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Article history: Several forms of cellulose nanomaterials, notably cellulose nanocrystals and cellulose nanofibrils, exhibit attrac-
Received 30 September 2016 tive properties and are potentially useful for a large number of industrial applications. These include the paper
Received in revised form 24 January 2017 and cardboard industry, use as reinforcing filler in polymer nanocomposites, basis for low-density foams, additive
Accepted 31 January 2017
in adhesives and paints, as well as a wide variety of filtration, electronic, food, hygiene, cosmetic, and medical
Available online 8 February 2017
products. This entry focuses on cellulose materials as filler in polymer nanocomposites. The ensuing mechanical
Keywords:
properties obviously depend on the type of nanomaterial used, but the crucial point is the processing technique.
Cellulose nanomaterial The emphasis is on the melt processing of such nanocomposite materials that has not yet been properly resolved
Cellulose nanocrystal and remains a challenge.
Cellulose nanofibrils © 2017 Elsevier Ltd. All rights reserved.
Nanocomposites
Processing
Mechanical properties
http://dx.doi.org/10.1016/j.cocis.2017.01.004
1359-0294/© 2017 Elsevier Ltd. All rights reserved.
2 A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8
Recently, TAPPI (Technical Association of the Pulp and Paper Industry) atom skeleton, but differ in their hydrogen bonding patterns. The Iα
has proposed to standardize the terminology (Standard Terms and form represents a triclinic phase with one-chain-per-unit cell, while
Their Definition for Cellulose Nanomaterial WI 3021) and below a the Iβ form represents a monoclinic phase with two-chains-per-unit
given degree of destructuration, the term CNF should be used. cell. The ratio of the two allomorphs Iα and Iβ differs greatly depending
This production route is normally associated to high energy con- on the species. The Iα phase is mainly found in celluloses produced by
sumptions for fiber delamination and different pretreatments have primitive organisms such as algae or bacteria while cellulose Iβ lies
been therefore proposed to facilitate this process, e.g. mechanical cutting, mainly in the cellulose produced by higher plants (cotton, wood,...)
acid hydrolysis, enzymatic pretreatment, and introduction of charged and animals such as in the envelope of marine animals.
groups through carboxymethylation or 2,2,6,6-tetramethylpiperidine- The elastic modulus EL of the crystalline regions of cellulose I in the
1-oxyl (TEMPO)-mediated oxidation. CNF appears as flexible filaments direction parallel to the chain axis was measured both experimentally
consisting of both individual and aggregated nanofibrils made of alter- and through atomistic molecular dynamics simulations. Some values
nating crystalline and amorphous cellulose domains (Fig. 1a). The are reported in Fig. 2 and Table 1. These values were determined at
width is generally in the range 3–100 nm depending on the source of room temperature and considering intramolecular hydrogen bonding.
cellulose, defibrillation process and pretreatment and the length is Much lower values were reported when intramolecular hydrogen
considered to be higher than 1 μm. It is worth noting that hydrophobic bonding was not taken into account, evidencing their important role
compounds are still present at the surface of CNF and that the surface in the determination of the crystallite modulus and chain deformation
charge is fixed by the pretreatment step. mechanism. Nevertheless, a broad range of values is observed and the
average experimental and predicted tensile modulus of cellulose I crys-
2.2. Cellulose nanocrystals tal depicted by horizontal lines in Fig. 2 is 124 GPa and 134 GPa, respec-
tively. It is therefore reasonable to consider that the tensile modulus
The chemically-induced destructuration strategy consists generally of crystalline cellulose I is around 130 GPa. The modulus of cellulose
in applying a controlled strong acid hydrolysis treatment to cellulosic fi- microfibrils is expected to result from a mixing rule of the modulus of
bers allowing dissolution of amorphous domains and therefore longitu- the crystal, the amorphous regions of cellulose and defects/air in the
dinal cutting of the microfibrils. The ensuing nanoparticles are generally sample. Its average value is around 100 GPa [13••].
