Poly(vinylidene fluoride)/Clay Nanocomposites Prepared by

Melt Intercalation: Crystallization and Dynamic Mechanical

Behavior Studies

L. PRIYA, J. P. JOG

Chemical Engineering Division, National Chemical Laboratory, Pune 411008 India

Received 18 October 2001; revised 12 April 2002; accepted 13 May 2002

Published online 00 Month 2002 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/polb.10223

ABSTRACT: The preparation and properties of poly(vinylidene fluoride) (PVDF)/clay

nanocomposites are reported for the first time. PVDF/clay nanocomposites were pre-
pared by melt intercalation with organophilic clay. The composites were characterized
with X-ray diffraction, differential scanning calorimetry, and dynamic mechanical
analysis. X-ray diffraction results indicated intercalation of the polymer into the inter-
layer spacing. PVDF in the nanocomposites crystallized in the ␤ form. Differential
scanning calorimetry nonisothermal curves showed an increase in the melting and
crystallization temperatures along with a decrease in crystallinity, as evidenced by the
melting and crystallization peaks. Isothermal crystallization studies showed an en-
hanced rate of crystallization with the addition of clay, as evidenced by a reduction in
the crystallization time. Dynamic mechanical analysis indicated significant improve-
ments in the storage modulus over a temperature range of ⫺100 to 150 °C. The tan ␦
peak signifying the glass-transition temperature of PVDF shifted to higher tempera-
tures. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1682–1689, 2002
Keywords: crystallization; dynamic mechanical analysis (DMA); intercalation; nano-
composites; poly(vinylidene fluoride) (PVDF); polymorphism

