Phase Transition in Poly(Vinylidene Fluoride) Investigated with Micro-Raman Spectroscopy

The phase transition from the non-polar α-phase to the polar β-phase of poly(vinylidene fluoride) (PVDF) has been investigated using micro-Raman spectroscopy, which is advantageous because it is a nondestructive technique. Films of α-PVDF were subjected to stretching under controlled rates at 80 °C, while the transition to β-PVDF was monitored by the decrease in the Raman band at 794 cm⁻¹ characteristic of the α-phase, along with the concomitant increase in the 839 cm⁻¹ band characteristic of the β-phase. The α→β transition in our PVDF samples could be achieved even for the sample stretched to twice (2×-stretched) the initial length and it did not depend on the stretching rate in the range between 2.0 and 7.0 mm/min. These conclusions were corroborated by differential scanning calorimetry (DSC) and X-ray diffraction experiments for PVDF samples processed under the same conditions as in the Raman scattering measurements. Poling with negative corona discharge was found to affect the α-PVDF morphology, improving the Raman bands related to this crystalline phase. This effect is minimized for films stretched to higher ratios. Significantly, corona-induced effects could not be observed with the other experimental techniques, i.e., X-ray diffraction and infrared spectroscopy.