Irreversible Adsorption Governs the Equilibration of Thin Polymer Films

We demonstrate that the enhanced segmental motion commonly observed in spin cast thin polymer films is a nonequilibrium phenomenon. In the presence of nonrepulsive interfaces, prolonged annealing in the liquid state allows, in fact, recovering bulk segmental mobility. Our measurements prove that, while the fraction of unrelaxed chains increases upon nanoconfinement, the dynamics of equilibration is almost unaffected by the film thickness. We show that the rate of equilibration of nanoconfined chains does not depend on the structural relaxation process but on the feasibility to form an adsorbed layer. We propose that the equilibration of the thin polymer melts is driven by the slow relaxation of interfacial chains upon irreversible adsorption on the confining walls.