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Cellular polyethylene-naphthalate (PEN) ferroelectrets are useful as soft and flexible electromechanical transducer materials. Improved cellular PEN foams are prepared by means of a "voiding + inflation + stretching" process and investigated with respect to their structure and their applications-relevant properties. It is found that most of the cellular voids have heights below 8 mu m. The polymer walls do not allow sufficient gas exchange between the voids and the ambient atmosphere, when the cellular films are exposed to atmospheric pressures between a millibar and a few bars. As expected for ferroelectrets, a threshold voltage for charging is observed: A reasonable piezoelectric coefficient d(33) is only found when the charging voltage is higher than 4 kV. Furthermore, d(33) increases with charging voltage and reaches saturation at approximately 8 kV. Annealing after charging or charging at elevated temperatures may enhance the thermal stability of the PEN ferroelectrets. The d(33) of properly annealed samples is stable up to the respective annealing temperatures, but the annealing process reduces the piezoelectric activity of charged ferroelectret films to some extent. Samples charged at suitable elevated temperatures show much better thermal stability than those charged at room temperature, but the charging temperature should be limited to values below the material's glass-transition temperature T-g. Furthermore, the relevant elastic modulus c(33) of PEN ferroelectrets may decrease upon thermal treatment.
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.
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.
A new arrangement of the optical elements in a Thermal-Pulse-Tomography (TPT) setup allows to scan micrometer structures in composite and heterogeneous samples such as polymer-dispersed liquid crystals (PDLCs). The non-destructive TPT technique allows the determination of three-dimensional profiles of polarization and space charge in dielectrics. The samples under study were 12 mu m thick films of a copolymer of vinylidene fluoride with trifluoroethylene P(VDF- TrFE) (65/35) with embedded liquid-crystal droplets. The poling process was performed in direct contact well above the coercive field of the copolymer. The 3D map obtained from scanning with a 10 mu m wide spot shows elliptically shaped areas with liquid-crystal droplets. Considering the droplets as oblate spheroids, their major axis lies in the x-y plane, while their minor axis in the z direction measures 0.5 mu m or more. This result is in good agreement with scanning electron micrographs. It is believed that the major axis is overestimated due to imaging of liquid-crystal clusters.