Gas transport and mechanical properties of PDMS-TFS/LDPE nanocomposite membranes

This study investigates the effect of trimethylsiloxy fumed silica (TFS) on the mechanical and gas permeation properties of polymer nano-composite membranes. The membranes were produced by coating TFS incorporated polydimethylsiloxane (PDMS) at different loadings (5, 10 and 15 wt.%) on a porous low density polyethylene (LDPE) substrate which was formed by a melt-extrusion/salt leaching technique. The PDMS-TFS/LDPE membranes were characterized by SEM, TGA and DMTA. The results showed that good affinity between the PDMS treated TFS particles and PDMS matrix was obtained leading to improved mechanical and thermal properties. For gas permeation, CH₄ and C₃H₈ at different upstream pressure (50 to 80 psig) and temperature (27 to 55 °C) were investigated. The results showed that the C₃H₈/CH₄ ideal selectivity (17.6) and C₃H₈ permeability (1.89?×?10⁴ Barrer) through 10 wt.% TFS loaded membranes (PDMS-TFS10%/LDPE) were 41 and 14% higher than the neat membranes (PDMS-TFS0%/LDPE), respectively. The permeation results also indicate that the performance stability under the conditions investigated makes PDMS-TFS/LDPE membranes interesting for industrial applications.     

Gas transport properties of CoAlPO4‐5/PC membranes

The transport phenomena of oxygen and nitrogen across a pure polycarbonate (PC) and CoAlPO₄‐5/PC membranes were studied. Various CoAlPO₄‐5 membranes with different cobalt content were added to polycarbonate membranes to improve the gas transport performance. Oxygen and nitrogen isotherms were studied. Solubility of oxygen and nitrogen was greatly increased by adding CoAlPO₄‐5 to the membranes, which also resulted in a higher solubility ratio of oxygen to nitrogen. It might be that a pinhole of the membrane caused the increase in diffusivity and a decrease in selectivity when excess CoAlPO₄‐5 was added. The results also showed that CoAlPO₄‐5 with a higher cobalt content would more effectively increase the gas solubility, but make only a minor change in the solubility ratio of oxygen to nitrogen. It was found that the increase in oxygen to nitrogen selectivity was mainly due to an increased diffusivity ratio of oxygen to nitrogen when CoAlPO₄‐5 was added into the membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 89–95, 2000     

Gas transport through ceramic membranes under super-critical conditions

In order to select and to apply a porous membrane under supercritical conditions, it is necessary to understand the transport mechanism affecting the permeation behaviour.This paper describes the investigation of gas transport through micro porous ceramic membranes consisting of several layers. The separation layer is made from TiO² with a nominal pore size diameter of 0.9 nm. Single gas permeation of helium, nitrogen, argon, methane, and carbon dioxide was measured in the temperature range of 293-443 K and in the pressure range of 1-10 MPa.Observation of the permeability of these membranes revealed that the transport of non?adsorbing gases under these conditions is governed by Knudsen diffusion and viscous flow.     

Gas transport properties of siloxane polyurethanes

Polyurethanes (PUs) were synthesized from toluenediisocyanates (TDIs) and a polymeric diol having polydimethylsiloxane and polyoxyethylene blocks of the ABA type, ended with OH groups. Prepolymers, prepared in toluene solution using ratios [NCO]/[OH] ≥ 2, were crosslinked with triisopropanolamine (TIPA) (ratio [OH]/[NCO] = 1.1) (two-step process). PUs were also obtained with a one-step process using, contemporaneously, TDI, block copolymer, and, as crosslinking agent, TIPA or the glyceride of ε-hydroxyhexanoic acid. Polydimethylsiloxane (PDMSO) was prepared as a reference material. The course of the reaction between block copolymer and TDI was studied by differential scanning calorimetry in the absence and presence of benzoyl chloride (BzCl). Without BzCl, with ratios [NCO]/[OH] > 2, uncontrolled crosslinking side reactions occur. The properties of the PU films obtained with the two methods were studied both for the density of crosslinking and for gas transport properties. The two-step polymers are less crosslinked than the others and are characterized by higher diffusion coefficients and by higher permeability to gases. The permeability order is 10^?9 (N cm³ cm^?1 cm^?1 cm Hg^?1 s^?1) for CH₄, O₂, CO, and N₂ and is 10 times higher for CO₂. The selectivity for the couple O₂/N₂ is higher than that obtained with PDMSO films. Considerable selectivities are shown for the couples CO₂/N₂ and CO₂/CO. © 1995 John Wiley & Sons, Inc.     

