Polymer Degradation and Stability 96 (2011) 1631e1638

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Inuence of cellulose nanowhiskers on the hydrolytic degradation behavior

of poly(D,L-lactide)
Everton Luiz de Paula a, Valdir Mano b, Fabiano Vargas Pereira a, *
a
b

Department of Chemistry, Federal University of Minas Gerais, Av. Antnio Carlos, 6627, Pampulha, CEP 31270-901 Belo Horizonte, MG, Brazil
Department of Natural Sciences, Federal University of So Joo Del-Rei, Praa Dom Helvcio, 74 Fbricas, CEP 36301-160 So Joo Del Rei, MG, Brazil

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 18 March 2011
Received in revised form
8 June 2011
Accepted 10 June 2011
Available online 7 July 2011

This paper reports the preparation of bionanocomposites based on poly(D,L-lactide) and cellulose nanowhiskers (PDLLA/CNWs) and studies the inuence of the CNWs on the hydrolytic degradation behavior of
the polylactide. The hydrolytic degradation process was studied in a phosphate buffer medium through the
sample weight loss and also by FTIR, DSC and TGA measurements. The presence of CNWs induced a strong
delay in the hydrolytic degradation of the PDLLA, even when the concentration of the nanollers was only
1%. This effect was related to the physical barrier created by the highly crystalline CNWs that inhibited water
absorption and hence retarded the hydrolytic degradation of the bionanocomposites. In addition, the
incorporation of cellulose nanocrystals in the PDLLA also made the biopolymer more thermally stable,
increasing the initial temperature of mass loss even after the degradation in phosphate medium. The results
presented here show the possibility of controlling the biodegradability and prolonging the service life of
a polylactide through the incorporation of a small quantity of nanollers obtained from renewable
materials.
2011 Elsevier Ltd. All rights reserved.

Keywords:
Hydrolytic degradation
Cellulose nanowhiskers
Poly(D,L-Lactide)
Bionanocomposite

1. Introduction
Polymeric nanocomposites are being used in a wide variety of
applications because of their versatility. The properties and behavior
of a nanocomposite system can be easily adjusted by changing the
composition of the nanoscale reinforcing component or the polymer
matrix [1,2].
Interest has recently increased in the use of biopolymers as
matrices for nanocomposites because of the environmental impact
caused by conventional plastics derived from petroleum. However,
the majority of these biopolymers have poor mechanical and thermal
properties that make them unsuitable for some applications. In this
way, inorganic nanoparticles [3e5] or natural organic llers [6,7] can
be added to different biopolymers to prepare different bio-based
nanocomposites with improved physicalemechanical properties.
Additionally, to produce a fully renewable and biodegradable
nanocomposite both, the polymer matrix and the nanoreinforcement have to be derived from renewable resources.
In this way, highly crystalline rod-like nanostructures obtained
from cellulose, called cellulose nanowhiskers (CNW) or cellulose
nanocrystals (CNC), have attracted signicant attention during the

* Corresponding author. Tel.: 33 31 3409 5753; fax: 33 31 3409 5700.

E-mail address: fabianovargas@yahoo.com (F.V. Pereira).
0141-3910/$ e see front matter 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2011.06.006

last decade as potential nanoreinforcements for different polymers

[8e10]. Cellulose is abundant in nature and is found in both plants
and bacteria. Cellulose molecules are stabilized laterally in the cell
walls by hydrogen bonding between hydroxyl groups, resulting in
the formation of bundles of microbrils. Upon controlled acid
hydrolysis, the microbrils undergo transverse cleavage along the
amorphous regions and release crystalline cellulose nanoparticles
or cellulose nanowhiskers [10]. These particles consist of highly
crystalline rod-shaped nanomaterials (the length and lateral
dimensions of which depend on the source of cellulose), presenting
a high modulus (around 100 GPa) [11].
One of the major challenges in the preparation of nanocomposites using CNW nanollers is the ability to achieve acceptable
levels of dispersion of the cellulose nanocrystals within a polymeric
matrix. The elementary crystallites commonly aggregate laterally
due to their high specic area and the strong hydrogen bonds
between them [12]. Several attempts have been made to achieve
a good dispersion of the nanowhiskers in different polymer matrices,
including the use of surfactants [13,14] and the chemical surface
modication of the whiskers [15e17].
Among biodegradable polymers, the family of polylactides has
recently received a great deal of investigation [18e21]. Lactic acid is
easily obtained by biotechnological processes (usually from lactobacillus) in an economically feasible manner. To produce polylactide, corn or sugar sources are processed to produce D-glucose,

