The temperature dependence of the gas permeation properties of poly (1-trimethylsilyl-1-propyne) [PMSP] /poly (1-phenyl-1-propyne) [PPP] blends and poly (TMSP-
co-PP) films was studied. As PP content increases, the activation energies of permeation (E
p) and diffusion (E
D) for various gases in these materials increase, but no distinct change in the heat of solution (ΔH
s) is observed. The increase in E
p is due to an increase in E
D. All E
D values are positive, while all ΔH
s values are negative. In pure PMSP, E
p is negative for most gases because |E
D| is much smaller than |ΔH
s|. When the PP content exceeds 40 vol% in poly (TMSP-
co-PP), however, Ep
becomes positive because |E
D| is now larger than |ΔH
s|. Furthermore, E
p decreases with increasing critical temperature (T
c) of the penetrants because ΔH
s decreases more than E
D increases. After storage in air, the gas permeabilities of thin PMSP/PPP (9 : 1) blend films are found to be much lower than those of thin poly (TMSP-
co-PP) (9 : 1) films. However, no substantial difference between the activation energies of permeation in these aged blend and copolymer films is observed. The gas permeabilities of thin poly (TMSP-
co-PP) films are reduced even further after thermal treatment.This permeability reduction is a consequence of a larger E
p in the heat-treated, copolymer films. E
p is higher because of an increase in E
D due to densification of these films by thermal treatment.
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