Research Article

Received: 26 May 2013 Revised: 14 August 2013 Accepted article published: 28 August 2013 Published online in Wiley Online Library: 2 October 2013

(wileyonlinelibrary.com) DOI 10.1002/pi.4610

Surface modification of cellulose nanocrystals

by grafting with poly(lactic acid)
Mercedes Peltzer,a∗ Aihua Pei,b,c Qi Zhou,b,c Lars Berglundc
and Alfonso Jiméneza

Abstract
The use of biopolymers obtained from renewable resources is currently growing and they have found unique applications
as matrices and/or nanofillers in ‘green’ nanocomposites. Grafting of polymer chains to the surface of cellulose nanofillers
was also studied to promote the dispersion of cellulose nanocrystals in hydrophobic polymer matrices. The aim of this study
was to modify the surface of cellulose nanocrystals by grafting from L-lactide by ring-opening polymerization in order to
improve the compatibility of nanocrystals and hydrophobic polymer matrices. The effectiveness of the grafting was evidenced
by the long-term stability of a suspension of poly(lactic acid)-grafted cellulose nanocrystals in chloroform, by the presence
of the carbonyl peak in modified samples determined by Fourier transform infrared spectroscopy and by the modification
in C1s contributions observed by X-ray photoelectron spectroscopy. No modification in nanocrystal shape was observed in
birefringence studies and transmission electron microscopy.

c 2013 Society of Chemical Industry

Keywords: cellulose nanocrystals; surface modification; grafting-from; ring-opening polymerization; L-lactide

INTRODUCTION sizes, in order to improve their dispersity in low density

The use of biopolymers obtained from renewable resources is
currently growing and they have found unique applications as
matrices and/or nanofillers in ‘green’ nanocomposites. The positive
impact of using natural nanofibers as fillers and as reinforcement
material in nanocomposites provides several advantages such
as their full biodegradability, low density, relatively low cost
and enhanced mechanical properties.1 – 3 The main idea of the
addition of cellulose nanofillers in this approach is to obtain new
and efficient nano-biocomposites with improved properties while
keeping their environmental character.4,5 Cellulose nanocrystals
(CNs) or nanowhiskers have been proposed as convenient nano-
reinforcements, since they are considered one of the best modifiers
for some biopolymers and they are obtained from an abundant
and renewable resource, cellulose. CNs are nanoparticles obtained
from highly crystalline cellulose extracted from cellulose fibers
such as bleached wood pulp, cotton or ramie fibers by acid
hydrolysis. The use of cellulose crystallites as nanofillers for
reinforcement in poly(lactic acid) (PLA) formulations has shown
important advantages over their inorganic counterparts (i.e.
laminated silicates) because of their unique characteristics, such as
biodegradability and biocompatibility, high stiffness, high aspect
ratio and low density.6 Nevertheless, the most important drawback
of using nanocrystals from polysaccharides as reinforcement in
nanocomposites is the poor compatibility between the hydrophilic
CNs and the hydrophobic polymer matrices, such as PLA.7
A stable dispersion of cellulose nanofibers and/or nanocrystals
in non-polar media, such as solvents or polymer matrices,
can be accomplished by the addition of surfactants8,9 or by
chemical modification of the nanocrystal surface.10 Other authors
have proposed functionalization of CNs by an esterification
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polyethylene.11 These grafting reactions and further blending with
low density polyethylene led to homogeneous nanocomposites
with a significant improvement in their elongation at break with
increasing length of the grafted chains. On the other hand, Siqueira
et al. grafted cellulose nanoparticles with long chain isocyanates,
obtaining nanoparticles with good dispersion in organic solvents
and allowing processing of nanocomposite films for a broad range
of polymeric matrices.5 In addition to these modifications, surface
acetylation has also been considered to reduce the polarity of
cellulose and to improve the dispersion and adhesion of the
CNs to polymer matrices.4,12,13 This is a simple and fast method,
where cellulose hydroxyl groups react with acetic anhydride. It was
reported that this modification of CNs resulted in good dispersion
in organic solvents and lower polarity in comparison with non-
modified nanocrystals. Good mechanical properties were observed
when modified CNs were blended with PLA. Another method for
CN modification was based on their partial silylation through
reaction with n-docecyl-dimethylchlorosilane in toluene in order
to improve their dispersion in PLA. Silylated cellulose showed
∗
Correspondence to: M. Peltzer, Analytical Chemistry, Nutrition and Food
Sciences Department, University of Alicante, PO Box 99, 03080 Alicante, Spain.
E-mail: mercedes.peltzer@ua.es
a Analytical Chemistry, Nutrition and Food Sciences Department, University of
Alicante, PO Box 99, 03080 Alicante, Spain
b School of Biotechnology, Royal Institute of Technology, AlbaNova University
Centre, SE-106 91 Stockholm, Sweden
c Department of Fiber and Polymer Technology, Royal Institute of Tecnology,

