Coarse-grained molecular dynamics simulation of activated penetrant transport in glassy polymers.

Membrane separations of gas mixtures strive to maximize the permeability of a desired species while keeping out undesired ones. Permeability vs. selectivity data from many polymer membranes for a given gas pair with diameters dA and dB are typically collected in a "Robeson plot"', and are bound from above by a line with a slope λ = (dB/dA)2 - 1. A microscopic understanding of this relationship, especially λ, is still missing. We perform molecular dynamics simulations of penetrant diffusion using three different coarse-grained polymer models over a wide range of penetrant sizes, temperatures, and monomer densities. The empirically relevant λ = (dB/dA)2 - 1 is only found for polymers that are either supercooled liquids with caged segmental dynamics or glasses and when the penetrant size is approximately half the Kuhn length of the chains, for which the penetrant diffusion is an activated process.