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E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

which is then fermented to produce lactic acid [22]. Using an

appropriate catalyst and heat, lactic acid is converted to the cyclic
lactide dimmer. A suitable catalyst can induce ring opening polymerization of the lactide dimer, producing poly(lactic acid). The
resulting plastic has mechanical properties that are intermediate
between the polyolens and other biopolymers [2], and it can be
used in a variety of applications, including biomedical uses [23]
such as sutures and medical implants, food products and packaging materials [2]. In addition, this biopolymer can be easily
processed by conventional processing techniques. The proportion
of the L and D isomeric forms will determine the properties of the
polymer, i.e., if the material is amorphous or semi-crystalline. A
racemic mixture of isomers L and D is usually called D,L-lactide. The
monomers L and D,L-lactide are used exclusively for the production
of polylactides and are called, poly(L-lactide) e PLLA, and poly(D, Llactide) e PDLLA, respectively [24]. The random distribution of
D and L units in the poly(D, L-lactide) hinders the orientation of the
chains, producing a polymer with mechanical properties that are
inferior to those of PLLA. In addition, because the PDLLA is an
amorphous polymer, it only presents a glass transition temperature
(ranging from 50 to 60  C).
The polylactides have also been studied in the preparation of
blends, copolymers and nanocomposites. Wan and colleagues [25]
produced polymeric PDLLA/chitosan membranes. Xiong and
colleagues [26] prepared the copolymer PDLLAPVPPDLLA to achieve a higher biodegradability compared to pure PDLLA, while Luo
and colleagues [27] prepared an amphiphilic poly(N-vinylpyrrolidone)-block-poly(D,L-lactide) (PVP-b-PDLLA) diblock copolymer. Recently, PDLLA has been studied for use in controlled drug
release systems. Zhang and colleagues [28] showed the production
of a porous tissue based on PDLLA porous biphasic calcium and
phosphate (BCP) that has applications in controlled drug release
systems.
The degradation of a synthetic polymer is caused by several
factors and results in the loss of physical properties [18,29]. This
process is complex and can proceed via hydrolysis (most often
catalyzed by enzymes) and/or oxidation (UV- or thermo-induced).
In the degradation mechanism, polymer chain scission and the
breakdown of the structure in the crystal lattice generally occurs.
Factors that can cause the degradation of a polymer can be related
to the processing conditions and also the environmental effects of
the matrix. Certain characteristics of polymers can inuence the
degradation process. In addition to the chemical structures of
polymers, other factors also inuence the rate of degradation such
as crystallinity due to the different chain packing arrangements of
each polymer. The amorphous structure of the PDLLA allows more
water to penetrate this structure, resulting in a faster degradation
than PLLA [30]. Some authors have studied the hydrolytic degradation of PDDLA and composites of this polymer [30e35]. For
example, Fu and co-workers [32] prepared a multi-arm star polymer by ring-opening polymerization of D,L-lactide using multifunctional epoxidized soybean oil as an initiator and concluded that
the degradation rate of the star-shaped polymer was slower than
that of the linear PDLLA. One explanation for this phenomenon was
that soybean oil can minimize the amount of trapped water,
therefore slowing the permeation of water into the polymer. In
another work, Chen et al. [35] observed greater hydrolytic degradation for the composites based on PDLLA/chitosan/tricalcium
phosphate than neat PDLLA. This behavior was explained in terms
of the hydrophilicity of the composites using contact angle and
water absorption measurements.
Investigations on polymer nanocomposites with different
biopolymers and using different nanollers, such as clay, carbon
nanotubes or CNWs, usually focus on improvements in the
mechanical or barrier properties. Thus, the possible inuence of the

