Carbon dioxide plasticization and conditioning effects in thick vs. thin glassy polymer films

Recent studies have shown that thin glassy polymer films undergo physical aging more rapidly than thick films. This suggests that thickness may also play a role in the plasticization and conditioning responses of thin glassy films in the presence of highly-sorbing penetrants such as CO2. In this paper, a carefully designed systematic study explores the effect of thickness on the CO2 plasticization and conditioning phenomena in Matrimid®, a polyimide commonly used in commercial gas separation membranes. Thin films are found to be more sensitive than thick films to CO2 exposure, undergoing more extensive and rapid plasticization at any pressure. The response of glassy polymers films to CO2 is not only dependent on thickness, but also on aging time, CO2 pressure, exposure time, and prior history. Finally, thin films experiencing constant CO2 exposure for longer periods of time exhibit an initial large increase in CO2 permeability, which eventually reaches a maximum, followed by a significant decrease in permeability for the duration of the experiment. Thick films, in contrast, do not seem to exhibit this trend for the range of conditions explored.