Copyright © 2012 American Scientific Publishers Journal of

All rights reserved Nanoscience and Nanotechnology

Printed in the United States of America Vol. 12, 4508–4513, 2012

Evaluation of the Influence of Nanoparticles’ Shapes on

the Formation of Poly(lactic acid) Nanocomposites
Obtained Employing the Solution Method
Luciana Macedo Brito and Maria Inês Bruno Tavares∗
Instituto de Macromoléculas Professora Eloisa Mano da Universidade Federal do Rio de Janeiro (IMA/UFRJ), Centro de Tecnologia,
Bloco J, Ilha do Fundão, Rio de Janeiro, RJ, CP: 68525, CEP: 21945-970, Brazil

PLA nanocomposites were prepared by adding organically modified montmorillonite clay (Viscogel
B8) and a homoionic clay (NT25), as well as unmodified silica (A200) and modified organic silica
(R972). All nanocomposites were obtained by the solution intercalation method using chloroform as
a solvent. The materials obtained were essentially characterized by X-ray diffraction and low-field
nuclear magnetic resonance relaxometry, through the measurement of proton spin-lattice relaxation
time (LF-NMR). Both clays and silicas used to obtain the polymeric nanocomposites showed good
dispersion in the polymeric matrix. The relaxation times were distinct for each type of nanopar-
ticle used. The nanocomposite formed with homoionic clay, NT25, presented an increase in the
relaxation data, indicating formation of intercalated nanocomposites, contrary to the action of the
organoclay Viscogel B8, which preferentially formed an exfoliated nanocomposite. When unmodified
and organo-modified silica were added to PLA, an increase in the relaxation time of the polymer
matrix wasDelivered
observed.byAccording
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to Technology
the relaxationto: University
data, of Southern
the organosilica R972California
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the A200.
Copyright: American Scientific Publishers
RESEARCH ARTICLE

Keywords: PLA, Nanocomposite, Relaxometry.

1. INTRODUCTION
Biodegradable and biocompatible polymers have attracted
significant attention in the past decade. They have become
the polymer matrix of choice for many applications in the
field of nanocomposites because they are environmentally
friendly, since they degrade under the action of physico-
chemical and biological factors in a humid environment.
They can be employed in many biomedical and phar-
maceutical applications, such as sutures and biologically
active controlled-release devices.1 The most important
advantage of biodegradable polymers is the disappearance
of implanted foreign materials from the body as a result
of their biodegradation. Important biodegradable poly-
mers used in biomedical applications are poly(lactic acid)
(PLA), poly(glycolic acid) (PGA), poly(e-caprolactone)
(PCL), poly(3-hydroxybutyrate) (PHB) and copolymers
made of polyglycolide, chitosan and soy protein.2–4
In this respect, poly(lactic acid) is rapidly gaining
recognition as one of the most advantageous biopoly-
mers. PLA is a biodegradable polyester synthesized from
∗
Author to whom correspondence should be addressed.
l- and d-lactic acid, the latter produced from the fer-
mentation of sugar and polysaccharides such as sugar
feedstocks and corn, wheat and other starch sources,
either by ring-opening polymerization or by condensation
polymerization.5
Polymer nanocomposites are a class of materials that
have gained substantial popularity, both in academia and
industry, due to their new properties, which are superior
to those of virgin polymers and conventional composites.3
Improvement of biodegradable polymers’ properties by the
addition of nanofillers has good potential for designing
eco-friendly materials for several applications, since the
efficiency of nanofillers can be significant thanks to their
high aspect ratio, even at a low loading (1–5 wt%). Vari-
ous nanocomposites have been developed in recent years.
The most extensively studied ones are based on layered
silicates, due to their availability and low cost.6–8 In the
case of biodegradable polymers, various authors9–11 have
recently reported the preparation and characterization of
PLA nanocomposites with modified and unmodified mont-
morillonites. Polymer/layered-silicate nanocomposites can
be prepared by solution intercalation casting, in situ poly-
merization and melt intercalation. In the first case, the

