Relaxation by reptation and tube enlargement: A model for polydisperse polymers

Abstract

Abstract Modern theories of the dynamics of concentrated polymeric liquids have not yet accounted for the effects of polydispersity to a sufficient extent. In order to approach quantitatively the problem of polydispersity, a model is proposed here which is based on the concept that the “tube” of constraints around a chain enlarges as the relaxation proceeds. Predictions of linear viscoelasticity obtained with this model compare favorably with experimental results on homopolymeric blends reported in the literature. However, the theory is limited to the case of very long chains and it embodies an arbitrary, if plausible, closure assumption in the self‐consistency scheme. Thus, quantitative agreement remains incomplete.