Competitive permeation of gas and water vapour in high free volume polymeric membranes

Highly permeable glassy polymeric membranes based on poly (1‐trimethylsilyl‐1‐propyne) (PTMSP) and a polymer of intrinsic porosity (PIM‐1) were investigated for water sorption, water permeability and the separation of CO₂ from N₂ under humid mixed gas conditions. The water sorption isotherms for both materials followed behavior indicative of multilayer adsorption within the microvoids, with PIM‐1 registering a significant water uptake at very high water activities. Analysis of the sorption isotherms using a modified dual sorption model which accounts for such multilayer effects gave Langmuir affinity constants more consistent with lighter gases than the use of the standard dual mode approach. The water permeability through PTMSP and PIM‐1 was comparable over the water activities studied, and could be successfully model ed through a dual mode sorption model with a concentration dependent diffusivity. The water permeability through both membranes as a function of temperature was also measured, and found to be at a minimum at 80 ° C for PTMSP and 70 °C for PIM‐1. This temperature dependence is a function of reducing water solubility in both membranes with increasing temperature countered by increasing water diffusivity. The CO₂ ‐ N₂ mixed gas permeabilities through PTMSP and PIM‐1 were also measured and model ed through dual mode sorption theory. Introducing water vapour further reduced both the CO₂ and N₂ permeabilities. The plasticization potential of water in PTMSP was determined and indicated water swelled the membrane increasing CO₂ and N₂ diffusivity, while for PIM‐1 a negative potential implied that water filling of the microvoids hampered CO₂ and N₂ diffusion through the membrane. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 719–728     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

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     

Suppression of CO2-plasticization by semiinterpenetrating polymer network formation

CO₂-induced plasticization may significantly spoil the membrane performance in high-pressure CO₂/CH₄ separations. The polymer matrix swells upon sorption of CO₂, which accelerates the permeation of CH₄. The polymer membrane looses its selectivity. To make membranes attractive for, for example, natural gas upgrading, plasticization should be minimized. In this article we study a polymer membrane stabilization by a semiinterpenetrating polymer network (s-ipn) formation. For this purpose, the polyimide Matrimid 5218 is blended with the oligomer Thermid FA-700 and subsequently heat treated at 265°C. Homogeneous films are prepared with different Matrimid/Thermid ratios and different curing times. The stability of the modified membrane is tested with permeation experiments with pure CO₂ as well as CO₂/CH₄ gas mixtures. The original membrane shows a minimum in its permeability vs. pressure curves, but the modified membranes do not indicating suppressed plasticization. Membrane performances for CO₂/CH₄ gas mixtures showed that the plasticizing effect indeed accelerates the permeation of methane. The modified membrane clearly shows suppression of the undesired methane acceleration. It was also found that just blending Matrimid and Thermid was not sufficient to suppress plasticization. The subsequent heat treatment that results in the s-ipn was necessary to obtain a stabilized permeability. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1547–1556, 1998     

Intrinsically microporous polyimides containing spirobisindane and phenazine units: Synthesis,characterization and gas permeation properties

A new diamine containing spirobisindane and phenazine units, namely, 3,3,3′,3′‐tetramethyl‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[cyclopenta[b]phenazine]‐7,7′‐diamine (TTSBIDA) was synthesized starting from commercially available 5,5′,6,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethyl‐1,1′‐spirobisindane (TTSBI). TTSBI was oxidized to 3,3,3′,3′‐tetramethyl‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[indene]‐5,5′,6,6′‐tetraone (TTSBIQ) which was subsequently condensed with 4‐nitro‐1,2‐phenylenediamine to obtain 3,3,3′,3′‐tetramethyl‐7,7′‐dinitro‐2,2′,3,3′‐tetrahydro‐1,1′‐spirobi[cyclopenta[b]phenazine] (TTSBIDN). TTSBIDN was converted into TTSBIDA by reduction of the nitro groups using hydrazine hydrate in the presence of Pd/C as the catalyst. A series of new polyimides of intrinsic microporosity (PIM‐PIs) were synthesized by polycondensation of TTSBIDA with commercially available aromatic dianhydrides. PIM‐PIs exhibited amorphous nature, high thermal stability (T₁₀ > 480 °C) and intrinsic microporosity (BET surface area = 59–289 m²/g). The gas permeation characteristics of films of selected PIM‐PIs were evaluated and they exhibited appreciable gas permeability as well as high selectivity. The CO₂ and O₂ permeability of PIM‐PIs were in the range 185.4–39.2 and 30.6–6.2 Barrer, respectively. Notably, polyimide derived from TTSBIDA and 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (PIM‐PI‐6FDA) exhibited high CO₂ and O₂ permeability of 185.4 and 30.6 Barrer with CO₂/CH₄ and O₂/N₂ selectivity of 43.1 and 5.1, respectively. The data of PIM‐PI‐6FDA for CO₂/CH₄ and O₂/N₂ gas pairs were located near Robeson upper bound. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 766–775     

