Crystallization of poly(vinylidene fluoride)-SiO₂ hybrid composites prepared by a Sol-gel process

Abstract

Organic-inorganic hybrid composites consisting of poly(vinylidene fluoride) (PVDF) and SiO₂ were prepared through a sol-gel process and the crystallization behavior of PVDF in the presence of SiO₂ networks was investigated by spectroscopic, thermal and x-ray diffraction measurements. The hybrid composites obtained were relatively transparent, and brittleness increased with increasing content of tetraethoxysilane (TEOS). It was regarded from FT-IR and DSC thermal analyses that at least a certain interaction existed between PVDF molecules and the SiO₂ networks. X-ray diffraction measurements showed that all of the hybrid samples had a crystal structure of PVDFγ-phase. Fresh gel prepared from the sol-gel reaction showed a very weak x-ray diffraction peak near 2θ=21° due to PVDF crystallization, and intensity increased gradually with time after gelation. The crystallization behavior of PVDF was strongly affected by the amount of SiO₂ networks. That is, SiO₂ content directly influenced preference and disturbance for crystallization. In polymer-rich hybrids, SiO₂ networks had a favorable effect on the extent of PVDF crystallization. In particular, the maximum percent crystallinity of PVDF occurred at the content of 3.7 wt% SiO₂ and was higher than that of pure PVDF. However, beyond about 10 wt% SiO₂, the crystallization of PVDF was strongly confined.