A fluctuation-dissipation theorem approach to mechanical relaxation in solid polymers

Abstract

Kubo theory formalism has been used to obtain expressions for shear and dilatational stress relaxation functions in terms of statistical mechanical time-dependent correlation functions. This is equivalent to obtaining expressions for the complex modulus or the complex viscosity for all frequencies. These results provide a basis for calculating the macroscopic consequences of molecular models presently used to provide qualitative understanding of relaxation peaks for solid polymers.

The shear and dilatational stress relaxation functions are quite different formally. For a particularly simple model it will be shown that the former is related to the frequency distribution of the kinetic energy and is also closely related to the dielectric relaxation function. The familiar results of the Rouse model are recovered in the results but no friction constant need be assumed in the present approach.