Influence of film stretching on crystalline phases and dielectric properties of a 70/30 mol% poly(vinylidenefluoride-tetrafluoroethylene) copolymer

Abstract

Polyvinylidene fluoride (PVDF)-based copolymers with tetrafluoroethylene (P(VDF-TFE)), trifluoroethylene (P(VDF-TrFE)) or hexafluoropropylene (P(VDF-HFP)) are of strong interest due to the underlying fundamental mechanisms and the potential ferro-, pyro- and piezo-electrical applications. Their flexibility and their adaptability to various shapes are advantageous in comparison to inorganic ferroelectrics. Here, we study the influence of stretching temperature on the crystalline phases and the dielectric properties in P(VDF-TFE) films by means of Dielectric Relaxation Spectroscopy (DRS), Fourier-Transform InfraRed spectroscopy (FTIR), Wide-Angle X-ray Diffraction (WAXD), Differential Scanning Calorimetry (DSC) and Dynamic Mechanical Analysis (DMA). Especially, the effect of stretching and the influence of the temperature of stretching on the mid-temperature (Tmid) transition are studied in detail. The results show that stretching has a similar effect as that on PVDF, and we observe an increase in the fraction of ferroelectric β-phase with a simultaneous increment in both melting point (Tm) and crystallinity (χc) of the copolymer. While an increase in the stretching temperature does not have a profound impact on the amount of ferroelectric phase, the stability of the ferroelectric phase seems to improve — as seen in the reduction of the Full Width at Half Maximum (FWHM) of the WAXD peaks in both parallel and perpendicular directions to the molecular chain axis. The observation is also supported by the reduction of dissipation losses with an increase in stretching temperature — as seen in DRS measurements. Finally, both stretching itself and the temperature of stretching affect the various molecular processes taking place in the temperature range of the Tmid transition.

Keywords

• p(vdf-tfe) copolymer
• dielectric properties
• crystalline phases
• film stretching
• mid-temperature transition