Argon sorption and partial molar volume in poly(ethyl methacrylate) above and below the glass transition temperature

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Abstract
Sorption and dilation isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5–85°C. At temperatures below the glass transition (Tg=61°C), sorption isotherms are well described by the dual‐mode sorption model; and isotherms above Tg follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above Tg (about 40 cm3/mol), whereas the volumes below Tg are smaller and dependent on both temperature and concentration (19–26 cm3/mol). By analyzing the experimental data according to the dual‐mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 Å3, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm3 from the temperature dependence of the dual‐mode parameters.