Molecular dynamics simulation of diffusion and permeation of gases in polystyrene

Molecular dynamics simulations are performed to study the diffusion and permeation of gases, including argon, nitrogen, methane, carbon dioxide, and propane, in polystyrene over a wide range of temperatures. A jumping mechanism is observed for the diffusion of diffusants in polymer. The calculated diffusion coefficients agree well with the experimental data and with the results of former simulation studies. The relation between the diffusion coefficient and the molecular diameter is confirmed by the results. Our calculated results on the temperature-dependence of diffusion coefficients show that for some gases a break is seen, at the glass transition temperature, in the Arrhenius plot of ln (D) versus 1/T, while for some other light gases, argon and nitrogen, the plot is linear over the whole temperature range. We have also calculated the permeability coefficients, using the diffusion coefficients calculated in this work and our recently published solubility coefficients [Eslami and Müller-Plathe, Macromolecules 2007; 40:6413]. Our results show that the calculated permeability coefficients are higher than the experimental data by almost the same trend observed in the solubility calculations, but the ratios of calculated permeabilities are in a very good agreement with experiment.