Abstract: | Sorption and diffusion of dichloromethane vapor were measured in atactic polystyrene films, obtained with different cooling conditions and after controlled aging times at different temperatures. The diffusional behavior is characterized by three zones, depending on temperature and penetrant activity. In Zone I, at low activity, the diffusion coefficient is independent of vapor concentration; Zone II is characterized by concentration-dependent diffusion, whereas in Zone III structural transformations are possible. The study of diffusion at three temperatures allowed building of a temperature-penetrant concentration diagram, which is very useful to visualize the different zones of behavior. The aging at room temperature has no effect on the curve of sorption as a function of vapor activity, whereas it determines two effects on the diffusion: a decrease of the zero concentration diffusion coefficient and a more and more anomalous behavior with the aging time. The aging at 70°C produces the same effects on the diffusion behavior as the aging at room temperature; in addition, a decrease sorption is observed at low penetrant activity. The possible presence of ordered domains, impermeable to the vapor, in the samples stored at 70°C, was suggested on the basis of sorption results. |