INTRODUCTION so need to be modified with organic surfactant

Polymer nanocomposites represent a new class of
materials with enhanced performance. Compared
with conventional filled grades of polymers, nano-
composites exhibit property improvements at
lower loadings of the inorganic fillers. As a result,
the specific properties of these nanocomposites
are markedly improved.
Clay is the most commonly used mineral for
the preparation of nanocomposites because of
its layered structure and the ease of dispersibil-
ity of the layers in suitable media. Clays are
hydrophilic because of surface OH groups and
Correspondence to: J. P. Jog (E-mail: jyoti@che.ncl.res.in)
Journal of Polymer Science: Part B: Polymer Physics, Vol. 40, 1682–1689 (2002)
© 2002 Wiley Periodicals, Inc.
1682
treatments. The organically modified clay is
then used for the preparation of nanocompos-
ites. The introduction of clay into the polymer is
known to dramatically enhance the mechanical,
thermal, and barrier properties because of the
high aspect ratio of the clay layers. Polymer
nanocomposites exhibit higher modulus,1–3 im-
proved dimensional stability, a decreased coef-
ficient of thermal expansion (CTE),2 increased
solvent resistance,4 enhanced ionic conductivi-
ty,5 and reduced gas permeability2,6 in compar-
ison with the host/base polymer. The study of
intercalated polymer/clay nanocomposites is of
fundamental interest because it provides a bet-
ter understanding of polymer chain dynamics in
nanoscopically confined states. The rheological
studies of these nanocomposites offer an excel-
 POLY(VINYLIDENE FLUORIDE)/CLAY NANOCOMPOSITES
lent tool for probing the polymer chain dynam-
ics in the confined state.7–9
Poly(vinylidene fluoride) (PVDF) is a crystal-
line polymer with a variety of interesting proper-
ties. PVDF has been one of the most studied poly-
mers because of its potential as piezoelectric and
pyroelectric materials. It is also being used in
nonlinear optics, microwave transducers, and bio-
medical applications. These properties, combined
with high elasticity and processing ability, pro-
vide a variety of technological applications for
this polymer. From a scientific point of view, it is
an interesting polymer because it exhibits mul-
tiphase character with four crystal forms (␣, ␤, ␥,
and ␦).10
In this article, we report the preparation of
nanocomposites of PVDF by a melt intercalation
technique with organophilic clay. Although there
are many reports on the preparation of polymer/
clay nanocomposites by melt intercalation, this is
the first report involving PVDF.
EXPERIMENTAL
Materials
PVDF (Solef 1008, Solvay, Belgium) was used.
The weight-average molecular weight (Mw) was
100 ⫻ 103, and the polydispersity index [weight-
average molecular weight/number-average mo-
lecular weight (Mw/Mn)] was 2.5
The organically modified bentonite clay sample
used in this study was Cloisite 6A, which was
generously donated by Southern Clay Products
(Texas). The clay was organically modified with a
tallow compound, dimethyl dihydrogenated tal-
low quaternary ammonium chloride (6A). The cat-
ion-exchange capacity of the clay sample was re-
ported to be 140 mequiv/100 g, and the organic
content was 47%.
Preparation of the Composites
The melt compounding of PVDF/6A clay compos-
ites was carried out with a Brabender plasti-
corder batch mixer at 200 °C and 60 rpm for 5
min. The clay sample was dried in an air circula-
tory oven at 60 °C for 8 h before the compounding.
Four compositions containing 1.5, 3, 5, and 7%
(w/w) clay were prepared.
The films used for X-ray diffraction (XRD) and
mechanical analyses were prepared by compres-
sion molding at 200 °C with a Carver model
1683
Table 1. Sample Codes and Compositions
Code Composition
P PVDF
PC1.5 PVDF/1.5% 6A
PC3 PVDF/3% 6A
PC5 PVDF/5% 6A
PC7 PVDF/7% 6A
F-15181 press. The sample codes and composi-
tions are presented in Table 1.
XRD
The structure of the clay in the polymer matrix
was evaluated with XRD measurements. A
Rigaku model Dmax 2500 X-ray diffractometer
with Cu K␣ radiation with a wavelength of 1.54 Å
and an energy value of 8.05 KeV was used for this
purpose. The basal spacing of the clay was esti-
mated from the (001) peak in the XRD pattern