4508 J. Nanosci. Nanotechnol. 2012, Vol. 12, No. 6 1533-4880/2012/12/4508/006 doi:10.1166/jnn.2012.6176

Brito and Tavares Evaluation of the Influence of Nanoparticles’ Shapes on the Formation of PLA Nanocomposites
inorganic material is thoroughly mixed and dispersed in
a polymer solution, resulting in the insertion of poly-
mer chains into the galleries of the clay, which swells.
In situ polymerization involves monomer insertion into
the clay galleries followed by polymerization. Finally,
in the melt intercalation process the molten polymer is
blended with the clay, optimizing the polymer/layered sil-
icate interactions and facilitating the insertion of the poly-
mer chains.12–14
Many techniques can be used together in complement to
investigate the properties and characteristics of nanocom-
posites, such as wide angle X-ray analysis (WAXS),
scanning electron microscopy (SEM), transmission elec-
tron microscopy (TEM), differential scanning calorime-
try (DSC), thermogravimetric analysis (TGA) and nuclear
magnetic resonance (NMR). Solid-state NMR enables ana-
lyzing samples using different techniques, which possess
distinct pulse sequences. The responses of all techniques
come from chemical shift displacements, signal inten-
sity and line width, as well as the relaxation time
parameter. 15–19
In particular, low-field NMR spectroscopy
has been shown to be a useful method to determine
proton relaxation times. 20–25
Its spectroscopy determines
the values of proton spin-lattice relaxation time, which
has a time constant T1 , and proton spin–spin relaxation
time, with time constant T2 . Both relaxation times allow
evaluating the sample behaviorbyatPublishing
Delivered the molecular level, to: University of Southern California
Technology
because they are sensitive to molecular motions atOn:
IP: 99.231.236.217 the Wed,
MHz scale. Hence, changes in molecular mobility American
Copyright: are nor- Scientific Publishers
mally detected and can be accompanied by T1 and T2
measurements. 21–28
The objective of this study was to compare the
effect of nanoparticle shape in the formation of PLA
nanocomposite films, employing two types of nanoparti-
cles, one lamellar—clay (montmorillonite), and the other
spherical—silica, through the solution method, and to
characterize them by measurement of proton spin-lattice
relaxation time, determined through LF-NMR.
2. MATERIAL
2.1. Samples
NatureWorks® PLA Polymer 2002D sample was supplied
by NatureWorks LLC. The organophylic clay Viscogel B8
was supplied by Bentec and the sodic clay NT25 by Ben-
tonit União Nord. Ind. e Com. Ltda.
2.2. Nanocomposite Preparation
The PLA nanocomposites were prepared by solution cast-
ing, employing chloroform as the solvent. First, a PLA
solution was prepared and was stirred at room temperature
for 24 h, using a magnetic stirrer. Then suspensions of
montmorillonite containing 1, 3 and 5% clay were added.
After blending the samples, the new solutions were stirred
J. Nanosci. Nanotechnol. 12, 4508–4513, 2012
again with the magnetic stirrer at room temperature for
24 h. This solution was poured into a glass plate and the
solvent was evaporated, using an oven with forced air cir-
culation for three days. Solvent elimination was confirmed
by its band disappearing using infrared spectroscopy. After
the solvent was completely removed, the film was taken
out for further analyses.
2.3. Methods
2.3.1. NMR Measurements
The relaxation measurements were performed with
a Maran NMR spectrometer (Resonance Instruments,
Oxford, UK), operating at 23 MHz for the hydrogen
nucleus. Proton spin-lattice relaxation times were deter-
mined directly by the traditional inversion-recovery pulse
sequence (recycle time—180 ––90 —acquisition), using
40 data points, with 4 scans for each and a range of 
varying from 0.1 to 2 s, with 10 s of recycle delay and
90 pulse of 4.5 ms, calibrated automatically by the instru-
ment’s software. The T1 values and relative intensities were
obtained by fitting the exponential data with the aid of
the WINFIT program. Distributed exponential fittings as
plots of relaxation amplitude versus relaxation time were
performed by using the WINDXP software.
2.3.2.
09 AprX-Ray
2014Analyses
15:38:58
RESEARCH ARTICLE
X-ray analyses were carried out in a Rigaku D/Max
2400 diffractometer, with nickel-filtered CuK radiation
of wavelength 1.54 Å, at room temperature. The 2 scan-
ning range was varied from 2 to 30 , with 0.02 steps,
operated at 40 KV and 30 mA.
2.3.3. Fourier-Transform Infrared Measurements
The infrared spectra were recorded with a Varian 3100
FTIR spectrometer at room temperature. A zinc selenide
(ZnSe) internal reflection element (IRE) with a fixed inci-
dence angle of 45 was used for attenuated total reflection
(ATR) measurements.
3. RESULTS AND DISCUSSION
3.1. FTIR
Since the PLA materials and their nanocomposite films
were obtained by the solution intercalation method, using
chloroform as the solvent, the first investigation after film
formation was of solvent elimination, which was accom-
panied by the FTIR technique through chloroform band
disappearance.24 The peaks located at about 1756 cm−1
and 1180 cm−1 , belonging to the CO stretching and
C–O–C stretching of PLA, were visible in all the IR
spectra.25 After three days of drying the films in an
4509
 Evaluation of the Influence of Nanoparticles’ Shapes on the Formation of PLA Nanocomposites Brito and Tavares

