Abstract
Poly(vinylidene fluoride) (PVDF) exhibits pronounced polymorphs. Its γ phase is attractive due to the electroactive properties. The γ-PVDF is however difficult to obtain under normal crystallization condition. In a previous work, we reported a simple melt-recrystallization approach for producing γ-phase rich PVDF thin films through selective melting and subsequent recrystallization. We reported here another approach for promoting the αγ′ phase transition to prepare γ-phase rich PVDF thin films. To this end, a stepwise crystallization and subsequent annealing process was used. The idea is based on a quick generation of a large amount of α-PVDF crystals with some of their γ-PVDF counterparts at suitable crystallization temperature and then annealing at a temperature above the crystallization temperature for enhancing the molecular chain mobility to overcome the energy barrier of phase transition. It was found that crystallizing the PVDF melt first at 152 °C for 4 h, then quenching to room temperature and finally annealing the sample at 160 °C for 100 h was the most efficient to produce γ-PVDF rich films. This is related to the melting and recrystallization of the α-PVDF crystals produced during quenching in the annealing process at 160 °C, which favors the formation of γ-PVDF crystals for triggering the αγ′ phase transition.
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References
Ling, Q. D.; Liaw, D. J.; Zhu, C.; Chan, D. S. H.; Kang, E. T.; Neoh, K. G. Polymer electronic memories: materials, devices and mechanisms. Prog. Polym. Sci. 2008, 33(10), 917–978.
Doll, W. W.; Lando, J. B. The polymorphism of poly(vinylidene fluoride) IV. The structure of high-pressure-crystallized poly(vinylidene fluoride). J. Macromol. Sci. B 1970, 4(4), 889–896.
Lovinger, A. J., in “Developments in Crystalline Polymers, Vol. 1”, ed. by Bassett, D. C. Springer, Netherlands, 1982, p. 195
Lovinger, A. J. Ferroelectric polymers. Science 1983, 220(4602), 1115–1121.
Chen, Z.; Kwon, K. Y.; Tan, X. Integrated IPMC/PVDF sensory actuator and its validation in feedback control. Sensor Actuat. A-Phys. 2008, 144(2), 231–241.
Chu, B.; Zhou, X.; Ren, K.; Neese, B.; Lin, M.; Wang, Q.; Bauer, F.; Zhang, Q. M. A dielectric polymer with high electric energy density and fast discharge speed. Science 2006, 313(5785), 334–336.
Lovinger, A. J. Annealing of poly(vinylidene fluoride) and formation of a fifth phase. Macromolecules 1982, 15(1), 40–44.
Li, M.; Wondergem, H. J.; Spijkamn, M. J.; Asadi, K.; Katsouras, I.; Blom, P. W. M. Revisiting the δ-phase of poly(vinylidene fluoride) for solution-processed ferroelectric thin films. Nat. Mater. 2013, 12(5), 433–438.
Kang, S. J.; Park, Y. J.; Bae, I.; Kim, K. J.; Kim, H. C.; Bauer, S.; Thomas, E. L.; Park, C. Printable ferroelectric PVDF/PMMA blend films with ultralow roughness for low voltage non-volatile polymer memory. Adv. Funct. Mater. 2009, 19(17), 2812–2818.
Kang, S. J.; Park, Y. J.; Hwang, J. Y.; Jeong, H. J.; Lee, J. S.; Kim, K. J.; Kim, H. C.; Huh, J.; Park, C. Localized pressure-induced ferroelectric pattern arrays of semicrystalline poly(vinylidene fluoride) by microimprinting. Adv. Mater. 2007, 19(4), 581–586.
Kang, S. J.; Bae, I.; Choi, J. H.; Park, Y. J.; Jo, P. S.; Kim, Y.; Kim, K. J.; Myoung, J. M.; Kim, E.; Park, C. Fabrication of micropatterned ferroelectric gamma poly(vinylidene fluoride) film for non-volatile polymer memory. J. Mater. Chem. 2011, 21(11), 3619–3624.
Lovinger, A. J. Crystalline transformations in spherulites of poly(vinylidene fluoride). Polymer 1980, 21(11), 1317–1322.
Lovinger, A. J. Crystallization and morphology of melt-solidified poly(vinylidene fluoride). J. Polym. Sci. Polym. Phys. Ed. 1980, 18(4), 793–809.
Tashiro, K.; Kobayahsi, M. Structural phase transition in ferroelectric fluorine polymers: X-ray diffraction and infrared/Raman spectroscopic study. Phase Transit. 1989, 18(3-4), 213–246.
Gregorio, R.; CapitãO, R. C. Morphology and phase transition of high melt temperature crystallized poly(vinylidene fluoride). J. Mater. Sci. 2000, 35(2), 299–306.
Lovinger, A. J. Conformational defects and associated molecular motions in crystalline poly(vinylidene fluoride). J. Appl. Phys. 1981, 52(10), 5934–5938.
Takahashi, Y.; Matsubara, Y.; Tadokoro, H. Mechanisms for crystal phase transformations by heat treatment and molecular motion in poly(vinylidene fluoride). Macromolecules 1982, 15(2), 334–338.
Zheng, Y.; Zhang, J.; Sun, X.; Li, H.; Ren, Z.; Yan, S. Crystal structure regulation of ferroelectric poly(vinylidene fluoride) via controlled melt-recrystallization. Ind. Eng. Chem. Res. 2017, 56(15), 4580–4587.
Meraga, C.; Marigo, A. Influence of annealing and chain defects on the melting behavior of poly(vinylidene fluoride). Eur. Polym. J. 2003, 39(8), 1713–1720.
Martins, P.; Lopes, A. C.; Lanceros-Mendez, S. Electroactive phases of poly(vinylidene fluoride): determination, processing and applications. Prog. Polym. Sci. 2014, 39(4), 683–706.
Tashiro, K.; Kobayashi, M.; Tadokoro, H. Vibrational spectra and disorder-order transition of poly(vinylidene fluoride) form III. Macromolecules 1981, 14(6), 1757–1764.
Wang, Y. T.; Liu, P. R.; Lu, Y.; Men, Y. F. Mechanism of polymorph selection during crystallization of random butene-1/ethylene copolymer. Chinese J. Polym. Sci. 2016, 34(8), 1014–1020.
Hu, D. D.; Ye, S. B.; Yu, F.; Feng, J. C. Further understanding on the three domains of isotactic polypropylene by investigating the crystalline morphologies evolution after treatment at different domains. Chinese J. Polym. Sci. 2016, 34(3), 344–358.
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Zheng, YR., Zhang, J., Sun, XL. et al. Enhanced αγ′ Transition of Poly(vinylidene fluoride) by Step Crystallization and Subsequent Annealing. Chin J Polym Sci 36, 598–603 (2018). https://doi.org/10.1007/s10118-018-2040-z
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DOI: https://doi.org/10.1007/s10118-018-2040-z