Macromolecules, Vol.37, No.18, 7051-7055, 2004
Modes of molecular motion in low molecular weight polystyrene
The variations with temperature of the viscosity, 1, and the relaxation times for various low molecular weight, unentangled polystyrenes (PS) are analyzed. We find that the temperature dependence of eta does not directly reflect the behavior of the global chain modes. Depending on molecular weight and temperature, eta can exhibit a stronger temperature dependence than even the local segmental modes. However, this is only a consequence of the strong temperature dependence of the recoverable compliance J(s) The Rouse relaxation time, tau(1), deduced from the product of the viscosity and the recoverable compliance, has the expected behavior. For example, this Rouse time for a PS of molecular weight equal to 2 kg/mol. has the same temperature dependence as that for self-diffusion; hence, there is no enhancement of translational diffusion in the polymer. The same conclusion was reached by Urakawa et al. [Urakawa, O.; Swallen, S. F.; Ediger, M. D.; von Meerwall, E. D. Macromolecules 2004, 37, 1558], although the analysis leading to it was different. The conclusion is consistent with two extant explanations of the enhancement of translational diffusion in small molecular glass-formers, one which invokes spatially heterogeneous dynamics and the other ascribing the effect to the different coupling parameters for the translational and rotational correlation functions.