Polymer Testing 61 (2017) 280e288

Contents lists available at ScienceDirect

Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

Effect of microcrystalline and nanocrystals cellulose fillers in materials

based on PLA matrix
Fernanda A. dos Santos, Gisele C.V. Iulianelli, Maria I.B. Tavares*
Universidade Federal do Rio de Janeiro, Instituto de Macromol

eculas Professora Eloisa Mano, Av. Horacio Macedo 2030, Bloco J, Rio de Janeiro-RJ, CEP
21945-970, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this work was to compare the effects of microcrystalline cellulose (MCC) and cellulose
Received 29 March 2017 nanocrystals (CNC) addition on the properties of PLA matrix. The CNC were obtained by acid hydrolysis of
Accepted 4 May 2017 the MCC. Both MCC and CNC were separately incorporated in PLA at ratios of 3, 5 and 7 wt%. In some
Available online 25 May 2017
compositions, organophilic silica (R972) was added to improve the cellulose-matrix compatibility. The
properties of the materials were evaluated by FTIR, XRD, NMR and mechanical tests. Functional groups
Keywords:
and crystalline structure of MCC and CNC were determined by FTIR and XRD, respectively. NMR T1H
Cellulose
values showed that films containing CNC presented better interfacial interaction than those containing
Biopolymers
NMR
MCC, and indicated that R972 acts as compatibilizer. MCC and CNC acted as nucleating agents for PLA
Mechanical properties crystallization and there was an improvement in the mechanical performance of materials with the
addition of CNC.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction strongly hydrogen bonded to one another [2]. MCC is typically

A great deal of attention has been paid to the use of cellulose as a
component in polymeric materials. The production of cellulose-
based materials has been the focus of much research due to their
high crystallinity, good processability, abundance, renewable and
biodegradable nature, as well as the outstanding mechanical
properties [1,2].
In general, the addition of cellulose-based fillers in polymer
matrices promotes better performance of the materials in relation
to their barrier, thermal and mechanical properties [1e3].
Many types of cellulose particles have been used as reinforce-
ment fillers in polymeric materials. These cellulose particles can be
differentiated from one another based on size, morphology, crys-
tallinity and crystal structure [1]. These characteristics are a
consequence of the cellulose source and the particle extraction
methods used.
Two of the most commonly cellulose particles used with this
purpose are microcrystalline cellulose (MCC) and cellulose nano-
crystals (CNC). MCC consists of a highly crystalline structure
composed of bundles of multi-sized cellulose microfibril aggregates
* Corresponding author.
E-mail address: mibtima@bol.com.br (M.I.B. Tavares).
derived by H2SO4 treatment of bleached kraft wood fibers, resulting
in partial depolymerization of their amorphous regions. This pro-
cess produces powder with particle sizes ranging between 10 and
50 mm in diameter [4].
CNC are rod or whisker shaped particles seen in the crystalline
regions of the cellulose fibrils produced by acid hydrolysis of wood
fibers, MCC and other sources [4,5]. This cellulosic material consists
of highly crystalline particles with high aspect ratios (3e5 nm wide,
50e500 nm in length).
Although cellulose particles and nanoparticles have been shown
to be efficient as reinforcement fillers for polymeric matrices, there
are some challenges to overcome in order to achieve good perfor-
mance, including the efficient dispersion of particles in the matrix,
the matrix-reinforcement compatibility and the development of
suitable methods for their processing [1].
In this work, we report the production of cellulose-based ma-
terials using PLA as matrix and MCC or CNC as reinforcement filler
[11e20]. A solution casting method, which can avoid the degra-
dation promoted by melting processes, was used to produce the
materials in a film form. Fourteen films were prepared varying the
concentration and type of cellulose filler. Organophilic silica R972
was added in some formulations to improve the compatibility be-
tween PLA and cellulosic filler, since the mix of hydrophilic cellu-
losic materials with hydrophobic polymers such as PLA only

http://dx.doi.org/10.1016/j.polymertesting.2017.05.028
0142-9418/© 2017 Elsevier Ltd. All rights reserved.
 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288 281

