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  • 1
    Electronic Resource
    Electronic Resource
    Selective permeation of hydrocarbon gases in poly(tetrafluoroethylene) and poly(fluoroethylene-propylene) copolymer (1980)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 25 (1980), S. 1755-1774 
    Details
    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 permeabilities and diffusivities of methane, ethane, propane, n-butane, and isobutane in commercially available poly(tetrafluoroethylene) (TFE) and poly(fluoroethylene-propylene) (FEP) Teflon have been measured in a Pasternak-type permeation cell. Experiments were carried out at upstream hydrocarbon partial pressures up to 50 torr (1000-60,000 ppm gas phase concentration) and temperatures from 40 to 195°C with films of 0.0508 and 0.127 mm thickness using nitrogen as carrier gas on the upstream and downstream sides of the membrane. The transient and steady-state permeation data are described well by a combination of Henry's law and Fick's law with a concentration-independent diffusion coefficient. Linear Arrhenius plots of both permeabilities and diffusivities were obtained. Linear correlations were found both between the activation energy for diffusion and the square of the gas molecule diameter, and between the logarithm of solubility at 90°C and the penetrant boiling point. Separation factors for binary mixtures of hydrocarbons were measured for TFE at 140°C and found to be similar to those predicted by individual permeabilities in most cases. Measurements with mixed gases were not made for FEP Teflon, but selectivities of FEP are expected to be similarly well described by the ratios of the pure gas permeabilities at the low partial pressures studied. The effect of annealing FEP Teflon for 24 hr at 200°C was found to produce an average of 20-30% reduction in solubility as well as a 9% increase in the activation energy for diffusion compared to as-received films. These effects are believed to be due to increased crystallinity in the sample upon annealing.
    Additional Material: 11 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1980.070250822
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  • 2
    Electronic Resource
    Electronic Resource
    The effects of morphology and hygrothermal aging on water sorption and transport in Kapton® polyimide (1986)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 1619-1629 
    Details
    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 comparison of water sorption and diffusion behavior in 2 mil, as-received, Kapton= Trademark of E.I. Dupont de Nemours Inc. film, and in otherwise identical but hygrothermally aged samples, suggests chemical differences between the samples. These differences can be related to known polyimide chemistry and the specific history encountered by the samples. Although the sorption isotherms are similar for an as-received 0.3 mil sample studied earlier and for the as-received 2 mil samples studied here, the diffusion coefficient of water in the as-received 2 mil sample is approximately 300% larger than in the as-received 0.3 mil sample. This large effect is believed to be related to the presence of small, paracrystalline aggregates with large aspect ratios. Differences in orientation measured by birefringence for the two samples suggest that the barrier properties of Kapton® are strongly affected by the detailed morphological organization of the ordered aggregates. Comparison of the sorption isotherms for the as-received and hygrothermally aged 2-mil films suggests a significant increase in the hydrophillic nature of the aged film. This change is consistent with an apparent chemical reaction between water and uncyclized amic acid residues in the film. The tendency for water to cluster in as-received Kapton® is essentially eliminated by the chemical modification associated with hygrothermal aging. The hygrothermal aging produces a dramatic reduction in the water vapor diffusion coefficient at low vapor activities but a rather modest change at high activities.
    Additional Material: 5 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1986.070310608
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  • 3
    Electronic Resource
    Electronic Resource
    The effect of sorbed penetrants on the aging of previously dilated glassy polymer powders. II. n-propane sorption in polystyrene (1987)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 34 (1987), S. 721-735 
    Details
    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: Both the rate and apparent equilibrium of propane sorption in glassy polystyrene were increased after swelling the polymer by exposure to a highly sorbing vapor. Cyclic sorption experiments revealed that the increase in rate and apparent equilibrium of sorption due to the preswelling treatment decayed only during vacuum aging. The presence of low levels of propane in the polymer during aging, however, appeared to arrest the decay in sorption capacity. These composite results, taken in conjunction with the results of previous work in our laboratory, suggest that the component of the total sorption which resides in nonequilibrium, distended interchain gaps retards the chain motions which otherwise lead to consolidation of the dilated glass.
