Free-volume hole properties near the surface of polymers obtained from slow positron annihilation spectroscopy

We have measured the positron annihilation lifetime spectra in an epoxy polymer using the electrotechnical laboratory (ETL) slow-positron facility as a function of positron energy from 0.2 to 3.0 keV. The ortho-positronium lifetime from the bulk increases near the surface while the intensity decreases. The results are interpreted in terms of a Ps free-volume model. A larger hole size and fraction near the polymeric surface are observed. A reduction of glass transition temperature near the surface is estimated from the WLF theory.