Restricted dynamics in oriented semicrystalline polymers: Poly(vinilydene fluoride)

The effect of confinement by crystals on the α relaxation, observed by dielectric broadband spectroscopy, in isotropic as well as in oriented semicrystalline poly(vinilydene fluoride), is analyzed on the basis of a new thermodynamic model. In both samples, it has been found that the average free-energy barrier, ΔF, for conformational rearrangements is of the same order of the dispersion barrier heights, δ(ΔF), around ΔF, i.e., the increase in the barrier height in conformational rearrangement is accompanied by an increase in the heterogeneity of constraining conditions. At a given temperature T, the readjustment free energy is larger in the oriented sample. This fact might be ascribed to either an enhanced effectiveness of confinement in the amorphous region due to the decrease of the amorphous layer thickness in the stacks, or to a change of the mean chain orientation or both. In addition, it is worth noting that in oriented poly(vinilydene fluoride) the regions of cooperative rearrangement are significantly larger. Moreover, independent of orientation, the size of these readjusting regions increase upon decreasing T. This feature, which underlies the Adam-Gibbs approach for liquids, is pointed out for the first time from direct data analysis in the case of confinement enhanced cooperativity. In addition to the above analysis, the samples have been characterized by differential scanning calorimetry, wide angle x-ray scattering, and small angle x-ray scattering.