Nonlinear stress relaxation of an entangled linear polystyrene in single step-strain flow: A quantitative theoretical investigation

The nonlinear stress relaxation of a nearly monodisperse, moderately entangled polystyrene solution (i.e., roughly seven entanglements per chain at equilibrium) in single step-strain flow is investigated quantitatively by a detailed comparison of an existing set of experimental data with a simulation based on the tube model. The proposed simulation enables the effects of primary nonlinear relaxation mechanisms other than chain retraction to be identified more clearly and investigated individually. Two peculiar nonlinear relaxation behaviors are observed in this experiment. One is concerned with an apparent enhancement in the stress relaxation at short times, and the other is responsible for a seeming slowdown of the stress relaxation at long times. These findings are discussed within the tube model, in view of the effects of convective constraint release, partial strand extension, and nonaffine deformation. (C) 2003 Wiley Periodicals, Inc.