7 Thermoplastic pellets were obtained
by polymerizing caprolactam with clay.
As most of the present-day polymers used for preparing
nanocomposites are synthetic materials, their processability,
biocompatibility, and biodegradability are much more limited
than those of natural polymers. Compared to the studies in
the field of conventional microcomposites and nanocom-
posites based on synthetic nonbiodegradable materials, only
limited work has been reported in the area of bionanocom-
posites. Another advantage of the natural nanofillers is their
availability and their resulting lower cost in comparison to
synthetic nanofillers.
Biomacromolecules, Vol. 6, No. 2, 2005 613
As reported above, one of the restrictions in lignocellulosic
based systems is the difficulty in achieving acceptable
dispersion levels of the filler within the polymeric matrix.
An alternative way to palliate this restriction consists of using
a latex, i.e., an aqueous suspension of polymer particles, or
a water soluble polymer to form the matrix. From the former,
it is well-known that emulsion polymerization can lead to
materials easily processed, either by film casting techniques
(water evaporation for paint applications for example) or by
freeze-drying (or more simply by flocculation) followed by
classical extrusion process. As a matter of fact, different
monomers can be statistically copolymerized to adjust the
glass-rubber transition temperature at a given value. More
generally, it is also possible to mix different types of water
suspensions including some polymer lattices and organic or
inorganic stabilized suspensions. We will see that, in addition
to some practical applications, the study of these systems
can help us to understand some physical properties as
geometric and mechanical percolation effects.
Whiskers are fibers which have been grown under
controlled conditions that lead to the formation of high-purity
single crystals.8 They constitute a generic class of materials
having mechanical strengths equivalent to the binding forces
of adjacent atoms. The resultant highly ordered structure
produces not only unusually high strengths but also signifi-
cant changes in electrical, optical, magnetic, ferromagnetic,
dielectric, conductive, and even superconductive properties.
The tensile strength properties of whiskers are far above those
of the current high-volume content reinforcements and allow
the processing of the highest attainable composite strengths.
The first references to the existence of definite crystalline
zones interposed in the amorphous structure of cellulose
materials were made by Nageli and Schwendener,9 who in
1877 already confirmed the optical anisotropy of vegetable
products both in cell walls and in fibers.
Commercial forms of microcrystalline cellulose as stable
thixotropic-gel systems involving aqueous colloidal disper-
sions consist of a hydrolyzed level-off degree of polymer-
ization (DP) at high-solids concentration. They were first
described by Battista and Smith in a patent10 issued in 1961.
This patent, along with a later publication11 and book,12
described a combination of two characteristic prerequisites
for producing colloidal phenomena from a fibrous high
polymer such as cellulose: (i) a controlled chemical pre-
treatment to destroy the molecular bonds whereby micro-
crystals are hinged together in a network structure and (ii)
an appropriate use of mechanical energy to disperse a
sufficient amount of the unhinged microcrystals in the
aqueous phase to produce the characteristic rheological
behavior and the smooth fat-like spreadability of the resulting
colloidal microcrystalline cellulose gels. It was clearly
demonstrated that stable gel systems were obtained only
when the mechanical energy was introduced into an aqueous
suspension of level-off DP cellulose in which the total solids
concentration was of the order of 5% or more and only if
the mechanical energy was severe enough to liberate a
minimum number of monocrystals to make a stable gel
possible.
614 Biomacromolecules, Vol. 6, No. 2, 2005
Figure 1. Chemical structure of cellulose.
The present paper is to provide a review of the literature
on cellulose whiskers, their properties, and their possible use
as a reinforcing phase in nanocomposite applications. Its
scope is mainly limited to the mechanical effects of
incorporating cellulose whiskers in polymer composites since
the phase separation phenomena and chiral nematic texture
of cellulose whisker suspensions was recently reviewed.13
2. Structure and Polymorphism of Cellulose:
Cellulose, the most widespread biopolymer, is known to
occur in a wide variety of living species from the worlds of
plants, animals, and bacteria as well as some amoebas. In
many of these, the main function of cellulose is to act as a
reinforcement material. This is, for instance, the case in plant
cells where the osmotic pressure of the inner cell has to be
counterbalanced by the tight winding of the cellulose within
the cell wall. It has been estimated that globally between
1010 and 1011 tons of cellulose are synthesized and also
destroyed each year.14
The structure and the morphology of cellulose have been
the subject of a large amount of work. It is a polydisperse
linear polymer of poly-β(1,4)-D-glucose residues (Figure 1).
The monomers are linked together by condensation such that
the sugar rings are joined by glycosidic oxygen bridges. In
nature, cellulose chains have a DP of approximately 10 000
glucopyranose units in wood cellulose and 15 000 in native
cellulose cotton.15 However, chain lengths of such large,
insoluble molecules are difficult to measure, due to enzymatic
and mechanical degradation which may occur during analy-
sis. A specific characteristic of lignocellulosic compounds
is the high density of hydroxyl groups which provides the
hydrophilic nature of these materials.
Cellulose displays six different polymorphs, namely I, II,
IIII, IIIII, IVI, and IVII with the possibility of conversion from
one form to another.16 For a long time, native cellulose
(cellulose I) attracted the interest of a large scientific
community in attempt to elucidate its crystal structure. In
1934, Meyer and Misch17 proposed a monoclinic unit cell
containing two antiparallel chains as a model for the cellulose
crystal. Different models were proposed latter because of
the Meyer-Misch model insufficiency to explain experi-
mental data obtained by other teams.18-20 The most important
factors that can explain the historic controversy in the
cellulose crystal structure are the dependence of the cellulose
structure on the origin of investigated cellulose and the
influence of the experimental investigation conditions.21,22
From cross polarization/magic angle spinning 13C nuclear
magnetic resonance (13C CP/MAS NMR) experiments, Attala
and VanderHart23,24 proposed that native cellulose was a
composite of two crystalline forms, namely a one-chain
triclinic structure IR and a two-chain monoclinic structure
Iβ. This model was supported by electronic diffraction study
of native cellulose from algal cell walls25 and by computa-
Azizi Samir et al.
Figure 2. Modified Frey-Wyssling model (Sarko and Marchessault,
1989)42 showing the cross-sectional structure of a cellulose microfibril
composed of six elementary fibrils 40 × 40 Å in width.
tional prediction.26 The fractions of IR and Iβ phases in any
native cellulose samples depend on the origin of the cellulose.
