Stretching-Induced Relaxor Ferroelectric Behavior in a Poly(vinylidene fluoride-co-trifluoroethylene-co-hexafluoropropylene) Random Terpolymer,Macromolecules

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Stretching-Induced Relaxor Ferroelectric Behavior in a Poly(vinylidene fluoride-co-trifluoroethylene-co-hexafluoropropylene) Random Terpolymer
Macromolecules ( IF 5.1 ) Pub Date : 2017-09-28 00:00:00 , DOI: 10.1021/acs.macromol.7b01205
Yue Li _{1,

2} , Thibaut Soulestin _{3,

4} , Vincent Ladmiral ₃ , Bruno Ameduri ₃ , Thierry Lannuzel ₄ , Fabrice Domingues Dos Santos ₄ , Zhong-Ming Li ₁ , Gan-Ji Zhong ₁ , Lei Zhu ₂

Affiliation

Relaxor ferroelectric (RFE) polymers exhibiting narrow hysteresis loops are attractive for a broad range of potential applications such as electric energy storage, artificial muscles, electrocaloric cooling, and printable electronics. However, current state-of-the-art RFE polymers are primarily poly(vinylidene fluoride-co-trifluoroethylene-co-X) [P(VDF-TrFE-X)] random terpolymers with X being 1,1-chlorofluoroethylene (CFE) or chlorotrifluoroethylene (CTFE). Potential dehydrochlorination at elevated temperatures can prevent the melt-processing of these Cl-containing terpolymers. It is desirable to achieve the RFE behavior for Cl-free terpolymers such as P(VDF-TrFE-HFP), where HFP stands for hexafluoropropylene. Nonetheless, HFP units were mostly excluded from the crystalline structure because of their large size, and thus no RFE behavior was observed when crystallized from the quiescent melt. Intriguingly, mechanical stretching could effectively pull the HFP units into the P(VDF-TrFE) crystals, forming nanosized ferroelectric (FE) domains with a strong physical pinning effect. Consequently, the RFE behavior was observed for the uniaxially stretched P(VDF-TrFE-HFP) film. Thermal annealing above the Curie temperature (ca. 50 °C) without tension led to the return of the normal FE behavior with broad hysteresis loops. However, thermal annealing above Curie temperature under tension prevented the exclusion of HFP units from the crystalline structure, and thus relatively stable RFE behavior was achieved. Various characterization techniques were utilized to unravel the structure–property relationships for these P(VDF-TrFE-HFP) films. In addition, the RFE behavior of P(VDF-TrFE-HFP) was compared to those of other terpolymers. This study provides a unique and simple strategy solely based on film processing to achieve the RFE behavior for P(VDF-TrFE)-based terpolymers.

中文翻译：

聚偏氟乙烯-共-三氟乙烯-共-六氟丙烯）无规三元共聚物中的拉伸诱导弛豫铁电行为

展宽的磁滞回线的弛豫铁电（RFE）聚合物对于广泛的潜在应用具有吸引力，例如电能存储，人造肌肉，电热冷却和可打印电子产品。然而，国家的最先进的电流RFE聚合物主要是聚（偏二氟共-trifluoroethylene-共-X）[P（VDF-TrFE-X）]无规三元共聚物，X为1,1-氯氟乙烯（CFE）或三氟氯乙烯（CTFE）。在高温下潜在的脱氯化氢作用可能会阻止这些含氯三元共聚物的熔融加工。希望获得不含氯的三元共聚物（例如P（VDF-TrFE-HFP））的RFE行为，其中HFP代表六氟丙烯。但是，由于HFP单元尺寸较大，因此大多数都未从晶体结构中排除，因此从静态熔体中结晶时未观察到RFE行为。有趣的是，机械拉伸可以有效地将HFP单元拉入P（VDF-TrFE）晶体，形成具有强物理钉扎效应的纳米铁电（FE）域。因此，观察到单轴拉伸的P（VDF-TrFE-HFP）薄膜的RFE行为。在居里温度（约50°C）以上进行热退火而无张力，导致具有宽磁滞回线的正常FE行为恢复。但是，在张力下居里温度以上的热退火阻止了HFP单元从晶体结构中排除，因此获得了相对稳定的RFE行为。这些P（VDF-TrFE-HFP）膜的各种表征技术被用来揭示其结构与性质之间的关系。此外，将P（VDF-TrFE-HFP）的RFE行为与其他三元共聚物的RFE行为进行了比较。这项研究仅基于薄膜处理提供了一种独特而简单的策略，以实现基于P（VDF-TrFE）的三元共聚物的RFE行为。在张力下居里温度以上的热退火阻止了HFP单元从晶体结构中排除，因此获得了相对稳定的RFE行为。这些P（VDF-TrFE-HFP）膜的各种表征技术被用来揭示其结构与性质之间的关系。此外，将P（VDF-TrFE-HFP）的RFE行为与其他三元共聚物的RFE行为进行了比较。这项研究仅基于薄膜处理提供了一种独特而简单的策略，以实现基于P（VDF-TrFE）的三元共聚物的RFE行为。在张力下居里温度以上的热退火阻止了HFP单元从晶体结构中排除，因此获得了相对稳定的RFE行为。这些P（VDF-TrFE-HFP）膜的各种表征技术被用来揭示其结构与性质之间的关系。此外，将P（VDF-TrFE-HFP）的RFE行为与其他三元共聚物的RFE行为进行了比较。这项研究仅基于薄膜处理提供了一种独特而简单的策略，以实现基于P（VDF-TrFE）的三元共聚物的RFE行为。比较了P（VDF-TrFE-HFP）与其他三元共聚物的RFE行为。这项研究仅基于薄膜处理提供了一种独特而简单的策略，以实现基于P（VDF-TrFE）的三元共聚物的RFE行为。比较了P（VDF-TrFE-HFP）与其他三元共聚物的RFE行为。这项研究仅基于薄膜处理提供了一种独特而简单的策略，以实现基于P（VDF-TrFE）的三元共聚物的RFE行为。

更新日期：2017-09-28

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