Gas separation properties of PIM-1 films treated by elemental fluorine in liquid perfluorodecalin

Abstract

Gas transport properties of PIM-1 films treated by elemental fluorine in a liquid perfluorodecalin were investigated. The investigation included an estimation of fluorine content in a fluorinated layer, pure and mixed gas permeability, diffusion and solubility coefficients measurement, ideal selectivity assessment and analysis of fluorination time effect on gas transport properties. An increase of treatment duration resulted in an increase of concentration of fluorine in the fluorinated layer as well as a depth of fluorination. The depths of fluorination linearly increased with square of fluorination time indicating a diffusion of fluorine in the fluorinated layer to be a restrictive stage of kinetics of fluorination. The effect of the drop in gas permeability was demonstrated to be dependent on the kinetic size of the penetrant. The comparison of liquid-phase and gas-phase regimes was performed, and it was shown that sharp decrease in gas permeability is observed for gas-phase regime at short times of fluorination already, whereas this decrease is more gradual for liquid-phase fluorination. According to a Barrie method, the gas transport parameters of the fluorinated layer of the modified PIM-1 films were calculated, which turned out to be much lower than those for the virgin PIM-1 polymer and slightly lower than the gas transport parameters for dry Nafion. The reduction of the gas permeability coefficients is mostly induced by a sharp decrease in the gas diffusion coefficients. According to combination of permeability and selectivity, the fluorinated PIM-1 samples show excellent results exceeding the 2008 Robeson upper bounds for H2/CH4, H2/CO2, H2/N2, He/CH4 and others gas pairs. Mixed gas experiments were also conducted for hydrogen-containing mixtures and fluorinated PIM-1 samples have demonstrated good separation characteristics for the model binary mixtures attaining separation factors as high as 115–143 (H2/CH4), 4.4–6.7 (H2/CO2) and 49–146 (He/CH4), which makes these materials promising for helium recovery from natural gas and hydrogen recovery from various catalytic and biohydrogen production mixtures. Ten-months aging of the PIM-1 sample fluorinated during 30 min showed a decline of permeability by 25 and 40%, respectively and a slight decrease of ideal selectivity.