The IR phase predominates for example in Valonia cellulose,
whereas the Iβ fraction prevails in cotton cellulose and it is
close to unity in tunicin (the cellulose from tunicate,27 a sea
animal). Details of the crystalline structure of these two forms
were reported by Kono et al.28 using 13C NMR technique
and by Nishiyama et al.29,30 using synchrotron X-ray and
neutron fiber diffraction. The estimation of the phase’s
composition of native cellulose is possible using different
techniques such as FT-IR,31 13C NMR,32,33 and synchrotron-
radiated X-ray diffraction.34 The IR phase is a meta-stable
form which can be converted to the more stable Iβ form by
annealing in a different medium.35,36
In addition to the crystalline phases, native cellulose
contains disordered domains which can be considered like
amorphous. Native cellulose may be assigned to a semicrys-
talline fibrillar material. The presence of disordered phases
was supported by experimental results from 13C CP/MAS/
NMR,37 tensile tests of cellulose fibers,38 and wide-angle
(WAXS)39 and small-angle X-ray scattering (SAXS).40
Cellulose chains are biosynthesized by enzymes, deposited
in a continuous fashion and aggregate to form microfibrils,
long threadlike bundles of molecules stabilized laterally by
hydrogen bonds between hydroxyl groups and oxygens of
adjacent molecules. Thus, all of the chains in one microfibril
would have to be elongated during biosynthesis at the same
rate. This extended chain conformation and microfibrillar
morphology result in a significant load-carrying capability.
Depending on their origin, the microfibril diameters range
from about 2 to 20 nm for lengths that can reach several
tens of microns. As they are devoid of chain folding and
contain only a small number of defects, each microfibril can
be considered as a string of cellulose crystals, linked along
the microfibril by amorphous domains and having a modulus
close to that of the perfect crystal of native cellulose
(estimated to be around 150 GPa41) and a strength that should
be in the order of 10 GPa. This modulus value is similar to
that of aramid fibers (Kevlar). Microfibrils aggregate further
to form cellulose fibers (Figure 2).42 Therefore, natural fibers
are themselves composite materials. They result from the
assembling of microfibrils embedded in a matrix mainly
composed of lignin.
However, discussion about the nature of the amorphous
phases and their role in the final morphology of native
cellulose is not yet closed. Using SAXS experiments, Muller
Recent Research into Cellulosic Whiskers Biomacromolecules, Vol. 6, No. 2, 2005 615

et al.43 reported the parallel alignment of cellulose mi-

crofibrils to the fiber axis. Results from inelastic neutron
scattering experiments44 suggest that the major part of the
disordered chains can be attributed to surface molecules of
the microfibrils. However, these disordered chains retain a
preferential orientation parallel to the microfiber axis. A
molecular model of amorphous cellulose phase was recently
proposed,45 and some physical properties such as density and
glass transition temperature were estimated. However, im-
portant work is necessary for the future comprehension of
properties of surface disordered phase in native cellulose.

3. Preparation of Cellulosic Whiskers Suspensions and

Their Properties
The amorphous regions act as structural defects and are
responsible for the transverse cleavage of the microfibrils
into short monocrystals under acid hydrolysis.46,47 This
procedure can be used to prepare highly crystalline particles
called microcrystalline cellulose (MCC).48 The preparation
of such colloidal aqueous suspensions of cellulosic whiskers
is described in detail elsewhere.49,50 Under controlled condi-
tions, this transformation consists of the disruption of
amorphous regions surrounding and embedded within cel-
lulose microfibrils while leaving the microcrystalline seg-
ments intact. It is ascribed to the faster hydrolysis kinetics
of amorphous domains compared to crystalline ones. MCC
is a naturally occurring substance, and it has proven to be
stable and physiologically inert. This material (a well-known
commercial name is Avicel) presents a high potential for
application in pharmaceutical (tablet binder), food (rheology-
control agent), paper, and composites manufacturing.
MCC consists generally of a stiff rodlike particle called
whiskers. Geometrical characteristics of cellulose whiskers
depend on the origin of cellulose microfibrils and acid
hydrolysis process conditions such as time, temperature, and Figure 3. Transmission electron micrograph from a dilute suspension
purity of materials. The most studied cellulose sources were: of hydrolyzed (a) cotton, (b) sugar-beet pulp and (c) tunicin.
valonia,51 cotton,52 wood pulp,53 and sugar-beet pulp.54,55
Figure 3 shows transmission electron micrographs (TEM)
obtained from dilute suspensions of cotton, sugar-beet pulp,
and tunicin (the cellulose extracted from tunicate) whiskers.
The length and lateral dimension are around 200 nm and 50
Å and 1 µm and 150 Å for cotton and tunicin whiskers,
respectively. Terech et al.56 used small-angle (neutron and
X-ray) scattering techniques to determine the precise shape
of tunicin whiskers. They demonstrated that the cross-
sectional shape of these rigid whiskers was rectangular with Figure 4. Photograph of an aqueous suspension of tunicin whiskers
observed between cross nicols, showing the formation of birefringent
a calculated value close to 88 × 182 Å. domains.
Dong et al.57 studied the effect of preparation conditions
(time, temperature, and ultrasound treatment) on the resulting depends on the dimensions of the dispersed particles, their
cellulose microcrystals structure from sulfuric acid hydrolysis size polydispersity and surface charge. The use of sulfuric
of cotton fiber. They reported a decrease in MCC length and acid for cellulose whiskers preparation leads to more stable
an increase in their surface charge with prolonged hydrolysis whiskers aqueous suspension than that prepared using
time. Characterization of cellulose whiskers were performed hydrochloric acid.63 Indeed, the H2SO4-prepared whiskers
using different techniques such as transmission electron present a negatively charged surface, whereas the HCl-
microscopy (TEM),57-59 X-ray and neutron diffraction,60 prepared whiskers are not charged. Another way to achieve
NMR,54,28 and atomic force microscopy (AFM).61,62 charged whiskers consists of the oxidation of the whiskers
MCC is insoluble in common solvents. However, it leads surface64,65 or the post-sulfation of HCl-prepared MCC.66
to the formation of colloidal suspensions when suspended The aqueous suspensions stability of these surface charged
in water (Figure 4). The stability of these suspensions whiskers has an electrostatic origin. Dispersion of MCC in
616 Biomacromolecules, Vol. 6, No. 2, 2005
low polarity solvents was made possible recently thanks to
coating or chemical modification of the MCC surface.
Coating of cotton and tunicin whiskers by a surfactant such
as Beycostat NA (BNA) was found to lead to stable
suspensions in toluene and cyclohexane.67,68 Goussé et al.69
stabilized tunicin microcrystals in tetrahydrofuran (THF) by
a partial silylation of their surface. Araki et al.64 prepared
original sterically stable aqueous and nonaqueous MCC
suspensions by grafting monoamino oligooxyethylene mono-
methyl ether at the MCC surface using a carboxylation-
amidation procedure. In a recent publication,70 we have
shown that it is possible to obtain stable whiskers suspensions
in dimethylformamide (DMF) without either addition of a
surfactant or any chemical modification. This should allow
avoiding the use of water as the solvent for composites
polymer electrolytes processing.