nanoller addition on the polymer degradation matrix remains to

be addressed, mainly if the nanoller is also a biodegradable
material.
The goal of the present work was to study the effect of the
addition of organic nanollers (cellulose nanowhiskers) on the
hydrolytic degradation behavior of a biodegradable matrix. To
achieve this aim, we studied the controlled hydrolytic degradation
behavior of a PDLLA/CNW nanocomposite in phosphate buffer
medium. The degradation process of the nanocomposites was
monitored using FTIR spectroscopy, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). To the best of our
knowledge, this is the rst time that the inuence of CNWs on the
degradation behavior of a biodegradable matrix has been
determined.
2. Experimental
2.1. Materials
Eucalyptus kraft wood pulp with high a-cellulose content
(96e98%) was generously supplied by Bahia Pulp Company
(Brazil). Sulfuric acid, sodium hydroxide, hydrogen peroxide and
sodium chlorite were purchased from Aldrich, So Paulo, Brazil.
Acetic acid 99% and hydrochloric acid were purchased from Synth,
So Paulo, Brazil. All reagents were used without further
purication.
2.1.1. Cellulose Nanowhisker Preparation
Sulfuric acid hydrolysis of eucalyptus wood pulp was performed
as described in the literature with minor modications [36,37].
Briey, the received wood pulp was treated with NaOH solution,
and then a bleaching treatment was performed using acetate buffer
and aqueous chlorite (1.7 wt% in water). Then, the wood pulp was
ground using a Willey mill until a ne particulate was obtained.
Subsequently, 10.0 g of cellulose was added to 160 mL of 65 wt%
sulfuric acid under strong mechanical stirring. Hydrolysis was
performed at 50  C for approximately 50 min. After hydrolysis, the
dispersion was diluted 2-fold, and the suspensions were then
washed using three cycles of centrifugation and resuspension. The
last washing was conducted through dialysis with deionized water
until the dispersion reached pHw6. Afterward, the dispersions
were sonicated (Unique Sonicator, 40 kHz) for approximately 5 min
and were nally ltered using a lter paper with a 20 mm pore size.
The nal concentration of the CNW dispersions was approximately
1 wt %.
2.1.2. Preparation of nanocomposites
The nanocomposites lms were prepared via a solution casting
method. Firstly, freeze-dried CNWs were dispersed in DMF (0.5%),
using sonication to achieve full dispersion in the solvent. The
dispersion of the cellulose nanocrystals in DMF was checked by
observing the ow birefringence between crossed polarizers (not
shown here). The appropriate amount of CNW/DMF dispersion was
added to a PDLLA solution with the same solvent to prepare nal
composites with the desired whiskers concentrations: 0%, 1%, and
5%. The samples were named PDLLA, PDLLA-1%, and PDLLA-5% for
0%, 1%, and 5% whisker content, respectively. After mixing for 12 h,
the mixtures were poured into a Teon plate and left for 18 h to
allow slow evaporation of the solvent. The lms were further dried
under vacuum for 8 h.
2.2. Hydrolytic degradation
The hydrolytic degradation of each of the samples (30 mg of dry
weight) was performed in 10 mL of phosphate-buffered solution

E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

1633

(pH 7.4). The phosphate-buffered solution was replaced by a fresh

solution every ve days. The asks were immersed in a water bath
at 37  C. At predetermined times (one week, two weeks, one
month, two and a half months and three months), samples were
removed from the buffered solution and rinsed several times with
distilled water. Subsequently, the samples were dried to remove the
buffer solution adhered on the surface of the lms and weighed to
determine the residual mass. After the hydrolytic degradation, the
specimens were rinsed, dried and placed in a desiccator for
characterization.