promotes weak adhesion [6e10]. 2.4. Characterization

The films were evaluated using X-ray diffraction, infrared
spectroscopy and tensile testing, plus unconventional NMR relax-
ometry through determination of proton spin-lattice relaxation
time (with a time constant T1H). The relaxation T1H parameter and
the domain distribution curve profile allowed evaluation of the
molecular dynamics and the homogeneity of the films [11].
2. Experimental
2.1. Materials
PLA 2002D in pellet form was supplied by Nature works; MCC
ph102 powder was obtained from Viafarma, and R972, organophilic
silica treated with dimethyldichlorosilane based hydrophilic silica,
was supplied by Evonik Industries.
2.4.1. FTIR
The infrared spectra were recorded with a Varian Excalibur 3100
FTIR spectrometer using the horizontal attenuated total reflectance
(HATR) accessory from Pike Technologies, with 100 scans and res-
olution of 4 cm1. The MCC and CNC samples were mixed with KBr
to form a fine powder. These powders were compressed into thin
pellets and then analyzed.
2.4.2. XRD
XRD was performed using a Rigaku diffractometer with CuKa
radiation (0.154 nm, 40 Kv, 120 mA) at room temperature, scanning
over a 2q range from 2 to 40
with a 0.05 step, at a rate of 1
/min.
Crystallinity measurements were obtained by XRD deconvolution.
All calculations were performed using Fityk software and the peaks
were deconvoluted using Gaussian peak function.

2.2. Isolation of CNC 2.4.3. NMR relaxometry

The MCC/H2O suspension was prepared at a ratio of 150 g/L, put
in a temperature-controlled bath at 0
C and stirred while
concentrated H2SO4 was added dropwise until 64% acid concen-
tration was reached. After acid addition, the suspension was heated
at 40
C with stirring for 2 h. The resulting suspension with CNC
was washed with deionized water using repeated centrifugation
cycles of 10 min at 12,000 rpm. The centrifugation step was fol-
lowed by resuspension of the solids of the mixture in new deion-
ized water and then the process was repeated until the supernatant
became turbid. The last washing step was conducted using dialysis
against deionized water until pH 5e6. After the dialysis, the sus-
pension was freeze-dried for 48 h to obtain powdered CNC.
The relaxation time was analyzed in a low-field NMR spec-
trometer (Maran Ultra 23 Oxford Instruments), using an 18 mm
NMR tube, operating at 23 MHz for hydrogen nucleus. The pulse
sequence used to obtain data on spin lattice relaxation time was
inversion-recovery and a 90
pulse of 4.7 ms was calibrated auto-
matically using the software package of the instrument. The
amplitude of free induction decay (FID) was sampled for 40 t data
points, ranging from 0.01 to 10000 ms, using four scans for each
point. The samples were analyzed at 27
C. The relaxation values
and relative intensities were obtained by fitting the experimental
data using WINFIT software. Distributed exponential fits on plots of
relaxation amplitude versus relaxation time were performed using
WINDXP software.

