High-Electric-Field-Induced Hierarchical Structure Change of Poly(vinylidene fluoride) as Studied by the Simultaneous Time-Resolved WAXD/SAXS/FTIR Measurements and Computer Simulations

A high electric field was applied cyclically to poly­(vinylidene fluoride) films, during which the simultaneous and time-resolved measurements of the two-dimensional wide-angle X-ray diffraction (WAXD), small-angle X-ray scattering (SAXS), and transmission-type Fourier transform infrared (FTIR) spectra were performed using a synchrotron X-ray radiation system. The inversion of the CF2 dipole moments caused by the alternate change of the electric field vector direction was detected to occur around ±80–100 MV/m as estimated by the electric-field-strength dependence of the IR band intensity. On the other hand, the WAXD peaks were found to show the maximal intensities at 0 and ±250–300 MV/m. In these regions, the 001 reflection of the β form and the 002 reflection of the δ form changed the intensities remarkably and periodically. These experimental data were interpreted, not by the idea of a simple inversion motion of the rigid polar chains (the planar zigzag chains of the form β and the TGTG̅ chains of the α and δ forms) but by the more complicated couplings between the rotation and tilting motions of the chain segments, the cooperative T-G conformational exchanges, and the associated inversion motion of the CF2 dipoles. The idea of the cooperative chain motions was supported by the density functional theory calculations performed under the external electric field. Different from the remarkable changes of the WAXD and FTIR data, the SAXS patterns did not show the detectable changes in these processes, indicating that the above-mentioned cooperative structural changes should occur in the crystalline regions with the stacked lamellar structure kept unchanged.