called cellulose nanocrystals (CNCs) according to TAPPI (Standard Cellulose nanomaterials should therefore act as excellent reinforcing
Terms and Their Definition for Cellulose Nanomaterial WI 3021) and nanomaterial in a polymeric matrix which modulus is around few GPa
are obtained as an aqueous suspension. These nanoparticles occur as in the best conditions, i.e. in its glassy state. However, homogeneously
high aspect ratio rod-like nanocrystals, or whiskers (Fig. 1b). Their geo- blending this nanomaterial with a polymeric matrix is challenging.
metrical dimensions depend on the origin of the cellulose substrate and
hydrolysis conditions. Sulfuric acid is classically used for the preparation 4. Processing of polymer nanocomposites
of CNC and this process induces the formation of negatively charged sul-
fate groups at it surface. The average length is generally of the order of Both CNC and CNF are generally obtained as diluted aqueous (or
a few hundred nanometers and the width is of the order of a few nano- at least polar liquid) dispersions. The stability of the colloidal suspen-
meters. An important parameter for CNCs is the aspect ratio, which is sion results from the presence of residual hemicelluloses for CNF and
defined as the ratio of the length to the width. charged sulfate groups in the case of sulfuric acid-hydrolyzed CNC.
Several applications have been envisaged for these nanoparticles. The pioneering works on the preparation of nanocellulose reinforced
However, owing to the structural function of cellulose in nature, the polymer nanocomposites consequently involved an aqueous medium
application of cellulose nanomaterials as a reinforcing phase for nano- to keep this natural dispersion of the nanoparticles. This mode of pro-
composite applications is the most prominent and broadly investigated cessing allows preserving the individualization state of the nanoparti-
end use. cles resulting from their colloidal dispersion in water. Water-soluble
polymers or polymer aqueous dispersions (latex) are therefore and
3. Stiffness of the cellulose nanomaterial continue to be favorable systems for such application.
Processing of nanocomposite materials from cellulosic nanoparticles
Cellulose is a ubiquitous structural semicrystalline polymer and and polymer latex was historically the first one reported in the literature
cellulose crystals give trees and plants their strength and light weight. [16••]. The nanocomposite system reported in this study consisted of
In nature, cellulose is found in the crystalline form of cellulose I (native CNC extracted from tunicate and the polymeric matrix was obtained
cellulose) which is a mixture of two polymorphs, cellulose Iα and Iβ. by the statistical copolymerization of styrene and butyl acrylate
These two crystalline forms have the same conformation of the heavy (poly(S-co-BuA)). Solid nanocomposite films were obtained by mixing
Fig. 1. Transmission electron micrographs from a dilute suspension of (a) cellulose nanofibrils prepared from Opuntia ficus-indica fibers [23], and (b) cellulose nanocrystals extracted from
ramie fibers [18].
A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8 3
Table 1
Longitudinal (EL) modulus of crystalline cellulose. The first column corresponds to data points reported on the x-axis in Fig. 1.
