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1.
The apparent solubility (S), concentration-average diffusivity (D), and permeability (P), for C0_2, CH_4 and N_2 through PPO and aryl-brominated PPO at 35℃for pressure ranging from 1 to 26 atm are reported. It is found that P, D, and S of the membranes to all the three gases vary with the extent of bromination. S increases with the increase of the percent of bromine in each case, but D to CO_2 increases remarkably only at higher degree of brominafion, and therefore, P to CO_2 is increased by more than 100% over a wide range ofpressure in the case. The solubility data are well described by the dual mode sorption model. It is found that the gas molecules sorbed by the Langmuir mode are relatively more immobilized and the contribution of the nonequilibrinm character of the polymer to gas permeation increases obviously for CO_2 and is hardly changed for CH_4 with increasing bromine content. These observations are interpreted in terms of changes in specific free volume (SFV)and the cohesive energy density (CED) of the polymers. 相似文献
2.
Kanchan Ghosal Rey T. Chern Benny D. Freeman Raj Savariar 《Journal of Polymer Science.Polymer Physics》1995,33(4):657-666
CO2, CH4, O2, and N2 permeability and solubility of unmodified and aryl-nitrated polysulfone were determined at 35°C and pressures up to 20 atm. The degree of nitration was varied from 0 to 2 nitro groups per repeat unit. The permeability and diffusion coefficients for all gases decreased with increasing degree of nitro substitution. The decrease in gas diffusivity is attributed to a combination of decreased fractional free volume and decreased torsional mobility with increasing degree of substitution. The solubilities of N2, O2, and CH4 do not show a systematic dependence on degree of substitution. However, CO2 solubility apparently goes through a minimum as the degree of substitution is increased. CO2 solubility may be influenced by a competition between increases in polymer polarity (favoring higher solubility) and lower free volume (favoring lower solubility) that accompanies increases in the polar nitro substituent concentration. CO2/CH4 solubility selectivity increases monotonically as the degree of substitution increases. CO2/CH4 permselectivity and diffusivity selectivity increased with increasing degree of substitution. © 1995 John Wiley & Sons, Inc. 相似文献
3.
F. R. Sheu R. T. Chern V. T. Stannett H. B. Hopfenberg 《Journal of Polymer Science.Polymer Physics》1988,26(4):883-892
Solubilities and diffusivities of CO2 and CH4 in two aromatic polyesters [Ardel® poly(bisphenol A phthalate) (PAr) and poly(phenolphthalein phthalate) (PPha)] and one polycarbonate [Lexan® (PC)], generated from independent sorption and permeation measurements at 35°C and up to 25 atm, are compared. The permeability ratio for CO2 over CH4, at 20 atm and 35°C, ranges from 24 for PC, to 21 for PAr, and 27 for PPha. However, the permeability of PPha and PAr are 40 and 120% higher, respectively, than that of PC. Less than 21% change in the gas diffusivity was observed; therefore, a major portion of the observed higher permeability of PPha and PAr is attributed to an increase in the gas solubility. These data are interpreted qualitatively in terms of changes in the calculated packing density, chain torsional mobility of the polymer, and gas-polymer attraction. 相似文献
4.
The gas permeability and sorption of CO2 and N2O was measured on cardo-poly(ether-ether-ketone) (C-PEEK) and poly(phenylene sulfide) (PPS) at 298 K. The results are discussed on the basis of the dual-mode model. Results obtained from measurements at 308 K are compared with literature data of poly(phenylene oxide) (PPO), poly(sulfone) (PSU) and poly(carbonate) (PC). While C-PEEK shows similar transport properties as PC and PSU, the values of PPS are distinctly lower. The solubility of CO2 in the various polymers as well as the correlation of the permeability coefficients of the same polymers for He, Ar, CO2, N2, and CH4 with the kinetic molecular diameter of the gases indicate a simple relation of the transport properties with the polymer density. 相似文献
5.
Diffusion, solubility, and permebility coefficients were measured for He, Co2, Ar, and CH4 in polybutadiene (PB) and in polybutadiene reacted in the solid state to various extents with aqueous bromine. Analysis of the sorption curves and X-ray emission spectra showed that the bromination created a heterogeneous membrane with an outer brominated skin and an unreacted core. At relatively low extent of bromination, the diffusion and permeability coefficients for CO2, Ar, and CH4 decreased by two orders of magnitude, while the transport coefficients for He were virtually unchanged. The permeability coefficients for CO2, Ar, and CH4 became immeasurably small after about 3% bromination. The ideal separation factor for gas pairs with different molecular size increased with bromination, suggesting applications in gas separation processes. © 1993 John Wiley & Sons, Inc. 相似文献
6.
