Gas permeation in thin films of “high free-volume” glassy perfluoropolymers: Part I. Physical aging

Physical aging of both thick and thin films of “high free-volume” glassy perfluoropolymers was studied by monitoring changes in pure gas permeability of O2, N2 and CH4. All permeability measurements were done at a fixed temperature of 35 °C for more than 1000 h of aging. Two grades of perfluoropolymers, Teflon AF and Hyflon AD, having different comonomer structures but with similar comonomer ratios were studied to understand the effect of comonomer type and content on the aging behavior. The effect of casting process (solution vs. spin coating) and solvent type (vapor pressure and boiling point) had a significant effect on the absolute permeability of both thick and thin films; however, the aging rates were more affected by thickness and solvent type rather than the casting process for similar thicknesses. After 1000 h of aging, the relative permeability for thin films of Teflon AF 2400 was decreased by 27% compared to only 10% for thick films prepared from Novec 7500 solvent. Teflon AF, which has a higher fractional free volume (FFV) than Hyflon AD, is believed to undergo significant aging well before the initial permeability measurement could be made (after ∼ 1 h of aging) and, therefore, Teflon AF materials showed a lower decrease in relative permeability compared to Hyflon AD for the same aging time. The comonomer type and content has a significant effect on the permeability; the initial absolute oxygen permeability for AF 2400 was an order of magnitude higher compared to AD 60. The physical aging of thin films of the various glassy perfluoropolymers was also tracked by recording changes in the refractive index and thickness with time by ellipsometry. The ellipsometry data also confirmed higher aging rates in Hyflon AD compared to Teflon AF materials. The volumetric aging rate, obtained from the change in the refractive index using the Lorentz–Lorenz equation, and the permeability reduction rate from the (P1000h/P1h) ratio showed an excellent linear correlation. The (P1000h/P1h) ratio also showed a stronger correlation with (Tg−35) °C than with FFV.