2.4.4. Mechanical properties

2.3. Preparation of the films Tensile testing was carried out with an Instron universal testing
machine, (model 4204). Modulus and tensile strength of the films
Four series of materials were prepared by solution casting using were determined. The tests were performed according to guide-
CHCl3 as solvent. Two of them were based on PLA, MCC and/or lines outlined in ASTM D882 at 22
C.
R972, and the others on PLA, CNC and/or R972. Separate dispersions
of PLA and the fillers in their respective concentrations were pre- 3. Results and discussion
pared. For the compositions containing R972, this material was
mixed together with cellulose (MCC or CNC) in the same dispersion. FTIR analysis (Fig. 1) demonstrated that infrared spectra of CNC
After being mechanically stirred for 24 h, the dispersions of poly- and MCC exhibited absorption peaks close to the characteristic
mers and fillers were mixed together for another 24 h, and then peaks of native cellulose. Additionally, the esterification of CNC
cast onto plates and kept in an oven to eliminate the solvent. promoted by acid hydrolysis was confirmed by the FTIR spectra.
Fourteen films were prepared according Table 1. A broad band at 3400 cm1 can be assigned to the stretching of
hydroxyl groups. The peaks at 2900 cm1 are caused by the
stretching of CeH [6]. The band at 1645 cm1 is due to water ab-
Table 1
sorption and is related to the bending modes of the water mole-
Produced formulations.
cules resulting from the strong interaction between cellulose and
Matrix Fillers (%) Film water, while the band around 1431 cm1 is attributed to eCH2
PLA without R972 groups [6]. These results indicate that the acid treatment of cellu-
e PLA lose did not alter its crystalline arrangement.
3% MCC PLA/3MCC It is possible to observe in the region at 1200e1000 cm1 that
5% MCC PLA/5MCC there is a significant difference in intensity between the infrared
7% MCC PLA/7MCC
3% CNC PLA/3CNC
absorption bands of MCC and CNC. This is the region of absorption
5% CNC PLA/5CNC of S]O and S-O bonds, characteristics of ester sulfate groups. Even
7% CNC PLA/7CNC although these absorptions are small, they are sufficient to increase
with R972 the relative intensities of these bands [7].
R972 PLA/R972
XRD analysis results of PLA and PLA/R972 films are presented in
3% MCCþ3% R972 PLA/3MCC/R972
5% MCCþ3% R972 PLA/5MCC/R972 Fig. 2. Because PLA is a semi-crystalline polymer, it was expected to
7% MCCþ3% R972 PLA/7MCC/R972 generate X-ray diffractometry peaks, however these samples
3% CNCþ3% R972 PLA/3CNC/R972 exhibited a broad halo in the XRD pattern, which suggest their
5% CNC þ3% R972 PLA/5CNC/R972 amorphous nature and reveals that the molding method employed
7% CNC þ3% R972 PLA/7CNC/R972
prevented the development of crystallinity.
282 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288

Fig. 1. X-Ray diffraction (XRD) patterns of PLA-based films.

Fig. 2. X-Ray diffraction (XRD) patterns of PLA/PLGA-based films.

XRD patterns of the films containing MCC (Fig. 3) exhibit peaks
corresponding to cellulose and PLA. From the literature, diffraction
peaks of cellulose are observed at 2q values of approximately 14.7
,
16.6
, and 22.6
[8] and those of PLA are observed at 16.9
, 19.4
,
and 22.6
[9]. The peak at 22.6
becomes more pronounced with
the gradual addition of MCC.
From XRD patterns of the films with CNC (Fig. 4), similar
behavior was observed. In general, the peaks at 22.6
became more
pronounced with the increase of CNC content, regardless of the
addition of R972. Therefore, according to XRD patterns of the films,
both MCC and CNC acted as nucleating agent for crystallization of
the PLA, since the PLA sample without cellulose presented amor-
phous behavior. Similar behavior was previously reported using
cellulosic fillers as reinforcement in many studies [10e13].
From the data in Table 2, it is evident that the addition of CNC or
MCC caused a gradual increase of degree of crystallinity with
increasing cellulose content. This effect was more pronounced on
the films containing CNC, probably due to its higher specific surface
area in relation to the MCC, which contributes to increasing the
contact area between the surfaces of cellulose particles and PLA.
 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288 283

Fig. 3. Domain curves for T1H values for the PLA-based films.

Fig. 4. Domain curves for T1H values for the PLA/PLGA-based films.

