Article

pubs.acs.org/JPCC

Enhanced Piezoelectric Properties of Electrospun Poly(vinylidene

uoride)/Multiwalled Carbon Nanotube Composites Due to High
Phase Formation in Poly(vinylidene uoride)
Yongjin Ahn, Jun Young Lim, Soon Man Hong, Jaerock Lee, Jongwook Ha, Hyoung Jin Choi,*,
and Yongsok Seo*,

Intellectual Textiles Research Center (ITRC) and RIAM School of Materials Science and Engineering, College of Engineering, Seoul
National University, Shillim-9-dong 56-1, Kwanakgu, Seoul, Republic of Korea 151-744

Hybrid Materials Research Center, Korea Institute of Science and Technology, Hawolgokdong 39-1, Sungbukku, Seoul, Republic of
Korea 130-650

Energy Materials Research Center, Korea Research Institute of Chemical Technology, P.O. Box 107, Yousungku, Taejon, Republic of
Korea 305-600

Department of Polymer Science and Engineering, Inha University, Yonghyun-dong, Namku, Incheon, Republic of Korea 402-751
ABSTRACT: We prepared poly(vinylidene uoride)
(PVDF)/multiwalled carbon nanotube (MWCNT) nanocomposites using the electrospinning process and investigated
the eects of varying the MWCNT content, as well as the
additional use of drawing and poling on the polymorphic
behavior and electroactive (piezoelectric) properties of the
membranes obtained. Fourier transform infrared spectroscopy
and wide-angle X-ray diraction revealed that dramatic
changes occurred in the -phase crystal formation with the
MWCNT loading. This was attributed to the nucleation eects
of the MWCNTs as well as the intense stretching of the PVDF
jets in the electrospinning process. The remanent polarization and piezoelectric response increased with the amount of
MWCNTs and piezoelectric -phase crystals. A further mechanical stretching and electric poling process induced not only highly
oriented -phase crystallites, but also very good ferroelectric and piezoelectric performances. In the drawn samples, the interfacial
interaction between the functional groups on the MWCNTs and the CF2 dipole of PVDF chains produced a large amount of phase content. In the poled samples, the incorporation of the MWCNTs made it easy to obtain ecient charge accumulation in
the PVDF matrix, resulting in the conversion of the -phase into the -phase as well as the enhancement of remanent
polarization and mechanical displacement.

most common and important ones. In the TGTG conformation (the -phase conformation), the dipole is inclined
relative to the normal axis, so the average dipole moment for
each monomer is very reduced. Furthermore, the unit cell of
the -PVDF lattice consists of two chains in a TGTG
conformation, whose dipole components normal to the chain
axis are antiparallel, thus neutralizing each other.4 As a result,
the -phase can be described as nonpolar, nonpiezoelectric, and
nonpyrroelectric. On the other hand, the -phase, which is in
an all-trans (TTTT) conformation, has all of its dipoles aligned
in the same direction normal to the chain axis. Its unit cell
consists of two all-trans chains packed with their dipoles
pointing in the same direction. The molecular dipoles in the phase are thus entirely aligned in one direction; this crystal
form can therefore generate the largest spontaneous polar-

INTRODUCTION
Poly(vinylidene uoride) (PVDF) has been studied extensively
because of its unique electroactive properties, including piezo-,
pyro-, and ferroelectric properties, as well as its other useful
properties, such as its exibility, light weight, and long-term
stability under high electric elds.1,2 PVDF is a semicrystalline
polymer with a typical crystallinity of 50%, whose molecular
structure consists of the repeated monomer unit
(CH2CF2)n. It is well-known that PVDF has ve distinct
crystallite polymorphs.3 The most common polymorph of
PVDF is the -phase, which has a monoclinic unit cell with a
TGTG (T = trans, G = gauche +, G = gauche ) conformation.
The piezoelectric crystallization polymorph is the -phase,
which has an all-trans (TTTT) conformation, with an
orthorhombic unit cell. The -phase also has an orthorhombic
unit cell, with a TTTGTTTG chain conformation. The other
two ( and ) polymorphs are the polar and antipolar
analogues of the and forms, respectively.3 The rst two
conformations (the -phase and the -phase) are by far the
2013 American Chemical Society

Received: January 31, 2013

Revised: April 29, 2013
Published: April 29, 2013
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EXPERIMENTAL SECTION
Materials. The polymer used in this experiment was a
semicrystalline PVDF (Atona, Kynar761) which has a number
average molecular weight of 5.2 105 Da. N,N-Dimethylacetamide (DMAc) and acetone solvent were purchased from
Fisher Scientic. MWCNTs (purity, >95%; average diameter,
1015 nm) were purchased from Hanwha Nanotech Corp.
(Korea).
Preparation of Functionalized MWCNTs. Heat treatment at 400 C was done in an oven for 3 h to remove
impurities such as amorphous carbon, catalyst metals, and
graphite particles.33,38 MWCNTs were then put in a
concentrated H2SO4/HNO3 (1:3, vol %) solution and stirred
for 48 h. Ultrasonication was applied for 2 h to remove further
impurities and to maximize the number of carboxylic acid
groups on the surface of the MWCNTs with little destruction
of the tube walls.39,40 Extra acid was removed by ltration
through a 0.4 m PVDF porous membrane. The MWCNT
slurry was rinsed with distilled water several times. The
MWCNTs were dried in a vacuum oven at 80 C overnight.
The functionalized MWCNTs were dispersed in DMAc solvent
by using an ultrasonic bath for 30 min. This MWCNT solution
was stable for a month.
Fabrication of Electrospun Membranes. Figure 1 shows
a schematic illustration of the setup used in this study. The