Vapour permeation and sorption in fluoropolymer gel membrane based on ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide

The emissions of hydrocarbons from fossil fuels into atmosphere entail both an economic loss and an environmental pollution. Membrane separations can be used for vapour recovery and/or vapour removal from the permanent gas stream, given that the appropriate membrane is identified. A neat poly(vinylidene fluoride-co-hexafluoropropylene) membrane is impermeable to both the representatives of aliphatic hydrocarbons and branched hydrocarbons, namely hexane and isooctane, whereas the permeation flux is enhanced by the presence of 80 mass % of the ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulphonyl)imide in the membrane, as detailed in this work. The permeabilities of hydrocarbon vapours were determined from the binary mixture containing hydrocarbon and nitrogen to simulate the real input of an air stream containing a condensable hydrocarbon. The diffusion coefficient determined from sorption measurements was higher for hexane, as would be expected for a smaller molecule, whereas both the sorption isotherms and permeabilities of the hydrocarbons studied were found to be almost identical. It is possible that the sorption effect predominates in the transport mechanism for VOCs/N₂ separations.     

Gas sorption,diffusion, and permeation in poly(dimethylsiloxane)

The permeability of poly(dimethylsiloxane) [PDMS] to H₂, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈, CF₄, C₂F₆, and C₃F₈, and solubility of these penetrants were determined as a function of pressure at 35 °C. Permeability coefficients of perfluorinated penetrants (CF₄, C₂F₆, and C₃F₈) are approximately an order of magnitude lower than those of their hydrocarbon analogs (CH₄, C₂H₆, and C₃H₈), and the perfluorocarbon permeabilities are significantly lower than even permanent gas permeability coefficients. This result is ascribed to very low perfluorocarbon solubilities in hydrocarbon‐based PDMS coupled with low diffusion coefficients relative to those of their hydrocarbon analogs. The perfluorocarbons are sparingly soluble in PDMS and exhibit linear sorption isotherms. The Flory–Huggins interaction parameters for perfluorocarbon penetrants are substantially greater than those of their hydrocarbon analogs, indicating less favorable energetics of mixing perfluorocarbons with PDMS. Based on the sorption results and conventional lattice solution theory with a coordination number of 10, the formation of a single C₃F₈/PDMS segment pair requires 460 J/mol more energy than the formation of a C₃H₈/PDMS pair. A breakdown in the geometric mean approximation of the interaction energy between fluorocarbons and hydrocarbons was observed. These results are consistent with the solubility behavior of hydrocarbon–fluorocarbon liquid mixtures and hydrocarbon and fluorocarbon gas solubility in hydrocarbon liquids. From the permeability and sorption data, diffusion coefficients were determined as a function of penetrant concentration. Perfluorocarbon diffusion coefficients are lower than those of their hydrocarbon analogs, consistent with the larger size of the fluorocarbons. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 415–434, 2000     

Mechanically Strong and Flexible Hydrolyzed Polymers of Intrinsic Microporosity (PIM‐1) Membranes

A systematic strategy to molecularly design flexible tough hydrolyzed polymers of intrinsic microporosity (hPIM‐1) films from the PIM‐1 polymer is explored in this study. Flexible films can be fabricated from N‐methyl‐2‐pyrrolidone (NMP) by appropriate hydrolysis conditions. The optimal weight ratio of NaOH/H₂O/EtOH in the base‐catalyzed reaction is 0.5/2/2. Because of the highly polar carboxylic acid groups, the resultant hPIM‐1 has a lower water contact angle. The hPIM‐1 has one‐half fractional free volume compared to PIM‐1 which is in good agreement with permeability. Moreover, hPIM‐1 follows as the same dual‐mode sorption model as PIM‐1. To the best of our knowledge, this is the first ever reported flexible hPIM‐1 film in the literature. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 344–354     