Additionally, sulfate groups can prevent the aggregation of CNC

particles driven by hydrogen bonding, leading to better filler-
matrix interfacial interaction. Pei et al. [14] reported that the
Table 2 nucleating effect of the cellulose is enhanced if a homogeneous
Degree of crystallinity (%) obtained for the polymer films.
cellulose dispersion in the PLA can be achieved.
Film Crystallinity (%) Regarding the silica addition [11], the crystallinity values were
PLA Amorphous higher than those of the films without silica when compared at the
PLA/R972 Amorphous same cellulose content, CNC or MCC, in most cases.
PLA/3MCC 20 ± 2,0 These results indicate that the addition of silica improved the
PLA/5MCC 35 ± 1,8
PLA-cellulose compatibility. R972 also can aid in reducing cellulose
PLA/7MCC 41 ± 1,0
PLA/3MCC/R972 25 ± 0,7 aggregations, promoting better dispersion of the cellulose particles.
PLA/5MCC/R972 34 ± 0,8 This behavior can be expected since the hydroxyl groups in silica
PLA/7MCC/R972 43 ± 1,0 can interact with the hydroxyl groups present at the surface of the
PLA/3CNC 28 ± 1,0
cellulose particles. Additionally, groups derived from the insertion
PLA/5CNC 37 ± 0,5
PLA/7CNC 43 ± 1,5
of dimethyldichlorosilane on the silica can interact with PLA chains,
PLA/3CNC/R972 30 ± 0,7 promoting improvement in the adhesion between phases.
PLA/5CNC/R972 38 ± 1,0 NMR studies of T1H data were employed to evaluate the influ-
PLA/7CNC/R972 45 ± 2,3 ence of the incorporation of MCC or CNC together with or without
284 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288

R972 on the molecular mobility of the PLA films and, consequently,

in the domain distribution curves of T1H. The relaxation data were
used to examine the sample homogeneity of the produced mate-
rials, in spite of been heterogeneous samples.
T1H relaxation parameter values were determined from mono-
exponential decay for all the materials; so just one value of this
parameter was determined for each sample and the T1H values are
listed in Table 3. In general, an increase in the relaxation time
means a decrease in the molecular mobility as a consequence of
new intermolecular interaction or chains molecular movement
restriction.
The T1H value for CNC and MCC was 158 ms and 186 ms,
respectively. The lower value of T1H for the CNC may be related to
its reduced molar mass in relation to that of MCC.
T1H value was 646 ms for the PLA film and 700 ms for the PLA
pellets. This lower T1H value confirms the loss of crystallinity
during film formation, caused by the solvent action, as noted from
Fig. 5. Fourier transform infrared spectroscopy (FTIR) spectrum obtained for the silica
XRD analysis. R972.
For the PLA films containing MCC, the T1H values decreased with
the progressive increase of filler content in relation to the T1H of the
PLA film. This result is due to the fact that MCC exhibits a T1H value
Domain distribution curves (Fig. 5) shows that only one domain
significantly lower than the PLA film (Table 3) and may indicate
is observed for PLA pellets, MCC and CNC, indicating that these
good dispersion and some intermolecular interaction between
materials present molecular homogeneity. From the domain dis-
phases. On the other hand, the addition of CNC resulted in an in-
tribution curves found for cellulose samples, it was noted that the
crease of the T1H value for the samples containing 3 and 5 wt% of
CNC has a broader domain curve, indicating its greater heteroge-
filler content, indicating that the addition of CNC in these pro-
neity in relation to the MCC. This result probably occurred due to
portions is capable of decreasing the molecular mobility of PLA
the presence of fractions of the CNC sample which differ in relation
chains, unlike MCC. This behavior is associated with the fact that
to the degree of sulfonation of their particles. This may have
the CNC are constituted of smaller particle, promoting better
occurred due to the formation of aggregates of MCC particles
cellulose-matrix interaction due to their higher surface area.
which, during the hydrolysis reaction, made it difficult to contact
Additionally, CNC are more rigid than MCC due to their higher
the sulfuric acid with a larger surface area of these particles, since
crystallinity. These factors contribute to the increase of the rigidity
part of their surfaces would be oriented toward the surface within
of the films. The lowest T1H value for the sample with 7 wt% of CNC
these aggregates.
is probably associated with aggregation of the filler in this
As seen in (Fig. 6 A and B), only one domain curve of T1H was
proportion.
observed for PLA and PLA/R972 films. PLA/R972 presented a smaller
Regarding the films with R972, the presence of the silica pro-
broadness in the base line of the domain compared to the film with
moted an increase in the T1H values when compared to those
R972. This behavior can be attributed to the changes in the mo-
without silica but with the same type and content of cellulose. This
lecular mobility, which is observed by an increase in the T1H value
result can be attributed to the rigid nature of R972 that does not
(Table 3), due to the increase in the sample rigidity according to
change the crystallinity profile of the matrix, but reduces the mo-
new intermolecular interactions (Fig. 6 CeF). shows the domain
lecular mobility of the films, resulting in a higher T1H value.
curves of PLA films containing cellulose with and without silica. For
Comparing the results obtained for the films with or without
most samples, the presence of two domains is evident. The domain
R972, a similar tendency is observed, i.e., the addition of only CNC
with higher intensity corresponds to the PLA; this domain is
was able to increase the T1H with the increase of the cellulosic filler
responsible for controlling the relaxing process. The lower intensity
content compared to PLA film. This behavior was observed up to
domain is attributed to the cellulose (MCC or CNC).
5 wt%. of CNC content.

