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  • 1
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Sorption kinetics and equilibria for methanol, ethanol, and n-propanol in 0.544 μm diameter poly(methyl methacrylate) microspheres were determined at 35°C over a wide range of relative pressures. Sorption isotherms were concave to the pressure axis at low relative pressures and convex to the pressure axis at higher relative pressures. These results, considered in the context of recently reported data for high pressure sorption of gases in polymeric glasses, suggest that the S-shaped isotherms reported here are examples of a generalized isotherm which describes sorption behavior of all penetrants in glassy polymers if an appropriate range of concentration is traversed by the experimental protocol. The effects of dialating the microspheres by preswelling with methanol were studied by subsequent low pressure sorption of water, methanol, ethanol, and n-propanol at 35°C. The preswollen microspheres exhibited initially higher sorption capacities than the as-Received samples, but tended to consolidate with time following the preswelling treatment. The aging process, monitored by periodic short-term sorption with the various penetrant probes, was arrested by contacting the microspheres with an activity of n-propanol sufficient to maintain a sorbed concentration of approximately 1 wt %. The aging was significantly retarded by the presence of low concentrations of water and ethanol. Conversely, the aging process appeared to be essentially unaffected by the presence of correspondingly low concentrations of methanol. The complex kinetics describing the sorption of the various penetrants ranged from Fickian diffusion to polymer relaxation-controlled absorption, depending upon penetrant, relative pressure, and prior exposure history. The low temperature preswelling of the microspheres markedly increased the rate of sorption as well as the respective apparent equilibrium sorption.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 20 (1982), S. 259-268 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effects of copolymerizing small amounts of an ionic moiety (0-7 mol %) into the backbone of a polycondensation polymer have been investigated by a combination of linear viscoelastic, steady-shear, and extensional testing. At a constant viscosity in dilute solution, both the zero-shear-rate viscosity and the maximum relaxation time in the melt increase monotonically with an increase in the ionic character. These effects are present after the data are normalized to remove the increase in the glass transition temperature Tg with increased ionic content. Large-strain, steady-shear flow experiments showed that the viscoelastic memory of the melt is affected by ionic content. An increase in ion content causes a decrease in the effect of strain on the memory function. This effect is not apparent in extensional flow experiments, which indicate that the ionic content does not affect the response if the tests are conducted at a constant temperature above Tg.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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