Gas transport properties of poly(2,2,4,4-tetramethyl cyclobutane carbonate)

Gas transport properties of semicrystalline films of poly(2,2,4,4-tetramethyl cyclobutane carbonate) (TMCBPC) were studied. Permeability coefficients for He, O₂, N₂, CH₄, and CO₂ at 35°C for pressures between 1 and 20 atm are reported as well as sorption isotherms for N₂, CH₄, and CO₂ at the same conditions. The permeability coefficients for TMCBPC are larger than corresponding values for the aromatic bisphenol-A polycarbonate (PC) and tetramethyl bisphenol-A polycarbonate (TMPC), even though the TMCBPC films are semicrystalline. These results are explained on the basis of the larger free volume available for permeation in this polymer. Significant TMCBPC plasticization by CO₂ was also observed and this causes typical time-dependent behavior. The plasticization process starts at very low pressures compared with the behavior of aromatic polycarbonates PC and TMPC. This early onset of plasticization seems to be related also to the larger free volume in the amorphous phase of TMCBPC which favors high gas sorption. The diffusion coefficients for TMCBPC are also larger than those reported for the aromatic polycarbonates PC and TMPC. Ideal gas separation factors were found to follow the usual trend; that is, as permeability increases, the ideal separation factor decreases. © 1993 John Wiley & Sons, Inc.     

Synthesis,characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

A new bis(catechol) monomer, namely, 4,4′‐((1r,3r)‐adamantane‐2,2‐diyl)bis(benzene‐1,2diol) (THADM) was synthesized by condensation of 2‐adamantanone with veratrole followed by demethylation of the formed (1r,3r)‐2,2‐bis(3,4 dimethoxyphenyl)adamantane. Polycondensation of THADM and various compositions of THADM and 5,5,6′,6′‐tetrahydroxy‐3,3,3′,3′‐tetramethylspirobisindane was performed with 2,3,5,6‐tetrafluoroterephthalonitrile (TFTPN) to obtain the homopolymer and copolymers. These polymers demonstrated good solubility in common organic solvents such as dichloromethane, chloroform, and tetrahydrofuran and could be cast into tough films from their chloroform solutions. GPC analysis revealed that number average molecular weights of polymers were in the range 48,100–61,700 g mol⁻¹, suggesting the formation of reasonably high molecular weight polymers. They possessed intrinsic microporosity with Brunauer‐Emmett‐Teller (BET) surface area in the range 703–741 m² g⁻¹. Thermogravimetric analysis of polymers indicated that 10% weight loss temperature was in the range 513–518 °C demonstrating their excellent thermal stability. THADM‐based polymer of intrinsic microporosity (PIM) showed P(CO₂) = 1080, P(O₂) = 232 and appreciable selectivity [α(CO₂/CH₄) = 22.6, α(CO₂/N₂) = 26.7, and α(O₂/N₂)= 5.7]. The gas permeability measurements revealed that with increase in the content of adamantane units in PIMs, selectivity increased and permeability decreased, following the trade‐off relationship. The gas separation properties of PIMs containing adamantane units were located close to 2008 Robeson upper bound for gas pairs such as CO₂/CH₄, CO₂/N₂, H₂/N₂, and O₂/N₂. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 16–24     

Transport properties of PVA/PEI/PEG composite membranes: sorption and permeation characterizations

Poly(vinylalcohol)/poly(ethyleneglycol)/poly(ethyleneimine) blend membranes were prepared by solution casting followed by solvent evaporation. The chemical structure of the prepared membranes was analyzed by FTIR and DSC. The sorption behavior as well as the permeabilities of the membranes for pure CO₂ and N₂ were investigated. The results show that the PVA/PEI/PEG membranes possess a higher permeability of CO₂ and a lower permeability of N₂. The membrane displays a CO₂ permeability of 27 Barrer, and a N₂ permeability of 3 Barrer at 25°C and 1 bar. CO₂ sorption behavior of the composite membrane, which can be classified as a dual-mode sorption model, and N₂ sorption behavior of the copolymeric membrane is in agreement with the Fickian diffusion model.      

