Phenylene motion in polycarbonate and polycarbonate/additive mixtures

Pulsed deuteron NMR line shapes have been analysed to characterize type and time scale of the phenylene group motion in glassy bisphenol-A polycarbonate. The motional mechanism involvesπ-flips about theC1C4 axis augmented by small angle fulctuations about the same axis, reaching a rms amplitude of ±35‡ at 380 K. The distribution of correlation times for theπ-flips is heterogeneous in nature and can be described either by a log-Gaussian or an asymmetric distribution with a more rapid decay at high correlation times comparable to the Williams-Watts distribution. From both distributions essentailly the same mean activation energy of 37 kJ/mol is obtained, whereas the temperature dependent widt…