Swelling and sorption in polymer–CO2 mixtures at elevated pressures



Experimental data on gas sorption and polymer swelling in glassy polymer—gas systems at elevated pressures are presented for CO2 with polycarbonate, poly(methyl methacrylate), and polystyrene over a range of temperatures from 33 to 65°C and pressures up to 100 atm. The swelling and sorption behavior were found to depend on the occurrence of a glass transition for the polymer induced by the sorption of CO2. Two distinct types of swelling and sorption isotherms were measured. One isotherm is characterized by swelling and sorption that reach limiting values at elevated pressures. The other isotherm is characterized by swelling and sorption that continue to increase with pressure and a pressure effect on swelling that is somewhat greater than the effect of pressure on sorption. Glass transition pressures estimated from the experimental results for polystyrene with CO2 are used to obtain the relationship between CO2 solubility and the glass transition temperature for the polymer. This relationship is in very good agreement with a theoretical corresponding-states correlation for glass transition temperatures of polystyrene-liquid diluent mixtures.