2.3. Water uptake

To verify whether the cellulose nanocrystals can hinder the
adsorption of water by the PDLLA polymer, water uptake experiments were conducted using distilled water at 37  C. The water
absorption was calculated as the difference between the weight of
the wet lm at each time point and the weight of the original dry
weight of the lm divided by the weight of the original dry weight
of the lm.

Fig. 1. TEM image of the eucalyptus CNWs. The scale bar is 200 nm.

3.2. Weight loss of the nanocomposites PDLLA/CNWs

2.4. Instrumental analysis
Transmission electron microscopy (TEM) images of CNWs were
taken using a FEI Tecnai G2-Spirit with 120 kV acceleration voltage.
The nanocrystals were deposited from aqueous dispersions on
a carbon- Formvar-coated copper (300-mesh) electron microscopy
grid. The samples were subsequently stained with 2% uranyl acetate
solution to enhance the microscopy resolution.
Fourier transform infrared spectroscopy (FTIR) was recorded
using a Perkin Elmer FTIR spectrometer (GX). The infrared spectra
were obtained in the 4000e400 cm1 region in lm samples on the
ZnSe window.
DSC experiments were conducted on a PerkinElmer DSC Diamond in a temperature range of 30200  C using 10 mg of sample
specimen, according to the following temperature program: from
30 to 200  C at 10  C min1; cooling from 200 to 30  C at
20  C min1; and heating from 30 to 200  C at 10  C min1.
Thermogravimetric analyses (TGA) were performed using a HiRes TGA 2950 thermogravimetric analyzer from TA instruments
with a heating ramp of 20  C min1 under air ow (74 cm3 min1)
from room temperature to 600  C.

A phosphate buffer solution (pH 7.4) was used for the hydrolytic degradation of PDLLA and its nanocomposites because this is
the most common buffer in studies for biomedical applications due
to the similarity with body uids, including pH. The hydrolytic
degradation in buffered medium was monitored for 12 weeks, and
the weight loss of the samples during this period is shown in Fig. 2.
Fig. 2 clearly shows the inuence of the CNWs on the degradation time of the PDLLA polymer. The mass remaining of the neat
biopolymer decreases linearly up to eight weeks, with only 20% of
the polymer mass remaining after 12 weeks. For the nanocomposite with only 1% CNWs, we observed a signicant difference
in degradation behavior compared with the neat PDLLA. The
PDLLA-1% exhibited only a small weight loss during the rst two
weeks, after which the nanocomposite was observed to have
a constant mass. No weight loss was observed for the nanocomposite with 5% CNWs, even after 12 weeks. This behavior
indicates that the presence of the CNWs in the matrix has a clear
delaying effect on the hydrolytic degradation of PDLLA.

3. Results and discussion

3.1. Cellulose nanowhisker characterization
Fig. 1 shows a typical TEM image of the eucalyptus CNWs. The
images were obtained from a diluted suspension (0.01%) and show
individual nanocrystals and some laterally-aggregated elementary
crystallites. The size of these agglomerated nanocrystals depends
on the sample preparation (for example, the use of ultrasound
waves to disperse the CNWs). Nevertheless, the presence of these
aggregates is highly expected even in suspension because of the
high specic area and strong hydrogen bonds established between
the whiskers. However, when the dispersing medium is removed,
as in the case of TEM sample preparation, bundles of whiskers can
be even more numerous than individualized rods [12,36]. From
several TEM images, the mean values of the length (L) and diameter
(D) of the isolated eucalyptus CNW were determined to be
145  25 nm and 6.0  1.5 nm, respectively, giving an aspect ratio
(L/D) of approximately 24.

Fig. 2. Residual mass of the neat PDLLA, PDLLA-1%, and PDLLA-5% as a function of
degradation time.

