Shear-stress fluctuations and relaxation in polymer glasses

Abstract

We investigate by means of molecular dynamics simulation a coarse-grained polymer glass model focusing on (quasistatic and dynamical) shear-stress fluctuations as a function of temperature T and sampling time Δt. The linear response is characterized using (ensemble-averaged) expectation values of the contributions (time averaged for each shear plane) to the stress-fluctuation relation μsf for the shear modulus and the shear-stress relaxation modulus G(t). Using 100 independent configurations, we pay attention to the respective standard deviations. While the ensemble-averaged modulus μsf(T) decreases continuously with increasing T for all Δt sampled, its standard deviation δμsf(T) is nonmonotonic with a striking peak at the glass transition. The question of whether the shear modulus is continuous or has a jump singularity at the glass transition is thus ill posed. Confirming the effective time-translational invariance of our systems, the Δt dependence of μsf and related quantities can be understood using a weighted integral over G(t).