ization and exhibits strong ferroelectric and piezoelectric

properties. These unique -phase-derived properties of PVDF
make it useful in a wide range of applications, including
actuators, biosensors, energy-harvesting materials, audio
devices, transducers, and nonvolatile memories.3,58 However,
it is not easy to obtain PVDF consisting of entirely -phase
crystals. In all-trans PVDF, the overlapping of neighboring
uorine atoms occurs, because the diameter of the uorine
atom (0.270 nm) is slightly larger than the space provided by
an all-trans carbon chain (0.256 nm).9 To diminish this overlap,
CF2 groups are tilted to the right and left, relative to their
original conformation. This deection of CF2 groups converts
the all-trans form into TGTG ( form) or TTTGTTTG (
form). Hence, the -phase is more easily formed than the phase in normal circumstances.
Although the crystal lattice energy of the -phase is slightly
higher than that of the -phase, direct -phase formation from
the melt is prohibited due to the high energy of the all-trans
conformations.1 -Phase formation can be accomplished via a
crystal phase transition from the -phase.10 The most common
technique for obtaining polar -PVDF involves mechanical
extension (drawing) and electrical poling.1113 Mechanical
drawing contributes to the transition of the original spherulitic
structure into a crystal array, in which the molecules are forced
into their most extended conformation (polar -phase), with all
of the dipole moments aligned in the same direction.10,11 The
application of an electric eld on both sides of the PVDF
electrets (poling) also results in the orientation of the crystallite
polar axis along the eld direction, which promotes a higher
spontaneous polarization for the -phase.12 Conversion of the
paraelectric phase to the ferroelectric phase has also been
achieved using diverse methods such as crystallization from a
polar solution under special conditions,13 crystallization from
the melt,14 application of high pressure,13 addition of additive
materials to PVDF,15 and formation of PVDF-based copolymers with triuoroethylene (TrFE) or hexauoropropylene.16,17 Recent additions to this list of techniques are the
use of blending with nanollers such as inorganic (ceramic,
metal, magnetic particles, nanoclay) materials1825 and electrospinning.2631 One of the materials recently tried as a nanoller
was carbon nanotubes (CNTs).3236 The PVDFCNT
composite showed remarkably enhanced ferro-, pyro-, and
piezoelectric properties when the carbon nanotubes were well
dispersed.
Nanocomposites made from PVDF and CNTs have the
potential to be smart materials, not only because of the
combination of the piezoelectric properties of PVDF and the
conducting properties of CNTs, but also because of the higher
levels of -phase formation in the electrospun nanobers and
thus the better piezoelectric properties.32,33 The electrospinning process involves the uniaxial stretching of a viscous
polymer solution using a large electric potential;37 this process
is expected to transform the -phase into a highly oriented phase. In the present study, we examined the formation of the
-phase in PVDF subjected to the electrospinning process; the
changes in ferroelectric and piezoelectric properties were
compared to those fabricated using a thermal press. 33
Electrospun PVDF membranes containing 0.051.0 wt %
carbon nanotubes were also produced to determine the eects
of multiwalled carbon nanotubes (MWCNTs) on the
formation of the induced -phase crystallites and on the
ferroelectric and piezoelectric properties.

Figure 1. Schematic illustration of the electrospinning system.

polymer solution lled the plastic syringe (Hamilton, 10 mL)

with a metal needle (0.34 mm in diameter) connected to a
high-voltage power supply of 14 kV. The syringe was placed in
an automatic pump (KD Scientic, model 220). A grounded
stainless steel plate was used for the collection of the
electrospun brous membrane with a thickness of approximately 100 m and dimensions of approximately 20 cm 30
cm. The distance from the needle tip to the collector was set as
15 cm. Electrospinning was done with an ejection rate of 40
L/min from the syringe. In the electrospinning control
chamber, the temperature and humidity were set at 25 C and
40%, respectively. After spinning, the electrospun membranes
were dried under vacuum at room temperature for 24 h.
Preparation of Drawn and/or Poled Membranes. The
electrospun membranes with a thickness of 100 m and a width
of 50 mm were mounted in the uniaxial stretching device.
Drawing was done at a deformation rate of 1 mm/s at 125 C.
All of the electrospun samples could be drawn up to 200%
elongation without producing any defects. After the drawing,
they were removed from the device and rapidly cooled to room
temperature. For the poling procedure, conducting aluminum
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solution blending. SEM images of the electrospun PVDF ber