CHCl3
CHCl3

NT25
PLA POWDER
Transmitance (%)

Transmitance (%)
PLA FILM 3%
PLA POWDER
R972
PLA FILM 3%
R972 0.1%
NT25 5%

NT25 3% A200

NT25 1% A200 0.1%

4000 3500 3000 2500 2000 1500 1000 500 4000 3500 3000 2500 2000 1500 1000 500
Wave number (cm–1) Wave number (cm–1)

Fig. 1. FTIR spectra of PLA and nanocomposites with NT25. Fig. 3. FTIR spectra of PLA and nanocomposites with silica.

oven with air circulation, no more solvent was detected The diffraction filler peaks of interest to characterize
in the FTIR. Figures 1 to 3 show the FTIR spectra of nanocomposites’ molecular organization and nanoparticle
the nanocomposite films after complete residual solvent dispersion are those which appear in the range of 2 to 5 ,
elimination. in 2 scale, which gives an indication of the clay disper-
sion mode in the polymeric matrix. These peaks are related
to the basal spacing, peaks of the clay’s d001 plane. NT25
3.2. X-Ray Analyses
is characterized by a single diffraction peak at 2 = 5.0 ,
The characterization of the PLA materials and their corresponding to the basal reflection (d001). On the other
nanocomposites was accomplished using conventional hand, Viscogel B8 is characterized by a single diffraction

Delivered by Publishing Technology to:peak
X-ray diffraction measurement, through a theta range from at 2 =of
University 352 , due toCalifornia
Southern the organophilic group’s incor-
 poration
2 to 40 , and by NMR relaxometry to measure the spin-
IP: 99.231.236.217 On: Wed, 09 Aprbetween the clay lamellae.
2014 15:38:58
Copyright: American Scientific Publishers
Both clay types appeared to have good interaction with
RESEARCH ARTICLE

lattice relaxation time in a low-field NMR.

Figures 4 and 5 show the XRD patterns obtained for
the PLA, clays and their nanocomposites. The pattern of
the PLA is characterized by a broad peak with maximum
at approximately 2 = 20 , indicating that its molecular
organization is completely amorphous. The XRD of the
polymer matrix was influenced by the presence of the
filler with respect to the molecular organization. Displace-
ment of the amorphous line to low angles was seen for all
nanocomposites, due to the filler dispersion.
the polymeric matrix, especially the NT25 (Fig. 5). Indeed,
a shift of the clay diffraction peak to lower angles was
observed for Viscogel B8, corresponding to an increase of
the interlayer distance. For the NT25 filler, there was dis-
placement of the polymer matrix peak and disappearance
of clay peaks for all nanocomposites. These observations
indicate that, at least, a mix nanocomposite with high exfo-
liation part was formed.

