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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: An improved cell which permits the measurement of permeabilities of membranes to gases over a wide range of temperatures and gas pressures is described. The measurements are made by the variable volume method, under constant pressure differential across the membrane. The cell lends itself particularly well to routine tests, because it does not require calibration or the use of vacuum techniques. The performance of the cell is discussed, and typical experimental results are presented. A modified permeability cell of the same type for high-pressure studies is also described. Measurements with this apparatus show that the rate of gas permeation obeys, in some cases, a single from of Fick's law, even under pressure differentials across the membrane as high as 800 psi (54 atm.). The paper also compares permeability data obtained by the variable volume and the variable pressure methods. The permeability of 0.002 in.-thick Alathon 15 polyethylene to oxygen and nitrogen was determined between 0 and 50°C. by the two methods, using the same sample of membrane in situ, and the measurements were found to agree within experimental error. Permeabilites of 0.010 in.-thick samples of Alathon 15 polyethylene to nitrogen, oxygen, helium, and carbon dioxide obtained in the same temperature range by the variable volume method were 15-30% higher than the corresponding data determined by the variable pressure method. This discrepancy could be due to the fact that the variable pressure measurements with the thicker membrances may not have been made under true steady-state conditions, although permeabilities were determined from apparently linear sections of permeated gas pressure vs. time curves. A critical re-examination of the methods used to determine permeability constants is suggested.
    Additional Material: 13 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 341-347 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility of CO2 and CH4 in five polyimides was measured at 35.0°C and at pressures up to 10 atm (147 psia). The concentration of the penetrant gases dissolved in the polymers can be represented satisfactorily as a function of penetrant pressure by the “dual-mode sorption” model. The solubility coefficients for CO2 and CH4, S(CO2) and S(CH4), increase in the polyimide order: \documentclass{article}\pagestyle{empty}\begin{document}$ {\rm PMDA - }4,4'{\rm - }m{\rm - APPS} 〈 6{\rm FDA - }4,4'{\rm - }m{\rm - APPS} 〈 6{\rm FDA - }4,4'{\rm - }p{\rm - APPP} 〈 6{\rm FDA - CDA} 〈 6{\rm FDA - 4,4' - }p{\rm - APPS} $\end{document} The magnitude of the solubility coefficients appears to depend primarily on the intermolecular forces between the penetrant gases and the polymers. The values of these coefficients are greater for the polyimides with larger mean interchain spacings, but no one-to-one correspondence appears to exist in this respect. The lower solubility of CO2 in PMDA-4,4'-m-APPS compared with that in the 6FDA polyimides may be due to the lower “excess” free volume of the former polymer. The ratio S (CO2)/S (CH4) varies relatively little for a variety of PMDA and 6FDA polyimides.
    Additional Material: 7 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1185-1185 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 38 (1989), S. 2131-2147 
    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: Permeability coefficients, P̄, for NH3 AND H2S in 11 different types of silicone membranes were measured in the temperature range from 10.0 to 55.0°C and at pressures up to 115 psig (∼ 7.8 atm). The values of P̄ for NH3 and H2S in different silicone polymers decrease considerably as the bulkiness of the functional groups in the side and backbone chains of these polymers increases. the substitution of Si—O bonds with stifer Si—C bonds in the backbone chains also results in a considerable decrease in gas permeability. the values of P̄ for NH3 and H2S increse exponentially with incresing δp, the pressure difference across the membrancs. The temperature dependence of NH3 and H2S varies greatly: P̄ can increase, decrease, or pass through a minimum with increasing temperature, depending on the nature of the silicone polymer. The temperature dependence of P̄ is also affected in some cases by Δp. The permeability behavior of silicone polymers to NH3 and H2S is compared with that to other penetrant gases, and the factors which might affect this behavior are discussed.
    Additional Material: 11 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 42 (1991), S. 2397-2403 
    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: Permeability coefficients, P̄, for H2 in 10 different types of silicone polymer membranes were measured in the temperature range of 10.0-55.0°C and at pressures up to 100 psig (∼6.8 atm). The values of P̄ decrease slightly with increasing Δp, the pressure difference across the membranes. The permeability of silicone polymers to H2 increases with an increase in temperature; the values of the energy of activation for permeation are in the range of 1.4-4.3 kcal/mol. The substitution of different functional groups in the backbone and side chains of silicone polymers has similar effects on the permeability of the polymers to H2 as observed in earlier studies with other light gases. P̄ for H2 decreases with an increase in the bulkiness of the substituted functional groups. The substitution of Si—O bonds with stiffer Si—C bonds in the backbone chains also results in a considerable decrease in permeability.
