Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent

The γ-phase poly (vinylidene fluoride) (PVDF) films are usually prepared using dimethyl sulfoxide (DMSO) solvent, regardless of preparation temperature. Here we report the crystallization of both α and γ-phase PVDF films by varying preparation temperature using DMSO solvent. The γ-phase PVDF films were annealed at 70, 90, 110, 130 and 160°C for five hours. The changes in the phase contents in the PVDF at different annealing conditions have been described. When thin films were annealed at 90°C for 5 h, maximum percentage of β-phase appears in PVDF thin films. The γ-phase PVDF films completely converted to α-phase when they were annealed at 160°C for 5 h. From X-ray diffraction (XRD), Fourier transform infrared spectrum (FTIR), differential scanning calorimetry (DSC) and Raman studies, it is confirmed that the PVDF thin films, cast from solution and annealed at 90°C for 5 h, have maximum percentage of β-phase. The β-phase PVDF shows a remnant polarization of 4.9 μC/cm2 at 1400 kV/cm at 1 Hz.

[1]  R. Gregorio,et al.  Effect of PMMA addition on the solution crystallization of the alpha and beta phases of poly(vinylidene fluoride) (PVDF) , 1995 .

[2]  L. Judovits Thermal analysis of poly(vinylidene fluoride) film , 2006 .

[3]  Masamichi Kobayashi,et al.  Molecular Conformation and Packing of Poly(vinylidene fluoride). Stability of Three Crystalline Forms and the Effect of High Pressure , 1972 .

[4]  W. Prest,et al.  The morphology and thermal response of high‐temperature–crystallized poly(vinylidene fluoride) , 1975 .

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

[6]  A. Ribeiro,et al.  Preparation and characterization of PVDF/CaCO3 composites , 2007 .

[7]  Andrzej Wasiak,et al.  Phase transitions during stretching of poly(vinylidene fluoride) , 1999 .

[8]  C. Yoon,et al.  Piezoelectric activity and field-induced crystal structure transitions in poled poly(vinylidene fluoride) films , 1979 .

[9]  K. Yao,et al.  Crystallization mechanism and piezoelectric properties of solution-derived ferroelectric poly(vinylidene fluoride) thin films , 2006 .

[10]  K. Yao,et al.  Ferroelectric poly(vinylidene fluoride) thin films on Si substrate with the β phase promoted by hydrated magnesium nitrate , 2007 .

[11]  Yasuhiro Takahashi,et al.  Kink Bands in Form I of Poly(vinylidene fluoride) , 1980 .

[12]  K. Okuda,et al.  Solution‐grown crystals of poly(vinylidene fluoride) , 1967 .

[13]  Yozo Chatani,et al.  Crystal Structures of Three Crystalline Forms of Poly(vinylidene fluoride) , 1972 .

[14]  Anton Peterlin,et al.  Nuclear magnetic resonance and x‐ray determination of the structure of poly(vinylidene fluoride) , 1966 .

[15]  A. Bottino,et al.  Characterization of PVDF membranes by vibrational spectroscopy , 2002 .

[16]  Ali Akbar Yousefi,et al.  Effect of tensile strain rate and elongation on crystalline structure and piezoelectric properties of PVDF thin films , 2007 .

[17]  E. Drioli,et al.  Poly(vinylidene fluoride) membranes by phase inversion: the role the casting and coagulation conditions play in their morphology, crystalline structure and properties , 2007 .

[18]  Munehiro Date,et al.  Hysteresis phenomena in polyvinylidene fluoride under high electric field , 1980 .

[19]  A. Salimi,et al.  FTIR STUDIES OF -PHASE CRYSTAL FORMATION IN STRETCHED PVDF FILMS , 2003 .

[20]  D. L. Chinaglia,et al.  Phase Transition in Poly(Vinylidene Fluoride) Investigated with Micro-Raman Spectroscopy , 2005, Applied spectroscopy.

[21]  M. Litt,et al.  The Crystal Structure of the ? Phase of Poly(vinylidene fluoride) , 1980 .

[22]  D. Das-gupta,et al.  Corona charging and the piezoelectric effect in polyvinylidene fluoride , 1978 .

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

[24]  Robert L. Miller,et al.  Crystallization of poly(vinylidene fluoride): Equilibrium melting point and heat of fusion of the α‐polymorph , 1976 .

[25]  Edward Bormashenko,et al.  Vibrational spectrum of PVDF and its interpretation , 2004 .

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

[27]  G. Zerbi,et al.  Chain conformations of polyvinylidene fluoride as derived from its vibrational spectrum , 1967 .

[28]  Ali Akbar Yousefi,et al.  Conformational changes and phase transformation mechanisms in PVDF solution-cast films , 2004 .

[29]  K. Tashiro,et al.  Molecular Vibrations of Three Crystal Forms of Poly(vinylidene fluoride) , 1975 .

[30]  Youn Jung Park,et al.  Micropatterning of semicrystalline poly(vinylidene fluoride) (PVDF) solutions , 2005 .