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E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

It is important to mention that we also performed tensile

mechanical tests on the nanocomposites (results not shown here),
to characterize the inuence of the CNWs on the mechanical
properties of the PDLLA polymer. The results showed that the
maximum tensile strength of the PDLLA/CNWs nanocomposite
(with 1% CNW) was approximately 25% greater than that of the neat
PDLLA.
3.3. Infrared spectroscopy (FTIR)
Degradation of poly(D,L-lactide) occurs via electrophilic attack
by water on the carbonyl ester groups present in the polymer. The
amorphous structure of PDLLA facilitates the diffusion of water in
the polymer matrix, accelerating the degradation process. Thus,
long polymer chains are converted into smaller chains and into
oligomers and monomers [38]. In this way, the degradation causes
an increase in the number of chains and consequently in the
number of terminal carboxyl groups. This degradation mechanism
of PDLLA can be conrmed by FTIR analysis. Fig. 2 shows the FTIR
spectra of the PDLLA and the nanocomposites before and after
degradation (after three months) in phosphate buffer.
The increase in the number of terminal carboxyl groups in the
PDLLA polymer after degradation is demonstrated by the appearance or increase in the absorbance of the band at 3508 cm1, which
corresponds to the OH stretching vibration, and by the appearance
of the 1602 cm1 band representing C]O bond stretching in
carboxylic acids. For the neat PDLLA polymer (Fig. 3a), the bands at
3508 cm1 and at 1602 cm1 were clearly observed after the
degradation process. For the PDLLA-1% composite (Fig. 3b), we also
detected the 1602 cm1 band after degradation, but the absorbance
intensity of the OeH stretching decreased compared to the neat
PDLLA sample after degradation. For the PDLLA-5% (Fig. 3c), the
stretching band related to carboxylic acids (1602 cm1) was not
detected, and the band at 3508 cm1 remained unchanged after
three months in phosphate buffer.
The above data indicate that the presence of CNWs delayed the
overall degradation process of the PDLLA. The amount of water
absorbed by the PDLLA polymer strongly inuences the rate of
chain scission [33]. In this way, one possible explanation for the
increase in stability under hydrolytic degradation conditions for
PDLLA is that the presence of cellulose nanocrystals in the matrix
acts as a physical barrier, preventing the absorption and/or the
diffusion of water within the polymer matrix.
3.4. Water uptake
The PDLLA polymer is well know to be able to absorb a considerable amount of water [30,31] during the rst few days of
hydrolysis due to its amorphous nature that allows water molecules to penetrate more easily than a semi-crystalline polymer,
such as PLLA. To verify whether the inuence of the CNWs on the
degradation behavior occurred by increasing the water resistance
of the biopolymer, we measured the water absorption. Because the
degradation occurs faster in phosphate buffer than in distilled
water, we used this last medium to detect the absorption of water,
avoiding the interference of the weight loss that occurs during the
degradation (as could be the case using phosphate buffer). Fig. 4
shows the water absorption for the neat PDLLA and the nanocomposites as a function of time. The neat PDLLA absorbs approximately 9% of its mass in water in one week and reaches 15% water
absorption in four weeks. For the nanocomposite with only 1%
CNWs, the water absorption values were much smaller, approximately 2% after two weeks, whereas the PDLLA-5% did not
demonstrate any water uptake after four weeks. These results show
that a small quantity of cellulose nanowhiskers inhibit water

Fig. 3. FTIR spectra of PDLLA and nanocomposites before (d) and after () degradation in phosphate buffer for three months: PDLLA (a), PDLLA-1% (b), and PDLLA-5% (c).
Scales in the left Y-axis are the absorbance values for the samples before degradation
and in the right Y-axis are the absorbance values obtained after degradation.

absorption and hence retard the degradation, modifying the

kinetics of the hydrolytic process in PDLLA polymers.
These results are in agreement with those of the residual mass
in the hydrolytic degradation experiment (Fig. 2), in which we
observed a much smaller weight loss for the sample with only 1%
CNWs and no degradation during the experiment in the PDLLA-5%
sample. Previous results demonstrated that for chitosan/CNWs and
also for starch/CNWs systems, the cellulose nanocrystals improved
the water resistance of these matrix, leading to a decrease in the
swelling in water [39e41].

