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Ferroelectric polymers exhibiting behaviour reminiscent of a morphotropic phase boundary

机译：铁电聚合物表现出让人联想到相变相边界的行为

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Piezoelectricity-the direct interconversion between mechanical and electrical energies-is usually remarkably enhanced at the morphotropic phase boundary of ferroelectric materials(1-4), which marks a transition region in the phase diagram of piezoelectric materials and bridges two competing phases with distinct symmetries(1,5). Such enhancement has enabled the recent development of various lead and lead-free piezoelectric perovskites with outstanding piezoelectric properties for use in actuators, transducers, sensors and energy-harvesting applications(5-8). However, the morphotropic phase boundary has never been observed in organic materials, and the absence of effective approaches to improving the intrinsic piezoelectric responses of polymers(9,10) considerably hampers their application to flexible, wearable and biocompatible devices. Here we report stereochemically induced behaviour in ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) copolymers, which is similar to that observed at morphotropic phase boundaries in perovskites. We reveal that compositionally tailored tacticity (the stereochemical arrangement of chiral centres related to the TrFE monomers(11,12)) can lead to intramolecular order-to-disorder evolution in the crystalline phase and thus to an intermediate transition region that is reminiscent of the morphotropic phase boundary, where competing ferroelectric and relaxor properties appear simultaneously. Our first-principles calculations confirm the crucial role of chain tacticity in driving the formation of this transition region via structural competition between the trans-planar and 3/1-helical phases. We show that the P(VDF-TrFE) copolymer with the morphotropic composition exhibits a longitudinal piezoelectric coefficient of -63.5 picocoulombs per newton, outperforming state-of-the-art piezoelectric polymers(10). Given the flexibility in the molecular design and synthesis of organic ferroelectric materials, this work opens up the way for the development of scalable, high-performance piezoelectric polymers.
机译：压电-机械能和电能之间的直接相互转换-通常在铁电材料的变质相边界处显着增强（1-4），这标志着压电材料相图中的过渡区域，并桥接了两个对称性不同的竞争相（ 1,5）。这种增强使得最近开发出了具有卓越压电性能的各种无铅和无铅压电钙钛矿，可用于执行器，换能器，传感器和能量收集应用（5-8）。但是，在有机材料中从未观察到吗相相界，并且缺乏有效的方法来改善聚合物的固有压电响应（9,10），极大地阻碍了它们在柔性，可穿戴和生物相容性设备中的应用。在这里，我们报告在铁电聚偏二氟乙烯-共-三氟乙烯（P（VDF-TrFE））共聚物中的立体化学诱导行为，这与在钙钛矿中的相变相界处观察到的行为相似。我们揭示了成分定制的策略（与TrFE单体相关的手性中心的立体化学排列（11,12））可以导致结晶相中分子内有序到无序的演化，从而导致中间过渡区域让人联想到晶相相界，其中竞争的铁电和弛豫特性同时出现。我们的第一性原理计算证实了链规整度通过跨平面相和3/1螺旋相之间的结构竞争在驱动该过渡区形成中的关键作用。我们发现具有分相组成的P（VDF-TrFE）共聚物的纵向压电系数为-63.5皮库仑/牛顿，优于最先进的压电聚合物（10）。鉴于有机铁电材料分子设计和合成的灵活性，这项工作为可扩展的高性能压电聚合物的开发开辟了道路。

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  • 来源
    《Nature》 |2018年第7725期|96-100|共5页
  • 作者

    Liu Yang; Aziguli Haibibu; Zhang Bing; Xu Wenhan; Lu Wenchang; Bernholc J.; Wang Qing;

  • 作者单位

    Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA;

    Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA;

    North Carolina State Univ, Dept Phys, Raleigh, NC USA;

    Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA;

    North Carolina State Univ, Dept Phys, Raleigh, NC USA;

    North Carolina State Univ, Dept Phys, Raleigh, NC USA;

    Penn State Univ, Dept Mat Sci & Engn, University Pk, PA 16802 USA;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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