    Additional Material: 5 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 11 (1973), S. 663-681 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Permeability, solubility, and diffusion coefficients have been determined for halothane (CF3CHClBr) and methoxyflurane (CHCl2CF2OCH3) in silicone rubber at temperatures from 17 to 60°C and at relative pressures from 0.05 to 0.96. The solubility of both penetrants in silicone rubber is a strong function of penetrant concentration (or relative pressure), and can be represented satisfactorily by the Flory-Huggins relation with single values of the interaction parameter χ. The solubility coefficients decrease with increasing temperature at constant pressure. Mutual diffusion coefficients exhibit maxima when plotted against penetrant concentration; these maxima are attributed to the mass flow of polymer together with dissolved penetrant. Intrinsic diffusion coefficients increase linearly with increasing concentration. The energies of activation for diffusion are low, probably because of the ease of segmental motion about the Si—O linkage. The diffusivity data are examined in terms of Fujita's “free volume” model and of transition-state theory. Permeability coefficients for the two penetrants are large, of the order of 10-6-10-5 cm3(STP)-cm/(sec-cm2-cm Hg), and increase markedly with increasing concentration or decreasing temperature. This behavior is regarded as a consequence of the low energies of activation for diffusion.
    Additional Material: 10 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 441-465 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Diffusion and solubility coefficients have been determined for the CO2-, CH4-, C2H4-, and C3H8-polyethylene systems at temperatures of 5, 20, and 35°C and at gas pressures up to 40 atm. Diffusion coefficients were obtained from rates of gas absorption in polyethylene rods under isothermal-isobaric conditions by means of a new diffusivity apparatus. The concentration dependence of the diffusion coefficients was represented satisfactorily by Fujita's free-volume model, modified for semicrystalline polymers, while the solubility of all the penetrants in polyethylene was within the limit of Henry's law. Semiempirical correlations were found for the free-volume parameters in terms of physicochemical properties of the penetrant gases and the penetrant-polymer systems. These correlations, if confirmed, should permit the prediction of diffusion and permeability coefficients of other gases and of gas mixtures in polyethylene as functions of pressure and temperature.
    Additional Material: 12 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 467-481 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Permeability coefficients have been measured for CO2, CH4, C2H4, and C3H8 in polyethylene membranes at temperatures of 5, 20, and 35°C and at applied gas pressures of up to 30 atm. The temperature and pressure dependence of the permeability coefficients was represented satisfactorily by an extension of Fujita's free-volume model of diffusion of small molecules in polymers. The results of the present steady-state permeability measurements provide further support for the conclusion reached from previous unsteady-state diffusivity measurements that Fujita's model is applicable to the transport of small molecules, such as CO2, CH4, C2H4, and C3H8, in polyethylene. It was previously thought that this model is applicable only to the transport of larger molecules, such as of organic vapors, in polymers.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 16 (1978), S. 735-751 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The solubility of carbon dioxide in symmetric (dense) cellulose 2.4-acetate has been measured at temperatures from 0 to 70°C and pressures up to 45 atm. The polymer samples were prepared by slowly drying asymmetric reverse osmosis membranes. The solubility isotherms can be described satisfactorily up to 60°C by the “dual-sorption” model for glassy polymers. The model cannot represent the experimental data above 60°C, possibly because of a second-order transition in the polymer between 60 and 70°C. An analysis of the dual-sorption parameters and of the heats of solution and “hole filling” suggests that the polymer samples contained a relatively large volume of microcavities. Gas solution appears to occur predominantly in microcavities, a large fraction of the penetrant moleculers being immobilized or partially immobilized. The solubilities obtained in this work are compared with similar data computed from time-lag measurements of other investigators, and the validity of the dual-sorption model is examined for the present case.
    Additional Material: 6 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Physics Edition 21 (1983), S. 1275-1298 
    ISSN: 0098-1273
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Steady-state permeability coefficients have been measured for equimolar mixtures of CO2-C2H4, CO2-C3H8, and C2H4-C3H8, as well as for a mixture of 74.9 mol % CO2 and 25.1 mol % C2H4 in polyethylene membranes. The measurements were made at 20, 35, and 50°C and at pressures of up to 28 atm. Each component of the permeating mixtures studied had the effect of increasing the permeability coefficient for the other component. Furthermore, at equal partial pressures and at the same temperature, the component exhibiting the highest solubility in the polymer had the largest effect in increasing the permeability coefficient of the other component. This behavior is in agreement with the predictions of a free-volume model for the permeation of gas mixtures proposed by Fang, Stern, and Frisch. From a quantitative viewpoint, the permeability coefficients for the components of the mixtures agreed, on the average, to better than 25% with the predicted values. The theoretical permeability coefficients can be estimated from the model by using parameters determined with the pure components only.
    Additional Material: 14 Ill.
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