Paper detail

A Force-Level Theory of the Rheology of Entangled Rod and Chain Polymer Liquids. II. Perturbed Reptation, Stress Overshoot, Emergent Convective Constraint Release and Steady State Flow

We numerically and analytically analyze the startup continuous shear rheology of heavily entangled rigid rod polymer fluids based on our self-consistent, force-level theory of anharmonic tube confinement. The approach is simplified by neglecting stress-assisted transverse barrier hopping, and irreversible relaxation proceeds solely via deformation-perturbed reptation. This process is self-consistently coupled to tube dilation and macroscopic rheological response. We predict that with increasing strain the tube strongly dilates, entanglements are lost, and reptation speeds up. As a consequence, a stress overshoot emerges not due to affine over-orientation, but rather to strong weakening of the entanglement network. Just beyond the stress overshoot the longest relaxation time is predicted to scale as the inverse shear rate, corresponding to the emergence of a generic form of convective constraint release (CCR). Its origin is a stress-induced local force that self-consistently couples the mesoscopic tube-scale physics with macroscopic mechanical response. Tube weakening at the overshoot occurs via the same qualitative mechanism that leads to microscopic absolute yielding in the nonlinear elastic scenario analyzed in the preceding paper. The stress overshoot and emergent CCR thus correspond to an elastic-viscous crossover due to deformation-induced disentanglement, which at long times and high shear rates results in a quantitatively sensible flow stress plateau and shear thinning behavior. We suggest that the predicted behavior for needles is relevant to flexible chain melts at low Rouse Weissenberg numbers if contour length equilibration is fast. Quantitative predictions for tube dilation in the steady state flow of chains melts are favorably compared to a recent simulation.