based membranes are shown in Figure 3. The electrospun

plates were attached to both sides of the electrospun

membranes. An electric eld of 500 kV/cm was applied in a
silicone oil bath (KF-96, Shin-Etsu Silicone Korea Co., Ltd.) at
120 C for 20 min. After being poled, the samples were
removed from the oil bath and rinsed with hexane and
methanol to remove the silicone oil. The samples were dried in
a vacuum for 1 day.
Morphology Observations. The morphology of the
electrospun membranes was observed using a scanning electron
microscope (Nova NanoSEM 200, FEI Co.). All specimens
were gold-coated by sputter coating prior to scanning electron
microscopy (SEM) observations. A transmission electron
microscope (Tecnai F20G2, FEI Co.) operated at 200 kV was
also used. For transmission electron microscopy (TEM)
observation, the bers were directly spun on the copper grids.
Analysis of the Crystalline Structure. Attenuated total
reection Fourier transform infrared spectroscopy (ATR-FTIR; Spectrum 65, Perkin-Elmer) was used with an average of
1000 scans in the 5001600 cm1 range. The crystal structures
were determined by wide-angle X-ray diraction (WAXD;
HTK 1200N high-temperature X-ray diractometer, PANalytical) using 40 kV and 100 mA. The samples were scanned in
the range of 1040, with a scan rate of 1 deg/min. The
incident and diraction X-ray beams were in the same plane,
vertical to the electrospun ber mat.
Analysis of the Degree of Porosity. The apparent
porosity of the membranes (P) was determined as P (%) = (1
(m/p)) 100, where m is the membrane density and p is
the pure polymer density. The density of PVDF was 1.77 g
cm3, and the membrane density was determined using the
volume and the weight of the membrane.41
Measurement of Ferroelectric and Piezoelectric
Properties. Using a vacuum thermal evaporator (MEP5000,
SNTEC), aluminum electrodes were thermally evaporated onto
both surfaces of the samples in a 10 15 mm rectangular area.
The metal deposition was conducted under a pressure of 106
Torr until a thickness of 200 nm was reached. Polarization
electric eld (PE) hysteresis loops were obtained using a
standard ferroelectric testing system (Radiant Technoloies,
RT66A) connected to a high-voltage interface (Trek). A
triangular wave with a pulse of 1 ms and a voltage of at least 2
kV was applied to the samples in the oil. The piezoelectric
response in the thickness direction, d33, was measured with a
PSV-400 scanning vibrometer (Polytec) using a power
amplier with a continuous sine wave at a voltage of 200 V
and a resonant frequency of 1 kHz.

Figure 3. SEM images of electrospun PVDF brous membranes. (a

c) Electrospun from PVDF (15 wt %)/DMAc/acetone (1:1 DMAc/
acetone weight ratio) solutions: (a) low-magnication image (3000),
(b) middle-magnication image (20000), (c) high-magnication
image (50000). (d) Electrospun from PVDF solutions with a
DMAc/acetone weight ratio of 80:20 (30000).

membranes consisted of bers, typically with diameters of less

than 1 m, with fully interconnected pores and a high degree of
porosity (nearly 80%). No bead or beaded ber was observed.
Several wrinkles were observed on the surfaces of the bers, as
shown in Figure 3b,c. This surface morphology resulted from a
mixed solution of DMAc with an equal weight of acetone. A
smooth surface without wrinkles was obtained when the
amount of DMAc in the mixed solvent was increased (Figure
3d).42 Choi et al. stated that bers of PVDF formed in a mixed
solvent system with high acetone content had pores, wrinkles,
and raised areas, whereas those prepared in a cosolvent with
increased amounts of DMAc showed a smooth surface.43
Bognitzki et al. also reported that the pore structure in the
bers made using dichloromethane as the solvent, which has a
low boiling point and a high vapor pressure, was signicantly
reduced when dichloromethane was replaced by a solvent with
the opposite properties.44 The morphological dierences
between the two bers were aected by the volatile solvents
during electrospinning.
Figure 4 shows TEM images of the nanobers containing
MWCNTs. It is evident that individual MWCNTs are well

RESULTS AND DISCUSSION

Figure 2 shows optical images of several electrospun PVDF
MWCNT composite nanobrous membranes. The MWCNTs
are uniformly dispersed due to the surface modication and
Figure 4. TEM image showing oriented MWCNT in the PVDF
nanobers.

dispersed in the PVDF matrix. Most of the nanotubes

embedded in the ber matrix were well oriented along the
ber axis without entangled nanotube bundles. Others reported
similar morphologies in nanobers containing CNTs.45,46 It
should be emphasized that the preparation of separate PVDF
and MWCNT solutions and their subsequent mixing is
important to prevent the reaggregation of the MWCNTs into

Figure 2. Optical images of the PVDF nanobrous membranes with

dierent amounts of MWCNTs: (a) 0 wt %, (b) 0.05 wt %, (c) 0.1 wt
%, (d) 0.2 wt %, (e) 0.5 wt %, (f) 1.0 wt % (400 magnication).
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Figure 5. (a) FTIR spectra and (b) WAXD patterns of (---) the thermally pressed PVDF lms and () the electrospun PVDF nanobrous
membranes.

Figure 6. (a) FTIR spectra and (b) WAXD patterns of the electrospun PVDF/MWCNT membrane.

elongated along the local axis, reducing the diameter of the jet
further. The elongation of the jet uids made it easier for the
polymer chain orientation along the ber axis to produce more
of the polar -phase. This could be corroborated in the WAXD
patterns shown in Figure 5b, where the four characteristic peaks
of the -phase at 2 = 18.0, 18.6, 20.2, and 26.8 correspond
to (100), (020), (110), and (021) reections, respectively. All
the peak intensities assigned to -phase crystals with a nonpolar
TGTG conformation were reduced, whereas the diraction
intensity of the characteristic phase peaks at 2 = 20.9
(assigned to the (110) reection) increased signicantly.50 The
-phase content of the PVDF electrospun nanobers was
approximately 33%. This indicates that electrospinning is a
more ecient process to provide the polar -phase than the
simple addition of MWCNTs to a PVDF melt.33 Although
more -phase was present due to the nanober stretching
eect, considerable amounts of the nonpolar -phase remained,
indicating that it was not possible to convert all of the -phase
into the -phase PVDF using solely the electrospinning
process.
In our previous study, we reported that the addition of
MWCNTs into PVDF could induce the -phase to convert to
the -phase via the accumulated charge induction at the
interphase.33 To precisely determine the inuence of the
MWCNTs on the formation of the -phase, the FT-IR spectra
(see Figure 6a) were normalized on the basis of the absorbance
peak at 877 cm1, which is proportional to the thickness of the
sample.51 The peaks at 840 and 1270 cm1 slightly increased in
intensity with the addition of MWCNTs. The -phase increase
with increasing MWCNT content was further conrmed using

