Effect of Interface Interaction on the Segmental Dynamics of Poly(vinylacetate) Investigated by Local Dielectric Spectroscopy

The segmental dynamics of poly(vinyl acetate) (PVAc) thin films were measured in the presence of an aluminum interface and in contact with an incompatible polymer, poly(4-vinylpyridine). The local dielectric relaxation was found to be faster in thin films than in the bulk; however, no differences were observed for the various interfaces, including a PVAc/air interface. These results show that capping of thin films, even with a rigid material, does not necessarily affect the dynamics, the speeding up herein for capped PVAc was equivalent to that for the air interface. The insensitivity of the dynamics to the nature of the interface affords a means to engineer thin films while maintaining desired mechanical properties. Our findings for PVAc also may explain the discordant results that have been reported in general for the effect of air versus rigid interfaces on the local segmental relaxation of thin films.