Permeability and diffusivity of CO2 in glassy polymers with and without plasticization

The description of permeability and diffusivity in glassy polymers has been revisited 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. The latter term does not contain any adjustable parameter since it is obtained directly from solubility isotherm data or can be even calculated in a predictive way by using well established predictive procedures as the Non Equilibrium Thermodynamics for Glassy Polymers (NET-GP) models. The mobility factor considered is endowed with an exponential dependence on penetrant concentration, following the usual trend commonly found experimentally, thus containing only two adjustable parameters. The resulting expressions for diffusivity and for permeability describe rather carefully the pressure dependence observed in glassy polymers, both in steady state permeation and in transient mass uptake, in all the cases inspected, even in the presence of the so called plasticization effects.