Estimation of free volumes of polystyrene by positron annihilation life-time technique

Differences of size, content, and size distribution of free volumes in linear and three-armed polystyrenes, synthesized by radical, and anionic processes, were observed by positron annihilation lifetime measurements. For the polystyrene samples of different architectures and molecular weight distributions, the temperature dependence of an average free volume radius was quite similar to each other. The radius increased with increasing temperature (T), from 0.27 nm (60 K) to 0.30 nm (glass transition temperature: T-g=363 K), then to 0.35 nm (423 K), showing alpha beta transition temperature about 300 K. With increasing T, the free volume content decreased from 35% (60 K) to 25% (260 K) for radically polymerized linear polystyrene and to 22% (320 K) for anionically polymerized three-armed polystyrene, and then turned to increase to 35% at 350 K and 400 K, respectively. In contrast, the content for anionically polymerized linear polystyrene decreased from 45% (60 K) to 33% (300 K) and turned to increase to 35% at 350 similar to 400 K. The free volume content decreased reciprocally with an increase in the molecular weight at 333 K, suggesting differences in molecular motion between the edge and middle portions of the chain molecule.