reaction with organic acids with aliphatic chains of different SE-100 44 Stockholm, Sweden

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Surface modification of cellulose nanocrystals
very good dispersion in the polymer matrix and it was reported
that, after the addition of only 1 wt% of modified nanocellulose,
the crystallization rate of PLA increased significantly. However,
the interfacial adhesion between PLA and the nanocrystals was
not improved since mechanical properties of the nanocomposites
were not enhanced by the CN modification.6
Grafting of polymer chains to the surface of cellulose nanofillers
was also studied to promote the dispersion of CNs in hydrophobic
polymer matrices. The catalytic ring-opening polymerization (ROP)
of lactones is the most common route for the synthesis of
polyesters based on bio-based monomers, such as lactic acid. This
reaction can be carried out in the melt or in solution by cationic,
anionic or coordination-insertion mechanisms, depending on the
catalyst. Stannous octoate (Sn(Oct)2 ) is the most common catalyst
in ROP processes due to its high effectiveness and low toxicity.7
Lönnberg et al.12 and Lin et al.14 grafted PCL from the surfaces
of cellulose nanofibers and nanocrystals, respectively, with good
dispersion of the cellulose nanofillers in hydrophobic polymer
matrices. PCL-grafted CNs were incorporated into a PLA matrix to
produce nano-biocomposites with high mechanical performance.
Recently, PLA chains were also chemically grafted on the surface of
CNs to enhance the compatibility between them and biopolymer
matrices such as PLA, resulting in a general improvement in the
physicochemical properties of the nano-biocomposites.15
The aim of this study was to modify the surface of CNs by grafting
from L-lactide by ROP in order to improve the compatibility of
nanocrystals and hydrophobic polymer matrices, such as PLA.
EXPERIMENTAL
Materials
Microcrystalline cellulose (MCC) Avicel PA-200 was purchased
from Sigma-Aldrich (Móstoles, Spain). Sulfuric acid was supplied
by Merck (Darmstadt, Germany). Chloroform and toluene were
also obtained from Sigma-Aldrich. L-Lactide 98% (Sigma-Aldrich)
and tin(II) ethylhexanoate (Sn(Oct)2 ) (95%, Aldrich) were used as
received.
Nanocrystal preparation
CNs were prepared by acid hydrolysis of MCC with H2 SO4 . MCC (20
g) was dispersed in 175 mL of 64 wt% H2 SO4 and then stirred at 600
rpm for 30 min at 45 ◦ C. The reaction was stopped by diluting the
suspension with 20-fold of distilled water and washed by succes-
sive centrifugations at 4500 rpm for an extra 20 min. Furthermore
nanocrystals were dialysed against deionized water for 7 days,
(a)
Figure 1. Scanning electron micrographs of cellulose nanocrystals: (a) 50 000×; (b) 100 000 × .
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followed by an ultrasonic treatment. Mixed bed ion exchange
resin (Dowex Marathon, Sigma-Aldrich, Stockholm, Sweden
MR-3 hydrogen and hydroxide form) was added to the cellulose
suspension for 48 h and then it was removed by filtration. This
procedure ensured that all ions linked to the cellulose molecules
were removed except the H+ counter ions associated with the
sulfate groups on the CN surfaces. A small amount of NaOH (1%)
was added in order to increase the pH until neutrality and to avoid
degradation of CNs during surface modification and processing at
high temperatures. The resultant CN aqueous suspensions were
approximately 0.5% (w/w) and the yield was ca 20%. Finally, CN
suspensions were lyophilized to ensure safe storage before use.
The nanocrystals obtained by following this procedure were
examined by SEM (FE-SEM, Hitachi S-4800) at an acceleration
voltage of 1 kV. A droplet of dilute CN suspension (0.1 wt%) was
deposited on a mica disc with a drop of poly-L-lysine solution
before testing.
Surface modification of CNs by grafting from PLA via ROP
of L-lactide
Grafting was carried out by the following procedure. 50 mg of
lyophilized CNs were dispersed in 10 mL of toluene under stirring
in a reaction flask for 24 h. Thereafter, L-lactide and toluene (15
mL) were added and the flask was immersed in an oil bath at
