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beta-phase poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) copolymer films were prepared by uniaxially stretching solution-cast or melt-quenched samples. Different preparation routes lead to different amounts of the crystalline alpha and beta phases in the films, as detected by means of Fourier-transform infrared spectroscopy and X-ray diffractometry. The beta phase is significantly enhanced in melt-quenched and stretched films in comparison to solution-cast and stretched films. This is particularly true for copolymer samples with higher HFP content. The beta- phase enhancement is also observed in ferroelectric-hysteresis experiments where a rather high polarization of 58 mC/ m(2) was found on melt-quenched and stretched samples after poling at electric fields of 140 MV/m. After poling at 160 MV/m, one of these samples exhibited a piezoelectric d(33) coefficient as high as 21 pC/N. An electric-field-induced partial transition from the alpha to the beta phase was also observed on the melt-quenched and stretched samples. This effect leads to a further increase in the applications-relevant dipole polarization. Uniaxially stretched ferroelectric- polymer films are highly anisotropic. Dielectric resonance spectroscopy reveals a strong increase of the transverse piezoelectric d(32) coefficient and a strong decrease of the transverse elastic modulus c(32) upon heating from 20 to 50 degrees C.
The influence of the solvent-evaporation rate on the formation of of. and P crystalline phases in solution-cast poly(vinylidene fluoride) (PVDF) films was systematically investigated. Films were crystallized from PVDF/N,N- dimethylformamide solutions with concentrations of 2.5, 5.0, 10, and 20 wt % at different temperatures. During crystallization, the solvent evaporation rate was monitored in situ by means of a semianalytic balance. With this system, it was possible to determine the evaporation rate for different concentrations and temperatures of the solution under specific ambient conditions (pressure, temperature, and humidity). Fourier-Transform InfraRed spectroscopy with Attenuated Total Reflectance revealed the P-phase content in the PVDF films and its dependence on previous evaporation rates. Based on the relation between the evaporation rate and the PVDF phase composition, a consistent explanation for the different amounts of P phase observed at the upper and lower sample surfaces is achieved. Furthermore, the role of the sample thickness has also been studied. The experimental results show that not only the temperature but also the evaporation rate have to be controlled to obtain the desired crystalline phases in solution-cast PVDF films.