Viscoplasticity and large-scale chain relaxation in glassy-polymeric strain hardening

A simple theory for glassy polymeric mechanical response which accounts for large scale chain relaxation is presented. It captures the crossover from perfect-plastic response to strong strain hardening as the degree of polymerization $N$ increases, without invoking entanglements. By relating hardening to interactions on the scale of monomers and chain segments, we correctly predict its magnitude. Strain activated relaxation arising from the need to maintain constant chain contour length reduces the $N$ dependence of the characteristic relaxation time by a factor $\sim \dot\epsilon N$ during active deformation at strain rate $\dot\epsilon$. This prediction is consistent with results from recent experiments and simulations, and we suggest how it may be further tested experimentally.