Macromolecules, Vol.27, No.12, 3282-3288, 1994
Methyl-Group Dynamics in Poly(Vinyl Methyl-Ether) - A Rotation Rate Distribution Model
The dynamics of the methyl side group in poly(vinyl methyl ether) (PVME) is investigated by means of time-of-flight quasi-elastic neutron scattering in the time range between 10(-11) and 10(-13) s. The quasi-elastic region of the experimental data is analyzed by using two alternative different models. One of them assumes that there exist two different families of CH3 in PVME moving at different rates and with a population which depends on temperature. The other model assumes a single type of CH3 groups but considers the existence of a random distribution of jumping rates for the methyl group rotation. Both models allow a good description of the experimental behavior. However, whereas the former results in a peculiar behavior of the model parameters, the latter leads to a simple and physical picture of the methyl group dynamics. In particular, a Gaussian distribution of the energy barriers for the CH3 rotational jumps which is centered at 8.4 kJ mol-1 and has a distribution width of +/-0.8 kJ mol-1 is found to be the origin of the distribution of jumping rates. Within the experimental uncertainties, the distribution of energy barriers does not change with temperature around the glass transition.
Keywords:ELASTIC NEUTRON-SCATTERING;POLY(METHYL METHACRYLATE);ALPHA-RELAXATION;GLASS-TRANSITION;POLYMER;MOTION