95 ◦ C. A catalytic amount of Sn(Oct2 ) (1 wt% of the monomer)
was added to the reaction mixture under a nitrogen flux. The
polymerization reaction was then allowed to proceed for 20 − 24 h.
The ratio between monomer (L-lactide) and CNs was 300:1 and
400:1; these samples were called CN-g-PLA 300 and CN-g-PLA 400,
respectively. In order to remove the adsorbed but not chemically
bonded polymer, the grafted CNs were washed with chloroform
with further centrifugation in the same experimental conditions.
Fourier transform infrared (FTIR) analysis of the supernatant was
carried out in order to confirm the efficiency of the washing
procedure until no polymer was detected in the supernatant.
Characterization
FTIR was performed on a Bruker Analitik IFS 66 equipped with a
Golden Gate single reflection attenuated total reflectance (ATR)
system. ATR infrared spectra were obtained in the 4000 − 600
cm−1 region, using 128 scans and 4 cm−1 resolution, in order to
compare the significant absorption bands for grafted cellulose and
the original CNs. Birefringence of the suspensions containing CNs
was studied with a setup containing a lamp, a magnetic stirrer and
two polarizing filters.
(b)
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Figure 2. Suspensions of unmodified cellulose nanocrystals (right vial) and
CN-g-PLA 400 (left vial) in chloroform after 24 h.
Transmission electron microscopy (TEM) images were recorded
with a JEOL JEM-2010 (Tokyo, Japan) using an accelerating voltage
of 100 kV. X-ray photoelectron spectroscopy (XPS) (K-ALPHA,
Thermo Scientific Walthlm (MA), USA) was used to analyse the
CN and CN-g-PLA surfaces. All spectra were collected using Al-K
radiation (1486.6 eV), with a twin crystal monochromator, yielding
a focused X-ray spot with a diameter of 400 nm, at 3 mA and 12
kV. The alpha hemispherical analyser was operated in the constant
energy mode with survey scan pass energies of 200 eV to measure
the whole energy band and 50 eV in a narrow scan to selectively
measure particular elements. Charge compensation was achieved
with the system flood gun providing low energy electrons and
(a)
Figure 3. Birefringence of the cellulose nanocrystals dispersed in chloroform: (a) CN; (b) CN-g-PLA 400.
(a)
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Figure 4. TEM of CNs (a) before and (b) after grafting.
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low energy argon ions from a single source. Thus, XPS was used
to provide the chemical bonding state as well as the elemental
composition of the CNs and CN-g-PLA surfaces.
RESULTS AND DISCUSSION
The homogeneity of the suspensions obtained after treatment
by acid hydrolysis of MCC was studied by obtaining the SEM
images of the CNs (Fig. 1). It can be observed that the presence of
CNs leads to individualized rod-like nanocrystals with high aspect
ratio. In addition, no agglomerates were observed because of the
dilution of the nanocrystals before lyophilization, the electrostatic
repulsion between surface-grafted sulfate ester groups resulting
from the sulfuric acid hydrolysis and the CNs repelling each other
and not flocculating.16
The main purpose of the surface modification of CNs is to achieve
their full dispersion in non-polar solvents and/or hydrophobic
polymers to make their blending with biopolymers such as
PLA easier. Figure 2 shows a photograph of suspensions of
unmodified CNs and grafted nanocrystals with PLA, both dispersed
in chloroform. As can be seen, the dispersion after the grafting
reaction was significantly improved due to the covalent bonding
of PLA chains with CNs. This result is an indication of the improved
performance of grafted CNs to obtain homogeneous blends with
hydrophobic polymers such as PLA.
However, it is important to maintain the CN structure after
grafting. At low concentrations, CN particles were randomly
oriented in aqueous suspensions as an isotropic phase. At higher
(b)
(b)
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Figure 5. FTIR spectra of unmodified and grafted CNs with PLA: (A) full spectra; (B) carbonyl peak area enlarged.