large bundles. The good MWCNT alignment was due to the

high extension of the electrospun jet. Well-separated
MWCNTs were randomly oriented in the electrospinning
solution, but they were aligned along the ow direction when a
straight line was developed at the Taylor cone. Moreover, due
to the elongation of the uid during jet travel, the nanotubes
were further spread out along the direction of motion of the jet.
In the same context, Dror et al. presented a theoretical model
to explain the alignment behavior of rodlike CNTs in
electrospinning,47 and Ge at el. also suggested that jet
elongation is a determining factor in orienting the carbon
nanotubes.48
FT-IR spectra of the electrospun PVDF nanobers and the
thermally pressed lms are presented in Figure 5a. The
characteristic absorption peaks of the -phase appear at 763,
976, 1150, 1211, and 1384 cm1, and those of the -phase
appear at 842 and 1274 cm1.49 The -phase is the most
abundant component in the crystal region of normal PVDF.33
The relative intensity of the -phase absorption peaks gradually
increased with electrospinning, while the intensity of the peaks
associated with the -phase drastically decreased. This
demonstrates that the elongational eect in the electrospinning
process induces the -phase conversion into the -phase. The
elongation of the jet occurs when the jet is issued from the
electrically charged surface of the droplet. The jet is elongated
many times its original length, becoming very long and slender.
After the jet is established, the inuence of Coulomb repulsion
between adjacent charges carried within the jet enables the
bending motion of the jet to create a coil shape.2731,37 This
Coulomb interaction causes the swirling motion of the jet to be
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electrostatic force responsible for drawing the jet; the amount

of -phase obtained from the stretching eect of the
electrospinning process therefore reaches a plateau value.
More -phase can be obtained in PVDF using the postdrawing
and poling process.33 The amount of -phase varied
signicantly with drawing and/or poling, as shown in Figure
8. In samples with an applied external electric eld and
mechanical stress, the intensities of the -phase FT-IR
absorption band and the -phase WAXD peaks diminished,
while the corresponding intensities for the -phase increased
dramatically.
Figure 9 shows a schematic illustration of the orientation of
the chains and MWCNTs during the processing of the

WAXD (Figure 6b). The intensities at 2 = 18.6 and 20.2,

which are related to the -phase, decreased while the -phase
peak at 20.9 increased signicantly. When functionalized
MWCNTs are dispersed in PVDF solutions, electrostatic
interactions act between the functional groups and the CF2
groups of the PVDF chains. MWCNTs act as nuclei to induce a
higher crystallization rate. In our previous study, we could
directly observe that the rate of crystallization increased with
decreasing PVDF crystal size, in step with the MWCNT
concentration.33 The interactions between the functional
groups on the MWCNTs and the CF2 dipole of PVDF
produce locally oriented -phase with signicant help from the
increased crystallization speed that occurs due to the presence
of the MWCNTs.
To quantitatively characterize the -phase content as a
function of the amount of MWCNTs in the composite
nanobers, the -phase content was calculated on the basis of
the WAXD data (Figure 7). Here, a few facts are worthy of

Figure 9. Schematic showing the proposed mechanism for chain

extension produced by electrospinning and mechanical drawing.

electrospun PVDF/MWCNT composite. For the drawn

samples, the chain orientation and the higher level of
interaction with the MWCNTs increase the -phase content.
Under the mechanical stress applied during drawing, the
alignment of polymer chains in the long planar conformation
(the -phase) is favored.4,53 Further conversion to the -phase
can be accomplished using the poling process. When the
external electric eld is applied in the direction perpendicular to
the chain axis of the PVDF bers, the -sequence chains rotate
to align their dipole moments in the direction favored by the
poled electric eld.54,55
The overall -phase contents after drawing and poling are
shown in Figure 10. The amount of -phase went over 90% in
the drawn PVDFMWCNT composite membranes, while the
electrospun and drawn pure PVDF membrane had ca. 80% phase content at a constant draw ratio. For the drawn samples,
the addition of more than 0.2 wt % MWCNTs did not produce
any noticeable change in the -phase content.33 This indicates
that the drawing process is quite ecient in producing changes
in the chain conformation. Although the poled samples show

Figure 7. Variation of the -phase content as a function of the

MWCNT loading.

note. First, just 0.05 wt % added MWCNTs brought about a

remarkable change in the crystalline structure. The extended
MWCNTs in the nanober increased the interaction with the
PVDF over a wider area, thus inducing more -phase. Second,
the amount of the -phase reaches a plateau at a concentration
of 1 wt % MWCNTs.33 It is well-known that the complex
viscosity increases when MWCNTs are homogeneously
dispersed and they have a stronger interaction with the
polymer matrix.52 Then the viscoelastic force which hampers
the elongation of the jet is also increased relative to the

Figure 8. (a) FTIR and (b) WAXD spectra of undrawn and unpoled, drawn, poled, and drawn and poled PVDF/MWCNT (0.2 wt %)
nanocomposite membranes.
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drawn and poled nanobrous pure PVDF lm. The neat

nanobrous PVDF lm still exhibited a higher Pr than a
thermally pressed PVDF lm.33 The good piezoelectricity in
the PVDF lms stemmed from the high remanent polarization,
i.e., the high lattice dipole moment after polarization.58 A wellsaturated hysteresis curve (the Pr and coercive eld values were
35.0 mC/cm2 and 75 MV/m) was observed for the electrospun
nanobrous PVDF lm, whereas no ferroelectric hysteresis
loop was observed for the thermally pressed pure PVDF thin
lms. This is due to the enhancment of the -phase form
produced by the elongation of the jet in the electrospinning
process: the -phase exhibits no net polarization, since the
chains are packed with dipoles in the opposite direction in the
unit cell, whereas the lamellae of the -crystals can rotate to
match the chain direction, producing a high degree of dipole
orientation.5658 Addition of MWCNTs further enhanced the
ferroelectric properties (Figure 11b). Pr reached 45 mC/cm2
with the addition of 0.2 wt % MWCNTs. The ferroelectricity
improvement in the composite membrane produced by the
inclusion of MWCNTs and the dierent drawing and poling
processes is summarized in Table 1.

