Surface relaxations in polymers

Near-edge X-ray absorption fine structure, NEXAFS, spectroscopy was used to investigate the relaxations of polystyrene, a typical amorphous polymer, near a free surface after the imposition of a small deformation. Using synchrotron radiation, the NEXAFS dichroic ratio was determined for both the Auger and total electron yield processes as a function of temperature to determine the orientation of the polymer in the first 1 and 10 nm from the free surface, respectively. Complete relaxation of the polymer . . was not seen for temperatures less than the bulk glass transition temperature. No evidence of enhanced mobility at the free surface was found. A planar relaxation of the polymer was found in the first nanometer from the free surface, whereas in the first 10 nm, the dominant relaxation was normal to the surface.