Mean permeability coefficients for CO2, O2, N2, and CH4 in seven types of 6FDA polyimides with branched or extended diamine moieties were determined at 35.0°C (95.0°F) and at pressures up to 10.5 atm (155 psia). In addition, solubility coefficients for CO2, O2, N2, and CH4 in six of these polyimides were determined at 35.0°C and at 6.8 atm (100 psia). Mean diffusion coefficients for the six gas/polyimide systems were calculated from the permeability and solubility data. The relationships between the chemical structure of the polyimides, some of their physical properties (glass transition temperature, mean interchain spacing, specific free volume), and their gas permeability, diffusivity, and solubility behavior are discussed. The 6FDA polyimides studied here exhibit a considerably lower selectivity for the CO2/CH4 and O2/N2 gas pairs than 6FDA polyimides with short and stiff aromatic diamines with comparable CO2 and O2 permeabilities. © 1993 John Wiley & Sons, Inc. 相似文献
7.
T. Uragami H. B. Hopfenberg W. J. Koros D. K. Yang V. T. Stannett R. T. Chern 《Journal of Polymer Science.Polymer Physics》1986,24(4):779-792
Sorption kinetics and equilibria as well as permeabilities and diffusion time lags for CO2 in Kapton polyimide film have been studied at temperatures from 35 to 55°C and pressures up to 0.78 atm. The sorption/desorption cycles indicate that the diffusivity of CO2 increases with increasing local penetrant concentration in the polymer. Both the permeability and time lag decrease with increasing upstream CO2 pressure. All of these results are described well by theoretical expression based on the dual-mode theory of sorption and transport in glassy polymers. 相似文献
8.
T. Hirose Y. Mi S. A. Stern Anne K. St. Clair 《Journal of Polymer Science.Polymer Physics》1991,29(3):341-347
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: 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. 相似文献
9.
10.
The permeability coefficients for He, O2, N2, CH4, and CO2 in miscible blends of polystyrene (PS) and tetramethyl bisphenol-A polycarbonate (TMPC) at 35°C and 1 atm driving pressure are reported. Sorption isotherms for CO2 and CH4 are also presented. The isotherms were fitted to the dual sorption model. The Langmuir capacity factor was found to follow an earlier correlation based on unrelaxed volume. For each gas, the permeability was found to go through a minimum when plotted against blend composition. This behavior is primarily the result of the volume change on mixing observed for this system. The attractive interaction between TMPC and PS is relatively strong as indicated by density and solubility data. The value of the binary interaction parameter was found to be of the same magnitude as that for poly(phenylene oxide) (PPO)-polystyrene (PS) blends. Considering the similarity of structure between PPO and TMPC, it is concluded that similar phenyl-phenyl interactions and conformational changes on blending may prevail in TMPC/PS blends. 相似文献
11.
《Journal of membrane science》1998,138(2):143-152
The effect of polyethyleneglycol (PEG) on gas permeabilities and selectivities was investigated in a series of miscible cellulose acetate (CA) blend membranes. The permeabilities of CO2, H2, O2, CH4, N2 were measured at temperatures from 30 to 80°C and pressures from 20 to 76 cmHg using a manometric permeation apparatus. It was determined that the blend membrane having 10 wt% PEG20000 exhibited higher permeability for CO2 and higher permselectivity for CO2 over N2 and CH4 than those of the membranes which contained 10% PEG of the molecular weight in the range 200–6000. The CA blend containing 60 wt% PEG20000 showed that its permeability coefficients of CO2 and ideal separation factors for CO2 over N2 reached above 2 × 10−8 [cm3 (STP) cm/cm2 s cmHg] and 22, respectively, at 70°C and 20 cmHg. Based on the data of gas permeability coefficients, time lags and characterization of the membranes, it is proposed that the apparent solubility coefficients of all CA and PEG blend membranes for CO2 were lower than those of the CA membrane. However, almost all the blend membranes containing PEG20000 showed higher apparent diffusivity coefficients for CO2, resulting in higher permeability coefficients of CO2 with relation to those of the CA membrane. It is attributed to the high diffusivity selectivities of CA and PEG20000 blend membranes that their ideal separation factors for CO2 over N2 were higher than those of the CA membrane in the range 50–80°C, even though the ideal separation factors of almost all PEG blend membranes for CO2 over CH4 became lower than those of the CA membrane over nearly the full range from 30° to 80°C. 相似文献
12.