E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

1635

Fig. 4. Water absorption of the neat PDLLA, PDLLA-1%, and PDLLA-5% as a function of
time at 37  C in distilled water.

Additionally, comparable results, where the presence of nanollers reduced the biodegradation rate of polylactides, have been
described [42,43]. Defeng et al. [42] reported the preparation of
PLA/carbon nanotube (CNT) nanocomposites and observed that the
addition of the nanollers retarded the biodegradation of the PLA
in soil. This result was related to the physical barrier promoted by
the CNT that can block the entry of water into the polymer matrix
to some extent. In another study, Fukushima et al. [43] studied the
degradation in compost of PLA and PLA nanocomposites based on
layered hydrated magnesium silicates (sepiolites) and found that
the presence of the nanoparticles seemed to partially delay the
degradation of the PLA matrix. This result was also explained in
terms of barrier effects, in which the nanollers acted as crosslinking entanglements leading to a lower water absorption in the
nanocomposite as compared to neat PLA. However, in some cases,
the presence of nanollers can enhance the degradation, as
described in several studies in which the authors studied the
hydrolytic [44] or compost degradation [18,45] in polylactide/
nanoclay nanocomposites. In these studies, the authors observed
that nanoclays exert a catalytic role on the degradation of the
polylactides, and these results were attributed to the high relative
hydrophilicity of the clays, facilitating the permeation of water into
the polymer matrix and thus accelerating the degradation process.
On the other hand, in this work the presence of the CNCs in the
amorphous PDLLA polymer could provide physical barriers, decreasing
the water absorption through the creation of a tortuous path for the
permeating of water. This behavior can be explained in terms of the
high degree of crystallinity of the nanocrystals which play an important role to hinder the absorption of water by the lms. We believe that
the high level of crystallinity of the CNCs (C.I. 87%, calculated from
XRD analysis), and also their rigid hydrogen-bonded network governed by a percolation mechanism were the responsible for the
improvement of barrier properties of the amorphous PDLLA polymer.
The high crystallinity of the nanowhiskers was also used to
explain the decrease in water vapor transmission rate for
membranes based on PVA/CNCs [46] and xylan/CNCs [47].
Interestingly, the results of the present work showed that the
barrier properties of PDLLA can be enhanced through the incorporation of cellulose nanoparticles in the matrix. This observation
is particularly important because one of the limitations of the use of
PDLLA is its low barrier properties.
3.5. Thermogravimetric analysis
Fig. 5 shows the thermograms of PDLLA (Fig. 5a) and the
nanocomposites (Fig. 5b and c) before and after degradation (also

Fig. 5. TGA curves of PDLLA and the nanocomposites before (d) and after (.)
degradation in phosphate buffer (during three months) with a heating rate of
20  C min1 under air ow: PDLLA (a), PDLLA-1% (b), and PDLLA-5% (c).

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E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

Table 1
TGA data (heating rate of 20  C min1) of PDLLA and PDLLA/CNW nanocomposites
before and after degradation.
% CNWs

Tbegin1/ C

Tend1/ C

Tbegin2/ C

Tend2/ C

0
1
5

290
302
316

410
400
402

260
299
307

354
400
378

Tbegin e temperature of the beginning of mass loss; Tend e temperature of the end of
mass loss; 1 and 2 refer to before and after degradation, respectively.