In 1959, Marchessault et al.50 reported the birefringent
character of acid-treated cellulose and chitin crystallites. The
birefringence of MCC aqueous suspensions can be observed
through a pair of cross-nicols. This birefringence results from
two origins: (i) a structural form anisotropy of cellulose
(∆n ≈ 0.05) and (ii) a flow anisotropy resulting from
alignment of MCC under flow generally operated before
observation. Shear induced alignment of cotton whiskers in
colloidal aqueous suspension was studied by Ebeling et al.71
using SAXS experiments. They demonstrated that this
alignment is shear rate-dependent, and it is completely
reversible. They suggest the presence of planar domains of
randomly oriented microcrystals which align at low shear
rates and are broken up at higher shear rates enabling
alignment of the individual whiskers. The whiskers appeared
to be randomly aligned prior to shearing and are horizontally
aligned along the shear direction when the shear rate exceeds
5 s-1. Ordering of diluted suspensions of cellulose whiskers
was evidenced using static and dynamic light scattering by
de Souza Lima and Borsali.72 These authors observed
numerous peaks in the scattered intensity, which were
interpreted in terms of electrostatic repulsive interactions
between whiskers. These interactions are of long-range order,
and the arrangement of whiskers was supposed to be in
cylindrical/hexagonal packing. Addition of salt to the
suspension induces destruction of this order and leads to
whiskers flocculation, demonstrating the role of the electro-
static interactions between whiskers to control both stability
and order.
As predict by Onsager,73 the cellulose whiskers can
undergo an orientational disorder-order phase transition
from a disordered isotropic phase to an orientationally
ordered phase. Whiskers point with equal probability in every
direction in the isotropic phase. However, they cluster around
a preferred direction in the anisotropic phase. Suspensions
divided in isotropic and anisotropic phases when a critical
concentration was reached.74 The phase transition depends
on the geometrical axial ratio of whiskers,73 their surface
charge,74,75 and their length polydispersity.76 Dong et al.77
reported an increase in the critical concentration at the phase
transition in the presence of counterions. The latter influence
also the stability of the cellulose whisker suspensions and
modify the temperature dependence of the phase separation.
Azizi Samir et al.
Cellulose whiskers are interesting model systems for the
study of shear dynamics of rigid rods in aqueous suspension.
Bercea and Navard78 reported the rheological comportment
of tunicin whiskers aqueous suspensions. They distinguished
two different behaviors according to whiskers concentration.
In the isotropic phase (c < 0.8 wt %) where whiskers are
randomly oriented, the decrease of the viscosity in relation
to shear rate increase can be explained by whiskers align-
ment. In the anisotropic phases (c > 0.8 wt %), the behavior
is similar to that of liquid crystal polymers with a weak shear
thinning region surrounded by two others shear thinning
regions.
Araki et al.63 studying H2SO4 and HCl-prepared cellulose
whiskers demonstrated that the charge of the surface is one
of the main parameter which control the interwhisker
interactions and so the rheological behavior of their suspen-
sions. The suspensions of charged whiskers showed no time
dependence in viscosity. However, the uncharged HCl-
prepared whisker suspensions were thixotropic at concentra-
tions above 0.5 wt % and antithixotropic below 0.3 wt %.
One of the most interesting characteristic of MCC aqueous
suspensions consists of their self-organization into stable
chiral nematic phases. Whiskers align in the same direction
to form nematic planes. The later are stacked such that the
angle of the director in each subsequent plan is offset
incrementally. It was suggested that the chiral ordering
origins from geometrical twists in the microcrystals and/or
helical distribution of their surface charge.53,79,80 Evidence
of the role of the twisted whiskers’ geometry in chirality
was reported when the chiral nematic order was obtained
for uncharged whiskers sterically stabilizated.64,68 Revol et
al.53 observed this chiral ordering of MCC aqueous suspen-
sions for various cellulose origins such as wood, cotton,
ramie, and bacterial cellulose. They also reported the
conservation of this structure after water evaporation. Sugi-
yama et al.81 reported the possibility to align cellulosic
whiskers and form a highly ordered cellulosic film. It was
achieved by drying diluted aqueous suspensions of tunicin
whiskers at room temperature under a strong homogeneous
7T magnetic field. Resulting films were examined using
polarized optical microscopy and TEM. The microcrystal axis
orientation perpendicular to the magnetic field direction was
confirmed by electron and X-ray diffraction. The anisotropic
magnetic susceptibility of the individual C-C, C-O, C-H,
and O-H bonds and their relative orientation in the crystal
were suggested to originate from the magnetic orientation.
However, a negligible role in alignment was attributed to
the ester groups at the whiskers surface that result from the
sulfuric acid hydrolysis.
Using this process to orient cellulose microcrystals, Revol
et al.82,83 created an important new material with original
optical properties. Solidified liquid crystals of cellulose with
the capability to reflect colored light were prepared from
wood pulp microcrystals suspensions. Optical properties of
these materials depend on both the cellulose origin and the
preparation conditions. The wavelength of reflected light can
be controlled by adjusting the ionic strength of the suspen-
sion. These new materials have a high application potential
like those for security papers.
Recent Research into Cellulosic Whiskers
4. Cellulosic Whiskers in Nanocomposite Applications
Since the first announcement of using cellulose whiskers
as a reinforcing phase by Favier et al.,84 new nanocomposite
materials with original properties were obtained by physical
incorporation of cellulose whiskers into a polymeric matrix.
Like for any multiphase materials, the properties of these
cellulosic nanocomposites depend on that of the two
constituents, namely whiskers and matrix in addition to
morphological aspects and their interfacial comportments
(whiskers/matrix interactions). Both natural and synthetic
polymers were explored as the matrix. Natural polymers such
as poly (β-hydroxyoctanoate) (PHO),85-87 starch,88 silk
fibroin,89 and cellulose acetate butyrate (CAB)90 reinforced
with cellulose whiskers were reported in the literature. Poly-
(styrene-co-butyl acrylate) (poly(S-co-BuA)),91,92 poly(vinyl
chloride) (PVC),93 polypropylene,94 waterborne epoxy,95 and
poly(oxyethylene)96 were used as synthetic matrixes.
Processing techniques have an important incidence on the
final properties of the composites. These techniques are
conditioned by both intrinsic properties of whiskers and
polymeric matrix (solubility, dispersibility, and degradation)
and the desired final properties such as geometrical shape.
Water is the preferred processing medium because of the
high stability of aqueous cellulose whisker dispersions and
the expected high level of dispersion of the filler within the
host matrix in the resulting composite film. Therefore, this
restricts the choice of the matrix to hydrosoluble polymers.
The use of aqueous dispersed polymers, i.e., latexes, is a
first alternative, which allows the use of hydrophobic
polymers as a matrix and ensures a good level of dispersion
of the filler indispensable for homogeneous composites
processing. A second alternative consists of dispersing
cellulose whiskers in an adequate (with regard to matrix)
organic medium. This was made possible by the coating
whiskers surface with a surfactant67 or by chemically
modifying their surface.64,69,97 The use of a surfactant is the
simplest method. However, the high amount of surfactant
required to coat this high specific surface filler (four times
higher than that of whiskers68) prohibits the use of this
technique in composite applications. The surface chemical
modification of cellulose whiskers is another way to disperse
cellulose whiskers in organic solvents. It generally involves
reactive hydroxyl groups from the surface of the whis-
kers.59,64,69 However, the mechanical performances of the
resulting composites were found to strongly decrease after
chemical modification as reported for chitin whiskers from
crab shell.98 Recently, it was shown70 that tunicin whiskers
could be dispersed in DMF without additives or any surface
modifications. This result opens the way for using some
hydrophobic polymers as a matrix in addition to allowing
additional possible chemical modifications of whiskers
especially those incompatible with the presence of water.
