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  • 11
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 61 (1996), S. 945-950 
    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: The effect of pressure on gas permeability of a rubbery polymer, 1,2-polybutadiene, is investigated for 15 gases with various molecular sizes and solubilities in the ranges of pressure up to 110 atm at 25°C. The permeability for slightly soluble gases (He, Ne, H2, N2, O2, and Ar) decreases with increasing pressure, and that for soluble gases (CH4, Kr, CO2, N2O, C2H4, Xe, C2H6, C3H6, and C3H8) increases with increasing pressure. Logarithms of permeability coefficient versus feed-gas pressure for the slightly soluble gases, CH4 and Kr, is linear within each pressure range, whereas such plots become convex toward the pressure axis for more soluble gases, such as CO2, N2O, C2H4, Xe, C2H6, C3H6, and C3H8. By analyzing the pressure dependence of permeability using sorption data of the gases, contributions of concentration and hydrostatic pressure to the gas diffusivity are estimated. © 1996 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
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  • 12
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 30 (1985), S. 401-410 
    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: The transport parameters of nine gases (O2, N2, CO2, He, Ne, Ar, Kr, Xe) through poly(vinyl benzoate) (PVB) have been measured by the time lag method above and below the glass transition temperature, Tg The results are compared with the related data of poly(vinyl acetate) (PVAc) by Meares and discussed as the effect of replacement of the methyl group by a phenyl group in the side chain of PVAc. Small molecules, such as H2, He, and Ne, diffuse more easily through PVAc than PVB, but the tendency is reversed for the larger gases. The activation energy for diffusion is proportional to the squares of the Lennard-Jones diameters of the gases below the Tg. On the other hand, above the Tg, linear relation is obtained to the cubes of the diameters. Solubility behavior is discussed by comparing the heats of solution for PVB and PVAc.
    Additional Material: 9 Ill.
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  • 13
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 34 (1987), S. 1657-1665 
    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: A gravimetric method was applied to determine the solubility of CO2 in poly(vinyl cyclohexanecarboxylate) below 1 atm. The temperatures were varied from 5 to 85°C, above and below the glass transition temperature. The sorption isotherms were concave to the pressure axis below Tg and they were tentatively analyzed by the dual-mode sorption model. Above Tg, the isotherms were linear and described by the Henry's law. Below 75°C, the diffusion coefficients of CO2 were also obtained from the half-time of the sorption process.
    Additional Material: 6 Ill.
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  • 14
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 1955-1964 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Plasticization of poly(ethyl methacrylate) (PEMA) by CO2 is investigated by dielectric relaxation spectroscopy. The dissipation factor of a dielectric cell containing the film and air gaps is measured as a function of frequency (1-10,000 kHz) and CO2 pressure (0-60 atm) over the temperature range 35-115°C. A maximum in the frequency dependence of the dissipation factor, which is attributed to the α relaxation of PEMA, shifts to higher frequency with increasing temperature, pressure, or concentration. The apparent activation energy of the isosteric relaxation decreases from 28 to 23 kcal/mol as the concentration is increased from 0 to 90 cm3 (STP)/cm3 (polym). The relaxation peak temperature at fixed frequency decreases with increasing concentration. The effect of hydrostatic pressure on the dielectric relaxation is estimated and compared with values for the PEMA-He and PEMA-Ar systems. The plasticizing effect of sorbed CO2 is discussed on the basis of the relaxation data.
    Additional Material: 9 Ill.
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  • 15
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 695-703 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Gas permeation measurements were performed by the time-lag method for 13 gases in poly [bis(trifluoroethoxy) phosphazene] above the mesophase transition, T (1) transition, of the crystals. Hysteresis was found in the temperature dependence of the permeability coefficients for CO2, O2, and N2 in the transition region as observed by dilatometry and differential scanning calorimetry. Independently the solubility of CO2 was determined gravimetrically above and below T(1). Noticeable change and hysteresis were also observed in the temperature dependence of the solubility coefficients. Diffusion of CO2 in the measophase is suggested from the permeation and sorption measurements. Gas transport parameters of CO2 in the mesophase are estimated, and the contributions of the mesophase and the crystalline phase to gas transport are considered.
    Additional Material: 7 Ill.
