Molecular Probe Diffusion in Thin Polymer Films: Evidence for a Layer with Enhanced Mobility Far above the Glass Temperature.

We studied experimentally the influence of interfaces on the dynamics in thin polymer films at temperatures far above the glass temperature (Tg + 80 °C). Polyisoprene (PI) was employed as a model system. We examined glass substrate supported films with thicknesses (d) spanning the range from 10 μm to 10 nm that correspond to d/Rg from 400 to 1, where Rg is the polymer radius of gyration. We employed fluorescence correlation spectroscopy (FCS) to monitor the translational diffusion of small fluorescent tracer molecules, dispersed at nanomolar concentrations in the PI matrix. In thick films, a single diffusion process correlated to the bulk segmental dynamics of the matrix polymer was present. However, when the film thickness was smaller than the normal dimension of the FCS observation volume, a second, faster diffusion process appeared, reflecting enhanced segmental dynamics near the free surface. Our results provide direct experimental evidence for the existence of a layer with enhanced mobility near the free surface of supported PI films at temperatures as high as 80 °C above the bulk Tg.