The first step in composites processing consists of mixing
the aqueous whiskers suspension and the dispersed or
solubilized polymer matrix. Homogeneous suspensions were
obtained by classical magnetic stirring at room temperature
or by using an autoclave reactor for mixing at high
temperatures. The suspensions were generally degassed under
vacuum to remove air. Three different techniques were used
Biomacromolecules, Vol. 6, No. 2, 2005 617
to prepare composites films: (i) by casting on Teflon or
propylene dishes followed by water evaporation at moderate
temperatures, (ii) by freeze-drying and hot-pressing, or (iii)
by freeze-drying, extruding, and hot-pressing the mixture.
Composite films were also obtained by cross-linking in situ
an unsaturated matrix after solvent casting using a thermal
or photo cross-linking agent.96,99
Experimental Investigation of Nanocomposite Films.
Morphological Characterizations. Simple naked eye exami-
nation of the film’s surface can prove the existence of
remaining air bubbles or the inhomogeneous aspect. This is
generally the case when either the degassing was not efficient
or the evaporation temperature was too high. The problem
can be complicated when the matrix is in the latex form.
Great intention must be made for the choice of both time
and temperature conditions during water evaporation with
respect to the latex particles coalescence process.
Scanning electron microscopy (SEM) is generally em-
ployed for the more extensive morphological inspection. It
consists of the observation of fractured surface films at liquid
nitrogen temperature. This technique allows for conclusions
about the homogeneity of the composite, presence of voids,
dispersion level of the whiskers within the continuous matrix,
presence of aggregates, sedimentation, and possible orienta-
tion of whiskers. By comparing the micrographs showing
the surface of fracture of the unfilled matrix and of
composites, cellulose whiskers can be easily identified. In
fact, they appear like white dots. Their concentration is a
direct function of the cellulose composition in the composite.
These shiny dots correspond to the transversal sections of
the cellulose whiskers. Their diameter determined by SEM
microscopy is much higher than the whiskers diameter. This
results from a charge concentration effect due to the
emergence of cellulose whiskers from the observed surface.
The topological dispersion of whiskers in the nanocom-
posite film strongly depends on the processing technique and
conditions. A SEM comparison between either cast and
evaporated or freeze-dried and subsequently hot-pressed
composites based on a copolymer of styrene and butyl
acrylate (poly(S-co-BuA)) matrix filled with wheat straw
whiskers92 demonstrated that the former were less homoge-
neous and displayed a gradient of whiskers concentration
between the upper and lower faces of the composite film.
This sedimentation phenomenon was confirmed using WAXS
by comparing the diffracted X-ray beams by the two faces.
It was suggested that this observation was most probably
induced by the processing technique itself. Favier100 reported
a large exploration of processing effects on the morphology
of tunicin whiskers filled poly(S-co-BuA) composites. She
used different techniques such as SEM, WAXS, MET, and
polarized light microscopy. The latter technique showed
homogeneity of the birefringent character of cast/evaporated
films and the existence of different colored domains in hot-
pressed and extruded/hot-pressed composites. From the
different experimental techniques, it was concluded that the
casting/evaporation technique results in the more homoge-
neous films, where the whiskers have a tendency to orient
randomly into horizontal plans. Heterogeneous composites
with numerous locally oriented domains of whiskers were
618 Biomacromolecules, Vol. 6, No. 2, 2005
obtained by the other techniques. Small angle neutron
scattering (SANS) is another way to check the dispersion of
the whiskers into the matrix. This technique was used by
Chazeau101 to conclude that there was an isotropic dispersion
of tunicate whiskers in plasticized poly(vinyl chloride) and
a lack of any aggregates.
Thermal Properties. The glass-rubber transition temper-
ature, Tg, of cellulose whisker filled polymer composites is
an important parameter, which controls different properties
of the resulting composite such as its mechanical behavior,
matrix chains dynamics, and swelling behavior. Differential
scanning calorimetry (DSC) and dynamic mechanical analy-
sis (DMA) can be used to evaluate Tg of polymers and
composites. In DSC experiments, Tg is generally taken as
the inflection point of the specific heat increment at the
glass-rubber transition. From DMA tests, not a transition
but a relaxation process is evidenced in this temperature
range. The temperature position of this relaxation process
(TR) depends on both Tg and the frequency of the measure-
ment. Its value can be taken as the temperature at the
maximum peak of the internal friction factor (tan δ )
E′′/E′) or the loss modulus (E′′), where E′ corresponds to
the storage tensile modulus. In shear solicitation, E′ and E′′
are replaced by the storage shear modulus, G′, and the loss
shear modulus, G′′, respectively.
For tunicin whisker filled composites, no modification of
Tg values was reported when increasing the amount of
whiskers, regardless the nature of the polymeric ma-
trix.84,88,93,100,102 Similar results were reported for bacterial90
and wheat straw92 cellulose whisker based composites. Hajji
et al.102 demonstrated that in addition to their independence
on the filler content, Tg’s of tunicin whiskers/poly(S-co-BuA)
composites are independent of the processing conditions. In
glycerol plasticized starch (amylopectin) based composites,
Anglès and Dufresne88 reported peculiar effects of tunicin
whiskers on the Tg of the amylopectin-rich fraction depending
on moisture conditions. For a low loading level (up to 3.2
wt %), a classical plasticization effect of water was reported.
However, an antiplasticization phenomenon was observed
for higher whiskers content (6.2 wt % and up). These
observations were discussed according to the possible
interactions between hydroxyl groups on the cellulosic
surface and amylopectin, the selective partitioning of glycerol
and water in the bulk amylopectin matrix or at the whiskers
surface, and the restriction of amorphous amylopectin chains
mobility in the vicinity of the amylopectin crystallite coated
filler surface. For tunicin whiskers/sorbitol plasticized starch,103
Tg’s were found to increase slightly up to about 15 wt %
whiskers and to decrease for higher whiskers loading.
Crystallization of amylopectin chains upon whiskers addition
and migration of sorbitol molecules to the amorphous
domains were proposed to explain the observed modifica-
tions.
In semicrystalline matrix based nanocomposites, the melt-
ing temperature (Tm) and heat of fusion (∆Hm) of the
thermoplastic matrix were determined from DSC measure-
ments. X-ray diffraction was also used as a technique to
elucidate the eventual modifications in the crystalline
structure of the matrix after the addition of the whiskers.
Azizi Samir et al.
