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Semicrystalline Organization of VDF- and TrFE-Based Electroactive Terpolymers: Impact of the trans-1,3,3,3-Tetrafluoropropene Termonomer
Macromolecules ( IF 5.1 ) Pub Date : 2017-04-12 00:00:00 , DOI: 10.1021/acs.macromol.7b00051 François Bargain 1 , Thibaut Soulestin 2 , Fabrice Domingues Dos Santos 3 , Vincent Ladmiral 2 , Bruno Améduri 2 , Sylvie Tencé-Girault 1
Macromolecules ( IF 5.1 ) Pub Date : 2017-04-12 00:00:00 , DOI: 10.1021/acs.macromol.7b00051 François Bargain 1 , Thibaut Soulestin 2 , Fabrice Domingues Dos Santos 3 , Vincent Ladmiral 2 , Bruno Améduri 2 , Sylvie Tencé-Girault 1
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In the search for fluorinated polymers with new electroactive properties, the radical polymerization of vinylidene fluoride (VDF), trifluoroethylene (TrFE), and trans-1,3,3,3-tetrafluoropropene (1234ze) was achieved. The crystalline organization and the electroactive properties of semicrystalline poly(VDF-ter-TrFE-ter-1234ze) terpolymer films with 1234ze molar contents ranging from 0 to 6%, obtained by solvent-casting, were investigated using a combination of structural, dielectric, and electromechanical techniques. For 0 mol % 1234ze, poly(VDF-co-TrFE) copolymers exhibited a Curie transition from the ferroelectric (FE) phase to the paraelectric (PE) phase at the Curie temperature (TC ∼ 95 °C). DSC, dielectric spectroscopy, and FTIR experiments revealed the preservation of this Curie transition (TC ∼ 75 °C) while increasing the termonomer content. WAXS measurements confirmed the persistence of the FE phase as the main phase at room temperature but also showed the appearance of a secondary ZFE phase (expanded FE phase incorporating 1234ze units) in lower proportion. The WAXS crystallinity was halved (42 to 23%) from 0 to 6 mol % 1234ze terpolymer annealed films. Furthermore, SAXS and WAXS experiments highlighted a decrease of the crystalline lamellae thickness and a significant modification of the electronic density distribution upon increase of 1234ze units. A new model for this particular arrangement of crystalline lamellae was thus proposed with the location of the ZFE phase at the interface between the FE crystalline lamellae and the amorphous phase. Finally, reduced remnant polarization (Pr ∼ 15 mC/m2) and transverse piezoelectric coefficient (d33 ∼ −5 pC/N), compared to those of the reference poly(VDF-co-TrFE) copolymer (Pr ∼ 50 mC/m2 and d33 ∼ −20 pC/N), were mainly assigned to the decrease of the FE phase content in terpolymer poled films.
中文翻译：
基于VDF和TrFE的电活性三元共聚物的半结晶组织：反式-1,3,3,3-四氟丙烯三元单体的影响
在寻找具有新电活性的氟化聚合物时，实现了偏二氟乙烯（VDF），三氟乙烯（TrFE）和反式-1,3,3,3-四氟丙烯（1234ze）的自由基聚合。通过结构浇铸，电介质沉积，溶剂浇铸等方法研究了通过溶剂浇铸获得的1234ze摩尔含量为0％至6％的半结晶聚（VDF- ter -TrFE- ter -1234ze）三元共聚物薄膜的晶体结构和电活性。和机电技术。对于0 mol％的1234ze，聚（VDF- co- TrFE）共聚物在居里温度（T C）下表现出从铁电（FE）相到顺电（PE）相的居里转变。约95°C）。DSC，介电谱和FTIR实验表明，该居里跃迁（T C约75°C），同时增加三聚体含量。WAXS测量证实了在室温下FE相仍是主要相的持久性，但还显示出次级ZFE相（含有1234ze单元的扩展FE相）的出现比例较低。WAXS结晶度从0至6 mol％1234ze三元共聚物退火膜减半（42至23％）。此外，SAXS和WAXS实验强调了增加1234ze单位后晶体薄片厚度的减小和电子密度分布的显着改变。因此，提出了一种针对晶体薄片的这种特殊排列的新模型，其中将ZFE相定位在FE晶体薄片与非晶相之间的界面上。最后，减少了剩余极化（P r〜15 MC /米2）和横向压电系数（d 33〜-5 PC / N），比起那些参考聚（VDF- CO -TrFE）共聚物（P - [R〜50 MC /米2和d 33〜 -20 pC / N）主要归因于三元共聚物极化膜中FE相含量的降低。
更新日期：2017-04-12
中文翻译：
基于VDF和TrFE的电活性三元共聚物的半结晶组织：反式-1,3,3,3-四氟丙烯三元单体的影响
在寻找具有新电活性的氟化聚合物时，实现了偏二氟乙烯（VDF），三氟乙烯（TrFE）和反式-1,3,3,3-四氟丙烯（1234ze）的自由基聚合。通过结构浇铸，电介质沉积，溶剂浇铸等方法研究了通过溶剂浇铸获得的1234ze摩尔含量为0％至6％的半结晶聚（VDF- ter -TrFE- ter -1234ze）三元共聚物薄膜的晶体结构和电活性。和机电技术。对于0 mol％的1234ze，聚（VDF- co- TrFE）共聚物在居里温度（T C）下表现出从铁电（FE）相到顺电（PE）相的居里转变。约95°C）。DSC，介电谱和FTIR实验表明，该居里跃迁（T C约75°C），同时增加三聚体含量。WAXS测量证实了在室温下FE相仍是主要相的持久性，但还显示出次级ZFE相（含有1234ze单元的扩展FE相）的出现比例较低。WAXS结晶度从0至6 mol％1234ze三元共聚物退火膜减半（42至23％）。此外，SAXS和WAXS实验强调了增加1234ze单位后晶体薄片厚度的减小和电子密度分布的显着改变。因此，提出了一种针对晶体薄片的这种特殊排列的新模型，其中将ZFE相定位在FE晶体薄片与非晶相之间的界面上。最后，减少了剩余极化（P r〜15 MC /米2）和横向压电系数（d 33〜-5 PC / N），比起那些参考聚（VDF- CO -TrFE）共聚物（P - [R〜50 MC /米2和d 33〜 -20 pC / N）主要归因于三元共聚物极化膜中FE相含量的降低。
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