Abstract
positron annihilation Lifetime Spectroscopy has been extensively applied in recent years to investigate the free volume in polymers owing to the capability of the electron-positron bound system (positronium) to probe the typical size of sub-nanometric cavities among the macromolecular chains. In this paper we show recent results obtained through this technique in some amorphous polymeric mem-branes(olyurethanes. PUs and polytrimethilsylilpropine PTMSP) after a brief survey of the general features of the annihilation process as well as of the experimental apparatus. Lifetime of o-ps decay({{{{ tau _3}}}}) in PUs increases going from sub {{{{ TAU _g}}}} to over {{{{ TAU _g}}}} temperatures following a sigmoid curve. The coefficient of dilatation of the free volume fraction is shown to be the sum of two contributes due to the variation with T of the number of holes and of their mean volume. PAL spectrum of PTMSP freshly prepared shows four lifetime components: {{{{ tau _3}}}} and {{{{ tau _4}}}}: only are useful for free volume study. Two kinds of holes of different equivalent radius are reported ({{{{ gamma _s}}}} 4.60 nm and {{{{ gamma _1}}}} 0.754) The equivalent volume does not change in a range of 100 K. however the physical aging increases density and decreases oxygen permeability while {{{{ gamma _s}}}} goes down to 0.374 and r1 to 0.735 The number of holes obtained from the intensities{{{{ IOTA _3}}}} and {{{{ IOTA _4}}}} of PAL spectra decreases with aging 21.7% and 3.5% for large and small holes respectively.