Nonequilibrium lattice fluids: A predictive model for the solubility in glassy polymers

The calculation of sorption isotherms for gases and vapors in glassy polymers is approached through a nonequilibrium equation of state procedure. The basic peculiar feature of the system, represented by the nonequilibrium structure of the mixture, is accounted for by introducing an order parameter for an isotropic glass. By revisiting the lattice fluid model by Sanchez and Lacombe (Macromolecules 1978, 11, 1145.), an expression for the Gibbs free energy of nonequilibrium lattice Quids is obtained in which the polymer species density in the solid mixture is considered as an order parameter and it is thermodynamically treated as an internal state variable. The absence of adjustable parameters makes the resulting model entirely predictive for the solubility, once the pseudoequilibrium volumetric data are available. The comparison of the predicted isotherms with the data for CO2-poly(carbonate) systems at 35 degrees C, obtained by Fleming and Koros (Macromolecules 1990, 23, 1353.) under different polymer prehistories, points out the remarkably good ability of the model to represent the sorption/desorption behavior and hysteresis experimentally observed.