Collective Motion in the Interfacial and Interior Regions of Supported Polymer Films and Its Relation to Relaxation

To understand the role of collective motion in the often large changes in interfacial molecular mobility observed in polymer films, we investigate the extent of collective motion in the interfacial regions of a thin supported polymer film and within the film interior by molecular dynamics simulation. Contrary to commonly stated expectations, we find that the extent of collective motion, as quantified by string-like molecular exchange motion, is similar in magnitude in the polymer air interfacial layer as the film interior and distinct from the bulk material. This finding is consistent with Adam Gibbs description of the segmental dynamics within mesoscopic film regions, where the extent of collective motion is related to the configurational entropy of the film as a whole rather than a locally defined extent of collective motion or configurational entropy.