Table 3
T1H values for the materials.

Materials T1H (ms) ± 2%

MCC 186
CNC 158
PLA pellet 700
PLA film 646
PLA/3 MCC 592
PLA/5 MCC 580
PLA/7 MCC 538
PLA/3 CNC 664
PLA/5 CNC 669
PLA/7 CNC 591
PLA/R972 658
PLA/3 MCC/R972 605
PLA/5 MCC/R972 585
PLA/7 MCC/R972 558
PLA/3 CNC/R972 672
PLA/5 CNC/R972 677
PLA/7 CNC/R972 596
Fig. 6. Fourier transform infrared spectroscopy (FTIR) spectra obtained from CNCs.
 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288
According to the domain curves distribution, the samples PLA/
5MCC/R972 (Fig. 6 D) and PLA/3CNC (Fig. 6 E) are more homoge-
neous since they present only one domain and no absorbed water,
due to the particle quantity. The other samples had two domains,
the lowest one are referring to moisture, because cellulose absorbs
humidity. From (Fig. 6), it was observed that the samples containing
7 wt% of filler, with and without silica, showed a wider domain
curve, indicating their greater heterogeneity. This finding was also
evidenced in the T1H values, which showed a lower value of T1H for
samples with 7 wt% of cellulose compared to those containing 3
and 5 wt% of filler, evidencing weaker interaction between the
phases.
The results for the tensile modulus of PLA/MCC and PLA/CNC
films with or without R972 are represented by (Figs. 7 and 8),
respectively.
The results showed that, when only MCC was added to the PLAx,
a substantial decrease in the elastic modulus of the films was
promoted. The modulus of the films PLA/3MCC, PLA/5MCC e PLA/
7MCC decreased by approximately 24, 28 and 18%, respectively,
compared to the PLA film, which was about 1700 MPa. This result
may be related to the significantly lower rigidity of the MCC
compared to PLA film, as observed by T1H experiment (Table 3),
and/or to the poor dispersion caused by MCC aggregates in the PLA
matrix due to the weak interaction between phases. Petersson and
Oksman [15] reported a similar result in their study on PLA/MCC
films obtained by solution casting. The authors observed a decrease
in modulus from 1700 MPa for neat PLA film to 1500 MPa for the
film containing 5 wt% of MCC. Nevertheless, Oksman et al. [16],
studying PLA/MCC extruded materials, reported an increase in
tensile modulus but a loss in tensile strength of the material with
increasing MCC content. The ability to strengthen MCC may be
associated with factors such as matrix/cellulose system and pro-
cessing conditions.
Fig. 7. Tensile strength of PLA-based films.
285
The results obtained for the tensile modulus of the films PLA/
MCC/R972 are showed in (Fig. 7). The increase on the tensile
modulus with a progressive addition of CMC in the presence of
R972 can be attributed to two reasons. The first is related to the
inherent high rigidity of the R972 and the other one is the fact that
R972 may be acting as a compatibilizing agent by improving the
interaction between the MCC and the PLA, thus MCC can act as
reinforcement, improving the matrix properties.
Unlike what was observed in PLA/MCC films, the addition of
only CNC in the PLA matrix promoted an increase in tensile
modulus values. For PLA/CNC films, it was possible to observe a
progressive increment in their tensile modulus of approximately 11,
26 and 32% for the materials containing 3, 5 and 7 wt% of CNC,
respectively (Fig. 8).
Although both MCC and CNC are cellulosic fillers, they differ in
morphology and size of their particles and, depending of the acid
used in the isolation of the nanocrystals, there may be differences
in the chemical nature of their surfaces. CNC particles are smaller
and have a higher degree of crystallinity than MCC. These materials
also differ in relation to their surfaces. During the hydrolysis, sul-
furic acid reacts with hydroxyl groups of cellulose, which yields
charged sulfate esters on the surface of nanocrystals [17]. The
presence of these negatively charged sulfate ester weakens the
interactions between the hydroxyl groups of cellulose surface. This
probably contributed to the dispersion of CNC in the PLA matrix, by
reducing the formation of aggregates of their particles.
Several studies have shown that the addition of small CNC
amounts is able to improve the modulus of different types of
polymeric matrices [3,18e20]. Similarly, in the analysis of the PLA/
CNC/R972 films (Fig. 8), a progressive increase in this property was