2nd wash

3rd wash

4th wash
5th wash

3300 2800 2300 1800 1300 800

Wavenumber (cm-1)

Figure 6. FTIR spectra of the chloroformic supernatant from washing steps.

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concentrations, suspensions of CNs should suffer a change in

their optical behaviour, from an isotropic to an anisotropic chiral
nematic liquid crystalline phase.17 Therefore, for further increases
in CN concentration, suspensions of CNs showed the birefringence
phenomenon.18 It has been suggested that a study of this
birefringence could give an indication of the degree of association
or isolation of CNs in a suspension.19 Figure 3 shows the clear
flow birefringence of CNs and grafted CNs. In both cases, strong
birefringence was observed. This result indicates the existence of a
nematic liquid crystalline alignment in both samples showing the
presence of CNs with the usual characteristics. This is an additional
indication of the good dispersion of CNs in chloroform, without
agglomeration and preserving the intact crystal shape.20
TEM images were recorded for neat and modified CNs. Dilute
suspensions (0.01 wt%) in chloroform for both samples were
prepared and a microdrop was deposited on a TEM grid for
further analysis. Figure 4 shows TEM images of CNs and CN-g-PLA
samples. Individual nanoparticles were observed in both cases and
the rod-like shape of the nanocrystals was also maintained after
grafting.
The surface modification of CNs was evaluated by FTIR for all
samples. Figure 5 shows the most relevant results obtained in these
tests. The main difference between spectra for non-modified and
grafted CNs was the presence of the peak at 1758 cm−1 (see Figure
5 (b)), corresponding to the stretching frequency of the carbonyl
group in PLA and/or lactic acid oligomers.14 The presence of this
peak in PLA suspensions has already been reported by Rincon-
Lasprill et al.21 These authors studied the synthesis and further
characterization of PLA in specific conditions. They reported that
the stretching band related to the carbonyl group shifted from
1727.1 to 1757.9 cm−1 after polymerization of the monomer
(lactide) to polymer (PLA). As expected, the intensity of that
peak increased for the sample with a higher initial concentration
of monomer (CN-g-PLA-400). This result could indicate that the
amount of PLA grafted from the CN surface could be controlled by
the added monomer to nanocrystal ratio. Lönnberg et al. also
reported that the variation of the
-caprolactone to initiator
ratio conditioned the length of PCL chains grafted to CNs
and consequently the amount of PCL grafted from the surface
increased.12 In addition, the intensity of the broad band around Figure 7. General XPS spectra for (a) unmodified CN; (b) CN-g-PLA 300; (c)
3300 cm−1 corresponding to the hydroxyl group present in the CN-g-PLA 400.
original cellulose structure clearly decreased with increase in
PLA concentration and the consequently higher efficiency in the technique and this led to a study of the chemical composition
polymer grafting. These results confirm the success of the grafting of all materials. In particular this technique helped to elucidate
procedure of CNs by ROP of L-lactide, initiated from the hydroxyl whether PLA was grafted from CNs and to evaluate whether
groups available on the CN surface and catalysed by tin octoate. the grafting reaction was successful. Spectra of unmodified and
FTIR was also used to evaluate the efficiency of the washing and modified CNs are shown in Figure 7 with carbon and oxygen atoms
purification steps after the grafting reaction. The main indication being the main components.
of the high efficiency of these processes was obtained from the The general carbon XPS signal in Fig. 7 could be resolved
spectra of chloroform supernatants after centrifugation in order to into several peaks corresponding to different chemical structures,
determine the absence of free PLA, polymerized during reaction which reflect the local environment of the carbon atoms.
but not grafted to CNs. These spectra were obtained after every Figure 8 shows the deconvolution of the general C1 peaks for
washing step and they are shown in Fig. 6. It should be noticed that all the studied materials. The C1 high resolution spectra could
the intensity of the characteristic peak of the PLA carbonyl group be resolved into four different peaks corresponding to C1, C2,
decreased with the successive washing and purification steps until C3 and C4 and their corresponding binding energies. It should
complete disappearance after the fifth step. Therefore, it can be be noted that the C1 peak corresponds to C−C/C−H linkages,
stated that no free PLA was present after five purification steps the C2 peak corresponds to C−O bonds in alcohol and ether
and consequently all PLA present in the materials is grafted to CNs functional groups, the C3 peak corresponds to O−C−O and C O
forming the CN-g-PLA samples. structures from acetal moieties and finally the C4 peak corresponds
The presence of PLA grafted on the CN surface was also to O−C O bonds representing the ester carbon contribution.5,11
confirmed by XPS tests. The main chemical elements and The quantification of the relative intensity of each peak after
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particularly the carbon based bonds were detected using this deconvolution is shown in Table 1.