CHCl3

B8
Transmitance (%)

PLA POWDER

PLA FILM 3%

B8 5%

B8 3%

B8 1%

4000 3500 3000 2500 2000 1500 1000 500

Wave number (cm–1)
Fig. 4. X-ray diffraction patterns of organoclay (Viscogel B8) and
Fig. 2. FTIR spectra of PLA and nanocomposites with B8. PLA/MMT nanocomposites.

4510 J. Nanosci. Nanotechnol. 12, 4508–4513, 2012

Brito and Tavares Evaluation of the Influence of Nanoparticles’ Shapes on the Formation of PLA Nanocomposites

4000 Table I. Proton spin-lattice relaxation times of PLA and PLA/NT25

nanocomposites determined by low-field NMR, employing 1 exponential
NT25 value with 2% error.

3000 PLA/NT25 T1 H (ms) (±2%)

Relative intensity

PLA 3%
PLA Film 3% 607
PLA + NT25 1% 620
2000 PLA + NT25 3% 625
NT25 5%
PLA + NT25 5% 533

1000 NT25 3% Table II. Proton spin-lattice relaxation times of PLA and PLA/B8
nanocomposites, determined by low-field NMR, employing 1 exponential
NT25 1% value with 2% error.

0 PLA/Viscogel B8 T1 H (ms) (±2%)

10 20 30 40
2θ (°) PLA Film 3% 607
PLA + B8 1% 593
Fig. 5. X-ray diffraction patterns of clay (NT25) and PLA/NT25 PLA + B8 3% 578
nanocomposites. PLA + B8 5% 519

The X-ray curves of the nanocomposites with silica are

shown in the Figure 6. The X-ray pattern of both sil- proving that formation of an intercalated nanocomposite is
ica types showed they have good dispersion in the PLA predominant.
matrix. No more information could be obtained from the The decrease in T1 H values with the increase of the
X-ray curves because the materials are largely amorphous. Viscogel B8 proportion indicates lower polymer–polymer
interaction and the generation of a polymer interface inter-
action with the nanoparticles, indicating the formation of
3.3. NMR Measurements a system with good exfoliation. The effect on the T1 H
The spin-lattice nuclear relaxation
Delivered times for the
by Publishing layered to:values
Technology
for the nanocomposites containing Viscogel B8 is
University of Southern California
nanocomposites are presented in IP: Tables
99.231.236.217
I (PLA/NT25) derived
On: Wed, 09 Apr from
2014the15:38:58
dispersion mode of the clay in the poly-
Copyright: clay Scientific Publishersto its better affinity with the polymer
American meric matrix, due

and II (PLA/Viscogel B8). The addition of the sodic
in the PLA matrix caused an increase in the spin-lattice
relaxation times in comparison to the PLA matrix. The
increase in relaxation time of the polymer indicates for-
mation of molecular structures that present low molecu-
lar mobility. In this specific case, this phenomenon can
be related to the formation of intercalated nanocompos-
ites, because polymer chains have their molecular motions
restricted when they are constricted between clay galleries,
PLA 3%
3000
R972
Relative intensity
RESEARCH ARTICLE
matrix, since this clay has an organic interlayer, facilitat-
ing the interaction between the polymer chain and filler
lamellae. The T1 H values decrease as the degree exfo-
liation increases, because when the polymer chains are
around the clay lamellae, they are under influence of para-
magnetic metals (which are present in the clay structure).
These influence the relaxation process, accelerating it, and
as a consequence the hydrogen atoms of the polymeric
matrix relax more quickly than those of the PLA itself.
These findings are in agreement with those already pub-
lished by Vanderhart et al. (2001) and Tavares et al. (2010
and 2011).
Table III shows the relaxation times of the PLA
nanocomposites formed employing unmodified and mod-
ified silica. The T1 H values showed an increase in the

2000 R972 0.1% nanocomposite relaxation time with increasing concentra-

tion of silica nanoparticles for both types of silica. There-
fore, for silica R972 a higher value was observed than for
A200
1000
Table III. Proton spin-lattice relaxation times of PLA and PLA/silica
A200 0.1% nanocomposites, determined by low-field NMR, employing 1 exponential
value with 2% error.

