Chain relaxation in thin polymer films: turning a dielectric type-B polymer into a type-A' one.

A molecular dynamics simulation study of chain relaxation in a thin polymer film is presented, studying the dielectric response of a random copolymer of cis and trans 1,4-polybutadiene, a type B polymer without net chain dipole moment, confined between graphite walls. We stress the orientational effect of the attractive walls, inducing polarization in the vicinity of the walls, while the center of the film stays bulk-like. This polarization leads to a net dipole moment of the adsorbed chains, which is perpendicular to their end-to-end vector, which we termed as type A' behavior. In this situation, the dipole moment relaxes only upon desorption of the chains from the wall, a dynamic process which occurs on timescales much longer than the bulk relaxation time of the polymer.