Crystal phase of poly(vinylidene fluoride‐co‐trifluoroethylene) synthesized via hydrogenation of poly(vinylidene fluoride‐co‐chlorotrifluoroethylene)

Trifluoroethylene addition and thermal treatment induced crystal phase transition in a series of poly(vinylidene fluoride-co-trifluoroethylene) [P(VDF-co-TrFE)] containing varied TrFE molar ratio (6, 9, 12, and 20 mol %) prepared from the hydrogenation of poly(vinylidene fluoride-co-chlorotrifluoroethylene have been investigated by means of Fourier transform infrared spectral (FTIR), X-ray diffraction (XRD), and differential scanning calorimetry (DSC) analyses. The comprehensive applications of the three techniques could distinguish α, β and γ phase of P(VDF-co-TrFE) very well. The multipeak fitting technique of DSC is successfully applied to calculate the percentage of different phases in the samples, which allows us to investigate the phase transition process of P(VDF-co-TrFE) precisely. It is found that the crystal phase of P(VDF-co-TrFE) films is turned from α + γ phase (6 mol % TrFE) to α + γ + β phase (9 and 12 mol % TrFE) to β phase (20 mol % TrFE) at high temperature, and from α + γ phase (6 mol % TrFE) to γ + β phase (9 mol % TrFE) to β phase (>12 mol % TrFE) at low fabricated temperature. Both the fabrication conditions and TrFE addition are responsible for the crystal phase transition of the hydrogenised P(VDF-co-TrFE). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

[1]  Zhicheng Zhang,et al.  Controlled hydrogenation of P(VDF-co-CTFE) to prepare P(VDF-co-TrFE-co-CTFE) in the presence of CuX (X = Cl, Br) complexes. , 2011, Chemical communications.

[2]  Zhuo Xu,et al.  Electric energy storage properties of poly(vinylidene fluoride) , 2010 .

[3]  N. Kim,et al.  Synergy effect of hybrid fillers on the positive temperature coefficient behavior of polypropylene/ultra‐high molecular weight polyethylene composites , 2010 .

[4]  Zhicheng Zhang,et al.  Energy storage study of ferroelectric poly(vinylidene fluoride-trifluoroethylene- chlorotrifluoroethylene) terpolymers , 2009 .

[5]  Qing Wang,et al.  Microstructures and Dielectric Properties of the Ferroelectric Fluoropolymers Synthesized via Reductive Dechlorination of Poly(vinylidene fluoride-co-chlorotrifluoroethylene)s , 2006 .

[6]  Qiming Zhang,et al.  A modular approach to ferroelectric polymers with chemically tunable curie temperatures and dielectric constants. , 2006, Journal of the American Chemical Society.

[7]  Zhicheng Zhang,et al.  High Dielectric VDF/TrFE/CTFE Terpolymers Prepared by Hydrogenation of VDF/CTFE Copolymers: Synthesis and Characterization , 2006 .

[8]  H. Ohigashi,et al.  Annealing effects on the Curie transition temperature and melting temperature of poly(vinylidene fluoride/trifluoroethylene) single crystalline films , 2001 .

[9]  Robert Y. Ting,et al.  TRANSVERSE STRAIN RESPONSES IN ELECTROSTRICTIVE POLY(VINYLIDENE FLUORIDE-TRIFLUOROETHYLENE) FILMS AND DEVELOPMENT OF A DILATOMETER FOR THE MEASUREMENT , 1999 .

[10]  K. Tashiro,et al.  Annealing effect on the ferroelectric phase transition behavior and domain structure of vinylidene fluoride (VDF)–trifluoroethylene copolymers: a comparison between uniaxially oriented VDF 73 and 65% copolymers , 1999 .

[11]  R. Gregorio,et al.  Effect of crystallization temperature on the phase transitions of P(VDF/TrFE) copolymers , 1998 .

[12]  Bette Hileman,et al.  Climate conference off to slow start , 1997 .

[13]  K. Kim,et al.  Curie transition, ferroelectric crystal structure and ferroelectricity of a VDF/TrFE (7525) copolymer: 2. The effect of poling on Curie transition and ferroelectric crystal structure , 1997 .

[14]  K. Tashiro,et al.  Annealing effect on ferroelectric phase transitional behavior of vinylidene fluoride-trifluoroethylene copolymers: An interpretation based on the concept of domain and trans-gauche conformational disorder , 1995 .

[15]  K. Kim,et al.  An infra-red spectroscopic study of structural reorganization of a uniaxially drawn VDF/TrFE copolymer in an electric field , 1994 .

[16]  R. Gregorio,et al.  Effect of crystallization temperature on the crystalline phase content and morphology of poly(vinylidene fluoride) , 1994 .

