Transport properties of dichloromethane in glassy polymers. II. Amorphous syndiotactic polystyrene films

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Abstract
Sorption and diffusion of dichloromethane vapor were measured in amorphous syndiotactic polystyrene films, obtained with different cooling conditions and after controlled aging times at different temperatures. The diffusional behavior, at the temperature of 25°C, was characterized by three stages, depending on penetrant activity. In the first stage, at low activity, the diffusion coefficient was independent of vapor concentration; the second stage was characterized by concentration‐dependent diffusion, whereas in the third stage, at high activity, the strong interaction solvent–polymer increased the mobility, allowing the polymer crystallization. The different cooling conditions neither have an effect on the diffusional behavior nor on the sorption curve. The aging, both at room temperature and at 70°C, did not change the diffusion parameters, but led to the appearance of more and more anomalous sorption behavior. The sorption curve, as a function of vapor activity, did not show any difference for the fresh and the aged‐at‐room temperature samples, whereas the samples aged at 70°C presented a lower sorption at low activity. The presence of ordered domains, impermeable to the penetrant at low activity, was suggested on the basis of sorption results. The solvent‐induced crystallization was investigated for all the samples. Crystallization was induced at an activity of 0.45 for the fresh and the aged‐at‐room temperature samples; at variance, the samples aged at 70°C crystallize at a slightly higher activity, reaching, nevertheless, a higher level of crystallinity. © 1993 John Wiley & Sons, Inc.

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