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70000

60000 Total (a)

50000

40000 C2

30000
C3
20000 C1

10000 C4

0
292 290 288 286 284 282 280
Binding Energy (eV)
25000
(b) 30000
Total
(c)
20000 C2 Total
25000
C1
20000 C2
15000
C1
C3
15000
10000 C3
C4 10000 C4

5000
5000

0 0
294 292 290 288 286 284 282 280 294 292 290 288 286 284 282 280
Binding Energy (eV) Binding Energy (eV)

Figure 8. Deconvolution of the C1 signal into its constituent contributions for unmodified and modified CNs: (a) unmodified CN; (b) CN-g-PLA 300; (c)
CN-g-PLA 400.

higher energies could also be caused by oxidation of the hydroxyl

Table 1. XPS analysis of cellulose nanocrystals before and after
grafting groups. This behaviour could be attributed to the chain grafting
to the nanocrystal surface providing an additional proof of the
C−C/C O−C O−C successful grafting of PLA to cellulose after following the process
Samples −Hx (%) C−O (%) −O (%) O (%) proposed in this study.
CN 8.5 40.1 9.2 1.3
CN-g-PLA 300 14.0 27.1 5.2 8.1 CONCLUSIONS
CN-g-PLA 400 26.0 25.8 2.5 9.7
A ‘grafting-from’ method to get CNs with active surfaces to be fur-
ther blended with hydrophobic polymers was developed. CNs were
prepared by acid hydrolysis of MCC and further modified by the
The presence of carbon atoms with three of their four typical ROP of L-lactide, initiated from the hydroxyl reactive groups avail-
bonds linked to oxygen atoms in unmodified CNs could be due to able in the CNs. Birefringence was observed in solutions of modified
the presence of residual cell wall polysaccharides with carboxylic nanocrystals in chloroform showing their intact crystal shape with
groups that could remain linked to the CNs or could be the result no apparent agglomeration. TEM images also evidenced that the
of the oxidation of the end groups of cellulose.7 In addition, crystal shape was maintained after modification. The effectiveness
the presence of carbon atoms without any oxygen bond could of the polymerization reaction was evidenced by spectroscopic
be explained only by the presence of some contaminants, since techniques and by the dispersion in non-polar solvents, showing
cellulose structures do not contain any carbon without oxygen the reduction of the polar character of the nanocrystals. In sum-
bonds.7 In Figure 8 and Table 1, it can be noted that considerable mary, the ‘grafting-from’ CNs with L-lactide is a very promising
changes were found in the proportion of each type of C atom, way to achieve good dispersion of nanocrystals through polymer
especially in the C1 peak referring to aliphatic chains (C−H) present matrices in order to obtain nano-biocomposites with improved
in grafted samples in comparison with the pristine cellulose. In properties. Further studies on blending of these new modified CNs
addition, a decrease in the intensity of the C2 peak with the with common biopolymers such as PLA are currently ongoing.
modification was observed due to the decrease in the number of
C−OH bonds, since cellulose −OH groups are considered to be
initiators of the ROP reaction. C3 and C4 peaks were shifted to ACKNOWLEDGEMENT
higher energies and their intensities were increased in modified The authors gratefully acknowledge the financial support from the
CNs due to the increase in the quantity of C O and O−C O Spanish Ministry of Economy and Competitiveness (project Ref.
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bonds by the presence of PLA in these materials. This shift to MAT2011-28468-C02-01).

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