It was reported that Tm values were nearly independent of
the filler content in plasticized starch88,103 and in poly-
(oxyethylene) (POE)104 filled with tunicin whiskers. The
same observation was reported for CAB reinforced with
native bacterial cellulose whiskers.90 For the CAB matrix,
Tm values were found to increase when the amount of
trimethylsilylated whiskers arises. The authors ascribed this
difference to the stronger filler-matrix interaction in the case
of chemically modified whiskers.
A significant increase in crystallinity of sorbitol plasticized
starch103 was reported when the tunicin whiskers content was
increased. This phenomenon was ascribed to an anchoring
effect of the cellulosic filler, probably acting as a nucleating
agent. The same effect was reported for POE based com-
posites104 and isotactic polypropylene (iPP) filled with
cellulosic whiskers coated with a surfactant.94 In these
systems, the nucleating effect was supported by optical
polarized light observations of composites during their
isothermal crystallization.
When whiskers are coated with surfactant, they are very
good nucleating agents for iPP. On the contrary, untreated
whiskers do not modify the crystallization of iPP. When
whiskers are grafted by maleated iPP, cellulose acts like an
antinucleating agent.94
It seems that the nucleating effect of cellulosic whiskers
is mainly governed by surface chemical considerations.
Indeed, Bonini94 did not observe any nucleating effect of
the iPP matrix when using either untreated or grafted with
anhydride maleic iPP tunicin whiskers. Grunert and Winter90
assumed from DSC measurements that native bacterial fillers
impede the crystallization of the CAB matrix, whereas
silylated ones help to nucleate the crystallization.
A transcrystallization phenomenon was reported for tunicin
whiskers filled semicrystalline matrixes such as PHO86 and
glycerol plasticized starch.88 It consists on a preferential
crystallization of the amorphous polymeric matrix chains
during cooling at the surface of the whiskers. For glycerol
plasticized starch based systems, the formation of the
transcrystalline zone around the whiskers was assumed to
be due to the accumulation of plasticizer in the cellulose/
amylopectin interfacial zones improving the ability of
amylopectin chains to crystallize. These specific crystalliza-
tion conditions were evidenced at high moisture content and
high whiskers content (>16.7 wt %) by DSC and WAXS. It
was displayed through a shoulder on the low-temperature
side of the melting endotherm and the observation of a new
peak in the X-ray diffraction pattern. This transcrystalline
zone could originate from a glycerol-starch V structure. In
addition, the inherent restricted mobility of amylopectin
chains was put forward to explain the lower water uptake of
cellulose/starch composites for increasing filler content.
Noishiki et al.89 studied silk fibroin/tunicin whisker
composites using IR spectroscopy. The silk fibroin was
prepared from silk cocoon dissolved in LiSCN and com-
posites were obtained by solution casting. The authors
reported a conformational change of fibroin chains from a
random coil to an ordered structure. This change seems
to be related to the highly ordered surface of cellulosic
whiskers.
Recent Research into Cellulosic Whiskers
Figure 5. Logarithm of the normalized storage shear modulus
(log G′T/G′200, where G′200 corresponds to the experimental value
measured at 200 K) vs temperature at 1 Hz for tunicin whiskers
reinforced poly(S-co-BuA) nanocomposite films obtained by water
evaporation and filled with 0 (b), 1 (O), 3 (2), 6 (4), and 14 wt % ([)
of cellulose whiskers.
Mechanical Properties. In the past 10 years, a great interest
was focused on investigating the use of cellulose micro-
crystals as a reinforcing phase in a polymeric matrix,
evaluating the mechanical properties of the resulting com-
posites, and elucidating the origin of the mechanical rein-
forcing effect. These investigations were performed in the
nonlinear range (classical tensile tests) and mainly in the
linear range (DMA). The latter allows the determination of
the mechanical behavior of the materials in a broad temper-
ature/frequency range and is strongly sensitive to the
morphology of the composite.
Favier et al.84,100 reported the first demonstration of the
reinforcing effect of cellulose whiskers. The authors mea-
sured by DMA in the shear mode a spectacular improvement
in the storage modulus after adding tunicin whiskers into a
poly(S-co-BuA) matrix. This increase was especially sig-
nificant above the glass-rubber transition temperature.
Figure 5 shows the isochronal evolution of the logarithm of
the relative storage shear modulus (log G′T/G′200, where G′200
corresponds to the experimental value measured at 200 K)
at 1 Hz as a function of temperature for such composites
prepared by water evaporation. In the rubbery state of the
thermoplastic matrix, the modulus of the composite with a
loading level as low as 6 wt % is more than 2 orders of
magnitude higher than the one of the unfilled matrix.
Moreover, the introduction of 3 wt % or more cellulosic
whiskers provides an outstanding thermal stability of the
matrix modulus up to the temperature at which cellulose
starts to degrade (500 K).
The reinforcing effect of tunicin whiskers was also
evidenced from tensile tests. Incorporation of these cellulosic
whiskers results in an improvement of both the elastic
modulus and the tensile strength of the composites.102,105,106
The macroscopic behavior of cellulosic whisker based
composites depends as for any heterogeneous materials, on
the specific behavior of each phase, the composition (volume
fraction of each phase), the morphology (spatial arrangement
of the phases), and the interfacial properties. Three main
parameters were reported to affect the mechanical properties
of such materials:
(i) The geometrical aspect ratio (L/d, L being the length
and d the diameter of the rodlike particle): this factor is linked
Biomacromolecules, Vol. 6, No. 2, 2005 619
to the origin of the cellulose used and whisker preparation
conditions. Fillers with a high aspect ratio give the best
reinforcing effect. Indeed, Favier100 showed that the highest
modulus increase in the rubbery state of the poly(S-co-BuA)
matrix and thermal stability were obtained with tunicin
whiskers (L/d ∼ 67) in comparison with bacterial (L/d ∼
60) or Avicel whiskers (L/d ∼ 10). It is worth noting that,
for these three different origins, the crystallinity of the raw
material is directly linked to the aspect ratio of the nano-
crystals. This demonstrates that the origin of the starting raw
lignocellulosic material governs the resulting reinforcing
effect via its degree of crystallinity.
Sakurada and Nukushina41 estimated the modulus of the
native cellulose perfect crystal to 150 GPa and Eichhorn and
Young107 reported a decrease of cellulosic whiskers’s Young
modulus when their crystallinity decreases. Dubief et al.85
reported a different mechanical behavior of composites based
on amorphous PHO when reinforced with tunicin or starch
microcrystals. More than 10 wt % of starch microcrystals
(with an aspect ratio close to unity) was needed to achieve
a reinforcing effect comparable to that provided by only 1
wt % of tunicin whiskers.