    Additional Material: 10 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1987.070340224
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  • 4
    Electronic Resource
    Electronic Resource
    Effects of film history on gas transport in a fluorinated aromatic polyimide (1988)
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 36 (1988), S. 1833-1846 
    Details
    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 effects of film formation procedures on transport properties are reported for a rigid-chained, fluorinated, aromatic polyimide. Residual dimethylacetamide (DMAC) solvent present in films formed under certain casting protocols produces complexities in the permeation behavior of helium and carbon dioxide. Specifically, helium permeabilities are lower, while those of carbon dioxide are higher, in a film containing 8 wt% residual DMAC than in an annealed film containing 〈 1 wt% DMAC. Significant differences in transport properties are also observed between films prepared using two different casting techniques. These differences appear to be due to differences in organization of chain segments within films. The results of this study emphasize the considerable care needed in formation and postformation processing of these materials to ensure optimum flux/selectivity properties in such applications.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/app.1988.070360810
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  • 5
    Electronic Resource
    Electronic Resource
    Comparison of three models for permeation of CO2/CH4 mixtures in poly(phenylene oxide) (1989)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 27 (1989), S. 1927-1948 
    Details
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Two models for the permeability of pure gases have been extended to include binary gas mixtures. The first is an extension of a pure gas permeability model, proposed by Petropoulos, which is based on gradients of chemical potential. This model predicts the permeability of components in a gas mixture solely on the basis of competition for sorption sites within the polymer matrix. The second mixed gas model follows an earlier analysis by Barrer for pure gases which includes the effects of saturation of Langmuir sites on the diffusion as well as the sorption processes responsible for permeation. This generalized “competitive sorption/diffusion” model includes the effect of each gas component on the sorption and diffusion of the other component in the mixture. The flux equations from these two models have been solved numerically to predict the permeability of gas mixtures on the basis of pure gas sorption and transport parameters. Both the mixed gas Petropoulos and competitive sorption/diffusion model predictions are compared with predictions from the earlier simple competitive sorption model based on gradients of concentration. An analysis of all three models is presented for the case of CO2/CH4 permeability in poly(phenylene oxide) (PPO). As expected, the competitive sorption/diffusion model predicts lower permeability than either of the models which consider only competitive sorption effects. The permeability depression of both CO2 and CH4 predicted by the competitive sorption/diffusion model is roughly twice that predicted by the competitive sorption model, whereas the mixed gas Petropoulos model predictions for both gases lie between the other two model predictions. For the PPO/CO2/CH4 system, the methane permeability data lie above the predictions of all three models, whereas CO2 data lie below the predictions of all models. Consequently, the competitive sorption/diffusion model gives the most accurate prediction for CO2, while the simple competitive sorption model is best for methane. The effects of mixed gas sorption, fugacity, and CO2-induced dilation were considered and do not explain the inaccuracies of any of the models. The relatively small errors in mixed gas permeability predictions using either of the three models are likely to be related to “transport plasticization” of PPO owing to high levels of CO2 sorption and its effect on polymer segmental motions and gas diffusivity.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1989.090270910
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  • 6
    Electronic Resource
    Electronic Resource
    Effect of isopropylidene replacement on gas transport properties of polycarbonates (1991)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 29 (1991), S. 731-746 
    Details
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The gas sorption and transport properties of a series of polycarbonates in which the isopropylidene unit of bisphenol A polycarbonate has been replaced with another molecular group are presented. Two new materials, bisphenol of norbornane polycarbonate (NBPC) and bisphenol Z polycarbonate (PCZ), are compared with several polymers which have been studied previously in this laboratory, including bisphenol A polycarbonate (PC), hexafluorobisphenol A polycarbonate (HFPC), and bisphenol of chloral polycarbonate (BCPC). The effect of molecular structure on chain mobility and chain packing is related to the gas transport properties. Dynamic mechanical thermal analysis and differential scanning calorimetry are used to judge chain mobility, while x-ray diffraction and free volume calculations give information about chain packing. Permeability measurements were made for He, H2, O2, N2, CH4, and CO2 at 35°C over a range of pressures up to 20 atm. Sorption experiments were also done for N2, CH4, and CO2 under the same conditions. The permeability coefficients of these polymers rank in the order HFPC ≫ NBPC〉PC〉BCPC ≫ PCZ for all of the gases. With the exception of BCPC, this order correlates well with fractional free volume. The low gas permeability of BCPC is attributed to a polarity effect. In general, bulky and relatively immobile substituents, as in HFPC and NBPC, can yield improved separation characteristics. The polar group of BCPC and the flexible cyclohexyl substituent of PCZ result in relatively low gas permeability.