Figure 10. Variation of the -phase content as a function of the

MWCNT loading (wt %): () undrawn and unpoled membranes,
() poled membranes, () drawn membranes, () drawn and poled
membranes.

high -phase contents too, stretching is more eective than

poling. It should be noted that the poling eects appeared
dierently here compared to those on the solution casting
membranes. In our previous study, the poling eects increased
steadily with increasing MWCNT amounts: a noticeable
increase in the -phase was observed when the MWCNT
amount reached a conducting threshold.33 However, the
electrospinning process used in this study already had the
nanobers elongated. A pure PVDF nanobrous membrane
showed a -phase content of approximately 33%. Stretching by
the electrospinning process helped the PVDF chain conformation to be arranged more easily (Figure 9). The addition
of the MWCNTs induced charge accumulation at the
boundary, which helped the PVDF chains to become arranged
in the -phase conformation.33 For the solution casting
membranes, depoling was observed with excessive MWCNT
addition that led to the -phase content decrease. For
electrospun samples, it seems that depoling did not happen
due to better dispersion of MWCNTs so that the charge
accumulation at the interface did not exceed the coercive
eld.33
The eects of MWCNT addition on the PE (polarization,
P, versus applied voltage, E) hysteresis are shown in Figure 11a.
The drawn and poled PVDF/MWCNT nanober composite
lms exhibited a larger remanent polarization (Pr) than the

Table 1. Summary of the Remanent Polarization (mC/m2)

of the PVDF/MWCNT Nanobrous Membranes Prepared
by Dierent Processing Conditions
MWCNT
amt
(wt %)

electrospun
nanobrous
membrane

poled
elctrospun
nanobrous
membrane

drawn
elctrospun
nanobrous
membrane

poled and drawn

elctrospun
nanobrous
membrane

0
0.05
0.1
0.2
0.5
1.0

35
41.9
42.8
43.9
44.9
44.8

43.2
49.8
51.5
51.7
51.3
52.5

53.8
56.8
55.4
56.5
56.8
57.7

55.5
58.4
57.7
58.5
58.5
60.8

The drawing and poling processes produced electrospun

PVDF/MWCNT composite membranes with larger Pr values
than pure electrospun PVDF or nonprocessed electrospun
PVDF/MWCNT membranes due to the higher degree of phase transformation. The stretched and poled PVDF/
MWCNT composite membranes showed much larger Pr values
(maximum of around 60 mC/cm2) than the neat PVDF
membranes (35 mC/cm2). Figure 12a,b shows the piezoelectric
actuation graph in the d33 direction, which is the membrane

Figure 11. (a) PE hysteresis loop for the electrospun PVDF membrane and PVDF membrane with MWCNTs (0.1 wt %). (b) Dependence of the
remanent polarization on the MWCNT content for the electrospun PVDF membranes.
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CONCLUSIONS

AUTHOR INFORMATION

Article

PVDF membranes of high -phase content could be obtained

using the electrospinning process, with the addition of small
amounts of MWCNTs (0.2 wt %). The electrospinning process
is similar in some ways to uniaxial mechanical stretching, which
helps the -phase conversion into the -phase. The addition of
long MWCNTs promoted the conversion of the PVDF
molecules -phase into the -phase by acting as nuclei in the
crystallization process and inducing charge accumulation at the
interface. The change of the physical properties could be
attributed to the alterations in the polymer microstructure
produced by drawing and poling and to the presence of the
carbon nanotubes. The cooperative eect of the drawing
process and MWCNTs led to a high degree of conversion from
the nonpolar -phase to the polar -phase in the electrospun
PVDF/MWCNT composite nanobers. The signicant eects
of the polymer chain orientation originated mainly from their
determining role in conning the dipole through chain rotation
under drawing and poling.
Dierently from the solution casting membranes, depoling
was not observed with the excessive MWCNT addition that led
to the -phase content decrease. For electrospun samples, it
seems that depoling did not happen because of better
dispersion of MWCNTs so that the charge accumulation at
the interface did not exceed the coercive eld. For the poled
samples, the amount of the -phase increased with increasing
amount of MWCNTs due to the ecient charge accumulation.
The high conversion of the -phase into the -phase was
improved remarkably by further drawing of the membranes,
which resulted in the rapid enhancement of the ferroelectric
and piezoelectric properties of the PVDF/MWCNT membranes.

Figure 12. (a, b) Displacement images of the electrospun PVDF

membrane. (c) Electromechanical displacement image of electrospun
PVDF membranes.

thickness direction, under the application of alternating sinewave voltages of 200 V to the electrospun PVDF membranes.
Each membrane experienced reciprocal vertical motions under
dierent electric elds. The cycling piezoelectric displacement
was achieved with a maximum displacement of 83 nm. The
frequency and waveforms of the displacement corresponded
well to the applied sine-wave forms.59,60 Addition of MWCNTs
to the membranes and the application of external stresses such
as drawing and poling changed the membrane motion (shown
in Figure 13): the onset and trends in these changes were in
line with the changes in the -phase content.