(ii) The processing method: as described above, morpho-
logical characteristics of cellulosic whisker based composites
depend on the processing technique. Water evaporation
seems to give the highest mechanical performance materials
compared to freeze-drying/molding and freeze-drying/extrud-
ing/molding techniques.100 This difference was suggested to
be due to the predominance of the whisker/whisker interac-
tions and their contribution to the overall reinforcing effect
in the evaporated films in relation to homogeneous fillers
dispersion into the matrix and the sedimentation phenom-
enon.108
A similar effect of processing techniques was reported for
chitin whisker filled poly(caprolactone)109 and natural rub-
ber.110 Hajji et al.102 studied the tensile behavior of poly(S-
co-BuA)/tunicin whisker composites prepared from different
manners. The authors classified processing methods in
ascending order of their reinforcement efficiency (tensile
modulus and strength): extrusion < hot pressing < evapora-
tion. This evolution was associated to probable breakage and/
or orientation of whiskers during processing.
(iii) The matrix structure and the resulting competition
between matrix/filler and filler/filler interactions. Classical
composite science tends to privilege the former as a condition
for optimal performance. In cellulose whisker based com-
posite materials, the opposite trend is observed. The higher
the affinity between the cellulosic filler and the host matrix
is, the lower the mechanical performances are. For instance,
the transcrystallization phenomenon reported for semicrys-
talline PHO on cellulose whiskers resulted in a disastrous
decrease of the mechanical properties (especially above the
melting temperature of the matrix) when compared to that
obtained for fully amorphous PHO.86 Similar results were
reported for plasticized starch reinforced with cellulose
whiskers.105 This strong loss of performance demonstrates
the event of outstanding importance of the filler/filler
interactions to ensure the mechanical stiffness and thermal
stability of these composites. This idea was supported by
620 Biomacromolecules, Vol. 6, No. 2, 2005
the decrease of the tensile storage modulus of composite
materials filled with bacterial cellulosic whiskers with a
silycilated surface.90 A similar loss of mechanical properties
was reported for a natural rubber matrix filled with chemi-
cally modified and unmodified chitin whisker.98
Mechanical Modeling. To understand the unusual reinforc-
ing effect observed for cellulose whisker based composites
at T > Tg at such low filler concentrations, comparisons
between experimental results and different mechanical ap-
proaches have been made. It is worth noting that at a
temperature either much lower or much higher than Tg of
the host matrix the tensile or shear behavior, as a first
approximation, can be considered as fully elastic. In fact,
the loss component of the tensile or shear modulus is more
than 10 times lower than the elastic one in these temperature
ranges. For this reason, we will only consider the elastic
behavior in the following.
Mean Field Approach. The theoretical mean field me-
chanical model of Halpin-Kardos111 has been extensively
used to predict the elastic modulus of short-fiber composites.
In this approach, fibers are assumed to be embedded in the
matrix to form a homogeneous continuum. The modulus,
the mechanical anisotropy, and the geometry of the fibers
are accounted for, but one assumes that there is no interaction
between the fibers. In particular, the mean-field approach is
based on the concept that a material made of short fibers,
homogeneously dispersed in a continuous matrix, is me-
chanically equivalent to the superposition of four plies.
Within each ply, the fibers are parallel to one another, and
the mutual orientation of the plies is 0, +45, +90, and -45°.
The mechanical properties of each ply can be derived from
the micromechanic equations of Halpin-Tsai (“self consis-
tent” approach):112
Eii (1 + ξii)Eiif + ξii(1 - VR)Em
) (i ) 1,2) (1)
Em (1 - VR)Eiif + (ξii + VR)Em
G12 (1 + VR)Gf + (1 - VR)Gm
) (2)
Gm (1 - VR)Gf + (1 + VR)Gm
where Eii is the stiffness in the fiber direction of a
unidirectional ply, E22 is the stiffness estimate perpendicular
to the fiber direction, G12 is the in-plane shear modulus
estimate, and VR is the volume fraction of fibers. The
subscripts m and f refer to the matrix and the filler,
respectively. The geometry of the filler is involved through
the ξii parameters, where L, l, and e are the length, the
width, and the thickness of the fibers, respectively. In our
case, l ) e ) d, the diameter of the whiskers, and it
follows:111
L L
ξ11 ) 2 ) 2
e d
l the behavior of a noncompletely connected set of objects.
ξ22 ) 2 ) 2 (3)
e
The engineering constants characteristics of the unidirectional
plies are then given by
Azizi Samir et al.
Eii
Qii ) (i ) 1,2)
1 - ν12ν21
Q12 ) ν12Q22 ) ν21Q11
Q66 ) G12 (4)
which leads to the following expressions for the invariant
terms The tensile modulus of the “quasi-isotropic” laminate,
1
U1 ) (3Q11 + 3Q22 + 2Q12 + 4Q66)
8
1
U2 ) (Q11 + Q22 - 2Q12 + 4Q66) (5)
8
the behavior of which is assumed to be close to that of the
short fiber composite, is then given by
4U2(U1 - U2)
EC ) (6)
U1
The Poisson’s ratio ν12 is approximately given by a mixing
rule
Q11
ν12 ) νmVm + νfVR ) ν (7)
Q22 21
Predicted modulus values from this model agree generally
very well with the experimental data in the glassy state but
fail to describe the rubbery modulus.84,85,92,93,102,108 Above Tg
of the matrix, the observed reinforcing effect in terms of
the increase in the modulus is found to be much higher than
possible for a composite only reinforced with discrete fibers.
It was concluded that the assumption of “no filler/filler
interaction” hypothesis seems to be wrong, despite the fact
that this model displayed limits when the stiffness of the
reinforcing phase is far above the continuous phase.113
An acceptable fit of experimental data could be obtained
by modifying the geometrical (aspect ratio) and/or stiffness
(modulus) properties of the cellulosic fillers.84,92 However,
the former results from experimental microscopical observa-
tions and the latter is not easily questionable. Therefore, the
description of the mechanical behavior of cellulosic whisker
based composites needs to take into account the topological
arrangement of the fillers and their interactions. The high
specific surface of whiskers and their numerous hydroxyl
groups suggest a hydrogen bonding type for the filler/filler
interactions and the formation of a possible fillers network
within the host matrix. This led to the idea of a percolation
type approach applied to cellulose whiskers reinforced
polymeric matrixes.
Percolation Approach. The term percolation for the
statistical-geometry model was first introduced in 1957 by
Hammersley.114 It is a statistical theory, which can be applied
to any system involving a great number of species likely to
be connected. The aim of the statistical theory is to forecast
By varying the number of connections, this approach allows
the transition from a local to an infinite “communication”
state to be described. The percolation threshold is defined
as the critical volume fraction separating these two states.
Recent Research into Cellulosic Whiskers
Various parameters, such as particle interactions,115 orienta-
tion,116 or aspect ratio117 can modify the value of the
percolation threshold.
The use of this approach to describe and predict the
mechanical behavior of cellulosic whisker based composites
suggests the formation of a rigid network of whiskers which
should be responsible for the unusual reinforcing effect
observed at high temperatures. The modeling consists of three
important steps:
(i) First, the calculation of the percolation threshold (VRc)
should be carried out. The volume fraction of whiskers
required to achieve geometrical percolation was calculated
using a statistical percolation theory for cylindrical shape
particles according to their aspect ratio and the effective
skeleton of whiskers was estimated.118 The latter corresponds
to the infinite length branch of whiskers connecting the
sample ends. Favier et al.118 used computer simulation and
showed that about 0.75 vol % tunicin whiskers (assuming
L/d ) 100) are needed to get a 3-D geometrical percolation.