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. 相似文献
13.
《Journal of Polymer Science.Polymer Physics》2018,56(18):1239-1250
Polymers containing CO2‐philic groups are of great interest for CO2/light gas separation membranes because the affinity toward CO2 can effectively increase CO2 solubility and thus permeability. In this study, polysulfones (PSUs) modified with different degrees of benzyldimethylamine (DMA), benzyltrimethylammonium fluoride (TMAF), and benzyltrimethylammonium iodide (TMAI) were synthesized using sequential post‐functionalization reactions and investigated for CO2/N2 and CO2/CH4 separation. The physical properties of these polymers were studied, including density, fractional free volume, and glass transition temperature. In contrast to the conventional wisdom that tertiary amines exhibit an affinity toward CO2, this study convincingly shows that the DMA substituent has a minimal impact on CO2 solubility and CO2/light gas solubility selectivity in PSUs under dry condition. On the other hand, incorporating TMAF and TMAI in PSU significantly increases CO2 solubility. Particularly, introducing TMAI with a molar ratio of 1.07 relative to PSU repeating units increases CO2/CH4 solubility from 4.4 to 5.2, CO2/CH4 permeability selectivity from 21 to 45, and CO2/N2 permeability selectivity from 24 to 33 at 35 °C, while the CO2 permeability decreases from 5.6 to 1.7 Barrers. The effect of these functional groups in PSUs on gas diffusivity and diffusivity selectivity can be satisfactorily described by the free volume model. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1239–1250 相似文献
14.
Permeability coefficients P for He, O2, N2, CO2 CH4, C2H4, C2H6, and C3H8 in 12 different silicone polymer membranes were determined at 35.0°C and pressures up to 9 atm. Values of P for CO2, CH4, and C3H8 were also determined at 10.0 and 55.0°C. In addition, mean diffusion coefficients D and solubility coefficients S were obtained for CO2, CH4, and C3H8 in 6 silicone polymers at 10.0, 35.0, and 55.0°C. Substitution of increasingly bulkier functional groups in the side and backbone chains of silicone polymers results in a significant decrease in P for a given penetrant gas. This is due mainly to a decrease in D , whereas S decreases to a much lesser extent. Backbone substitutions appear to have a somewhat lesser effect in depressing P than equivalent side-chain substitutions. The selectivity of a silicone membrane for a gas A relative to a gas B, i.e., the permeability ratio P (A)/P (B), may increase or decrease as a result of such substitutions, but only if the substituted groups are sufficiently bulky. The selectivity of the more highly permeable silicone membranes is controlled by the ratio S (A)/S (B), whereas the selectivity of the less permeable membranes depends on both the ratios D (A)/D (B) and S(A)/S(B). The permeability as well as the selectivity of one silicone membrane toward CO2 were significantly enhanced by the substitution of a fluorine-containing side group that increased the solubility of CO2 in that polymer. 相似文献
15.
S. A. Stern S. S. Kulkarni H. L. Frisch 《Journal of Polymer Science.Polymer Physics》1983,21(3):467-481
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. 相似文献
16.
R. T. Chern W. J. Koros B. Yui H. B. Hopfenberg V. T. Stannett 《Journal of Polymer Science.Polymer Physics》1984,22(6):1061-1084
Sorption isotherms for pure CO2 and pure CH4 in Kapton H® polymide films at 60°C are reported for pressures up to 20 atm and are analyzed in terms of the dual-mode sorption model. An experimental scheme for the measurement of steady-state permeabilities of both pure and mixed gas feeds is described. Permeabilities of Kapton to the individual components at 60°C are presented for a mixture comprised of 32.2% CO2 in CH4 as functions of feed pressure up to 590 psi (absolute). The permeabilities for the individual penetrants in the mixed feed are lower than the respective purecomponent values at the corresponding partial pressures. Furthermore, the permeabilities of both penetrants drop as the feed pressure is increased at constant composition. The dual-mobility transport model used to analyze the data postulates that the observed pressure and composition dependence of the permeabilities is due to competition between penetrants for a limited microvoid sorption capacity in the glassy polymer. It is demonstrated that in addition to flux depressions due to dual-mode effects, nonideality of the gas phase must be accounted for to explain the substantial flux depressions observed for the CO2/CH4 mixtured used in this study. 相似文献
17.