Experimental determination
1 Ramie fibers (cellulose I) X-ray diffraction 134 Sakurada et al. (1962). J. Polym. Sci. 57, 651
2 122–135 Matsuo et al. (1990). Macromolecules 23, 3266
3 138 Nishino et al. (1995). J. Polym. Sci. Part B: Polym. Phys. 33, 1647
4 Cellulose Iβ Raman 143 Šturcova et al. (2005). Biomacromolecules 6, 1055
5 Cellulose I 57–105 Rusli and Eichhorn (2008). Appl. Phys. Lett. 93, 033111
6 Ramie fibers (cellulose I) Inelastic X-ray scattering 220 Diddens et al. (2008). Macromolecules 41, 9755
7 Cellulose Iβ AFM 145–150 Iwamoto et al. (2009). Biomacromolecules 10, 2571–2576
Theoretical determination
1 Cellulose I 77–121 Meyer and Lotmar (1936). Helv. Chim. Acta 19, 68
2 56 Treloar (1960). Polymer 1, 290
3 172.9 Tashiro and Kobayashi (1985). Polym. Bull. 14, 213
4 76 Jaswon et al. (1968). Proc. Roy. Soc. 306, 389
5 Cellobiose (two hydrogen 136 Kroon-batenburg et al. (1986). Polym. Commun. 27, 290
bonds - cellulose I)
6 Cellulose I 167.5 Tashiro and Kobayashi (1991). Polymer 32, 1516
7 Cellulose I 134–135 Reiling and Brickmann (1995). Macromol. Theory Simul. 4, 725
8 Cellulose Iα 127.8 Neyertz et al. (2000). J. Appl. Polym. Sci. 78, 1939
9 Cellulose Iβ 115.2
10 Cellulose Iβ 124–155 Tanaka and Iwata (2006). Cellulose 13, 509
11 Cellulose Iα 136–155 Eichhorn and Davies (2006). Cellulose 13, 291
12 Cellulose Iβ 116–149
13 Cellulose Iβ 156 Bergenstråhle et al. (2007). J. Phys. Chem. B 111, 9138
14 Disaccharide cellulose Iβ 85.2 Cintrón et al. (2011). Cellulose 18, 505
Disaccharide cellulose Iβ 99.7
Extended cellulose Iβ chains (10–40 glucoses) 126.0
15 Cellulose Iβ 139.5 Wu et al. (2013). Cellulose 20, 43
16 Cellulose Iβ 206 Dri et al. (2013). Cellulose 20, 2703
17 Cellulose Iβ 107.8 Wu et al. (2014). Cellulose 21, 2233
18 Cellulose Iβ 196 Dri et al. (2014). Modelling Simul. Mater. Sci. Eng. 22, 085012
19 Cellulose Iβ 138 Djahedi et al. (2015). Carbohydr. Polym. 130, 175
4 A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8
Fig. 3. Common chemical modifications of cellulose nanocrystal (CNC) [21••]. [PEG: poly(ethylene glycol); PEO: poly(ethylene oxide); PLA: poly(lactic acid); PAA: poly(acrylic acid);
PNiPAAm: poly(N-isopropylacrylamide); PDMAEMA: poly(N,N-dimethylaminoethyl methacrylate)].
modification based on the “grafting onto” strategy with different cou- and grafted by an esterification reaction. The homogeneity and thermal
pling agents (labeled with blue arrows in Fig. 3); and (3) polymer sur- resistance of the ensuing nanocomposite was found to increase with the
face modification based on the “grafting from” strategy with the radical length of the grafted chains (Fig. 4a). From this Figure, it can be seen that
polymerization of ring opening polymerization (ROP), atom transfer neat LDPE is obviously translucent as any low thickness polymeric film
radical polymerization (ATRP) and single-electron transfer living radi- with a relatively low degree of crystallinity. When adding 10 wt.%
cal polymerization (SET-LP) (labeled with yellow arrows in Fig. 3). of CNC, the film becomes dotted with black. These heterogeneities
Experimental conditions should avoid swelling media and peeling reveal the poor and inhomogeneous dispersion of the filler within
effect of surface-grafted chains inducing their dissolution in the reac- the polymeric matrix as well as thermal degradation of the cellulosic
tion medium. The chemical grafting process has therefore to be mild nanomaterial. When using chemically modified CNC, the occurrence of
in order to preserve the integrity of the nanoparticle. However, cova- these aggregates progressively vanishes and the appearance of the com-
lent functionalization of the nanofiller normally involves complicate posite film becomes similar to the one of the unfilled film. However,
and expensive steps which can be prohibitive for most industrial uses. the question arises again regarding the process that is generally lengthy
The most convenient, as well as industrially and economically viable and cumbersome.
