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Both the Xe sorption isotherms and 129Xe NMR spectra of poly(2,6-dimethyl-1,4-phenylene oxide), PPO, were obtained across a temperature range of –55 °C to +80 °C to investigate the temperature dependence of the gas sorption and the unrelaxed volume of PPO. All of the obtained sorption isotherms were analyzed based on the dual-mode sorption model, and the Langmuir saturation constant, CH′, which corresponds to the unrelaxed volume, was determined by curve fitting. The values of CH′ increased linearly with decreasing temperature, and the obtained temperature was almost identical to the glass transition temperature, Tg, of PPO when the CH′ value was extrapolated to 0. The 129Xe NMR chemical shift of 129Xe in the PPO showed a nonlinear, low-field shift with increasing Xe pressure at temperatures below the Tg. The mean volumes of individual microvoids were determined at each temperature based on the 129Xe NMR chemical shift analysis, assuming a fast exchange of the Xe atoms between the Henry and Langmuir sorption sites. The temperature dependence of the individual microvoid volumes was similar to that of CH′.

Temperature dependence of the mean size of polyphenyleneoxide microvoids, as studied by Xe sorption and 129Xe NMR chemical shift analyses