Two-Stage Evolution of Gamma-Phase Spherulites of Poly (Vinylidene Fluoride) Induced by Alkylammonium Salt

Abstract

We investigated the evolution of the γ-phase spherulites of poly(vinylidene fluoride) (PVDF) added to 1 wt% of tetrabutylammonium hydrogen sulfate during the isothermal crystallization at 165 °C through polarized optical microscopy and light scattering measurements. Optically isotropic domains grew, and then optical anisotropy started to increase in the domain to yield spherulite. Double peaks were seen in the time variation of the Vv light scattering intensity caused by the density fluctuation and optical anisotropy, and the Hv light scattering intensity caused by the optical anisotropy started to increase during the second increase in the Vv light scattering intensity. These results suggest the two-stage evolution of the γ-phase spherulites, i.e., the disordered domain grows in the first stage and ordering in the spherulite increases due to the increase in the fraction of the lamellar stacks in the spherulite without a change in the spherulite size in the second stage. Owing to the characteristic crystallization behavior, the birefringence in the γ-phase spherulites of the PVDF/TBAHS was much smaller than that in the α-phase spherulites of the neat PVDF.