Site-distribution models, glassy polymer

The following three multicomponent transport models have been used to explain the depression of the permeability of a component in a mixture relative to its pure component value (Fig. 21) the Petropoulos model and the competitive sorption model, both of which assume that direct competition for diflfiisive pathways within the glass is negligible, and a more general permeability model in which direct competition can occur between penetrant molecules for both sorption sites and diffusion pathways. All three of the models presented here are based upon the framework of the dual-mode model. It is worth mentioning that the site-distribution model has recently been extended to accoimt for diffusion (98) and that free volume models exist for transport in glassy polymers (99). 

In glassy polymers tire interactions of tire penetrant molecules witli tire polymer matrix differ from one sorjDtion site to anotlier. A limiting description of tire interaction distribution is known under tire name of tire dual-soriDtion model [, 60]. In tliis model, tire concentration of tire penetrant molecules consists of two parts. One obeys Henry s law and tire otlier a Langmuir isotlienn ... 

In the dual-mode sorption and transport model the pressure-dependence of a (= C/p), P and 0 in gas-glassy polymer systems arises from the pressure-dependent distribution of the sorbed gas molecules between Langmuir sites and Henry s law dissolution. Although k, Dg and are assumed to be constant, the average or effective solubility and diffusion coefficients of the entire ensemble of gas molecules change with pressure as the ratio of Henry s to Langmuir s population, C /C, changes continuously with pressure [eq. (14)]. 

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