Corresponding Author

*E-mail: ysseo@snu.ac.kr (Y.S.); hjchoi@inha.ac.kr (H.J.C.).

Notes

The authors declare no competing nancial interest.

Figure 13. Comparison between the actuation performance of the PVDF and PVDF/MWCNT membranes with various MWCNT contents and
further treatment (drawing or drawing and poling).
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(20) Song, Y. M.; Jhao, Z. D.; Yu, W. X.; Li, B.; Chen, X. F.
Morphological Structures of Poly(vinylidene fluoride)/Montmorillonite Nanocomposites. Sci. China, Ser. B: Chem. 2007, 50, 790796.
(21) Cui, C.; Baughman, R. H.; Iqbal, Z.; Kazmar, T. R.; Dahlstrom,
D. K. Improved Piezoelectric Ceramic/Polymer Composites for
Hydrophone Applications. Synth. Met. 1997, 85, 13911392.
(22) Ploss, B.; Ploss, B.; Shin, F. G.; Chan, H. L. W.; Choy, C. L.
Pyroelectric or Piezoelectric Compensated Ferroelectric Composites.
Appl. Phys. Lett. 2000, 76, 27762778.
(23) Swarup, M.; Sudip, K.; Batabyal; Arun, K. Nandi Preparation
and Characterization of SilverPoly(vinylidene fluoride) Nanocomposites: Formation of Piezoelectric Polymorph of Poly(vinylidene
fluoride). J. Phys. Chem. B 2006, 110, 1231812326.
(24) Dang, Z.; Wang, H.; Zhang, Y.; Qi, J. Morphology and Dielectric
Property of Homogeneous BaTiO3/PVDF Nanocomposites Prepared
via the Natural Adsorption Action of Nano Sized BaTiO3. Macromol.
Rapid Commun. 2005, 26, 11851189.
(25) Ramasundaram, S.; Yoon, S.; Kim, K. J.; Park, C. Preferential
Formation of Electroactive Crystalline Phases in Poly(Vinylidene
fluoride)/Organically Modified Silicate Nanocomposites. J. Polym. Sci.,
Part B: Polym. Phys. 2008, 46, 21732187.
(26) Andrew, J. S.; Clarke, D. R. Effect of Electrospinning on the
Ferroelectric Phase Content of Poly(vinylidene difluoride) Fibers.
Langmuir 2008, 24, 670672.
(27) Andrew, J. S.; Clarke, D. R. Enhanced Ferroelectric Phase
Content of Polyvinylidene Difluoride Fibers with the Addition of
Magnetic Nanoparticles. Langmuir 2008, 24, 84358438.
(28) Liu, Y. L.; Li, Y.; Xu, J. T.; Fan, Z. Q. Cooperative Effect of
Electrospinning and Nanoclay on Formation of Polar Crystalline
Phases in Poly(vinylidene fluoride). ACS Appl. Mater. Interfaces 2010,
2, 17591768.
(29) Yu, L.; Cebe, P. Crystal Polymorphism in Electrospun
Composite Nanofibers of Poly(vinylidene fluoride) with Nanoclay.
Polymer 2009, 50, 21332141.
(30) Huang, S.; Yee, W. A.; Tjiu, W. C.; Liu, Y.; Kotaki, M.; Boey, Y.
C.; Ma, J.; Liu, T. X.; Lu, X. H. Electrospinning of Polyvinylidene
Difluoride with Carbon Nanotubes: Synergistic Effects of Extensional
Force and Interfacial Interaction on Crystalline Structures. Langmuir
2008, 24, 1362113626.
(31) Nasir, M.; Matsumoto, H.; Minagawa, M.; Tanioka, A.; Danno,
T.; Horibe, H. Formation of -Phase Crystalline Structure of PVDF
Nanofiber by Electrospray Deposition: Additive Effect of Ionic
Fluorinated Surfactant. Polym. J. 2007, 39, 670674.
(32) Levi, N.; Czerw, R.; Xing, S.; Iyer, P.; Carroll, D. L. Properties of
Polyvinylidene Difluoride-Carbon Nanotube Blends. Nano Lett. 2004,
4, 12671271.
(33) Kim, G. H.; Hong, S. M.; Seo, Y. Piezoelectric Properties of
Poly(vinylidene fluoride) and Carbon Nanotube Blends: Beta-Phase
Development. Phys. Chem. Chem. Phys. 2009, 11, 1050610512.
(34) Pal, K.; Kang, D. J.; Zhang, Z. X.; Kim, J. K. Synergistic Effects
of Zirconia-Coated Carbon Nanotube on Crystalline Structure of
Polyvinylidene Fluoride Nanocomposites: Electrical Properties and
Flame-Retardant Behavior. Langmuir 2010, 26, 36093614.
(35) Yu, S.; Zheng, W.; Yu, W.; Zhang, Y.; Jiang, Q.; Zhao, Z.
Formation Mechanism of -Phase in PVDF/CNT Composite
Prepared by the Sonication Method. Macromolecules 2009, 42,
88708874.
(36) Swarup, M.; Arun, K.; Nandi. Piezoelectric Polymorph in
Poly(Vinylidene fluoride)-Functionalized Multiwalled Carbon Nanotube Nanocomposite Films. J. Phys. Chem. C 2007, 111, 1467014680.
(37) Ramakrishna, S.; Fujihara, K.; Teo, W. E.; Lim. T. C.; Ma, Z. R.
An Introduction to Electrospinning and Nanobers; World Scientic Co.:
Singapore, 2005.
(38) Kim, B. S.; Sigmund, W. M. Functionalized Multiwall Carbon
Nanotube/Gold Nanoparticle Composites. Langmuir 2004, 20, 8239
8242.
(39) Zhang, J.; Zou, H.; Qing, Q.; Yang, Y.; Li, Q.; Liu, Z.; Guo, X.;
Du, Z. Effect of Chemical Oxidation on the Structure of Single-Walled
Carbon Nanotubes. J. Phys. Chem. B 2003, 107, 37123718.

