IEEE TRANSACTIONS ON ULTRASONICS, FERROELECTRICS, AND FREQUENCY CONTROL, . 60, . 3, MARCH 2013 441
0885–3010/$25.00
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2013 IEEE
Electromechanical Properties
of Relaxor Ferroelectric
P(VDF-TrFE-CFE)-P(VDF-CTFE) Blends
Lee J. Gorny, Sheng-Guo Lu, Sheng Liu, and Minren Lin
Abstract—Electromechanical properties of the relaxor fer-
roelectric poly(vinylidene fluoride–trifluoroethylene–chloroflu-
oroethylene) [P(VDF-TrFE-CFE)] terpolymer blended with a
small amount of poly(vinylidene fluoride-chlorotrifluoroethyl-
ene) [P(VDF-CTFE)] copolymer, which possesses a much high-
er elastic modulus than that of the neat terpolymer, were in-
vestigated. It was observed that the presence of small amount
of P(VDF-CTFE) does not affect the microstructure of the
crystalline phase. However, the uniaxially stretched blended
films show a slight increase in the crystallinity and increased
or similar induced polarization at high electric fields compared
with the neat terpolymer, likely caused by the interface effect.
Consequently, for blends with P(VDF-CTFE) less than 5 wt%,
the transverse strains S
1
along the stretching direction for uni-
axially stretched blended films are nearly the same as those of
neat P(VDF-TrFE-CFE), whereas the elastic modulus along
the S
1
-direction increases with the P(VDF-CTFE) content. As
a result, the blended films exhibit a higher elastic energy den-
sity and electromechanical coupling factor k
31
compared with
the neat terpolymer.
I. I
E
polymer materials which can generate
high strain with high elastic energy density are attrac-
tive for a broad range of applications [1]–[4]. This paper
investigates a polymer blend approach to further improve
the electromechanical response of the relaxor ferroelec-
tric poly(vinylidene fluoride–trifluoroethylene–chlorofluo-
roethylene) [P(VDF-TrFE-CFE)] terpolymer. P(VDF-
TrFE)-based relaxor ferroelectric polymers exhibit large
electrostrictive strains with high elastic energy densi-
ties [5]–[9]. In this paper, it will be shown that blending
P(VDF-TrFE-CFE) relaxor ferroelectric terpolymer with
a small amount of P(VDF-CTFE) [chlorotrifluoroethylene
(CTFE)] 91/9 mol% copolymer results in polymer films
having an elastic modulus that is nearly doubled along the
polymer film stretching direction. Transverse strains S
1
obtainable in the same direction of the blended films are
similar to the neat terpolymer. Consequently, the elastic
energy density and electromechanical coupling factor are
improved compared with the neat terpolymer. It has also
been observed that the blended films exhibit higher elec-
trical breakdown strengths, which are also highly desirable
for reliable electromechanical applications.
II. E
P(VDF-TrFE-CFE)/P(VDF-CTFE) blended films with
0, 2.5, 5, and 10 wt% copolymer were prepared using a so-
lution-cast method. P(VDF-TrFE-CFE) 63/37/7.5 mol%
terpolymers were synthesized by a suspension polymeriza-
tion process and copolymer P(VDF-CTFE) 91/9 mol%
was purchased from Solvay (Brussels, Belgium) [10]. Ter-
polymer and copolymer solutions were mixed together by
proper ratio (using N, N-dimethyl formamide as a sol-
vent). The mixed solution was cast on a glass plate and
dried at 70°C for 5 h.
The green films were then stretched uniaxially to in-
crease the polar phase and improve the electromechani-
cal response. For most electromechanical applications
using polymer films, the useful material characteristics
are strain, elastic energy density, and electromechanical
coupling factor. Stretching these films increases the trans-
verse strain, elastic modulus along the stretching direc-
tion, and breakdown strength markedly. After stretching,
films were further annealed at 100°C for 15 h in a vacuum
oven. This vacuum annealing process further removes the
residual solvent and improves the crystallinity. Normal
film thickness for this study is 25 μm after stretching.
In this study, the electromechanical response of the
blended films along the stretching direction with differ-
ent stretching ratios was investigated. It was found that
the transverse strain S
1
along the stretching direction in-
creases with stretching ratio to about 4 to 5 times the
original film length. Further stretching the film beyond
that stretching ratio does not increase the strain levels un-
der fields lower than 150 MV/m nor the elastic modulus.
Hence, this paper will focus on the uniaxially stretched
blended films with 5 times stretching ratio (the film is
uniaxially stretched to 5 times the original length).
Data presented in this paper were obtained using the
following equipment. The microstructure of the blends
was studied using X-ray diffraction (XRD) (Scintag Cu
K
α
diffractometer, Scintag Inc., Cupertino, CA). Differen-
Manuscript received February 2, 2011; accepted December 5, 2012.
This work was supported by the National Institutes of Health under
grant number R01-EY018387-02.
L. J. Gorny, S.-G. Lu, and M. R. Lin are with the Materials Research
Institute, The Pennsylvania State University, University Park, PA (e-
mail: sglu@gdut.edu.cn).
L. J. Gorny is also with the Mechanical and Nuclear Engineering De-
partment, The Pennsylvania State University, University Park, PA.
S.-G. Lu is also with the School of Materials and Energy, Guangdong
University of Technology, Guangzhou, China.
S. Liu is with the Electrical Engineering Department, The Pennsylva-
nia State University, University Park, PA (e-mail: sul26@psu.edu).
DOI http://dx.doi.org/10.1109/TUFFC.2013.2587