Lateral diffusion of single poly(ethylene oxide) chains on the surfaces of glassy and molten polymer films

Fluorescence correlation spectroscopy was used to show that the temperature-dependent diffusion coefficient of poly(ethylene oxide) (PEO) adsorbed on polystyrene and different poly(alkyl methacrylate) (PAMA) films in aqueous solution exhibited a maximum close to (but below) the surface glass transition temperature, T_gs, of the film. This elevated diffusion was observed over a small range of temperatures below T_gs for these surfaces, and at other temperatures, the diffusion was similar to that on silicon, although the diffusion coefficient for PEO on polystyrene at temperatures above T_gs did not completely decrease to that on silicon, in contrast to the PAMA surfaces. It is concluded that the enhanced surface mobility of the films near the surface glass transition temperature induces conformational changes in the adsorbed PEO. The origin of this narrow and dramatic increase in diffusion coefficient is not clear, but it is proposed that it is caused by a coupling of a dominant capillary mode in the liquid surface layer with the polymer. Friction force microscopy experiments also demonstrate an unexpected increase in friction at the same temperature as the increase in diffusion coefficient.