Polymer, Vol.40, No.11, 3033-3040, 1999
Temperature and time dependence of orthopositronium formation in polystyrene
Three measurement protocols were performed to investigate the temperature dependence of positron lifetime spectra for polystyrene over the temperature range -70 to 180 degrees C. The polystyrene samples were first subjected to a heating schedule in sequential 10 degrees C increments. This was followed by a cooling schedule, again in 10 degrees C increments. The third schedule involved rejuvenation of the specimen above T-g between each measurement. The measured lifetime spectra were resolved into three components. We observed a minimum in the temperature dependence of the o-Ps intensity I-3 at similar to 20 degrees C for polystyrene specimens subjected to the heating and cooling schedules, but not for the rejuvenated samples. The influence of the duration of e(+)-irradiation on the lifetime and intensity of o-Ps annihilation was investigated under isothermal conditions. A decrease in o-Ps intensity I-3 with duration of exposure to e(+)-irradiation was found whose rate was maximal at 23 degrees C. The results suggest that the time dependence of the o-Ps intensity in the glass can be interpreted within the framework of the spur-model. Specifically, the variation of I-3 is ascribed to the formation at low temperature of free radicals with small electron affinities. After correcting for the e(+)-irradiation effect, no significant aging effect in the glassy state was detected in the o-Ps intensity and lifetime.
Keywords:POSITRON-ANNIHILATION;FREE-VOLUME;BRANCHED POLYETHYLENE;LIFETIME SPECTROSCOPY;POLYCARBONATE;RELAXATION;PROBE