Membrane plasticization is the process whereby penetrant dissolution causes membrane swelling or dilation, which in turn, can increase membrane diffusivity and solubility and lead to long time frame polymer relaxation processes. In this work, the effect of temperature upon the plasticization of a rigid polyimide, poly(4,4'-hexafluoroisopropylidene diphthalic anhydride-2,3,5,6-tetramethyl-1,4-phenylenediamine) (6FDA-TMPDA), by carbon dioxide is investigated. It is found that across the full range of temperatures studied, plasticization has little effect on carbon dioxide solubility as all results can be characterized by a standard dual mode sorption model. However, the effect upon diffusivity is significant and this can be described by both an exponential relationship with penetrant concentration and an Arrhenius relationship with temperature. The polymer relaxation processes induced by plasticization are also temperature dependent. However, the total proportion of penetrant sorption associated with such relaxation processes is relatively unaffected by temperature. This paper shows that plasticization effects are dominated by Henry's law dissolution. Conversely, while Henry's Law species contribute most to diffusion at high temperatures, at lower temperatures the movement of Langmuir component species also contributes to the total diffusion coefficient.

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A study has been conducted to clarify the relationship between polymer structure, annealing temperature, and the extent of plasticization by high‐pressure CO2 for two typical polyimide membranes; BTDA‐DAPI (poly(3,3′‐4,4′‐benzophenone tetracarboxylic–dianhydride diaminophenylindane) and 6FDA‐TMPDA (poly(2,2′‐bis(3,4′‐dicasrboxyphenyl) hexafluoropropane dianhydride–2,3,5,6‐tetramethyl‐1,4‐phenylenediamine). Both membrane materials are exposed to varying levels of thermal annealing at 200 and 250 °C. The effect of this heat treatment on free volume is examined using positron annihilation lifetime spectroscopy (PALS), whereas fluorescence spectroscopy is used to monitor changes in electronic structure. Results show that thermal annealing causes a reduction in both the size and number of free volume elements. A strong relationship is found between the fluorescence peak intensity for 6FDA‐TMPDA and both the membrane gas permeability and plasticization pressure. This correlation is most likely the result of the formation of charge transfer complexes, particularly at 250 °C. However, the formation of covalent crosslinks at these temperatures cannot be discounted. No fluorescence is observed for BTDI‐DAPI. Although thermal annealing has a significant effect on the extent of plasticization in both polymers, it is found that the rate of plasticization is unaffected by the annealing temperature. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1879–1890, 2008