Direct Comparison of Surface and Bulk Relaxation of PS - A Temperature Dependent Study

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy was used to measure simultaneously the relaxation rates of polystyrene (PS) molecules at the free surface and in the bulk. The samples were uniaxially oriented at room temperature via a modified cold rolling process. The density of the oriented samples as determined by liquid immersion technique is identical to that of bulk PS. At temperatures below its bulk glass transition temperature the rate of surface and bulk chain relaxation was monitored by measuring the partial-electron yield (PEY) and the fluorescence NEXAFS yields (FS), respectively, both parallel and perpendicular to the stretching direction. The decay rate of the dichroic ratios from both PEY and FY at various temperatures was taken as a measure of the relaxation rate of surface and bulk molecules respectively. In addition, the decay rate of the optical birefringence was also measured to provide an independent measure of the bulk relaxation. Relaxation of PS chains was found to occur faster on the surface relative to the bulk. The magnitude of the surface glass transition temperature suppression over the bulk was estimated to be 18 \r { }C based on the measured temperature dependence of the relaxation rates.