Strong Reduction in Amplitude of the Interfacial Segmental Dynamics in Polymer Nanocomposites

Despite the wide use of polymer nanocomposites (PNCs) in various applications, our understanding of the microscopic parameters controlling their macroscopic properties remains limited. In this study, we examine the dielectric strength of segmental dynamics, Delta epsilon(IL)(T) in the interfacial polymer layer surrounding the nanoparticles in PNCs. The presented analysis reveals a significant drop in Delta epsilon(IL)(T) and its anomalous temperature dependence in the polymer layer adsorbed to nanoparticles. The drop in Delta epsilon(IL)(T) was observed in all samples regardless of whether segmental relaxation time in the interfacial layer was slower or faster than in the bulk polymer, excluding interpretation of the dead layer. We ascribe the observed decrease in the dielectric strength to the restricted amplitude of segmental relaxation in the interfacial/adsorbed layer. Our results provide a new perspective on discussion of dynamics in the interfacial layer in PNCs and thin polymer films, demonstrating that not only segmental relaxation time but also its amplitude can be strongly affected by the interface.