Free-volume hole model for positronium formation in polymers: surface studies

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Abstract
Positron annihilation lifetime and Doppler broadening of annihilation radiation experiments are performed in a polyurethane film using the mono-energetic slow positron probe as a function of positron energies. Significant variations of positron annihilation signals are observed at a short distance from the surface . The ortho-positronium lifetime in the polymer increases near the surface, while its intensity decreases. The intensity results are consistent with the description of a free-volume hole model for positronium formation proposed by Brandt, Berko and Walker. This study further confirms that positron annihilation spectroscopy is a sensitive probe for the characterization of physical properties of sub-nanometre defects, such as free volumes and holes for polymeric materials.