The authors calculated the effective skeleton by eliminating
the finite length branches. The following relation was found
between the percolation threshold (VRc) and aspect ratio of
rodlike particles100
0.7
VRc ) (8)
L/d
Flandin et al.119 performed DC electrical conductivity
measurements to evaluate the tunicin whiskers percolation
threshold. In this study, the surface of the cellulosic filler
was covered with conductive polypyrrole before incorpora-
tion in a latex matrix. The coated whiskers were characterized
by SEM. The final sticks have an average length of about 2
µm and a diameter of 160 nm. The percolation threshold
was determined to be about 3 vol % in agreement with the
percolation theory and experimental data120 for an aspect ratio
close to 15. The electrical percolation threshold is generally
lower than the geometrical one, which provides the mechan-
ical stiffness. The presence of the continuous path can be
enough to make system conducting but is not necessary
sufficient to ensure the rigidity of the whole system.
(ii) The second step is the estimation of the modulus of
the percolating filler network. It is obviously different from
the one of individual whiskers and depends on the origin of
the cellulose, preparation procedure of the whiskers, and
obviously the nature and strength of interwhisker interactions.
This modulus can be assumed to be that of a paper sheet for
which the hydrogen bonding forces provide the basis of its
stiffness. Experimental tensile tests were performed on films
prepared from the evaporation of a suspension of cellulose
whiskers in a Teflon mold. For tunicin91,100 and wheat straw
cellulose whiskers,92 the tensile modulus was around 15 and
6 GPa, respectively. The apparent tensile modulus of a
cellulose whisker network can be calculated by a 3-D finite
elements simulation.118,121 The linking elements were con-
sidered as beams with adjustable stiffness. All of the
calculated values were lower than 1 GPa. For link modulus
values below 1 GPa, the network modulus was found to
increase with increasing whisker concentration and seemed
to increase linearly with the link modulus. For a higher
Biomacromolecules, Vol. 6, No. 2, 2005 621
Figure 6. Schematic representation of the series-parallel model. R
and S refer to the rigid (cellulosic filler) and soft (polymeric matrix)
phases, respectively, and ψ is the volume fraction of the percolating
rigid phase.
linking modulus, the modulus of the percolating network
tends toward the value for totally rigid links.
(iii) The description of the composite requires the use of
a model involving three different phases, viz., the matrix,
the filler percolating network, and the nonpercolating filler
phase. The simplest model consists of two parallel phases,
namely, the effective whiskers skeleton and the rest of the
sample. Ouali et al.122 extended the classical phenomenologi-
cal series-parallel model of Takayanagi123 and proposed a
model in which the percolating filler network is set in parallel
with a series part composed of the matrix and the nonper-
colating filler phase (Figure 6).
In this approach, the elastic tensile modulus Ec of the
composite is given by the following equation:
(1 - 2ψ + ψVR)ESER + (1 - VR)ψER2
Ec ) (9)
(1 - VR)ER + (VR - ψ)ES
The subscripts S and R refer to the soft and rigid phase.
The adjustable parameter, ψ, involved in the Takayanagi et
al. model corresponds in the Ouali et al. prediction to the
volume fraction of the percolating rigid phase. With b being
the critical percolation exponent, ψ can be written as
ψ)0 for VR < VRc
( )
VR - VRc b
ψ ) VR for VR > VRc (10)
1 - VRc
where b ) 0.4124,125 for a 3D network.
This percolation approach was found to fit satisfactory
the experimental data, especially for high filler load-
ing.84-86,100,102,108 At high temperatures when the polymeric
matrix could be assumed to have a negligible stiffness, the
calculated stiffness of the composites is simply the product
of that of the percolating fillers network by the volume
fraction of percolating fillers phase
Ec ) ψER (11)
Figure 7 shows the comparison between experimental and
predicted data from both the Halpin-Kardos model and the
percolation approach. In this figure, the logarithm of the
relative storage tensile modulus measured at Tg + 50 K
(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.

It is clearly observed in Figure 7 that the calculated curve

based on the percolation approach allows accounting for the
reinforcing effect in poly(S-co-BuA) based systems. The
discrepancy observed between the calculated curve based and
the experimental data at low filler content is probably due
to the fact that the prediction does not account for the
distribution of the whiskers lengths. Above this critical
percentage, the calculated curve based on the percolation
theory precisely fits the observed E′ values.
On the contrary, calculation underestimates the relaxed
modulus of amorphous PHO based composites. The experi-
mental data for the PHO based systems are 5 times higher
than the predicted one. This discrepancy was ascribed to the
latex particle size that could affect the whiskers network
Figure 7. Logarithm of the relative storage tensile modulus measured
at Tg + 50 K (log E′CTg+50K/E′mTg+50K, where E′CTg+50K and E′mTg+50K formation.85 The latex particle size was around 150 nm and
correspond to the value measured at Tg + 50 K for the composite 1 µm for poly(S-co-BuA) and PHO, respectively. Indeed,
and the matrix, respectively) vs volume fraction of tunicin whiskers: the particles act as impenetrable domains to whiskers during
comparison between the experimental data for poly(S-co-BuA) (b),
the film formation due to their high viscosity. Increasing
PHO (O), and glycerol plasticized starch based systems conditioned
at 35 (2), 43 (4), 58 ([), and 75% RH (]) and predicted data from particle size leads to an increase of the excluded volume
the Halpin-Kardos model (s) or from the percolation approach (- - -). and to a decrease of the percolation threshold.
For glycerol plasticized starch based systems, the reinforc-
Table 1. Parameters Used for Plotting Figure 7
ing effect is very low and even lower than the predicted data
Fm Tg from the mean field approach. This observation was ex-
matrix (g cm-3) νma (K)
plained by competitive interactions between the components
poly(S-co-BuA) 1.1 0.5 273 and by a plasticizer accumulation in the cellulose/amylopec-
PHO 1.019 0.5 250
starch 35% RH 1.1 0.5 300
tin interfacial zone.105 This plasticizer accumulation phe-
starch 43% RH 1.1 0.5 274 nomenon, enhanced in moist conditions, could most probably
starch 58%RH 1.1 0.5 271 interfere with hydrogen-bonding forces that are likely to hold
starch 75%RH 1.1 0.5 260 the percolating cellulose whiskers network within the matrix.