observed with gradual CNC addition. The increment was 8, 33 and
39%, respectively, for the films with 3, 5 e 7 wt% of CNC in relation to
the modulus of the PLA/R972 film, which was about 1800 MPa.
286 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288
Fig. 8. Tensile strength of PLA/PLGA-based films.
Comparing the pair of films PLA/CNC and PLA/CNC/R972 (Fig. 8)
with the same cellulose content, it is possible to observe similar
behavior found to that of systems containing MCC, i.e. when R972
was added together cellulose the modulus values were increased.
This result may have been caused by the synergic effect of the
nanoparticles and the excellent dispersion of both types of nano-
particles in the matrix. This indicates that silica R972 reduced the
interfacial tension between the PLA and CNC. This probably
occurred because of the presence of hydroxyl group on the silica
surface, which interacted through hydrogen bonds with cellulose,
and also because of good interaction between R972 and PLA due to
the presence of dimethyldichlorosilane, employed as the modifier
of the silica, which can promote a compatibilization effect in the
system formed by PLA/MCC/R972. Additionally, the nanometer-
scale silica particles ensure a large specific surface area, allowing
greater surface interaction between both particle fillers.
The results for the tensile strength of the PLA/MCC and PLA/CNC
films with or without R972 are represented by (Figs. 9 and 10),
respectively.
For PLA/MCC films (Fig. 9), a significant decrease in tensile
strength compared to pure PLA film was observed, which showed
tensile strength of 28.5 MPa. Property values for the PLA/3MCC and
PLA/5MCC films were very similar and showed a decrease in tensile
strength of approximately 39 and 40%, respectively, while PLA/
7MCC film exhibited a reduction in tensile strength about 49%.
The decrease of tensile strength with the addition of MCC as
well as of the tensile modulus of these same films may be related to
unsatisfactory dispersion and the presence of large aggregates of
MCC in the PLA matrix.
Increasing the concentration of MCC may have afforded greater
proximity of the particles that, due to their chemical nature,
consequently formed aggregates. This formation of aggregates
prevents full engagement of the filler by the matrix, which can lead
to stress concentration and, consequently, a reduction of the me-
chanical properties of the matrix.
The tensile strength of the PLA/MCC/R972 films increased for
those containing 3 and 5% of MCC in relation to the PLA/R972 film.
PLA/7MCC/R972 presented the lowest tensile strength for this se-
ries of films.
Compared to the PLA/R972 film, the formulations PLA/MCC/
R972 with 3e5 wt% of MCC showed an increase in tensile strength
of approximately 13 and 18%, respectively, and the PLA/MCC/R972
film with 7 wt% of MCC exhibited a decrease of 32%. Probably, the
decrease in tensile strength of the PLA/7MCC/R972 film was due to
the formation of aggregates of particles of MCC, even in the pres-
ence of silica, showing that the optimal concentration of MCC to
achieve maximum performance for tensile strength was 5 wt%.
The highest value for tensile strength observed in the samples
prepared with R972 compared to those without adding the silica
indicates better stress transfer from the matrix to the reinforce-
ment at the filler-polymer interface.
However, comparing the PLA and PLA/R972 films (Fig. 9), there
was a small reduction in tensile strength with the addition of silica.
Therefore, only the presence of silica or MCC could not promote an
increase in tensile strength. On the other hand, the addition of both
R972 and MCC was capable of causing an increase in this property,
depending on the cellulose concentration added in the film.
(Fig. 10) shows that the PLA films containing CNC exhibited a
decrease in tensile strength compared to that for pure PLA film.
PLA/3CNC, PLA/5CNC and PLA/7CNC films exhibited reductions in
tensile strength of approximately 31%, 13% and 41%, respectively.
For the PLA/CNC/R972 films, the tensile strength showed an
increase of 4, 34 and 21%, respectively, for the films with 3, 5, and
7 wt% of CNC compared with that for the PLA/R972 film.
 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288 287

