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Title: 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?

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. Althoughmore » the hysteresis loops became somewhat slimmer as a result of small crystallite sizes, the RFE behavior with slim hysteresis loops was still not achieved. Furthermore, 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.« less
Authors:
 [1] ; ORCiD logo [2] ; ORCiD logo [3] ;  [3] ;  [4] ;  [4] ; ORCiD logo [2] ; ORCiD logo [2] ; ORCiD logo [2] ;  [2] ; ORCiD logo [5]
  1. Sichuan Univ., Sichuan (People's Republic of China); Case Western Reserve Univ., Cleveland, OH (United States)
  2. Sichuan Univ., Sichuan (People's Republic of China)
  3. Piezotech S.A.S., Pierre-Benite Cedex (France)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States)
  5. Case Western Reserve Univ., Cleveland, OH (United States)
Publication Date:
Report Number(s):
BNL-207899-2018-JAAM
Journal ID: ISSN 0024-9297
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 14; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1462416

Huang, Yanfei, Xu, Jia -Zhuang, Soulestin, Thibaut, Dos Santos, Fabrice Domingues, Li, Ruipeng, Fukuto, Masafumi, Lei, Jun, Zhong, Gan -Ji, Li, Zhong -Ming, Li, Yue, and Zhu, Lei. 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?. United States: N. p., Web. doi:10.1021/acs.macromol.8b01155.
Huang, Yanfei, Xu, Jia -Zhuang, Soulestin, Thibaut, Dos Santos, Fabrice Domingues, Li, Ruipeng, Fukuto, Masafumi, Lei, Jun, Zhong, Gan -Ji, Li, Zhong -Ming, Li, Yue, & Zhu, Lei. 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?. United States. doi:10.1021/acs.macromol.8b01155.
Huang, Yanfei, Xu, Jia -Zhuang, Soulestin, Thibaut, Dos Santos, Fabrice Domingues, Li, Ruipeng, Fukuto, Masafumi, Lei, Jun, Zhong, Gan -Ji, Li, Zhong -Ming, Li, Yue, and Zhu, Lei. 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?". United States. doi:10.1021/acs.macromol.8b01155.
@article{osti_1462416,
title = {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?},
author = {Huang, Yanfei and Xu, Jia -Zhuang and Soulestin, Thibaut and Dos Santos, Fabrice Domingues and Li, Ruipeng and Fukuto, Masafumi and Lei, Jun and Zhong, Gan -Ji and Li, Zhong -Ming and Li, Yue and Zhu, Lei},
abstractNote = {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. Furthermore, 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.},
doi = {10.1021/acs.macromol.8b01155},
journal = {Macromolecules},
number = 14,
volume = 51,
place = {United States},
year = {2018},
month = {7}
}