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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    Macromolecules 25 (1992), S. 4321-4324 
    ISSN: 1520-5835
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 35 (1988), S. 1715-1724 
    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 of CO2 in poly(vinyl benzoate) was gravimetrically measured at pressures up to 1 atm. Sorption isotherms were determined above and below the glass transition temperature Tg from 5 to 85°C. The isotherms were analyzed by the dual-mode sorption model assuming that the plasticizing effect of sorbed CO2 is negligible at this pressure range. The solubilities and Henry's law dissolution parameters were compared with those obtained by the high-pressure sorption and permeation measurements. Henry's law dissolution parameters were in good agreement with one another. However, the solubilities first determined here were smaller than those determined by the high-pressure sorption experiment at the same temperature. It was clear that the Langmuir capacity of the present specimen was smaller in spite of similar high-pressure CO2 exposure. Relaxation of the polymer was expected to be one of the reasons. This expectation was confirmed from the observation and analysis of sorption isotherms after two kinds of treatments. After annealing above Tg, the Langmuir capacity was shown to be decreased to 1/2 or even to 1/3 from the sorption isotherms below 45°C. This means that the conditioning to the high-pressure CO2 surely has a large effect on the nature of glassy polymer. Just after high-pressure CO2 exposure at 25°C, increased solubility was observed. Furthermore, the slow decrease of solubility, that is, the decrease of conditioning effect, was also followed from the continual measurements at 25°C. This result reflects not only the characteristic of sorption capacity after high-pressure CO2 exposure, but also the relaxation of polymer in glassy state.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 1525-1539 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A gravimetric method for determining precisely the solubility of gases in polymers at high pressure is described. The solubilities of N2 and CO2 in low-density polyethylene (LDPE); CO2 in polycarbonate (PC); and N2, CH4, C2H6, and CO2 in polysulfone (PSUL) have been measured as a function of pressure up to 50 atm. Most of the measured sorption isotherms agreed closely with published data, but reproducible and time-dependent hysteresis in the sorption of CO2, C2H6, and CH4 in glassy polymers, PC, and PSUL, was observed in this study for the first time. Like the well known conditioning effect of high-pressure CO2 on the sorption capacity of glassy polymers, these hysteresis phenomena are believed to be due to the plasticizing effect of sorbed gases. On the basis of the current data, the dual-mode sorption model including the plasticization by sorbed gas is discussed and a primitive equation for the concentration of sorbed gases in a quasiequilibrium state of sorption or desorption is proposed.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
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  • 4
    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.
    Type of Medium: Electronic Resource
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  • 5
    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.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 225-234 
    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 isotherms for argon in poly(ethyl methacrylate) (PEMA) are reported for pressures up to 50 atm over the temperature range 5-85°C. At temperatures below the glass transition (Tg=61°C), sorption isotherms are well described by the dual-mode sorption model; and isotherms above Tg follow Henry's law. However, isotherms for dilation due to sorption are linear in pressure at all temperatures over the range investigated. Partial molar volumes of Ar in PEMA are obtained from these isotherms. The volumes are approximately constant above Tg (about 40 cm3/mol), whereas the volumes below Tg are smaller and dependent on both temperature and concentration (19-26 cm3/mol). By analyzing the experimental data according to the dual-mode sorption and dilation model, the volume occupied by a dissolved Ar molecule and the mean size of microvoid in the glass are estimated to be 67 129 Å3, respectively. The cohesive energy density of the polymer is also estimated as 61 cal/cm3 from the temperature dependence of the dual-mode parameters.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 31 (1993), S. 693-697 
    ISSN: 0887-6266
    Keywords: permeation of high-pressure gases in poly(ethylene-co-vinyl acetate) ; copolymer, ethylene-vinylacetate, permeation of gases in ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: A previously proposed theoretical treatment to elucidate the pressure dependence of gas permeability is improved in order to apply it to polymer-gas systems in which gas dissolution follows the Flory-Huggins equation. Permeation rates of N2, CH4, and CO2 in poly(ethylene-co-vinyl acetate) are measured in the pressure range below 90 atm at 10-40°C, and the effect of pressure on permeability is found for each gas. The data are analyzed using the improved method to estimate the contributions of concentration and hydrostatic pressure to the pressure dependence of permeability. The concentration effect decreases with increasing temperature, whereas the hydrostatic-pressure effect is almost independent of temperature. Crystallinity dependence of the concentration effect is discussed in connection with high-pressure permeation data of other semicrystalline polymers reported elsewhere. © 1993 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 2243-2250 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of He, H2, N2, O2, Ar, CH4, C2H6, and C2H6 in polybutadiene and the dilation of the polymer due to sorption of the gases are investigated over the pressure range 0-50 atm at 25°C. For CO2 the measurements are made at temperatures ranging from 15 to 80°C. Partial molar volumes of the gases in the polymer are determined. The temperature dependence of partial molar volume is discussed on the basis of the data for CO2. The Flory-Huggins interaction parameters of CO2, C2H4, and C2H6 are also estimated.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 28 (1990), S. 1297-1308 
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of N2, O2, Ar, CH4, CO2, C2H4, and C2H6 in poly (dimethyl siloxane) liquid and rubber and the dilation of the polymers due to sorption of the gases are studied at 25°C under pressures up to 50 atm. In the liquid, the sorption isotherms for low-solubility and high-solubility gases are described by Henry's law and the Flory-Huggins equation, respectively. Gas sorption in the rubber, which contains a 29 wt % silica filler, follows the dual-mode sorption model, though marked hysteresis is observed in the sorption of O2 and CH4. The dilation isotherms increase linearly or exponentially in both polymers with increasing pressure. Considering that gas molecules adsorbed into micropores of the filler particles do not participate in the dilation, partial molar volumes of the dissolved gases in the rubber are determined from data of sorption and dilation. The values are nearly equal to the partial molar volumes in the liquid (48-60 cm3/mol).
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
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  • 10
    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
    Type of Medium: Electronic Resource
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