Heterogeneous dynamics of poly(vinyl acetate) far above Tg: a combined study by dielectric spectroscopy and quasielastic neutron scattering.

We have investigated the dynamics of poly(vinly acetate) using broadband dielectric spectroscopy (DS) covering over 14 decades in frequency up to 20 GHz and high-resolution quasielastic neutron-scattering (QENS) technique. The dielectric results have been interpreted in terms of the phenomenological Kohlrausch-Williams-Watts [G. Williams and D. C. Watts, Trans. Faraday Soc. 66, 80 (1970); F. Alvarez, A. Alegria, and J. Colmenero, Phys. Rev. B 47, 125 (1993)] description. Because of the wide frequency range covered by DS, it provides a precise determination of dynamics over a wide temperature range and it revealed a crossover in polymer dynamics at 387 K through different dielectric parameters, viz., characteristic times, asymmetric shape parameter, and dielectric strength. Moreover, shape parameter is found to be higher in comparison to other typical polymeric systems. The characteristic relaxation times observed by QENS displayed an anomalous dependence of momentum transfer, indicating the possible existence of heterogeneities in the system even at the high temperatures. In addition, spin-lattice relaxation times, T(1), were found to be decoupled from dielectric characteristic times. Based on these results, a model was proposed to account for heterogeneities where we consider coexistence of different regions with standard polymeric behavior but with different characteristic times, leading to a distribution of relaxation times. The model is found to account for the anomalous behavior and an inherent shape parameter is found to account for the shape of alpha relaxation. This model is also found to predict the T variation of T(1) characteristic time scales at all temperatures. The origin of the heterogeneous domains is believed to lie in the microstructure of polymer chains.