processing method for cellulose nanomaterial reinforced thermoplastic A possible way for overcoming self-aggregation of the cellulose
polymer nanocomposites is most probably melt processing such as nanomaterial during melt extrusion consists in using never-dried nano-
extrusion or injection-molding. This is well supported by the fact that particles. Liquid feeding of CNF dispersed in a mixture of water, acetone
the commercial exploitation of cellulose nanomaterials has already and glycerol triacetate and subsequent extrusion with polylactic acid
commenced. Moreover, it can be considered as a green process since (PLA) was reported [19]. However, effective venting and vacuum ports
no solvent is involved. However, the inherent incompatibility between are needed. Moreover, only low filler content composites (1 wt.%) can
hydrophilic cellulose and generally hydrophobic polymer matrix, be prepared because of the high viscosity of the CNF dispersion.
as well as thermal stability issues need to be addressed. This last Therefore, many researchers have quite recently directed their
point is particularly sensitive for sulfuric acid-hydrolyzed CNC because research to a simplest physical functionalization of the cellulose
the acid hydrolysis process introduces less thermally stable sulfate nanomaterial and preferably favoring water as dispersing medium.
groups on the surface. Nevertheless, these issues can be quite easily The guideline consists of adding to the nanoparticle aqueous dispersion
tackled, e.g. by chemically modifying the surface of the nanoparticles a water-soluble molecule that can homogeneously diffuse and disperse
as detailed above. Generally, good results can be obtained as shown in in the liquid medium. At least part of this molecule needs to present
Fig. 4a. In this study, organic acid chlorides-grafted CNCs extracted favorable interactions with the cellulosic surface to coat it. Upon drying
from ramie fibers were extruded with low density polyethylene the irreversible aggregation of the nanoparticles through hydrogen
(LDPE) [11]. Aliphatic chains presenting different lengths were used bonding is avoided because of this coating. The homogeneous
A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8 5
(a)
(b)
(c)
3% 6% 3% 6%
LDPE
5%CNC
Fig. 4. Photographs of extruded CNC reinforced nanocomposite films: (a) neat LDPE film and extruded nanocomposite films reinforced with 10 wt.% of unmodified and C18 acid chloride-
grafted CNC [11]; (b) PP reinforced with various contents of quaternary ammonium salt-coated CNC (M-CNC) or 3 wt.% neat CNC, and neat PP (from left to right) [28]; (c) neat LDPE,
and LDPE reinforced with 3 or 6 wt.% of neat CNC or PEO-coated CNC (M-CNC) (from left to right) [31•]; (d) neat LDPE, and LDPE reinforced 5 wt.% neat CNC or various contents of
(PEO–PPO–PEO)-coated CNC (M-CNC) [29].
dispersion of this dried material within a polymeric matrix during melt would probably avoid this phenomenon. This strategy was explored
processing can therefore be simplified especially if the coating material using polyoxyethylene (PEO) which is a water-soluble and polar poly-
can present favorable interactions with the dispersing medium. mer [6]. The favorable interactions between PEO chains and cellulosic
Such kind of molecule can be a surfactant. Indeed, surfactants were evidenced from rheological measurements. A progressive de-
are usually organic compounds that are amphiphilic, i.e. containing crease in the viscosity was observed when adding CNC to an aqueous
both hydrophobic groups (the tail) and hydrophilic groups (the head). PEO solution up to a critical nanocrystal content after which the vis-
Since sulfuric acid-hydrolyzed CNC are negatively charged, the strength cosity started to increase. This phenomenon evidenced strong interac-
of the interactions between the cellulosic surface and the surfactant tions between PEO chains and nanoparticle surface. The effect observed
molecule can be enhanced using cationic surfactants such as quaternary can also be understood as the effect of depletion forces. The critical CNC
ammonium salts. Such a strategy was investigated and the negatively content corresponding to the minimum viscosity value decreased as
charged sulfate groups borne by CNC were profitably used to ionically the molecular weight of PEO decreased because of stronger affinity of
adsorb quaternary ammonium salt by a simple aqueous method [28]. hydroxyl end groups of PEO with cellulose than its ether oxygen groups
Improved thermal stability of surfactant-coated CNC was observed com- [3,31]. PEO-coated CNC obtained after freeze-drying the aqueous mixture
pared to neat CNC. After removal of unadsorbed quaternary ammonium was used to prepare nanocomposites with LDPE [6,31], polystyrene (PS)
salt molecules by dialysis, the mixture was freeze-dried and the modi- [22] or PLA [2] matrix by melt extrusion. Improved dispersibility and re-
fied CNC was extruded with polypropylene at 190 °C. Hydrophobized duced thermal degradation of the nanoparticles were observed showing
CNC dispersed well in different nonpolar solvents and polypropylene, the compatibilizing action of PEO (Fig. 4c). It was also shown that phys-
which was impossible for neat CNC as shown in Fig. 4b. The neat PP ical interaction of the polymer was enhanced when chemically grafting
film is translucent as any low thickness semicrystalline polymeric film. the same polymer on the surface of the nanoparticles [22].
