Permeability and solubility of carbon dioxide in different glassy polymer systems with and without plasticization

Abstract

The description of permeability and solubility of CO2 in different complex polymer matrices in the glassy state is analyzed by considering the diffusion coefficient as the product of a kinetic factor, mobility, and a thermodynamic factor associated to the concentration dependence of the chemical potential of the diffusing species, according to what recently presented for different pure polymers [Minelli and Sarti, J. Membr. Sci. 435 (2013) 176–185]. The thermodynamic factor is calculated in a predictive way by using the nonequilibrium lattice fluid model (NELF) or is obtained directly from experimental solubility isotherms, when pure component parameters for the NELF model are not available. The mobility factor is considered to depend exponentially from penetrant concentration, following the usual trend commonly found experimentally, and its expression contains only two adjustable parameters. The permeability model is used to describe steady state permeation of CO2 in a series of complex glassy phases, formed by polysulfone (PSf) and polyphenylene oxide (PPO) with different plasticizers, glassy polymer blends, glassy random copolymers and crosslinked polyimides. The analysis shows that in all the cases examined, the model used is able to describe the experimental trends in a simple and effective way, accounting for all the different behaviors observed, in which permeability is either decreasing or increasing with upstream pressure and even when permeability is non-monotonous and presents a minimum value due to the so-called plasticization effect. A general correlation is also found for both model parameters: the infinite dilution mobility correlates well with the reciprocal fractional free volume, according to the FFV theory, while the plasticization factor is associated to the swelling coefficient of the polymer matrix.