ACKNOWLEDGMENTS
This work was supported by the National Research Foundation
of Korea (NRF) (Basic Research Program RIAM 041-2004-ID00224, ITSTD Program RIAM AC 2509 (Grant 041720096070), RIAM NR03-09 (Grant 0417-20090027), and the
SRC/ERC program (Grant R11-2005-065)) and by Ministry of
Knowledge & Econonics (Original Material Technology
Program RIAM I-AC14-10 (Grant 0417-20100043)). H.J.C.
acknowledges partial nancial support from the NRF (Grant
NRF-2009-0080253).

REFERENCES

(1) Wang, J.; Li, H.; Liu, J.; Duan, Y.; Jiang, S.; Yan, S. On the
Transition of Carbon-Coated Highly Oriented PVDF Ultrathin Film
Induced by Melt Recrystallization. J. Am. Chem. Soc. 2003, 125, 1496
1497.
(2) Ohigashi, H.; Koga, K. Ferroelectric Copolymers of Vinylidenefluoride and Trifluoroethylene with a Large Electromechanical
Coupling Factor. Jpn. J. Appl. Phys. 1982, 21, L455457.
(3) Nandi, A. K.; Mandelkern, L. The influence of chain structure on
the equilibrium melting temperature of poly(vinylidene fluoride). J.
Polym. Sci., Part B: Polym. Phys. 1991, 29, 12871297.
(4) Lovinger, A. J. Ferroelectric Polymers. Science 1983, 220, 1115
1121.
(5) Fujisaki, S.; Ishiwara, H.; Fujisaki, Y. Low-Voltage Operation of
Ferroelectric Poly(vinylidene fluoride-trifluoroethylene) Copolymer
Capacitors and Metal-Ferroelectric-Insulator-Semiconductor Diodes.
Appl. Phys. Lett. 2007, 90, 162902.
(6) Inacio, P.; Marat-Mendes, J. N.; Dias, C. J. Development of a
Biosensor Based on a Piezoelectric Film. Ferroelectrics 2003, 293, 351
356.
(7) Xin, Y.; Li, Z.; Odum, L.; Cheng, Z. -Y. Piezoelectric Diaphragm
as a High Performance Biosensor Platform. Appl. Phys. Lett. 2006, 89,
223508.
(8) Elvin, N. G.; Elvin, A. A.; Spector, M. A Self-Powered Mechanical
Strain Energy Sensor. Smart Mater. Struct. 2001, 10, 293299.
(9) Furukawa, T. Ferroelectric Properties of Vinylidene Fluoride
Copolymers. Phase Transitions 1989, 18, 143211.
(10) Salime, A.; Yousefi, A. A. Analysis Method. FTIR Studies of Phase crystal Formation in Stretched PVDF Films. Polym. Test. 2003,
22, 699704.
(11) Sencadas, V.; Moreira, V. M.; Lanceros-Mendez, S.; Pouzada, A.
S.; Gregorio, R. Alpha-to-Beta Transformation on PVDF Films
Obtained by Uniaxial Stretch. Mater. Sci. Forum 2006, 872, 514516.
(12) Eisenmenger, W.; Schmidt, H.; Dehlen, B. Space charge and
dipoles in polyvinylidenefluoride. Braz. J. Phys. 1999, 29, 295305.
(13) Miller, R. L.; Raisoni, J. Single Crystals of Poly(vinylidene
Fluoride). J. Polym. Sci., Part B: Polym. Phys. 1976, 14, 2325.
(14) Lovinger, A. Crystallization of the Phase of Poly(vinylidene
fluoride) from the Melt. J. Polym. 1981, 22, 412413.
(15) Song, D.; Yang, D.; Feng, Z. Formation of -Phase Microcrystals
from the Melt of Poly(vinylidene fluoride) (PVF2)-PMMA Blends
Induced by Quenching. J. Mater. Sci. 1990, 25, 5764.
(16) Lando, J. B.; Doll, W. W. The Polymorphism of Poly(vinylidene
fluoride). I. The Effect of Head-to-Head Structure. J. Macromol. Sci.,
Part B: Phys. 1968, 2, 205218.
(17) Farmer, B. J.; Hopfinger, A. J.; Lando, J. B. Polymorphism of
Poly(vinylidene fluoride). Potential Energy Calculations of the Effects
of Head-to-Head Units on the Chain Conformation and Packing of
Poly(vinylidene fluoride). J. Appl. Phys. 1972, 43, 42934303.
(18) He, X.; Yao, K. Crystallization Mechanism and Piezoelectric
Properties of Solution-Derived Ferroelectric Poly(Vinylidene fluoride)
Thin Films. Appl. Phys. Lett. 2006, 89, 112909.
(19) Priya, L.; Jog, J. P. Intercalated Poly(vinylidene fluoride)/Clay
Nanocomposites: Structure and Properties. J. Polym. Sci., Part B:
Polym. Phys. 2003, 41, 3138.
11798