When adding neat CNC, the film became homogeneously darker as a re- Other polymers can be used as cellulose nanomaterial carrier, but
sult of the thermal degradation of the cellulosic filler. The appearance improved compatibilization could be obtained with block copolymers
of the nanocomposite films reinforced with up to 10 wt.% quaternary consisting of hydrophilic and hydrophobic sequences. A triblock
ammonium salt-coated CNC was similar to that of neat PP showing (PEO–PPO–PEO) copolymer having two hydrophilic ends with high af-
that the coating was able to both protect the surface sulfate groups and finity with cellulosic surface attached to hydrophobic polypropylene
improve the dispersion of the nanoparticles. oxide (PPO) displaying higher affinity with hydrophobic polymers was
Melt processing techniques such as extrusion or injection-molding used to coat CNC [29]. The aspect of the nanocomposite films obtained
involve high shear. Under these conditions small adsorbed molecules from these coated CNC and LDPE is shown in Fig. 4d. Again, limited ther-
(surfactants) could be removed from the nanoparticle surface and mal degradation and improved dispersibility were observed for coated
blended with the matrix. Wrapping the cellulosic nanomaterial with CNC.
longer molecules, i.e. macromolecules, bearing moieties susceptible to Another option consists in coating the cellulosic nanomaterial using
interact physically with the cellulosic surface and with an apolar matrix the same polymer as for the matrix using a dissolution/precipitation
6 A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8
Fig. 6. Evolution of the loss angle tangent versus temperature at 1 Hz for NR films reinforced with (a) CNC and (b) CNF extracted from the rachis of date palm tree. Filler content: 0 (●),
1 (○), 2.5 (▲), 5 (Δ), 7 5 (×), 10 (■), and 15 wt.% (□) [7].
All these studies used a wet processing method, i.e. the nanocom- Apart these two phenomena which are inherent to the melt pro-
posites were prepared from never-dried CNC, allowing keeping the cessing technique, the homogeneous dispersion of hydrophilic cellu-
good dispersion state of the cellulosic nanomaterial in water and en- losic nanomaterials within a generally hydrophobic polymer matrix
suing homogeneous dispersion in the polymeric matrix after water requires their coating to hinder the formation of inter-particle hydrogen
evaporation. We have previously seen that different strategies can bonding. The reactivity of surface hydroxyl groups can be turned off
be used to avoid the irreversible aggregation of the nanoparticles by surface chemical grafting or physical coating of the nanoparticles as
upon drying and promote their homogeneous dispersion with limited previously explained. However, this strategy introduces defects and de-
thermal degradation within a hydrophobic matrix by melt extrusion. teriorates the cellulose nanoparticle percolation, and the full potential of
However, disappointing mechanical properties are reported for these the nanofiller is lost leading to mechanical properties which are far from
systems, far from the expectations observed for wet-processed nano- the expectations.
