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Beta Phase Crystallization and Ferro- and Piezoelectric Performances of Melt-Processed Poly(vinylidene difluoride) Blends with Poly(methyl methacrylate) Copolymers Containing Ionizable Moieties
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2020-07-24 , DOI: 10.1021/acsapm.0c00351 Alexandre De Neef 1, 2 , Cédric Samuel 2 , Harvey Amorín 3 , Gregory Stoclet 4 , Ricardo Jiménez 3 , Philippe Dubois 1 , Jérémie Soulestin 2 , Jean-Marie Raquez 1
ACS Applied Polymer Materials ( IF 4.4 ) Pub Date : 2020-07-24 , DOI: 10.1021/acsapm.0c00351 Alexandre De Neef 1, 2 , Cédric Samuel 2 , Harvey Amorín 3 , Gregory Stoclet 4 , Ricardo Jiménez 3 , Philippe Dubois 1 , Jérémie Soulestin 2 , Jean-Marie Raquez 1
Affiliation
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Poly(methyl methacrylate-co-methacrylic acid) (PMMA-co-MAA) copolymer containing ionizable moieties is here investigated as a melt processing additive for poly(vinylidene difluoride) (PVDF) to develop high-quality ferro- and piezoelectric polymer films by extrusion-calendering. The PVDF/PMMA-co-MAA miscibility and the β-phase crystallization from the melt state at high cooling rates were first explored by flash differential scanning calorimetry (FDSC). Transposition to the melt-processing of thin films by extrusion-calendering was attempted, and direct production of β-crystals in high amounts was confirmed at a specific content of 5 wt % PMMA-co-MAA. Ferro- and piezoelectric properties were subsequently investigated, and classical ferroelectric-type hysteresis loops clearly appeared at room temperature for AC electric fields higher than 900–1200 kV/cm. Enhanced remanent polarizations (Pr) were observed with only 5 wt % PMMA-based additives, and the best ferroelectric performances were identified for PVDF/PMMA-co-MAA blends, in agreement with a higher β-phase content. Stable piezoelectric properties are also highlighted with maximal piezoelectric coefficient (d33) of 11 pC/N for these formulations. A linear relationship is found between d33 and Pr in accordance with several models, and in this respect, the origin and optimization of the remanent polarization was investigated. Crystal transformations were revealed during high-voltage AC poling, and high-quality ferroelectric behaviors with high Pr values up to 7 μC/cm2 were obtained at elevated poling temperatures for PVDF/PMMA-co-MAA blends (theoretical d33 up to 16 pC/N) approaching the theoretical limit value for perfectly poled β-crystals. This study clearly opens up interesting perspectives in the development of cost-effective electroactive polymer films using industrially relevant processes and demonstrates that PVDF-based blends with miscible functional PMMA copolymers represent an interesting approach for this purpose.
中文翻译：
含电离部分的聚甲基丙烯酸甲酯共聚物与熔融加工的聚偏二氟乙烯共混物的β相结晶以及铁电和压电性能
本文研究了含有可电离部分的聚（甲基丙烯酸甲酯-共-甲基丙烯酸）（PMMA-共-MAA）共聚物作为聚偏二氟乙烯（PVDF）的熔融加工助剂，以开发高质量的铁和压电聚合物薄膜。挤出压延。首先通过闪式差示扫描量热法（FDSC）探索了PVDF / PMMA- co- MAA的可混溶性和高冷却速率下熔融态的β相结晶。尝试通过挤出压延转变为薄膜的熔融加工，并证实在5 wt％PMMA- co的特定含量下可以大量直接生产β晶体。-MAA。随后研究了铁电和压电特性，并且对于高于900-1200 kV / cm的交流电场，在室温下显然出现了经典的铁电型磁滞回线。仅使用5 wt％的基于PMMA的添加剂，观察到增强的剩余极化率（P r），并且与较高的β相含量相符，PVDF / PMMA- co- MAA共混物具有最佳的铁电性能。这些配方的最大压电系数（d 33）为11 pC / N，也突出了稳定的压电性能。在d 33和P r之间发现线性关系根据几种模型，在这方面，研究了剩余极化的起源和优化。晶体变换高压交流极化时被揭露，并具有高的高质量的铁电行为P - [R值高达7μC/厘米2在升高的温度下极化得到为PVDF / PMMA- CO -MAA共混物（理论d 33高达16 pC / N）接近完美极化的β晶体的理论极限值。这项研究清楚地打开了使用工业相关方法开发具有成本效益的电活性聚合物薄膜的有趣观点，并证明了基于PVDF的共混功能性PMMA共聚物的共混物代表了一种有趣的方法。
更新日期：2020-09-11
中文翻译：
含电离部分的聚甲基丙烯酸甲酯共聚物与熔融加工的聚偏二氟乙烯共混物的β相结晶以及铁电和压电性能
本文研究了含有可电离部分的聚（甲基丙烯酸甲酯-共-甲基丙烯酸）（PMMA-共-MAA）共聚物作为聚偏二氟乙烯（PVDF）的熔融加工助剂，以开发高质量的铁和压电聚合物薄膜。挤出压延。首先通过闪式差示扫描量热法（FDSC）探索了PVDF / PMMA- co- MAA的可混溶性和高冷却速率下熔融态的β相结晶。尝试通过挤出压延转变为薄膜的熔融加工，并证实在5 wt％PMMA- co的特定含量下可以大量直接生产β晶体。-MAA。随后研究了铁电和压电特性，并且对于高于900-1200 kV / cm的交流电场，在室温下显然出现了经典的铁电型磁滞回线。仅使用5 wt％的基于PMMA的添加剂，观察到增强的剩余极化率（P r），并且与较高的β相含量相符，PVDF / PMMA- co- MAA共混物具有最佳的铁电性能。这些配方的最大压电系数（d 33）为11 pC / N，也突出了稳定的压电性能。在d 33和P r之间发现线性关系根据几种模型，在这方面，研究了剩余极化的起源和优化。晶体变换高压交流极化时被揭露，并具有高的高质量的铁电行为P - [R值高达7μC/厘米2在升高的温度下极化得到为PVDF / PMMA- CO -MAA共混物（理论d 33高达16 pC / N）接近完美极化的β晶体的理论极限值。这项研究清楚地打开了使用工业相关方法开发具有成本效益的电活性聚合物薄膜的有趣观点，并证明了基于PVDF的共混功能性PMMA共聚物的共混物代表了一种有趣的方法。
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