Fig. 9. Tensile modulus of PLA-based films.

Fig. 10. Tensile modulus of PLA/PLGA-based films.

The PLA/CNC/R972 films showed higher values of tensile 4. Conclusions

strength compared to those found for the PLA/CNC films with the
same CNC content. The highest value for tensile strength obtained
from CNC based films was achieved when both CNC and R972 were
added concomitantly at 5 wt% CNC content. These results indicate
better stress transfer from the matrix to the reinforcement at the
filler-polymer interface with R972 addition.
PLA and PLA/R972 bionanocomposite films reinforced with CNC
or MCC fibres were successfully produced by a casting method.
The FTIR analysis of the cellulose fillers confirmed that the acid
treatment of the MCC promoted the increase of their crystallinity
and also the insertion of sulfate groups in its surface, generating
288 F.A. dos Santos et al. / Polymer Testing 61 (2017) 280e288
CNC. This analysis also showed that the acid treatment did not
affect the crystalline structure of cellulose.
The XRD studies demonstrated that both cellulose fillers can act
as nucleating agent for the crystallization of PLA. The use of silica as
the sole type of filler did not affect the crystallinity of the matrix,
but when silica were added concomitantly with MCC or CNC, a
more pronounced increase in the crystallinity was observed
because of the synergic effects of the two types of filler. This effect
can be attributed to strong interaction forces between silica and
cellulose.
NMR analysis demonstrated that both cellulose fillers and silica
exert different effects on the T1H parameter reflected by change in
molecular mobility. The increase in T1H values found for systems
containing 3 and 5 wt% of CNC compared to PLA film indicates
better interaction between the phases. The use of R972 intensified
this result, indicating a compatibilizing effect. Moreover, analysis of
the domain curves distribution showed that 7 wt% of cellulose filler
with or without silica resulted in more heterogeneous films, but the
distribution of the particles was not affected.
Regarding mechanical properties, the silica used in this study
did not act as reinforcement filler for PLA, since no improvement in
the mechanical performance was observed. However, it did
enhance the reinforcement effect of the both cellulose fillers such
that, when both kinds of nanoparticles (cellulose and silica) were
used simultaneously, mechanical performance was improved.
As expected, the results obtained for the analytical techniques
used in this study indicate better dispersion of cellulose in the
polymer matrix in the presence of silica, and increased particle-
matrix interaction for both cellulose fillers. However, for CNC sys-
tems this result was more pronounced, as proved by T1H values.
Acknowledgment
The authors are thank you to FAPERJ and CAPES for the financial
support of this research.
References
[1] F.A. dos Santos, G.C.V. Iulianelli, M.I.B. Tavares, The use of cellulose nanofillers
in obtaining polymer nanocomposites: properties, processing, and applica-
tions, Mater. Sci. Appl. 7 (5) (2016) 257.
[2] M.A. Hubbe, O.J. Rojas, L.A. Lucia, M. Sain, Cellulosic nanocomposites: a review,
Bioresources 3 (3) (2008) 929.
[3] F.A. Santos, M.I.B. Tavares, Development of biopolymer/cellulose/silica nano-