with Bragg’s law.
Dynamic Mechanical Analysis (DMA)
Dynamic mechanical properties of the samples
were studied on compression-molded films with a
Rheometrics model IIIE dynamic mechanical an-
alyzer in the tensile mode. The dynamic re-
sponses were tested from ⫺100 to 150 °C at a
frequency of 10 rad/s and a strain of 0.1% in the
autostrain mode.
Differential Scanning Calorimetry (DSC)
A PerkinElmer DSC-2 was used for nonisothermal
and isothermal crystallization studies. The samples
were heated and cooled at 10 °C/min, and the melt-
ing and crystallization parameters were deter-
mined from the heating and cooling scans, respec-
tively. The isothermal crystallization was studied
from 140 to 160 °C in a nitrogen environment at a
flow rate of 20 cc/min. The sample was heated to the
melt temperature of 200 °C and was held for 1 min
to ensure complete melting. Then, the sample was
quenched at 160 °C/min to a crystallization temper-
ature (Tc) at which the crystallization exotherm was
recorded on a time base. The crystallization half-
time (t1/2) was used as a characteristic parameter
of the crystallization process and was calculated
with the Avrami equation.11–13
1684 PRIYA AND JOG
Figure 1. XRD of PVDF and PVDF/6A nanocomposites: 6A, PC1.5, PC3, PC5, and
PC7.
RESULTS AND DISCUSSION
XRD
Figure 1 compares the XRD patterns of the
PVDF/6A nanocomposites. The clay exhibited
three well-defined peaks at 33, 18, and 11 Å cor-
responding to the d001, d002, and d003 planes. For
the nanocomposites, the d002 peak observed at 18
Å for pristine clay disappeared, whereas the peak
at 11 Å shifted to 14 Å. The new peak positions
observed at 28 and 14 Å, corresponding to the d001
and d002 planes, can be ascribed to the intercala-
tion of the polymer in the intergallery space. d001
showed reduced intensity for all the nanocompos-
ites. The lower intensities of the diffraction peaks
for the nanocomposites in comparison with those
for pristine clay (26,698 cps) indicated disorder-
ing of the layered clay due to intercalation of the
polymer between the interlayers. At a lower clay
percentage (PC1.5 and PC3), a second-order dif-
fraction peak could be observed. However, at a 7%
clay content, a significant reduction in the peak
intensity suggested the presence of partially ex-
foliated structures,14 –16 and no higher order
peaks were observed. The results of the XRD
analysis can be explained on the basis of the in-
tercalation of the polymer in the intergallery
space. At a low percentage (PC1.5 and PC3), the
intercalation took place without much disruption
of the ordered layer structure, leading to higher
order peaks. However, at a higher clay percentage
(PC7), polymer intercalation led to disorder in the
platelets. This resulted in a decrease in the XRD
peak intensity. The percentage intercalation and
exfoliation were calculated from the XRD pat-
terns according to the procedure reported by
Ishida et al.17 The nanocomposites showed an
increase in the percentage intercalation with an
increase in the clay percentage.
Figure 2 compares the XRD patterns of pris-
tine PVDF and PVDF in the nanocomposites. The
pristine PVDF clearly exhibited an ␣ form, as
evidenced by the peaks at the 2␪ values 17.2, 17.9,
and 19.5° corresponding to the d-spacings of 5.07,
4.9, and 4.5 Å, respectively. The XRD patterns of
PVDF in the nanocomposites do not show the
characteristic peaks of the ␣ form. However, it
exhibits broad peaks at 18.3 and 19.9° corre-
sponding to the ␤ form. Therefore, PVDF crystal-
lized in the ␤ form in the presence of the clay.
The ␤ form of PVDF is of great interest because
it exhibits various interesting physical properties
such as piezoelectricity and pyroelectricity. It is
obtained when PVDF is crystallized under high
pressure or by drawing at a low temperature or
ultradrawing at a high temperature.10 For a
PVDF/poly(methyl methacrylate) (PMMA) blend,
Yang et al.18 noted that PVDF crystallized in the
␤ form when the blend was crystallized from so-
lution. This was observed only for the blend com-
position with a low PVDF content (⬍5%). How-
ever, for a higher PVDF content, when the do-
 POLY(VINYLIDENE FLUORIDE)/CLAY NANOCOMPOSITES 1685