composites, even if improvement is generally observed compared to This effect was well exemplified for chitin nanocrystal (ChNC)
direct extrusion of unmodified nanoparticles. In addition, it is worth reinforced NR [17]. Neat ChNC as well as chemically modified ChNC
noting than in most cases a semicrystalline polymeric matrix was used using different coupling agents, namely phenyl isocyanate (PI), alkenyl
and it was clearly shown that cellulose nanomaterials generally act as succinic anhydride (ASA), and 3-isopropenyl-α,α’-dimethylbenzyl
nucleating agent inducing an increase of the degree of crystallinity of isocyanate (TMI) were prepared. All nanocomposite materials were
the matrix. This enhanced crystallinity of the polymeric matrix obvious- obtained by casting-evaporation thus avoiding mechanical degradation
ly participates to the improvement in the stiffness of the material, which and orientation of the nanorods. The liquid processing medium for
is difficult to dissociate from the real direct reinforcing effect of the hydrophilic neat ChNC was water (NR in latex form) whereas it was
nanoparticle. However, a recent publication showed that the dimen- toluene for hydrophobic modified ChNC (a solvent for NR). Even if im-
sions of CNC have a stronger impact on the crystallinity of the matrix proved filler/matrix adhesion was evidenced for the various chemical
and mechanical stiffness of the nanocomposite than its volume fraction, treatments, the mechanical performances of the composites strongly
and that the mechanical reinforcing effect is mostly caused by the CNC- decrease after the chemical modification. This loss of performance was
induced crystallinity of the matrix [25]. attributed to the partial or total destruction of the three-dimensional
A probable cause of this unexpected poor mechanical reinforcement ChNC network assumed to be present in the unmodified composites.
behavior results from the high shear rates involved in the extrusion
process. Indeed, a mechanical degradation (length decrease) of CNC
upon melt extrusion was reported [1]. Moreover, it can obviously 6. Conclusions
induce orientation of the elongated nanoparticles in the extrusion direc-
tion, limiting the formation of a percolating network, which is the basis Cellulose nanomaterials can be extracted from any cellulosic source
of the reinforcing effect of cellulose nanomaterials. This preferential ori- in the form of cellulose nanofibrils (CNF) or cellulose nanocrystals
entation phenomenon was evidenced using small angle X-ray scattering (CNC) using a mechanical or acid hydrolysis treatment, respectively.
(SAXS) experiments for CNC reinforced LDPE prepared by extrusion and Both nanomaterials display high stiffness and are lightweight making
was found to be amplified for increasing CNC contents [29]. It was also them ideal candidates for the preparation of polymer nanocomposites.
observed using 2D–small amplitude oscillary shear (2D–SAOS) experi- Casting-evaporation from an aqueous (or at least polar) medium is
ments for injection-molded CNC reinforced polybutyrate adipate tere- the most suited processing method, since it preserves the dispersion
phthalate (PBAT) [26]. The effect of a thermal annealing treatment state of the nanoparticles in this medium as well as the surface hydroxyl
of CNC reinforced injection-molded nanocomposites on the possible groups leading to unexpected mechanical properties. This slow wet
auto-reorganization of the nanofiller as a first step to create an isotropic process gives the highest mechanical performance materials compared
material, the initial condition to induce 3D–network formation under to other processing techniques. Indeed, during liquid evaporation
mild conditions, was investigated [26]. Even if the high viscosity of the strong interactions between nanoparticles can settle and promote the
polymer melt limited the movement of the nanoparticles and hindered formation of a strong percolating network through H-bonding. This
the formation of the desired percolating network, a spatial reorganiza- network ensures the mechanical stiffness of the material, the intrinsic
tion of the nanorods was observed after short conditioning time. It sug- stiffness of the nanoparticles surprisingly playing only a minor role.
gested that it should be possible to partially alter the organization of the However, it occurs only above their percolation threshold although
particle within the polymeric matrix imposed by the injection-molding this continuous network is overexploited and often mentioned in
process. However, adequate lower shear rates melt processing should the literature even if the filler content is lower than the percolation
limit both the breakage of CNC and its orientation. threshold. This strategy is probably well adapted for niche applications.
8 A. Dufresne / Current Opinion in Colloid & Interface Science 29 (2017) 1–8
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of special interest.
••
of outstanding interest.