《Journal of membrane science》2001,186(2):183-193
We have determined the intrinsic gas transport properties of He, H2, O2, N2, CH4, and CO2 for a 6FDA-durene polyimide as a function of pressure, temperature and aging time. The permeability coefficients of O2, N2, CH4, and CO2 decrease slightly with increasing pressure. The pressure-dependent diffusion coefficients and solubility coefficients are consistent with the dual-sorption model and partial immobilization. All the gas permeabilities increase with temperature and their apparent activation energies for permeation increase with increasing gas molecular sizes in the order of CO2, O2, N2, and CH4.The percentages of permeability decay after 280 days of aging are 22, 32, 36, 40, 42, and 30% for He, H2, O2, N2, CH4, and CO2, respectively. Interestingly, except for H2 (kinetic diameter of 2.89 Å), the percentages of permeability decay increase exactly in the order of He (kinetic diameter of 2.6 Å), CO2 (3.30 Å), O2 (3.46 Å), N2 (3.64 Å), and CH4 (3.80 Å). The apparent activation energies of permeation for O2, N2, CH4, and CO2 increase with aging because of the increases in activation energies of diffusion and the decreases in solubility coefficients. The activation-energy increase for diffusion is probably due to the decrease in polymeric molar volume because of densification during aging. The reduction in solubility coefficient indicates the available sites for sorption decreasing with aging because of the reduction of microvoids and interstitial chain space. 相似文献
18.
Polydimethylsiloxane (PDMS) is the most commonly used membrane material for the separation of condensable vapors from lighter gases. In this study, a composite PDMS membrane was prepared and its gas permeation properties were investigated at various upstream pressures. A microporous cellulose acetate (CA) support was initially prepared and characterized. Then, PDMS solution, containing crosslinker and catalyst, was cast over the support. Sorption and permeation of C3H8, CO2, CH4, and H2 in the prepared composite membrane were measured. Using sorption and permeation data of gases, diffusion coefficients were calculated based on solution‐diffusion mechanism. Similar to other rubbery membranes, the prepared PDMS membrane advantageously exhibited less resistance to permeation of heavier gases, such as C3H8, compared to the lighter ones, such as CO2, CH4, and H2. This result was attributed to the very high solubility of larger gas molecules in the hydrocarbon‐based PDMS membrane in spite of their lower diffusion coefficients relative to smaller molecules. Increasing feed pressure increased permeability, solubility, and diffusion coefficients of the heavier gases while decreased those of the lighter ones. At constant temperature (25°C), empirical linear relations were proposed for permeability, solubility, and diffusion coefficients as a function of transmembrane pressure. C3H8/gas solubility, diffusivity, and overall selectivities were found to increase with increasing feed pressure. Ideal selectivity values of 9, 30, and 82 for C3H8 over CO2, CH4, and H2, respectively, at an upstream pressure of 8 atm, confirmed the outstanding separation performance of the prepared membrane. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
19.
Kazuhiro Tanaka Masaaki Okano Hiroyuki Toshino Hidetoshi Kita Ken-Ichi Okamoto 《Journal of Polymer Science.Polymer Physics》1992,30(8):907-914
Permeability and solubility coefficients for H2, CO2, O2, CO, N2, and CH4 in polyimides prepared from 6FDA and methyl-substituted phenylenediamines were measured to investigate effects of the substituents on gas permeability and permselectivity. The methyl substituents restrict internal rotation around the bonds between the phenyl rings and the imide rings. The rigidity and nonplanar structure of the polymer chain, and the bulkiness of methyl groups make chain packing inefficient, resulting in increases in both diffusion and solubility coefficients of the gases. Polyimides from tetramethyl-p-phenylenediamine and trimethyl-m-phenylenediamine display very high permeability coefficients and very low permselectivity due to very high diffusion coefficients and very low diffusivity selectivity, as compared with the other polyimides having a similar fraction of free space. This suggests that these polyimides have high fractions of large-size free spaces. 相似文献
20.
The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH4 > N2 > O2 > CO2. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO2 decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO2‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004 相似文献