0 PLA/silica T1 H (ms) (±2%)

10 20 30 40
2θ (°) PLA Film 3% 607
PLA + A200 0.1% 627
Fig. 6. X-ray diffraction patterns of both silica (A200 and R972) and
PLA + R972 0.1% 639
PLA/silica nanocomposites.

J. Nanosci. Nanotechnol. 12, 4508–4513, 2012 4511

 Evaluation of the Influence of Nanoparticles’ Shapes on the Formation of PLA Nanocomposites Brito and Tavares

300
400

PLA 3% PLA 3%
Relative intensity

Relative intensity
200

200 PLA+NT25 5%

A200 0.1%
100
PLA+NT25 3%

0
PLA+NT25 1% 0 R972 0.1%

10 100 1000 10000 100000 1000000 1E7 10 100 1000 10000 100000 1000000 1E7
Time (μs)
Time (μs)
Fig. 7. Distribution curves obtained by low-field NMR of PLA and
Fig. 9. Distribution curves obtained by low-field NMR of PLA and
PLA/NT25 nanocomposites.
PLA/silica nanocomposites.

the PLA film and silica A200. The increase in the relax- indicates the formation of material with a more ordered
ation parameter values indicates there was a decrease in structure and predominance of an exfoliated structure.26
molecular mobility due to good silica/polymer interaction, Figure 9 shows the domain curves for the nanocom-
posites containing 0.1% PLA/A200 and 1% PLA/R972.
as well as silica dispersion after they were incorporated in
The distribution of the domain curves provides informa-
the PLA matrix.
tion on the molecular mobility; interaction of the polymer
The domain curves, generated from the relaxation time
matrix with the nanoparticles and structural organization.
measurements, show the behavior of the molecular struc-
For the silica systems, the silica introduction changed the
tural according to the changes caused by the incorpora-
molecular organization, due to the base broadening of the
tion of nanoparticules in the polymeric matrix. Figures 7
Delivered by Publishing Technology to:nanocomposites.
University of Southern Californiathe fact that the inser-
This corroborates
and 8 show the domain curvesIP:for99.231.236.217
the PLA/NT25 On:andWed, 09 Apr 2014 15:38:58
tion of nanoparticles caused an increase in the chain disor-
PLA/Viscogel B8 nanocomposites, respectively.
Copyright: American Scientific Publishers
RESEARCH ARTICLE

der, generating different forms of molecular organization.

The domain curves shown in Figures 7 and 8 indi-
The small deviation of the domain curves to higher values
cate that no significant changes in domains occurred in
is the result of the increase in the relaxation values, shown
the nanocomposites formed with sodic clay NT25. On the
in the Table III, confirming the decrease in the chains’
other hand, the domains formed in the nanocomposites
molecular mobility.
prepared with Viscogel B8 at concentrations of 1 and 5%
Finally, the appearance of only one domain for all
were wider than for the PLA itself. This result indicates
nanocomposite types, in contrast to the polymer matrix,
that mixed (exfoliated and intercalated) nanocomposites
indicates that the nanoparticles used did not cause changes
were formed. At a concentration of 3%, the domain curve
in the basic molecular structure of the PLA.
was slightly narrower than in the PLA. This narrowing

4. CONCLUSIONS

400
According to the results obtained, the measurement of
the relaxation time can elucidate the molecular mobil-
PLA 3%
ity changes in the PLA matrix caused by the addition of
Relative intensity

nanoparticles. Low-field 1 H NMR relaxometry was par-

PLA+ B8 5%
ticularly useful to study the non-exfoliated and exfoliated
200
PLA/clay nanocomposite materials.
PLA+ B8 3%
Acknowledgment: We are grateful to CNPq for the
financial support of this work.
0
PLA+ B8 1%

References and Notes

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Received: 14 November 2011. Accepted: 13 February 2012.

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RESEARCH ARTICLE

J. Nanosci. Nanotechnol. 12, 4508–4513, 2012 4513