measured after three months) in phosphate buffer. Table 1

summarizes the data obtained from the thermogravimetric
curves for the stages of mass loss.
In a thermal decomposition of a polylactide, the dominant
reaction pathway [48] (which Tmxw360  C) is an intramolecular
transesterication of the polylactide, giving rise to the formation of
cyclic oligomers. Also, CO, CO2, methylketene, acetaldehyde and
possible H2O from fragmentation reactions can be identied as
a result of primary pyrolysis. In addition, polylactides samples
contaminated with residual Sn from the polymerization process can
show a preceding selective depolymerization step (Tmx w 300  C)
which produces lactide exclusively [48].
Aside from the improvements in mechanical and barrier properties, adding nanollers to a polymer matrix could also lead to an
increase in the degradation temperature. The results obtained in this
work reveal that the incorporation of cellulose nanocrystals in PDLLA
improves the thermal stability of this biopolymer, increasing its
initial temperature of mass loss by approximately 12  C and 26  C for
1% and 5% CNW content, respectively. A more interesting nd is the
effect of the CNW addition on the thermal properties after degradation in phosphate medium. With the addition of only 1% of CNWs
in the matrix, the initial temperature of mass loss increases by
approximately 39  C (from 260 to 299  C), and this effect is more
pronounced with the addition of 5% of CNWs (Tbegin2 307  C). These
results demonstrate that the addition of CNWs to PDLLA induces
a considerable change in the thermal properties of the polymer. In
addition, whereas the thermal properties of the neat PDLLA change
from Tbegin1 290  C (before degradation) to Tbegin2 260  C (after
degradation), the Tbegin of the nanocomposites undergo slight variations during the degradation process (comparing the Tbegin1 and
Tbegin2 values of the nanocomposites). The same behavior was
observed for Tend: the signicant difference observed between Tend
before and after the degradation for the neat PDLLA was not observed
for the nanocomposites.
The analysis of the residual mass after degradation process up to
600  C resulted in more than 98% of thermal degradation for all the
samples (less than 2% solid residue).

Before the degradation process, the Tg values were observed to

depend on the addition of CNWs (Table 2). The increase in these
values with concentration of whiskers in the nanocomposites can
be explained in terms of the restriction of the chain motions
imposed by the presence of the nanocrystals [49], which act as
microdomains preventing the movement of polymer chains.
DSC measurements were also used to investigate the degradation of the neat PDLLA and the nanocomposites, and the results are
presented in Fig. 6.
PDLLA is an amorphous polymer and does not show a crystallization peak. However, during the degradation process of the lactides, crystalline domains appear in the degraded polymer matrix.
Some authors have suggested that this phenomenon is due to the
rearrangement of small chains that are generated during the
degradation [50e52]. The formation of crystalline domains in the
structure of PDLLA was conrmed by DSC analysis only for the neat
PDLLA, in which an endothermic peak appeared at 91  C (Fig. 6). For
the nanocomposites, we did not observe a signal related to the
crystalline domains, even when the CNW content was only 1 wt%.
Moreover, we observed that the Tg value was increased by the
degradation process for the neat PDLLA, and for this sample, the
region of the Tg in the DSC curve broadened after degradation (not
shown here). The crystalline domains that originated during the
degradation process act as a type of cross-linking, hindering the
motion of polymer chains and consequently increasing the Tg.
However, for the nanocomposites PDLLA-1% and PDLLA-5%, no
increase in the Tg values was observed after the degradation
process (Table 2). In this case, because the presence of CNWs
strongly delays the degradation process of the polymer, the Tg
values were not affected. These DSC results are in agreement with
the results obtained from weight loss measurements and FTIR,
showing that the cellulose nanocrystals delay the degradation of
the PDLLA matrix.
Although PDLLA is an amorphous polymer, we observed that its
degradation induces a partial crystallization. Li and Vert [53]
emphasized that the degradation process is more complex than
just the relationship between the amorphous and crystalline parts.
Using different PDLLA lms, these authors showed that the
degradation process is heterogeneous, occurring more rapidly in
the center than at the surface when the lm is in contact with
aqueous media. At the beginning of the process, the degradation
likely occurs mainly on the surface due to the gradient of water
absorption, but as the concentration of carbonyl groups increases in
the center, these groups serve as catalysts for the process. Lam and