fusion of PVDF decreased from 10.4 to 9.6 cal/g.

The decrease in the heat of fusion indicated a
lower extent of crystallinity for the PVDF nano-
composites. The crystallinity percentage of PVDF
was calculated with a value of the heat of fusion
for the 100% crystalline PVDF as 25 cal/g.19 The
crystallinity percentage of PVDF decreased from
42 to 38% with the addition of clay, as can be seen
in Table 2.
The crystallization during cooling took place
under nonisothermal conditions. The nonisother-
mal crystallization curves show that PVDF in
PVDF/clay nanocomposites crystallized at a
higher temperature (ca. 152 °C) with respect to
pristine PVDF (141 °C). Therefore, a shift of
about 10 –11 °C in the nonisothermal crystalliza-
tion peak of PVDF indicates that the crystalliza-
tion process was enhanced in the presence of clay
platelets.

Isothermal Crystallization
The isothermal crystallization of PVDF and
PVDF/clay nanocomposites was studied for the
determination of the effect of clay on the isother-
mal crystallization behavior. Figure 3 illustrates
the temperature dependence of t1/2, calculated
with the Avrami equation,11–13 on Tc for PVDF
and nanocomposites. Over the temperature range
Figure 2. XRD showing the ␣ form of pristine PVDF studied, PVDF/clay nanocomposites exhibited a
and the ␤ form of PVDF in PVDF/6A nanocomposites: shift in Tc to higher temperatures for all the nano-
(a) P, (b) PC1.5, (c) PC3, (d) PC5, and (e) PC7. composites. This indicates that the crystallization
process of PVDF in the nanocomposites was ac-
celerated because of the presence of clay. A simi-
lar enhancement of crystallization was reported
main size of PVDF was larger than 150 nm,
for PP/clay17 and PET/clay nanocomposites.21
PVDF crystallized as bulk. The observed ␤ form
However, the extent of the change in the crystal-
in the PVDF/PMMA blends was attributed to the
lization behavior was not sensitive to composition
crystallization of PVDF in a spatially confined
because all the curves corresponding to different
state. In this study, the presence of the ␤ form in
percentage compositions overlapped.
the PVDF/6A nanocomposites may also be attrib-
uted to the crystallization of PVDF in a confined
DMA
state.
DMA is often used to study relaxations in poly-
mers. An analysis of the storage modulus and tan
Nonisothermal Crystallization and Melting
Table 2. Tm, Tc, and Crystallinity Percentage for
Table 2 presents the melting temperature (Tm), PVDF and PVDF/Clay Nanocomposites
crystallization temperature (Tc), and degree of
crystallinity of PVDF in PVDF/clay nanocompos- Code Tm (°C) Tc (°C) Crystallinity (%)
ites. Tm’s of PVDF/6A nanocomposites shifted
from 173.6 to 178 –181 °C (Table 2). Tm’s of the ␣ P 173.6 141.4 46.9
and ␤ forms were reported to be 172 and 178 °C, PC1.5 178.1 151.6 45.4
respectively.10 The higher Tm of PVDF in the PC3 178.6 151.7 42.8
PC5 180.7 152.0 38.3
nanocomposites, therefore, supports the XRD re-
PC7 181.1 151.2 38.3
sults suggesting the ␤ form of PVDF. The heat of
1686 PRIYA AND JOG

Table 3. E⬘c/E⬘p Values for Compositions at Different

Temperatures

E⬘c/E⬘p

Code ⫺100 °C 20 °C

PC1.5 1.25 0.96

PC3 1.32 0.93
PC5 2.34 1.2
PC7 2.55 1.54

creased with an increase in the clay content.3,22 A

Figure 3. Temperature dependence of t1/2 for PVDF
and PVDF/clay nanocomposites.
␦ curves is very useful in ascertaining the perfor-
mance of a sample under stress and temperature.
Figure 4 shows the storage moduli of PVDF
and PVDF/clay nanocomposites. PVDF nanocom-
posites showed higher values of the storage mod-
ulus over the entire temperature range of the
study (⫺100 to 150 °C). The storage modulus in-
similar increase in the dynamic storage modulus
was reported for polymer/clay nanocompos-
ites.20,23
The effectiveness of clay as a reinforcement can
be elucidated as follows. The increase in the stor-
age modulus of the nanocomposites is expressed
in terms of the ratio of the modulus of the com-
posite (Ec⬘) to the modulus of the pristine polymer
(Ep⬘). Table 3 presents Ec⬘/Ep⬘ at two tempera-
tures. Ec⬘/Ep⬘ increased with an increase in the
clay percentage. At a very low clay percentage
and a low temperature (⫺100 °C), the increase
was about 25%; however, at room temperature, a