[17]  Guo-Rong Li,et al.  The possibility of formation of large ferroelectric domains in a copolymer of vinylidene fluoride and trifluoroethylene , 1992 .

[18]  T. Hattori,et al.  Crystallization, field‐induced phase transformation, thermally induced phase transition, and piezoelectric activity in P(vinylidene fluoride‐TrFE) copolymers with high molar content of vinylidene fluoride , 1990 .

[19]  K. Kim,et al.  Spectroscopic analysis of the crystalline and amorphous phases in a vinylidene fluoride/trifluoroethylene copolymer , 1989 .

[20]  T. Nishi,et al.  Effect of crystallization condition on the ferroelectric phase transition in vinylidene fluoride/trifluoroethylene (VF2/F3E) copolymers , 1988 .

[21]  K. Tashiro,et al.  Vibrational spectroscopic study of the ferroelectric phase transition in vinylidene fluoride-trifluoroethylene copolymers: 1. Temperature dependence of the Raman spectra , 1988 .

[22]  R. Ting,et al.  Thermodynamic and morphological studies of the solid-state transition in copolymers of vinylidene fluoride and trifluoroethylene , 1988 .

[23]  A. Chiba,et al.  Study of annealing effects on the structure of vinylidene fluoride-trifluoroethylene copolymers using WAXS and SAXS , 1987 .

[24]  Decai Yang,et al.  β-phase formation of poly(vinylidene fluoride) from the melt induced by quenching , 1987 .

[25]  H. Ohigashi,et al.  Piezoelectricity and related properties of vinylidene fluoride and trifluoroethylene copolymers , 1986 .

[26]  E. Thomas,et al.  On the α→β transition by deformation of highly oriented poly(vinylidene fluoride) , 1984 .

[27]  Yoshihide Higashihata,et al.  Piezoelectric properties of rolled vinylidene fluoride and trifluoroethylene copolymer , 1984 .

[28]  K. Tashiro,et al.  Structural study on ferroelectric phase transition of vinylidene fluoride-trifluoroethylene copolymers (III) dependence of transitional behavior on VDF molar content , 1984 .

[29]  Masamichi Kobayashi,et al.  Structure and ferroelectric phase transition of vinylidene fluoride-trifluoroethylene copolymers: 2. VDF 55% copolymer , 1984 .

[30]  A. J. Lovinger,et al.  Crystallographic changes characterizing the Curie transition in three ferroelectric copolymers of vinylidene fluoride and trifluoroethylene: 2. Oriented or poled samples , 1983 .

[31]  Takeshi Yamada,et al.  Ferroelectric properties of vinylidene fluoride‐trifluoroethylene copolymers , 1981 .

[32]  K. Tashiro,et al.  Structural study on ferroelectric phase transition of vinylidene fluoride-trifluoroethylene random copolymers , 1981 .

[33]  Takeshi Yamada,et al.  Ferroelectric‐to‐paraelectric phase transition of vinylidene fluoride‐trifluoroethylene copolymer , 1981 .

[34]  Junichi Sako,et al.  Piezoelectricity of vinylidene fluoride-trifluoroethylene copolymers , 1981 .

[35]  T. Yagi,et al.  Transition Behavior and Dielectric Properties in Trifluoroethylene and Vinylidene Fluoride Copolymers , 1980 .

[36]  E. Fukada,et al.  Crystalline phase transition in the copolymer of vinylidenefluoride and trifluoroethylene , 1980 .

[37]  T. Yagi Transitions and Relaxations in Poly(trifluoroethylene) , 1979 .

[38]  T. Yagi,et al.  A Fluorine-19 NMR Study of the Microstructure of Vinylidene Fluoride–Trifluoroethylene Copolymers , 1979 .

[39]  T. Yagi Studies on Microstructure of Poly(trifluoroethylene) Chain by Fluorine-19 NMR and Monte Carlo Simulation , 1979 .

[40]  Steven C. Roth,et al.  Electric‐field‐induced phase changes in poly(vinylidene fluoride) , 1978 .

[41]  W. Prest,et al.  The formation of the G phase from the a and polymorphs of polyvinylidene fluoride , 1978 .

[42]  A. Hopfinger,et al.  Polymorphism of poly(vinylidene fluoride): potential energy calculations of the effects of head‐to‐head units on the chain conformation and packing of poly(vinylidene fluoride) , 1972 .

[43]  G. R. Crane,et al.  Pyroelectricity and Optical Second Harmonic Generation in Polyvinylidene Fluoride Films , 1971 .

[44]  H. Kawai,et al.  The Piezoelectricity of Poly (vinylidene Fluoride) , 1969 .