Theory for the Elementary Time Scale of Stress Relaxation in Polymer Nanocomposites.

We construct a microscopic theory for the elementary time scale of stress relaxation in dense polymer nanocomposites. The key dynamical event is proposed to involve the rearrangement of cohesive segment-nanoparticle (NP) tight bridging complexes via an activated small NP dilational motion, which allows the confined segments to relax. The corresponding activation energy is determined by the NP bridge coordination number and potential of mean force barrier. The activation energy varies nonlinearly with interfacial cohesion strength and NP concentration, and a universal master curve is predicted. The theory is in very good agreement with experiments. The underlying ideas are relevant to a variety of other hybrid macromolecular materials involving hard particles and soft macromolecules.