Effects of physical aging on solubility,diffusivity, and permeability of propane and n-butane in poly(4-methyl-2-pentyne)

The effects of physical aging on the solubility, diffusivity, and permeability of propane and n-butane in a hydrocarbon-based disubstituted polyacetylene, poly(4-methyl-2-pentyne) (PMP), were studied. As the relative pressure of propane and n-butane increased, the solubility of both hydrocarbons increased. Like other glassy polymers, the sorption isotherms for propane and n-butane in all PMP films were concave to the relative pressure axis, indicating dual-mode sorption behavior. The diffusion of propane and n-butane in PMP followed typical Fickian diffusion in a plane sheet. The propane diffusivity in both the unaged and aged films increased with increasing concentration of propane sorbed in the film. The n-butane diffusivity in aged films also increased with increasing n-butane concentration. However, unaged films showed the opposite behavior: the diffusivity decreased with increasing n-butane concentration. These diffusion phenomena are a consequence of the interplay between thermodynamic and mobility factors. The permeabilities of propane and n-butane decreased monotonically with increasing penetrant concentration, similar to the behavior observed in other common glassy polymers. The relaxation of the nonequilibrium excess free volume in PMP films induced the decrease in both solubility and diffusivity. As a result, the permeability of propane and n-butane in PMP decreased upon physical aging. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2407–2418, 2004