3.6. DSC results

To evaluate the thermal behavior of the PDLLA with the incorporation of the CNWs, we also conducted DSC measurements with
the nanocomposites before and after degradation. The glass transition temperatures (Tg) obtained from these curves are summarized in Table 2. The values were obtained from the second heating
run.
Table 2
DSC data obtained from the second heating run (at 10  C min1) on PDLLA and
PDLLA/CNWs before and after degradation.
Sample

Tg/ C
Before degradation

After degradation

PDLLA
PDLLA-1%
PDLLA-5%

53
55
56

57
54
55

Fig. 6. DSC curves (second heating, at 10  C min1) of the samples after degradation
for twelve weeks in phosphate buffer.

E. Luiz de Paula et al. / Polymer Degradation and Stability 96 (2011) 1631e1638

colleagues [54] conrmed this self-catalysis characteristic, showing

that non-porous membranes are degraded faster than porous
membranes because the latter facilitated the spread of the degradation products dissolved in the aqueous environment, thus
hindering self-catalysis. In our case, we concluded that the cellulose
nanowhiskers act in the rst stage of the degradation, hindering
the degradation by decreasing water absorption. Because of this
mechanism, only a small concentration of CNWs can have
a pronounced effect on the degradation behavior of the polymer.
As mentioned, to prepare the composite studied in this work,
we rstly achieved a good dispersion of the CNWs in the polar
organic solvent DMF. We then used the solvent casting method to
prepared nanocomposites with PDDLA without using any type of
compatibilizer, surfactant or chemical modication of the CNWs.
This strategy of using DMF as a dispersion medium for freeze-dried
CNWs, which has been previously used by other authors [55,56],
has been described as a method to prepare CNWs nanocomposites
using organic solvents.
Finally, because we observed a large change in the degradation
rate of the PDLLA polymer with the addition of only 1% CNWs, we
believe that this work can represent a rst step toward the use of
nanollers obtained from renewable resources to control the
biodegradability of a polylactide and could be extended to other
biodegradable polymers.
4. Conclusions
The inuence of the cellulose nanowhiskers on the hydrolytic
degradation behavior of a bionanocomposite based on PDLLA was
studied in a phosphate buffer medium. The nanocomposites were
prepared by a simple solvent casting method using DMF as
a solvent to disperse the freeze-dried CNWs before the preparation
of the nanocomposites.
The CNWs induced a strong delay in the PDLLA degradation,
even when the concentration of the nanollers was only 1%. The
cellulose nanocrystals delay the degradation because they act as
a physical barrier, hindering the absorption and/or the diffusion of
water among the polymer chains and consequently modifying the
kinetics of the hydrolytic process. This behavior was explained in
terms of the high degree of crystallinity of the nanocrystals which
improve the barrier properties of the lms, through the creation of
a tortuous path for the permeation of water.
The incorporation of cellulose nanocrystals in the PDLLA also
makes the biopolymer more thermally stable, increasing its initial
temperature of mass loss even after degradation in phosphate
medium. In addition, Tg values increased with whiskers concentration due to the restriction of the chain mobility resulting from
the presence of the nanocrystals.
Finally, the results presented here showed the possibility to
prolong the service life and to control the degradation rate of the
PDLLA biopolymer, through the preparation of a nanocomposite,
introducing a small quantity of nanollers obtained from renewable materials: the cellulose nanocrystals.
Further work will study the biodegradability of PDLLA/CNWs
nanocomposites by compost and investigate nanocomposites with
different low concentrations of CNWs to achieve control over the
biodegradability of these materials.
Acknowledgments
The authors thank CAPES (Nanobiotec e EDT N 04/2008),
FAPEMIG (PPP- EDT N 021/2008) and Pr-reitoria de PesquisaUFMG for their nancial support. Centro de Microscopia-UFMG is
gratefully acknowledged for the TEM images.

1637

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