structured hybrid materials and their characterization by NMR relaxometry,
Polym. Test. 47 (2015) 92.
[4] R.J. Moon, A. Martini, J. Nairn, J. Simonsen, J. Youngblood, Cellulose nano-
materials review: structure, properties and nanocomposites, Chem. Soc. Rev.
40 (2011) 3941.
[5] W. Bai, J. Holbery, K. Li, A technique for production of nanocrystalline cellulose
with a narrow size distribution, Cellulose 16 (3) (2009) 455.
[6] S.Y. Oh, D.I. Yoo, Y. Shin, H.C. Kim, H.Y. Kim, Y.S. Chung, W.H. Park, J.H. Youk,
Crystalline structure analysis of cellulose treated with sodium hydroxide and
carbon dioxide by means of X-ray diffraction and FTIR spectroscopy, Carbo-
hydr. Res. 340 (15) (2005) 2376.
[7] D.L. Pavia, Introduction to Spectroscopy: Brooks/Cole, Cengage Learning, 2009.
[8] N. Terinte, R. Ibbett, K.C. Schuster, Overview on native cellulose and micro-
crystalline cellulose I structure studied by x-ray diffraction (waxd): compar-
ison between measurement techniques, Lenzing. Ber. 89 (2011) 118.
[9] M.Z. Rong, M.Q. Zhang, Y. Liu, G.C. Yang, H.M. Zeng, The effect of fiber treat-
ment on the mechanical properties of unidirectional sisal-reinforced epoxy
composites, Compos. Sci. Technol. 61 (10) (2001) 1437.
[10] M.C. Silva, S.V. de Oliveira, E.M. Araújo, Propriedades mec^
rmicas de
anicas e te
sistemas de PLA e PBAT/PLA, REMAP 9 (2) (2014) 112.
[11] A.S. Almeida, M.I.B. Tavares, E.O. da Silva, R.P. Cucinelli Neto, L.A. Moreira,
Development of hybrid nanocomposites based on PLLA and low-field NMR
characterization, Polym. Test. 31 (2) (2012) 267.
[12] G. Siqueira, J. Bras, A. Dufresne, Cellulose whiskers versus microfibrils: influ-
ence of the nature of the nanoparticle and its surface functionalization on the
thermal and mechanical properties of nanocomposites, Biomacromol 10 (2)
(2009) 425.
[13] J. Lu, T. Wang, L.T. Drzal, Preparation and properties of microfibrillated cel-
lulose polyvinyl alcohol composite materials, Compos Part A Appl S 39 (2008)
738.
[14] A. Pei, Q. Zhou, L.A. Berglund, Functionalized cellulose nanocrystals as bio-
based nucleation agents in poly(l-lactide) (PLLA) e crystallization and me-
chanical property effects, Compos. Sci. Technol. 70 (5) (2010) 815.
[15] L. Petersson, K. Oksman, Preparation and properties of biopolymer-based
nanocomposite films using microcrystalline cellulose, ACS Symp. Ser. 938
(2006) 132.
[16] K. Oksman, A.P. Mathew, D. Bondeson, I. Kvien, Manufacturing process of
cellulose whiskers/polylactic acid nanocomposites, Compos. Sci. Technol. 66
(15) (2006) 2776.
[17] X.M. Dong, J.-F. Revol, D.G. Gray, Effect of microcrystallite preparation con-
ditions on the formation of colloid crystals of cellulose, Cellulose 5 (1) (1998)
19.
[18] M. Peresin, H. Youssef, J. Zoppe, J.J. Pawlak, R. Orlando, Nanofiber composites
of polyvinyl alcohol and cellulose nanocrystals: manufacture and character-
ization, Biomacromol 11 (3) (2010) 674.
[19] C. Zhang, Y. Dan, J. Peng, L.-S. Turng, R. Sabo, C. Clemons, Thermal and me-
chanical properties of natural rubber composites reinforced with cellulose
nanocrystals from southern pine, Adv. Polym. Sci. (2014), http://dx.doi.org/
10.1002/adv.21448.
[20] X. Cao, H. Dong, C.M. Li, New nanocomposite materials reinforced with flax
cellulose nanocrystals in waterborne polyurethane, Biomacromol 8 (3) (2007)
899.