Viscoelastic Dynamics of Confined Polymer Melts

Abstract

The frequency-dependent shear response of an ultrathin polymer melt (polyphenylmethylsiloxane) confined between adsorbing surfaces (parallel plates of mica) is described. The sinusoidal deformations were sufficiently small to give linear response, implying that measurement did not perturb the film structure. A remarkable transition was observed with decreasing thickness. When the film thickness was less than five to six times the unperturbed radius of gyration, there emerged a strong rubber-like elasticity that was not characteristic of the bulk samples. This result indicates enhanced entanglement interactions in thin polymer films and offers a mechanism to explain the slow mobility of polymers at surfaces.