Microscopic theory of linear, entangled polymer chains under rapid deformation including chain stretch and convective constraint release

Abstract

A refined version of the Doi and Edwards tube model for entangled polymer liquids is presented. The model is intended to cover linear chains in the full range of deformation rates from linear to strongly nonlinear flows. The effects of reptation, chain stretch, and convective constraint release are derived from a microscopic stochastic partial differential equation that describes the dynamics of the chain contour down to the length scale of the tube diameter. Contour length fluctuations are also included in an approximate manner. Predictions of mechanical stresses as well as the single chain structure factor under flow are shown. A comparison with experimental data is made in which all model parameters are fixed at universal values or are obtained from linear oscillatory shear measurements. With no parameter modification the model produces good agreement over a wide range of rheological data for entangled polymer solutions, including both nonlinear shear and extension.