    Additional Material: 16 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1991.090290612
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  • 7
    Electronic Resource
    Electronic Resource
    The transport properties of polyimide isomers containing hexafluoroisopropylidene in the diamine residue (1994)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 32 (1994), S. 1915-1926 
    Details
    ISSN: 0887-6266
    Keywords: polyimide ; membrane ; permeation ; isomers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The effect of modification of the central moiety of the dianhydride residue and isomerism on the gas transport and physical properties were compared for six polyimides containing the hexafluoroisopropylidene group in the diamine residue. Substitution of bulkier groups within the dianhydride residue resulted in disruption of chain packing and slight increases in resistance to chain motions which led to an increase in permeability with little loss in selectivity. The permeabilities and diffusivities in the meta connected polyimide isomers were considerably lower than in the para connected polyimide isomers. Similarly, the permselectivities in the meta connected isomers were consistently higher than in the para connected isomers. These lower permeabilities and higher permselectivities were a result of the more dense packing and a significant suppression of small scale motions in the meta connected isomers. The suppression of segmental mobility in the meta connected isomers was indicated by an increase in the sub Tg transition temperatures in these materials relative to the para connected isomers. The differences in transport properties for these polyimides were attributed to contributions by several factors, including: (1) total free volume (2) distribution of free volume (3) intersegmental resistance to chain motions, and (4) intrasegmental resistance to chain motions. © 1994 John Wiley & Sons, Inc.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1994.090321109
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  • 8
    Electronic Resource
    Electronic Resource
    Gas transport properties of polymers based on spirobiindane bisphenol (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 487-494 
    Details
    ISSN: 0887-6266
    Keywords: gas separations ; diffusion ; gas sorption ; spirobiindane bisphenol ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Transport properties of pure gases in polycarbonates, polyesters, and polyetherimides based on 6,6′-dihydroxy-3,3,3′,3′-tetramethyl-1,1′-spiro biindane (SBI) and bisphenol-A (BPA) are compared at 35°C. The SBI monomer contains two spiro-linked five-membered rings which are fused to the phenyl rings at the meta and para positions to the hydroxyl groups. This molecular structure gives SBI-based polymers with higher fractional free volume (FFV) and lower intramolecular motions as compared to the BPA-based analogs. The inhibition of chain packing due to the SBI moiety yields polymers with much higher permeabilities for all the gases studied, despite the hinderance of mobility associated with the SBI structure. Simultaneous increase in selectivity was also observed for some gas pairs. Oxygen permeabilities up to 5.9-fold higher with increases of up to 13% in O2/N2 selectivities were observed for a polyester based on SBI as compared to its analog based on BPA. Higher permeabilities of up to 4.3-fold for He and up to 4.8-fold for CO2 were observed due to the substitution of SBI for BPA. Not surprisingly, lower values of He/CH4 and CO2/CH4 selectivities were obtained for the more open SBI-containing polymers. The changes in fractional free volume and inhibition of small-scale mobility for some materials caused by the SBI moiety were measured and used in the interpretation of the gas transport properties. The individual contributions of diffusivity and solubility to the overall transport behavior of the polymers are discussed and correlated to the structural alterations caused by the SBI substitution for BPA monomer. © 1995 John Wiley & Sons, Inc.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1995.090330317
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  • 9
    Electronic Resource
    Electronic Resource
    Thermally stable polyimide isomers for membrane-based gas separations at elevated temperatures (1995)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 33 (1995), S. 135-146 
    Details
    ISSN: 0887-6266
    Keywords: polymer membranes ; temperature ; gas separations ; polyimides ; activation energy for permeation ; heat of sorption ; activation energy for diffusion ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The temperature dependence of gas sorption and transport properties is examined for two polyimide isomers. The permeabilities and solubilities of five gases in these materials are reported over an extensive temperature range from 35 to 325°C. Also, the activation energies for permeation, the heats of sorption, and the activation energies for diffusion obtained for both polyimides are compared and correlated with physical properties of the polymers and penetrants. The influence of temperature on the selective properties of these membrane materials is discussed for three gas separations; He/N2, CO2/CH4, and O2/N2. Thorough analysis of these data provides insight into the influence of the subtle difference in chain structure of the two isomers. The performance of the 6FDA-6Fp DA as a separation membrane at high temperatures suggests that it is an outstanding candidate for use in novel elevated temperature applications. ©1995 John Wiley & Sons, Inc.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1995.090330114
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  • 10
    Electronic Resource
    Electronic Resource
    Sorption of CO2, C2H4, N2O and their binary mixtures in poly(methyl methacrylate) (1986)
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part B: Polymer Physics 24 (1986), S. 175-188 
    Details
    ISSN: 0887-6266
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Sorption of carbon dioxide, ethylene, and nitrous oxide in poly(methyl methacrylate) (PMMA) at 35°C has been characterized for each gas as a pure component and for mixtures of carbon dioxide/ethylene and carbon dioxide/nitrous oxide. Pressures up to 20 atm were examined. Pure-component sorption isotherms are concave to the pressure axis for each of the gases. This behavior is accurately described by the dual-mode sorption model. Using only the purecomponent dual-mode parameters and the generalization of the model for gas mixtures, one can predict the total concentration of gas sorbed in the polymer to within an average deviation of ±2.01% for the CO2/C2H4/PMMA system and ±0.98% for the CO2/N2O/PMMA system. In both systems, for each component of the mixture, sorption levels were lower than corresponding pure-component sorption levels at pressures equal to the partial pressure of the respective components in the mixture. Depression of the sorbed concentration in mixture situations appears to be a general feature of the above systems and can be substantial in some situations. For the CO2/C2H4/PMMA system, use of pure-component sorption data to estimate the total sorbed concentration in the mixture would be in error by as much as 40% if one failed to account for competition phenomena responsible for depression in mixed-gas situations. Mixture pressures as high as 20 atm were studied for both systems and in the CO2/N2O/PMMA system sorbed concentrations reach 33.90 [cm3(STP)/cm3 polymer] without any significant deviation from model predictions.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/polb.1986.180240117
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