Kinetic Polymer Arrest in Percolated SWNT Networks

Particle–polymer attractions in nanocomposites can cause significant heterogeneities in the polymer dynamics and remarkably impact the material properties. Dynamical perturbations are generally expected to be limited to interfacial polymer segments. However, composites with highly anisotropic nanoparticles usually exhibit very low percolation thresholds. In such systems, the overlapping interfacial regions could result in a complex polymer relaxation behavior that is unanticipated from dilute nanoparticle dispersions in polymer matrices. To understand this behavior, we examine a system of percolated single-wall carbon nanotubes (SWNT) in a polymer matrix, PMMA, which is known to have strong interfacial binding. Neutron spectroscopy measurements on the composites reveal not only an interfacial polymer layer that is transiently pinned to the SWNT surface, but suggest that the percolated network forms a kinetic cage that dramatically restricts both local and cooperative relaxations of noninterfacial polymer segments. These findings should help guide theories and simulations of hierarchical polymer dynamics in nanocomposites.