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  • 1
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Forced Rayleigh scattering, a relatively recently developed optical technique, is used to measure tracer diffusion coefficients in polymer-solvent mixtures near the system glass transition temperature, Tg. The technique has a wider range of potential application than has yet been realized, and so is presented in some detail. The objectives were to obtain data necessary to scrutinize free volume theory, and to understand so-called anomalous, non-Fickian diffusion effects observed by others in polymer-solvent mixtures near Tg. Data on dye tracer diffusion coefficients in the systems polyvinyl acetate-toluene, polystyrene-toluene, and polystyrene-tri-m-tolyl phosphate were obtained over a polymer concentration range from infinite dilution to 96 wt. %. Small molecule diffusion coefficients are seen to vary by as much as nine orders of magnitude (10-14 to 10-5 cm2/s) over this concentration range. The data are in reasonable accord with expectations based on the Duda-Vrentas version of free-volume theory.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 2607-2627 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The technique of forced Rayleigh scattering has been used to examine the tracer diffusion of probe photochromic dyes, azobenzene and methyl red, in poly (vinyl acetate)/ toluene solutions, as a function of polymer concentration (0-96% by weight) and temperature (5-45°C). It is demonstrated that the dye diffusivity can be quantitatively scaled to the solvent diffusivity, thus permitting direct application of predictions for two-component systems. The results have been interpreted using the free volume theories of Fujita and Vrentas and Duda. While both approaches are able to describe the concentration dependence extremely well, the Vrentas-Duda expression has the virtue of being employed without any freely adjustable parameters. However, neither theory is particularly successful in predicting the observed temperature dependence.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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