CO2-induced plasticization phenomena in glassy polymers

A typical effect of plasticization of glassy polymers in gas permeation is a minimum in the relationship between the permeability and the feed pressure. The pressure corresponding to the minimum is called the plasticization pressure. Plasticization phenomena significantly effect the membrane performance in, for example, CO₂/CH₄ separation processes. The polymer swells upon sorption of CO₂ accelerating the permeation of CH₄. As a consequence, the polymer membrane loses its selectivity. Fundamental understanding of the phenomenon is necessary to develop new concepts to prevent it.In this paper, CO₂-induced plasticization phenomena in 11 different glassy polymers are investigated by single gas permeation and sorption experiments. The main objective was to search for relationships between the plasticization pressure and the chemical structure or the physical properties of the polymer. No relationships were found with respect to the glass-transition temperature or fractional free volume. Furthermore, it was thought that polar groups of the polymer increase the tendency of a polymer to be plasticized because they may have dipolar interactions with the polarizable carbon dioxide molecules. But, no dependence of the plasticization pressure on the carbonyl or sulfone density of the polymers considered was observed. Instead, it was found that the polymers studied plasticized at the same critical CO₂ concentration of 36±7 cm³ (STP)/cm³ polymer. Depending on the polymer, different pressures (the plasticization pressures) are required to reach the critical concentration.     

Pervaporation properties of crosslinked poly(dimethylsiloxane) membranes for the removal of hydrocarbons from water

The pervaporation (PV) performance of crosslinked poly(dimethylsiloxane) dimethylmethacrylate (PDMSDMMA) membranes for an aqueous solution of various hydrocarbons was studied using sorption–diffusion theory. Three chlorinated hydrocarbons (chloroform, trichloroethylene, and tetrachloromethane) and three aromatic hydrocarbons (benzene, chlorobenzene, and toluene) were used as the permeants. When aqueous solutions of 0.05 wt % hydrocarbon were permeated through the crosslinked PDMSDMMA membranes, they showed high hydrocarbon/water selectivity and permeability during PV. The hydrocarbon/water selectivity of the crosslinked PDMSDMMA membranes was significantly dependent upon the permeants; in particular, chloroform removed the hydrocarbons most efficiently in this study. The results of the temperature dependence of the PV performance and hydrocarbon absorption into the membrane revealed that the difference in hydrocarbon/water selectivity for various aqueous solutions of hydrocarbons during PV depended significantly on the molar volume and diameter of the hydrocarbons. The permeation and removal mechanism of hydrocarbons from water through crosslinked PDMSDMMA membranes can be explained by a qualitative model based on the diffusion jump model. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2079–2090, 2006     

Azide‐based Cross‐Linking of Polymers of Intrinsic Microporosity (PIMs) for Condensable Gas Separation

Cross‐linked polymers of intrinsic microporosity (PIM)s for gas separation membranes, were prepared by a nitrene reaction from a representative PIM in the presence of two different diazide cross‐linkers. The reaction temperature was optimized using TGA. The homogenous membranes were cast from THF solutions of different ratios of PIM to azides. The resulting cross‐linked structures of the PIMs membranes were formed at 175 °C after 7.5 h and confirmed by TGA, XPS, FT‐IR spectroscopy and gel content analysis. These resulting cross‐linked polymeric membranes showed excellent gas separation performance and can be used for O₂/N₂ and CO₂/N₂ gas pairs, as well as for condensable gases, such as CO₂/CH₄, propylene/propane separation. Most importantly, and differently from typical gas separation membranes derived from glassy polymers, the crosslinked PIMs showed no obvious CO₂ plasticization up to 20 atm pressure of pure CO₂ and CO₂/CH₄ mixtures.

     

Cross‐linked Copolyimide Membranes for the Separation of Gaseous and Liquid Mixtures

Cross‐linked polymer structures gain increasing attention as membrane materials because they can fullfill the demands for industrial applications. Thereby, not only good separation characteristics but also high temperature stability and chemical resistancy are required. Furthermore, it is important that the membrane materials be plasticization resistant, because it is found that this causes strong increasing permeability with a drastic loss in selectivity. Plasticization effects occur with polyimide membranes in the presence of high CO₂concentrations, hydrocarbons as propylene, propane, or aromatics. Unfortunately, these components are present in mixtures with high relevance being separated economically by membrane units or hybrid processes. In this article, the advantages of cross‐linked 6FDA (4,4′hexafluoro isopropylidene diphthalic acid anhydride)‐copolyimides are discussed based on experimental results for the separation of propylene/propane, benzene/cyclohexane, and high‐pressure CO₂/CH₄mixtures. Additionally, opportunities for implementing the membrane units in conventional separation processes are discussed.     

