Influence of diffusivity and sorption on helium and hydrogen separations in hydrocarbon, silicon, and fluorocarbon-based polymers

The permeability-selectivity upper bounds show that perfluoropolymers have uniquely different separation characteristics than hydrocarbon-based polymers. For separating helium from hydrogen, these differences are particularly dramatic. At a given helium permeability, the upper bound defined by perfluoropolymers has helium/hydrogen selectivities that are 2.5 times higher than that of the upper bound defined by hydrocarbon-based polymers. Robeson hypothesized that these differences in transport properties resulted from the unusual sorption relationships of gases in perfluoropolymers compared to hydrocarbon-based polymers, and this paper seeks to test this hypothesis experimentally. To do so, the gas permeability, sorption, and diffusion coefficients were determined at 35 °C for hydrogen and helium in a series of hydrocarbon-, silicon-, and fluorocarbon-based polymers. Highly or completely fluorinated polymers have separation characteristics above the upper-bound for helium/hydrogen separation because they maintain good diffusivity selectivities for helium over hydrogen and they have helium/hydrogen sorption selectivities much closer to unity than those of hydrocarbon-based samples. The silicon-based polymer had intermediate sorption selectivities between those of hydrocarbon-based polymers and perfluoropolymers. Comparisons of hydrogen and helium sorption data in the literature more broadly extend the conclusion that helium/hydrogen sorption selectivity is rather different in hydrocarbon and fluorocarbon-based media.