Ff E11f E22f Gf The absence of whiskers network formation was also
tunicin whiskers (g cm-3) ν fb L /d c (GPa)d (GPa)d (GPa)d mentioned for PVC based composites.93,101,106 For semicrys-
talline PHO reinforced with tunicin whiskers, the cellulosic
1.58 0.3 67 150 15 5
network was assumed to originate from the formation of
vRc ER interwhisker links through transcrystalline layers grown on
percolation approach (vol %)e b (GPa) the cellulose surface.86 This resulted in a disastrous decrease
1 0.4 15 of the mechanical properties of the composite material as
a The matrix being in the rubbery state at T + 50 K. b Cellulose being soon as the melt temperature of the matrix was reached.
g
in the crystalline state. c Estimated from TEM. d Average value from However, a suitable in situ thermal treatment was found to
literature.41,126-130 e Calculated from eq 8. allow restoring the cellulose whiskers network through
correspond to the value measured at Tg + 50 K for the hydrogen bonding.
composite and the matrix, respectively) is plotted as a The comparison between predicted and experimental data
function of tunicin whiskers content expressed in volume demonstrates the major role of filler/filler interaction in the
fraction. Experimental data were obtained for tunicin whis- final mechanical behavior of the composites based on
kers reinforced poly(S-co-BuA),100 amorphous PHO,85 and cellulosic whiskers. Moreover, the percolation approach
glycerol plasticized starch conditioned in different moisture allows accounting for the spectacular thermal stabilization
conditions.105 For poly(S-co-BuA) based systems, the shear of composite’s modulus observed at high temperatures. This
modulus values from ref 100 were converted into tensile cellulosic network was reported to have no specific effect
moduli assuming a mixing rule for the Poisson’s ratio. The on the modulus in the glassy state of the matrix.85,102 In the
various parameters used for plotting Figure 7 are collected rubbery state of the matrix, nonlinear tensile tests performed
in Table 1. For the glycerol plasticized starch based systems, on tunicin whisker reinforced poly(S-co-BuA) displayed the
it is worth noting that the matrix appeared as a complex progressive destruction of the percolating network.102 Suc-
heterogeneous system composed of glycerol-rich domains cessive tensile test experiments carried out on nanocomposite
dispersed in an amylopectin-rich continuous phase. Each materials based on chitin whiskers obtained from crab shell
phase exhibited its own glass-rubber transition, for which and natural rubber131 help us to understand the existence of
the temperature decreases as the moisture content increases a three-dimensional nanocrystals network formed as a result
owing to the plasticizing effect of water. The values of Tg of hydrogen bonding forces. This test consists of stretching
reported in Table 1 correspond to the amylopectin-rich the sample up to a certain elongation, then releasing the force,
domains. The calculated curves are similar whatever the and stretching again the material up to a higher elongation,
nature of the matrix because the relative moduli are reported. etcetera. A clear decrease in modulus values of the samples
Recent Research into Cellulosic Whiskers
during the first stretching cycles indicated the progressive
damaging of the percolating network, which was initially
present.
Interfacial Phenomena. DMA experiments can provide
additional information on the microstructure of heterogeneous
materials from the characteristics of the relaxation process
associated to the modulus drop at the glass-rubber transition.
It is displayed through the concomitant energy dissipation
process giving rise to a maximum of the mechanical loss
factor, tan δ, and loss modulus, E′′. In particular, in
nanocomposite materials, interfacial phenomena are expected
to be important owing to the high specific area of the
involved fillers. For tunicin whiskers, the geometrical specific
area is around 170 m2 g-1, and for a 6 wt % filled composite,
they are of the order of 100 000 cm2 of surfaces per cm3 of
material.87 Studying tunicin whiskers reinforced PVC com-
posites, Chazeau et al.101,132 claimed the presence of an
immobilized polymeric matrix layer in the vicinity of the
filler. The changes in the shear loss modulus induced by the
cellulosic filler were discussed using a mean field approach
and assuming a three-phase system.
Noishiki et al.89 investigated nanocomposite films based
on silk fibroin reinforced with tunicin whiskers. It was
observed that the cellulose surface caused morphological
modifications of silk fibroin chains. The highly ordered
tunicin whiskers surface induced the silk crystallization at
the filler-matrix interface.
For tunicin whiskers and PHO based composites, signifi-
cant differences were observed depending on the nature of
the matrix.133 When a semicrystalline PHO was used as the
matrix, the molecular mobility of amorphous macromolecular
chains was reported to be only slightly affected by the
presence of cellulose whiskers, owing to a possible trans-
crystallization phenomenon leading to a coating of the filler
with the crystalline phase. In contrast, the flexibility of chains
in the surface layer was lowered by the conformational
restrictions imposed by the cellulose surface, when an
amorphous PHO was used as the matrix. This phenomenon
resulted in a broader interphase and in a broadening of the
relaxation process associated to the glass-rubber transition.
A physical model based on a percolation approach, suitable
for the prediction of the reinforcing effect of cellulose
whiskers, was used to predict the mechanical loss angle. The
ratio of the experimental and predicted magnitude of the main
relaxation process of the composite was used to calculate
the thickness of the interphase.
Possible Applications. Cellulose crystallites in the form
of microcrystalline cellulose are currently utilized widely
industrially. Novel applications in a diverse range of fields
were recently presented,134 from iridescent pigments to
biomolecular NMR studies. In the nanocomposite field, up
to now, cellulose whiskers were only used as geometrically
and structurally well-defined model cellulosic filler and no
practical industrial application was envisaged. This is mainly
ascribed to the duration of the preparation technique.
However, two important applications may be cited. The first
one concerns the solidified liquid crystals for optical ap-
plications like in security paper (refs 82 and 83). The second
is related to the use of these whiskers as mechanical
Biomacromolecules, Vol. 6, No. 2, 2005 623
reinforcing agents for low-thickness polymer electrolytes for
lithium batteries application.96,99,135-137 For the latter, it is
worth noting that the filler content is generally relatively low,
below 10 wt%, avoiding significant decrease of the ionic
conductivity.
5. Conclusions
The present contribution, reporting 10 years worth of work
performed on the processing and behavior of new nanocom-
posite materials of thermoplastic polymers reinforced by
polysaccharide microcrystals, can be considered as an effort
aimed at providing further knowledge to a research area
presenting yet a variety of pending issues. It was shown that
the use of high aspect ratio cellulose whiskers induces a
mechanical percolation phenomenon leading to outstanding
and unusual mechanical properties through the formation of
a rigid filler network. In addition to some practical applica-
tions, the study of such model systems can help to understand
some physical properties as geometric and mechanical
percolation effects.
Cellulose can also be used as a microfibrillar filler, which
is more accessible in terms of available amounts and
preparation. The mechanical behavior is then very sensitive
to the cellulose purification level and cellulose microfibrils
individualization state.
The subject generates substantial interests, and the variety
of possible sources of cellulose for preparing nanocrystals
is broad. Polysaccharide nanocrystals can also be obtained
from other abundant renewable resources such as chitin and
starch by acid hydrolysis. For the former, they appear as
rodlike particles with an aspect ratio related to the origin of
the chitin, whereas for the latter, the nanoparticles consist
of platelets with nanometer scale dimensions. Practical
applications of such fillers and transition into industrial
technology require a favorable ratio between the expected
performances of the composite material and its cost. There
are still significant scientific and technological challenges
to take up.
Acknowledgment. The authors thank the Région Rhône-
Alpes for financial support.
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