Permeability of pure and mixed gases in silicone rubber at elevated pressures

The transport properties of silicone rubber are reported at 35°C for a series of pure gases (He, N₂, CH₄, CO₂, and C₂H₄) and gas mixtures (CO₂/CH₄ and N₂/CO₂) for pressures up to 60 atm. The effects of pressure and concentration on the permeability of various gases have been analyzed to consider plasticization and hydrostatic compression effects. Over an extended pressure and concentration range, both compression of free volume and eventual plasticization phenomena were observed for the various penetrants. In pure component studies, plasticization effects tended to dominate hydrostatic compression effects for the more condensible penetrants (C₂H₄ and CO₂) while the reverse was true for the low sorbing N₂ and He. These issues are discussed in terms of penetrant diffusion coefficients versus pressure to clarify the interplay between the opposing effects for the penetrants of markedly different solubilities. Additional insight into the somewhat complex interplay of the plasticization and hydrostatic compression effects are given by mixed gas permeation results. It was found that the permeability of nitrogen in a 10/90 CO₂/N₂ and a 50/50 CO₂/N₂ mixture was increased by the presence of CO₂ because the plasticizing nature of CO₂ is able to overcome nitrogen's compression effect.     

Highly selective multilayer polymer thin films for CO2/N2 separation

Multilayer thin films of poly(ethylene oxide) (PEO) and poly(methacrylic acid) (PMAA), deposited via layer‐by‐layer (LbL) assembly from aqueous solutions, are investigated for CO₂/N₂ separation. Eight and ten bilayer (217 and 389 nm thick, respectively) PEO/PMAA thin films deposited on a 25 μm polystyrene substrate exhibit CO₂/N₂ selectivities of 142 and 136, respectively. These are the highest reported to‐date for this gas pair separation using a homogeneous polymer film. While further work remains to improve CO₂ permeability, these results indicate the potential of LbL assemblies as standalone CO₂ separation membranes for low‐flux/high‐purity applications, or as part of a composite and/or mixed‐matrix membrane for high‐flux applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1730–1737     

Design,synthesis, and gas permeation properties of polyimides containing pendent imidazolium groups

Film‐forming polymers containing ionic groups have attracted considerable attention as emerging materials for gas separation applications. The aim of this article was to synthesize new film‐forming polyimides containing imidazolium groups (PI‐IMs) and establish their structure–performance relationship. In this context, a new aromatic diamine, namely, N¹‐(4‐aminophenyl)‐N¹‐(4‐(2‐phenyl‐1H‐imidazol‐1‐yl)phenyl)benzene‐1,4‐diamine (ImTPADA), was synthesized and polycondensed with three aromatic dianhydrides, namely, 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4‐(4,4‐isopropylidenediphenoxy) bis(phthalic anhydride), and 4,4′‐oxydiphthalic anhydride to form the corresponding polyimides containing pendent 2‐phenylimidazole groups (PI‐IEs). Next, PI‐IMs were prepared by N‐quaternization of pendent 2‐phenylimidazole groups present in PI‐6FDA using methyl iodide followed by anion exchange with bis(trifluoromethane)sulfonimide lithium salt (LiTf₂N). PI‐IEs and PI‐IMs exhibited reasonably high molecular weights, amorphous nature, good solubility, and could be cast into self‐standing films from their DMAc solutions. Thermogravimetric analysis showed that 10% weight loss temperature of PI‐IEs and PI‐IMs were in the range 545–475 °C and 303–306 °C, respectively. Gas permeability analysis of films of PI‐IEs and PI‐IMs was investigated by variable‐volume method and it was observed that incorporation of ionic groups into PI‐6FDA resulted in increased permeability while maintaining selectivity. In particular, polymer bearing Tf₂N⁻ anion exhibited high CO₂ permeability (33.3 Barr) and high selectivity for CO₂/CH₄ (41.1) and CO₂/N₂ (35.4). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1721–1729     

Transport of water and gases through EVA copolymer films,EVA70/PVC,and EVA70/PVC/gluten blends

