Influence of crystallization-induced amorphous phase confinement on α- and β-relaxation molecular mobility in parylene F

The molecular mobility of cooperative segmental (α-process) and local (β-process) motions in semicrystalline fluorinated parylene (PA-F) films has been studied using broadband dielectric spectroscopy in a wide temperature range. Particularly, the α-relaxation is, for the first time in a semicrystalline polymer, probed well above the glass transition temperature (∼10Tg) based on the PA-F strong difference between Tg and the crystallization temperature (Tc ∼ 16Tg). The influence of the amorphous phase confinement on the chain dynamics, induced by increasing crystallinity, is also explored. Thus, in the range of Tg, the α-relaxation is described by two crossover Vogel-Fulcher-Tamman characteristics, and the high temperature one presents an exacerbated low fragility. The space confinement of the amorphous regions, as characterized by x-ray diffraction, shows an important mobility restriction of both the α- and β-relaxations. The β-process, which has been related to CF2 group local motions, does not present a ...