Nonlinear Viscoelasticity Raised at Low Temperatures by Intermolecular Cooperation of Bulk Amorphous Polymers

We performed dynamic Monte Carlo simulations of stress relaxation in parallel-aligned and uniaxially stretched bulk amorphous polymers at low temperatures. We observed an extra-slowing down in the early stage of stress relaxation, which causes nonlinear viscoelasticity as deviated from Debye relaxation and Arrhenius-fluid behaviors observed previously at high temperatures. Meanwhile, fluctuation analysis of stress relaxation revealed a substantial increase in the stretch fractions of polymers at the transient periods of high-temperature Debye relaxation. Structural analysis of free volume further revealed the scenario that, at low temperatures, the modulus of polymer entropy elasticity decreases with temperature and eventually loses its competition to the imposed modulus (Deborah number becomes larger than one), and hence upon stress relaxation under constant strains, monomers are firstly accumulated nearby two stretching ends of polymers, resulting in tentative global jamming like physical cross-linking there, and thus retarding the coming transient state of stress relaxation. We concluded that intermolecular cooperation raises physical crosslinking for nonlinear viscoelasticity of polymer stress relaxation as well as the rubbery states unique to bulk amorphous polymers. The new microscopic mechanism of the fluid-rubbery transition of polymers may bring insights into the intermolecular cooperation mechanism of glass transition of small molecules, if the fluid-rubbery transition is regarded as an extrapolation of glass transition from low to high molecular weights.