AbstractPositron Annihilation Lifetime Spectroscopy (PALS) measurements were conducted on polycarbonate subjected to either thermal expansion or to tensile and compressive strains. It was found that thermal expansion affected both the nanometer hole size and the hole number density, whereas mechanical stress affected mainly the size of existing holes, and did not generate or eliminate holes in the quasielastic deformation region. The effect of stress on yield and postyield behavior of this glassy material was also investigated. The deduced hole volume fraction of this polymer at 25°C was 6.8 ± 0.5% from the thermal expansion experiment and 7.2 ± 1.2% from the mechanical loading experiment. When the specimen was under compression, the hole volume fraction was found to continuously decrease. This can be considered as evidence of the inability of the free volume concept in explaining the yield behavior of glassy polymers. ©1995 John Wiley&Sons,