The transport of water vapor and gases (oxygen or carbon dioxide) through poly(ethylene‐co‐vinyl acetate) (EVA) films of different VA contents and through EVA₇₀/PVC and EVA₇₀/PVC/gluten blend films, was analysed by permeation measurements. In the case of water, a plasticization effect on the material is observed for EVA films with more than 33percnt; wt. of VA content and also for the EVA₇₀/PVC blend. For EVA of 19 wt.percnt; VA, there is no plasticization, while for LDPE (low density polyethylene) and EVA of 4.5 wt.percnt; VA, the water diffusion coefficient decreases with increasing the water content. A negative plasticization effect was accounted for by an empirical model and attributed to the formation of water clusters in the non polar polymers. The increase in water sorption extent with the VA content leads to a steady increase in the water permeability in the EVA copolymers while for the EVA₇₀/PVC blend, the reduced water permeability is explained by the interaction between chlorinated units and polar groups. In the case of gas permeation, both for O₂ and CO₂ and whatever the VA content of the copolymer used, the experimental curves are characterized by a constant diffusion coefficient. This result is not surprising as it is generally admitted that, gases sorb into rubbery polymers according to Henry's law. By mixing PVC with the EVA of 70percnt; wt. VA, the diffusion coefficients of CO₂ and O₂ are greatly reduced (6 times).     

Gas transport through homogeneous and asymmetric polyethersulfone membranes

Both homogeneous and asymmetric polyethersulfone (PES) membranes were prepared by solvent casting. The sorption and permeation behavior of CO₂, O₂, and N₂ using these two kinds of cast PES membranes and commercially available homogeneous PES film was investigated to extract the pressure dependence of gas permeability and the permselectivity for CO₂ relative to N₂, and to confirm the validity of the working assumption that a skin layer in an asymmetric membrane can be essentially replaced by a thick homogeneous dense membrane. The pressure dependence of the mean permeability coefficient to CO₂ in homogeneous membranes obeys the dual-mode mobility model. The ideal separation factor for CO₂ relative to N₂ at an upstream pressure of 0.5 MPa attains ca. 40, while the permeability to CO₂ is about 2.7 Barrer at the same upstream pressure. The same separation factor in asymmetric membranes amounts to 35. The diffusion behavior for the skin layer in an asymmetric membrane with a thin skin layer can be simulated approximately by that in a homogeneous dense membrane. © 1993 John Wiley & Sons, Inc.     

Sorption and transport of hydrocarbon and perfluorocarbon gases in poly(1‐trimethylsilyl‐1‐propyne)

Pure gas solubility and permeability of H₂, O₂, N₂, CO₂, CH₄, C₂H₆, C₃H₈, CF₄, C₂F₆, and C₃F₈ in poly(1‐trimethylsilyl‐1‐propyne) (PTMSP) were determined as a function of pressure at 35°C. Permeability coefficients of the perfluorinated penetrants are approximately an order of magnitude lower than those of their hydrocarbon analogs, and lower even than those of the permanent gases. In striking contrast to hydrocarbon penetrants, PTMSP permeability to fluorocarbon penetrants decreases with increasing penetrant size. This unusual size‐sieving behavior in PTMSP is attributed to low perfluorocarbon solubilities in PTMSP coupled with low diffusion coefficients relative to those of their hydrocarbon analogs. In general, perfluorocarbon penetrants are less soluble than their hydrocarbon analogs in PTMSP. The difference in hydrocarbon and perfluorocarbon solubilities in high free volume, hydrocarbon‐rich PTMSP is much smaller than in hydrocarbon liquids and liquidlike polydimethylsiloxane. The low solubility of perfluorocarbon penetrants is ascribed to the large size of the fluorocarbons, which inhibits their dissolution into the densified regions of the polymer matrix and reduces the number of penetrant molecules that can be accommodated in Langmuir sites. From the permeability and sorption data, diffusion coefficients were calculated as a function of penetrant concentration. With the exception of H₂ and the C₃ analogs, all of the penetrants exhibit a maximum in their concentration‐dependent diffusion coefficients. Resolution of diffusion coefficients into a mobility factor and a thermodynamic factor reveals that it is the interplay between these two terms that causes the maxima. The mobility of the smaller penetrants (H₂, O₂, N₂, CH₄, and CO₂) decreases monotonically with increasing penetrant concentration, suggesting that the net free volume of the polymer–penetrant mixture decreases as additional penetrant is added to PTMSP. For larger penetrants mobility either: (1) remains constant at low concentrations and then decreases at higher penetrant concentrations (C₂H₆, CF₄, and C₂F₆); (2) remains constant for all concentrations examined (C₃H₈); or (3) increases monotonically with increasing penetrant concentration (C₃F₈). Presumably these results reflect the varying effects of these penetrants on the net free volume of the polymer–penetrant system. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 273–296, 2000