Molecular organization and viscosity of a thin film of molten polymer between two surfaces as probed by force measurements

Measurements are presented of the force between two molecularly smooth mica surfaces immersed in liquid poly(dimethylsiloxane) (Dow Corning 200 of nominal viscosity 50 cS) over a range of film thicknesses from 3 to 200 nm. There is a repulsion, attributed to conformational restrictions, when the polymer molecules are confined to a gap less than about 15 nm thick. In extremely thin films (<5 nm) the force is an oscillatory function of thickness with a repeat spacing corresponding to the width of the polymer molecule, which suggests that the polymer segments are arranged in layers near the solid surfaces. Dynamic force measurements show that the polymer has a viscosity equal to its bulk value even in very thin films, but a region next to each surface, only about one radius of gyration thick, does not flow. Saturation of the polymer with water destabilizes the film when it is very thin.