Abstract
The sub-nano-sized microcavities in microporous thermally rearranged (TR) polymers can be tuned by varying the conditions of thermal rearrangement. Relatively small cavities were formed by thermal rearrangement of poly(o-hydroxylamide) (PHA) precursors compared to the cavities formed by that of polyimide precursors. TR polymers derived from PHAs, so-called TR-β-polymers, are known to exhibit a well-tuned cavity structure that can be used for H2/CO2 separation. According to a solution-diffusion model, both the permeability and selectivity for H2/CO2 separation were improved at elevated temperatures due to a significant increase in H2 diffusion and a decrease in CO2 sorption. In this study, gas solubility and permeability of five representative small gas molecules (H2, N2, O2, CH4, and CO2) through TR-β-polymer membranes were characterized between 20°C and 65°C for gas solubility measurement and between 35°C and 300°C for gas permeability measurement. These measurements allowed for the calculation of thermodynamic factors such as the activation energy and heat of sorption.
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