dx.doi.org/10.1021/jp4011026 | J. Phys. Chem. C 2013, 117, 1179111799

The Journal of Physical Chemistry C

Article

(40) Zhang, X. X.; Deng, C. F.; Xu, R.; Wang, D. Z. Oxidation

Resistance of Multi-Walled Carbon Nanotubes Purified with Sulfuric
and Nitric Acids. J. Mater. Sci. 2007, 42, 83778380.
(41) Cao, J. H.; Zhu, B. K.; Ji, G. L.; Xu, Y. Y. Preparation and
Characterization of PVDF-HFP Microporous Flat Membranes by
Supercritical CO2 Induced Phase Separation. J. Membr. Sci. 2005, 266,
102109.
(42) Xia, Z.; Ma, S.; Qiu, X.; Wu, Y.; Wang, F. Influence of Porosity
on the Stability of Charge and Piezoelectricity for Porous
Polytetrafluoroethylene Film Electrets. J. Electrost. 2003, 59, 5769.
(43) Choi, S. W.; Kim, J. R.; Ahn, Y. R.; Jo, S. M.; Cairns, E. J.
Characterization of Electro Spun PVDF Fiber-Based Polymer
Electrolytes. Chem. Mater. 2007, 19, 104115.
(44) Bognitzki, M.; Czado, W.; Frese, T.; Schaper, A.; Hellwig, M.;
Steinhart, M.; Greiner, A.; Wendorff, J. H. Nanostructured Fibers via
Electrospinning. Adv. Mater. 2001, 13, 7072.
(45) Hou, H.; Ge, J. J.; Zeng, J.; Li, Q.; Reneker, D. H.; Andreas, G.;
Cheng, S. Z. D. Electrospun Polyacrylonitrile Nanofibers Containing a
High Concentration of Well-Aligned Multiwall Carbon Nanotubes.
Chem. Mater. 2005, 17, 967973.
(46) Gao, J.; Yu, A.; Itkis, M. E.; Bekyarova, E.; Zhao, B.; Niyogi, S.;
Haddon, R. C. Large-Scale Fabrication of Aligned Single-Walled
Carbon Nanotube Array and Hierarchical Single-Walled Carbon
Nanotube Assembly. J. Am. Chem. Soc. 2004, 126, 1669816699.
(47) Dror, Y.; Salalha, W.; Khalfin, R.; Cohen, Y.; Yarin, A. L.;
Zussman, E. Carbon Nanotubes Embedded in Oriented Polymer
Nanofibers by Electrospinning. Langmuir 2003, 19, 70127020.
(48) Ge, J. J.; Hou, H.; Li, Q.; Graham, M. J.; Greiner, A.; Reneker,
D. H.; Harris, F. W.; Cheng, S. Z. D. Assembly of Well-Aligned
Multiwalled Carbon Nanotubes in Confined Polyacrylonitrile Environments: Electrospun Composite Nanofiber Sheets. J. Am. Chem. Soc.
2004, 126, 1575415761.
(49) Kobayashi, M.; Toshiro, K.; Tadokoro, H. Molecular Vibrations
of Three Crystal Forms of Poly(vinylidene fluoride). Macromolecules
1975, 8, 158171.
(50) Gregorio, R.; Nociti, N. C. P. S. Effect of PMMA Addition on
the Solution Crystallization of the and Phases of Poly(vinylidene
fluoride) (PVDF). J. Phys. D: Appl. Phys. 1995, 28, 432436.
(51) Tashiro, K.; Kobayashi, M.; Tadokoro, H. Vibrational Spectra
and Disorder-Order Transition of Poly(Vinylidene fluoride) Form III.
Macromolecules 1981, 14, 17571764.
(52) Lee, S. H.; Cho, E. N. R.; Jeon, S. H.; Youn, J. R. Rheological
and Electrical Properties of Polypropylene Composites Containing
Functionalized Multi-Walled Carbon Nanotubes and Compatibilizers.
Carbon 2007, 45, 28102822.
(53) He, X.; Yao, K.; Gan, B. K. Phase Transition and Properties of a
Ferroelectric Poly(Vinylidene fluoride-hexafluoropropylene) Copolymer. J. Appl. Phys. 2005, 97, 084101.
(54) Naegele, D.; Yoon, D. Y. Orientation of Crystalline Dipoles in
Poly(vinylidene fluoride) Films under Electric Field. Appl. Phys. Lett.
1978, 33, 132134.
(55) Seggern, H. Von; Fedosov, S. N. Conductivity-Induced
Polarization Buildup in Poly(Vinylidene fluoride). Appl. Phys. Lett.
2002, 81, 28302832.
(56) Tashiro, K. In Ferroelectric Polymers: Chemistry, Physics, and
Applications; Nalwa, H. S., Ed.; Marcel Dekker: New York, 1995;
Chapter 2.
(57) Kepler, R. G. In Ferroelectric Polymers: Chemistry, Physics, and
Applications; Nalwa, H. S., Ed.; Marcel Dekker: New York, 1995;
Chapter 3.
(58) Mohammadi, B.; Yousefi, A. A.; Bellah, S. M. Effect of Tensile
Strain Rate and Elongation on Crystalline Structure and Piezoelectric
Properties of PVDF Thin Films. Polym. Test 2007, 26, 4250.
(59) Lee, J. S.; Kim, G. H.; Hong, S. M.; Choi, H. J.; Seo, Y. Surface
Functionalization of a Poly(vinylidene fluoride): Effect on the
Adhesive and Piezoelectric Properties. ACS Appl. Mater. Interfaces
2009, 12, 29022908.

(60) Furukawa, T.; Wen, J. X.; Suzuki, K.; Takashima, Y.; Date, M.
Piezoelectricity and Pyroelectricity in Vinylidene Fluoride/Trifluoroethylene Copolymers. J. Appl. Phys. 1984, 56, 829834.

11799

dx.doi.org/10.1021/jp4011026 | J. Phys. Chem. C 2013, 117, 1179111799