Can Relaxor Ferroelectric Behavior Be Realized for
Poly(vinylidene fluoride-co-chlorotrifluoroethylene)
[P(VDF–CTFE)] Random Copolymers by Inclusion of CTFE Units
in PVDF Crystals?
Version 2 2018-07-13, 18:26
Version 1 2018-07-13, 18:21
Posted on 2018-07-13 - 18:26
Relaxor ferroelectric (RFE) polymers
are attractive for various
electrical applications such as electrostrictive actuation, electromechanical
sensors, electric energy storage, and electrocaloric cooling because
of their high dielectric constants and low hysteresis loss. Current
state-of-the-art RFE polymers include poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF–TrFE)]-based random
copolymers and terpolymers. However, the high costs due to a safety
concern of TrFE make their near-term commercialization difficult.
It is highly desirable to explore the opportunity of TrFE-free PVDF
copolymers [e.g., P(VDF–CTFE); CTFE is chlorotrifluoroethylene]
to achieve the RFE behavior by inclusion of CTFE in PVDF crystals
(i.e., isomorphism). In this work, two strategies were employed to
include CTFE in PVDF crystals. First, high-pressure crystallization
was used to obtain extended-chain crystals via the pseudohexagonal
paraelectric phase. Structural analyses indicated that CTFE units
were largely excluded from the γ unit cells and ferroelectric
domains of PVDF but located as kinks inside the extended-chain lamellae.
As a result, no RFE behavior was observed because of large ferroelectric
γ domains. The second strategy utilized mechanical stretching
at low temperatures (−20 to 0 °C) to obtain oriented small
β crystallites (ca. 5–7 nm). Structural analyses indicated
that CTFE units were excluded from the β unit cells, locating
at the crystal–amorphous interfaces. Although the hysteresis
loops became somewhat slimmer as a result of small crystallite sizes,
the RFE behavior with slim hysteresis loops was still not achieved.
This study demonstrated that CTFE units were too large to be included
in the tightly packed PVDF unit cells, whether the α, γ,
or β phase. In the future, it is desirable to explore other
PVDF copolymers with a smaller comonomer such as 1-chloro-1-fluoroethylene.
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Huang, Yanfei; Xu, Jia-Zhuang; Soulestin, Thibaut; Domingues Dos Santos, Fabrice; Li, Ruipeng; Fukuto, Masafumi; et al. (2018). Can Relaxor Ferroelectric Behavior Be Realized for
Poly(vinylidene fluoride-co-chlorotrifluoroethylene)
[P(VDF–CTFE)] Random Copolymers by Inclusion of CTFE Units
in PVDF Crystals?. ACS Publications. Collection. https://doi.org/10.1021/acs.macromol.8b01155
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AUTHORS (11)
YH
Yanfei Huang
JX
Jia-Zhuang Xu
TS
Thibaut Soulestin
FD
Fabrice Domingues Dos Santos
RL
Ruipeng Li
MF
Masafumi Fukuto
JL
Jun Lei
GZ
Gan-Ji Zhong
ZL
Zhong-Ming Li
YL
Yue Li
LZ
Lei Zhu