Positron lifetime spectroscopy has been applied to estimate the free volume hole size distribution in polycarbonate (PC) and in polystyrene (PS) at room temperature. The hole radius density distributions are determined from the ortho-positronium lifetime distributions obtained via a Laplace inversion of the measured positron lifetime spectra. The hole volume density distributions and the number density distributions of holes are estimated from the hole radius density distributions. All of the distributions may be well approximated by single Gaussians. The hole radius and the hole number density distributions have centres (q) and (qn) at 0.29 nm and 0.1 nm3 in PC, and 0.28 nm and 0.09 nm3 in PS. The FWHM of the corresponding distributions are 0.042 nm and 0.040 nm3 (PC), and 0.039 nm and 0.34 nm3 (PS), respectively. Both, the shape and the width of the distributions correlate well with the free volume theory of Bueche. The possible influence of different effects, such as a nonspherical shape of holes and a scanning of several holes by positronium before annihilation, on the mean hole size and the hole size distribution as detected by the positron lifetime method is finally discussed.

We summarize the results of a recent positron annihilation study of the phase behaviour of CO 2 confined in Vycor glass. Particular emphasis is placed on the phase diagram of the confined fluid and on the usefulness of the positron annihilation technique in determining the mechanisms underlying phase transitions of fluids in porous solids.

The structure of solid confined in porous Vycor glass has been studied as a function of temperature via x-ray diffraction. The confined solid has the same structure as the bulk solid but with a slightly larger lattice constant of 5.644 Å at 150 K compared to the bulk lattice constant of 5.624 Å at the same temperature. Broad diffraction peaks are observed indicating that the solid phase of the in the pores forms in small crystallites approximately 160 Å in diameter. This is comparable to the pore dimensions in the Vycor indicating that solidification occurs separately in each of the pores. A large temperature-independent static disorder, analogous to the Debye - Waller factor, was observed in the form of strong damping of the Bragg peaks with increasing Q.

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