Figure 4. Temperature dependence of the storage modulus (E⬘) for PVDF and PVDF/
clay nanocomposites.
 POLY(VINYLIDENE FLUORIDE)/CLAY NANOCOMPOSITES
Figure 5. Tan ␦ versus the temperature for PVDF and PVDF/clay nanocomposites.
decrease in the Ec⬘/Ep⬘ ratio resulted from the
softening of the matrix phase. As the clay percent-
age increased from 1.5 to about 7%, Ec⬘/Ep⬘ sig-
nificantly increased from 1.25 to 2.55, correspond-
ing to an increase in the modulus from 25 to
155%. Even at a high temperature (i.e., 120 °C)
well above the glass-transition temperature (Tg)
of the polymer, the increase in the modulus was
about 50% for a 7% clay content. The significant
improvement in the storage modulus at tempera-
tures higher than Tg of PVDF clearly confirms the
reinforcing effect of clay in PVDF/clay nanocom-
posites.
Figure 5 shows the tan ␦ curves of PVDF and
PVDF/clay nanocomposites. The tan ␦ curve
shows a peak at about ⫺50 °C for PVDF, which
corresponds to Tg of PVDF. For PVDF/clay nano-
composites, the tan ␦ peak shifts to a higher tem-
perature by approximately 6 – 8 °C, and the area
under the tan ␦ peak decreases, as can be seen in
Figure 5. The shift of the tan ␦ peak to a higher
temperature may be ascribed to hindered cooper-
ative motion of polymer chains. A similar increase
was reported for polyimide/clay nanocomposites
by Agag et al.24 In addition to the tan ␦ peak
around ⫺50 °C, the nanocomposites exhibited two
more tan ␦ peaks at 20 and 60 °C. In PVDF, a
high-temperature transition (␣) was reported at
1687
about 80 °C and was assigned to the liberation of
polymer chains in the crystalline regions. The
high-temperature peak (60 °C), therefore, could
be ascribed to this ␣ transition. The peak at 20 °C
may correspond to the release of a constrained
amorphous phase. The presence of such re-
strained polymer chain relaxation has been noted
in other polymers and polymer composites.25 In
particular, an additional tan ␦ peak at tempera-
tures higher than Tg was observed by Tsagaro-
poulous and Eisenberg26 in several polymers
filled with fine silica. The presence of a high-
temperature tan ␦ peak was assigned to the glass
transition of regions containing chains of reduced
mobility. As noted earlier, the crystallinity of the
nanocomposites was lower than that of the pris-
tine polymer, suggesting a higher amorphous con-
tent. Because the tan ␦ peak is related to the
amorphous content of the polymer, it is expected
that the nanocomposites with higher amorphous
contents would show higher tan ␦ peak values.
However, the tan ␦ peak was lower for the com-
posites than for the pristine polymer. The reduced
tan ␦ peak signifies restricted molecular motion of
PVDF in PVDF/clay nanocomposites, which could
be ascribed to the presence of a constrained frac-
tion, as defined by Kojima and coworkers.27,28 A
similar decrease in the tan ␦ peak was observed
1688 PRIYA AND JOG
Figure 6. Dependence of the CTE on the weight per-
centage of clay.
for polyamide-6/silica nanocomposites by Yang et
al.29 They attributed it to the good adhesion be-
tween the polymer and silica particles. Therefore,
the reduced tan ␦ peak (␣ transition) and the
presence of an additional tan ␦ peak at a temper-
ature higher than Tg suggest the presence of a
constrained fraction with reduced mobility of
polymer chains. This constrained fraction was
also responsible for the increase in modulus, as
shown by Shelley et al.28
Nanocomposites are known to exhibit better
dimensional stability than pristine polymer. The
CTE can be used as a tool to measure the dimen-
sional stability. The coefficient of expansion was
measured from ⫺100 to 150 °C. Figure 6 depicts
the variation of CTE as a percentage of the clay.
CTE decreased sharply at a 1.5% clay content by
about 50%. A further increase in the clay content
resulted in a decrease in the CTE. The addition of
clay platelets, therefore, reduced the CTE signif-
icantly. The lower CTE values for the nanocom-
posites confirmed the dimensional stability of the
nanocomposites.24
CONCLUSIONS
We have shown that PVDF/clay nanocomposites
can be prepared by a melt intercalation technique
with organophilic clay. The XRD results showed a
marginal shift in the peak position with reduced
intensity. The reduced intensity suggested the
presence of a partially delaminated structure due
to intercalation of the polymer in silicate layers.
The nonisothermal and isothermal crystallization
studies showed enhanced crystallization of
PVDF. DMA indicated improved storage modulus
over the temperature range studied, and the ex-
tent of the increase was dependent on the clay
percentage. Tg increased by approximately 6 – 8
°C, indicating restricted chain mobility in the
nanocomposite. The tan ␦ peak curves exhibited
two peaks corresponding to Tg of the polymer and
the release of a constrained phase due to clay. The
interesting result of this work is the presence of
the ␤ form of PVDF crystallized in the presence of
clay.
L. Priya thanks Council of Scientific and Industrial
Research (CSIR) (New Delhi, India) for providing a
junior research fellowship.
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