Influence of crystallization-induced amorphous phase confinement onα- andβ-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 modification of its activation energy (Ea ∼ 30.8 kJ mol−1) with confinement, showing that it happens in the pure amorphous regions. The dielectric strength analysis of each process, through the Onsager-Kirkwood-Fröhlich (OKF) theory, has demonstrated that a rigid amorphous phase is strongly involved in the very high temperature range well above Tg. In the range around Tg, a peculiar behavior of the low temperature α-relaxation dielectric strength is reported, in agreement with the OKF temperature decreasing dependency that has been related to cooperative rearranging regions in the pure amorphous phase. The disappearance of the α-relaxation with the amorphous phase confinement leads to a transformation from 2D to 3D crystallite arrangements of the PA-F chains in correlation with the formation of spherulitic structures.