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  • 16
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 30 (1992), S. 1177-1181 
    ISSN: 0887-6266
    Keywords: plasticization of poly(ethyl methacrylate) by dissolved argon ; poly(ethyl methacrylate) plasticization by dissolved argon ; sorption of argon in poly(ethyl methacrylate) ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
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  • 17
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 35 (1997), S. 1049-1053 
    ISSN: 0887-6266
    Keywords: thermodynamic interaction ; Flory-Huggins parameter ; rubbery polymer ; gas ; Henry's law coefficient ; partial molar volume ; Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The Flory-Huggins interaction parameters χ for 23 gases (He, Ne, Ar, Kr, Xe, H2, N2, O2, N2O, CO2, CH4, C2H4, C2H6, C3H6, C3H8, 1,3-C4H6, four C4H8's, n-C4H10, iso-C4H10, and n-C5H12) in five rubbery polymers (1,2-polybutadiene (PB), poly(ethylene-co-vinyl acetate)) (EVAc), polyethylene (PE), polypropylene (PP), and poly(dimethyl siloxane) (PDMS) were determined from either literature data on Henry's law coefficient and partial molar volume or those on sorptive dilation for each polymer/gas system. Values of χ for the gases increased in the order of PDMS 〈 PP ≡ PB 〈 EVAc ≡ PE. Among the gases except He and H2 whose χ values are not reliable, Ne and Xe have respectively the highest and the lowest values of χ for the polyolefins. The χ values of the hydrocarbons were compared together with previously reported χ values of n-alkanes C3-C10. The dependencies of χ upon concentration and temperature were discussed on the basis of the literature data. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 1049-1053, 1997
    Additional Material: 3 Ill.
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  • 18
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 535-547 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: High-pressure sorption (up to 50 atm) for CO2, N2, and Ar in poly(vinyl benzoate) (PVB) was studied at temperatures from 25 to 70°C by a gravimetric method utilizing an electromicrobalance. The results are described by Henry's law above the glass transition temperature Tg for all gases. The dual-mode sorption model, Henry's law plus a Langmuir isotherm, applies to the sorption isotherms of N2 and Ar in the glassy state, and the dual-mode parameters are given. For CO2, a new type of sorption isotherm is observed below Tg. The isotherm is concave to the pressure axis in the low-pressure region and turns into a straight line with increasing CO2 pressure which can be extrapolated back to the coordinate origin. The linear part of the isotherm is characteristic of the rubbery state, while the nonlinear part stems from glassystate behavior. The “glass transition solubility” of CO2, at which PVB film changes from the glassy to the rubbery state, decrease as the temperature increases. The disappearance of microvoids, that is, the decrease of the Langmuir capacity, may be due to a large plasticizing effect of sorbed CO2. The difference between the N2 and Ar isotherms and the CO2 isotherm is discussed from this standpoint.
    Additional Material: 10 Ill.
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  • 19
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 26 (1988), S. 159-177 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Dilation of polysulfone (PSUL) and crystalline poly(ethylene terephthalate) (PET) films accompanying sorption of carbon dioxide is measured by a cathetometer under high pressure up to 50 atm over the temperature range of 35-65°C. Sorptive dilation isotherms of PSUL are concave and convex to the pressure and concentration axes, respectively, and both isotherms exhibit hysteresis. Each dilation isotherm plotted versus pressure and concentration for the CO2-PET system shows an inflection point, i.e., a glass transition point, at which the isotherm changes from a nonlinear curve to a straight line. Dilation isotherms of PET below the glass transition point are similar to those of the CO2-PSUL system, whereas the isotherms above the glass transition point are linear and exhibit no hysteresis. Partial molar volumes of CO2 in these polymers are determined from data of sorptive dilation. On the basis of the extended dual-mode sorption model and the current data, primitive equations for gas-sorptive dilation of glassy polymers are proposed.
    Additional Material: 13 Ill.
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  • 20
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 879-892 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption and dilation in the system poly(ethyl methacrylate) (PEMA) and carbon dioxide are reported for pressures up to 50 atm over the temperature range 15-85°C. The sorption isotherms were obtained gravimetrically. The dilation accompanying sorption was measured directly with a cathetometer. At low temperatures the sorption and dilation isotherms were concave toward the pressure axis in the low-pressure region and turned to convex with increasing pressure. As the experimental temperature approached and exceeded the glass transition temperature of 61°C, both isotherms became convex or linear over the whole range of pressure. Partial molar volumes of CO2 in PEMA were obtained from sorption and dilation data, which were described well by the extended dual-mode sorption and dilation models developed recently. The temperature dependence of the dual-mode parameters and the isothermal glass transition are discussed.
    Additional Material: 9 Ill.
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