Characterization of polymer films using a slow positron beam

Polymer structures have been investigated using positron annihilation lifetime spectroscopy (PALS) with a slow positron beam as well as a conventional radioactive source (Na-22). The properties of the free volume holes near the polymer surface were studied as a function of the positron implantation energy. The longest lifetime was associated with ortho-positronium (o-Ps) annihilation in the free volume holes. In polytetrafluoroethylene film, the lifetime of o-Ps was observed to decrease with increasing positron implantation depth, and a significant change in the o-Ps lifetime was found at a short distance (about 10 nm) from the surface, while its intensity increased. This result implies that near the polymer surface the free volume holes become larger that in the bulk. The effect of temperature on the polymer sub-surface layers was also studied. For high molecular weight polystyrene, the glass transition temperature for the sub-surface was lower than that for the bulk and thermal expansion coefficient of the sub-surface layers was found to be larger than the bulk value.