Viscosity, Self-Diffusion, and Allied Effects in Solid Polymers

Abstract

An attempt has been made to explain the observed viscous behavior of bulk polymers. It is found that the viscosity and diffusion may be represented by a theory which takes into account the coupling together of the molecules. Two equivalent treatments are given. One makes use of a segmental friction factor in the same manner as the common formulation of dilute solution viscosity of polymers. The second method uses the concept of segmental jumping. Since both are equivalent, an expression for the friction factor is found in terms of the segmental jumping frequency. Using this fact it is possible to calculate the segmental jumping frequency from bulk viscosity data. A simple application leads to the result that the jumping frequency is about 0.3 sec−1 at the transition temperature in polystyrene. In addition a simple relation is found to hold between bulk viscosity and diffusion constant. The proportionality constant is easily evaluated and so one is now able to obtain self-diffusion constants directly from viscosity data.