Dynamic Heterogeneity of Filler-Associated Interphases in Polymer Nanocomposites

Dynamically inhomogeneous polymer systems exhibit interphases with mobility gradients. These are believed to play key roles in the material's performance. A prominent example is particle-filled rubber, a special case of a crosslinked polymer nanocomposite, where favorable rubber-filler interactions may give rise to a nanoscale immobilized layer around the filler, including regions of intermediate mobility. Such intermediate domains may either form a separate shell-like layer or be a manifestation of dynamic heterogeneities, in which case the intermediately mobile material would be dispersed in the form of nanometer-sized subdomains. In this contribution, bidirectional proton NMR spin diffusion (SD) experiments applied to silica-filled acrylate rubber are combined with numerical simulations to provide microscopic insights into this question. While model calculations for different scenarios fit the given data similarly well for longer SD mixing time, the short-time data do support the presence of dynamic heterogeneities.