Polyorganophosphazene membranes: preparation and transport properties

Polyphenoxyphosphazene, polycumylphenoxyphosphazene, polybutylphenoxyphosphazene and their copolymers were synthesized. Asymmetric and homogeneous membranes for liquid-liquid and gas separations were prepared. The ultrafiltration membranes were characterized by a cut-off higher than 100,000 Daltons. The gas separation membranes, tested with O₂, N₂, CO₂ and CH₄, were characterized by permeabilities similar to the ones of rubbery polymers and selectivities similar to the ones of glassy polymers.     

Gas transport properties of electrospun polymer nanofibers

Although the basic principles of gas flow through unidirectional fibers have been widely studied and well understood since the 1950s, questions arise when these principles are applied to electrospun polymer nanofibers. Classic theories based on orderly packed coarse fibers are inadequate in accounting for the influences of random fiber distribution and slip flow. In this work, a mechanistic model in terms of fiber volume fraction and fiber radius is presented to determine the through-plane permeability of electrospun nanofiber layers. The fibrous system is subdivided into a series of cells of orthogonal fibers with random volumes. A single factor is proposed to quantify the effect of randomness of fiber distribution on flow behaviors. When the fiber radius is comparable with the mean free path of air molecules, the slip flows in the nanoscale fibrous media are particularly explored. The solutions obtained are successfully validated through comparison with experimental and numerical results. It is demonstrated that the through-plane permeability of electrospun nanofibers is enhanced by the slip effect and randomly distributed fibers are more permeable than ordered structures.     

Gas permeation properties of new type asymmetric membranes

We have developed a new type of asymmetric membranes having a homogeneous hyperthin skin layer, which was used as a polyimide synthesized by 2,2-bis(3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA) and 2,2-bis(4-amino phenyl) hexafluoro-propane (BAAF). The skin layer thicknesses of the 6FDA-BAAF polyimide asymmetric membranes were 40–60 nm, and the porosity was 10^-6% when a defect size was assumed as 5 nm. The permselectivity of 6FDA-BAAF polyimide asymmetric membranes after silicone coating had α of 40 for CO₂/CH₄ and a flux of 1.0 [Nm³/m²-h-atm] (=3.7 × 10⁻⁴ [cm³(STP)/cm² s cmHg]) for CO₂, α of 4.3 for O₂/N₂ and a flux of 2.0 × 10⁻¹ [Nm³/m²/h/atm] (=7.1 × 10⁻⁵ [cm³(STP)/cm²s cmHg]) for O₂. These values were constant for large-scale manufacturing. © 1996 John Wiley & Sons, Inc.     

Self-doped sulfonated polyaniline ultrafiltration membranes with enhanced chlorine resistance and antifouling properties

Membranes heavily rely on chlorination to diminish (bio)fouling, but chlorination can also lead to membrane degradation. We developed sulfonated polyaniline (S-PANI) ultrafiltration (UF) membranes with improved chlorine resistance and intrinsic antifouling properties. The S-PANI membranes were synthesized through Non-solvent Induced Phase Separation (NIPS). Membrane performance was evaluated under harsh chlorine conditions (250 ppm sodium hypochlorite for 3 days under different pH conditions). The S-PANI membranes showed improved chlorine resistance including a stable performance without changes in model foulant BSA rejection. In contrast, PANI membranes suffered critical structural damage with complete leakage and commercial PES membranes showed a 76% increase in pure water flux and a noticeable change in BSA rejection. Small changes in S-PANI membrane performance could be linked to membrane structural changes with pH, as confirmed by SEM, IR spectroscopy, and contact angle measurements. Additionally, the S-PANI membranes showed better antifouling properties with a high flux recovery ratio in comparison to PANI membranes using alginic acid, humic acid, and BSA model foulants. Chemical cleaning by sodium hypochlorite re-instated the transport properties to its initial condition. Overall, the developed S-PANI membranes have a high chlorine tolerance and enhanced antifouling properties making them promising for a range of UF membrane applications.     

Characterization, magnetic and transport properties of polyaniline synthesized through interfacial polymerization

The present work describes the interfacial polymerization of aniline in the absence or presence of surfactants. Polyaniline was readily obtained in the semi-oxidized doped state and was cast from the aqueous phase. The structural and morphological characteristics of the polyanilines were deduced from X-ray Diffractometry and Scanning Electron Microscopy. Various morphologies were obtained depending on the surfactant addition. Conductivity measurements recorded for HCl doped polyaniline nanoneedles from 5 to 330 K showed a T_c value at 230 K, where their transport behaviour changes from metallic-like above T_c to semiconductive below T_c. Furthermore, extensive magnetic measurements have been performed as a function of applied field and temperature.     

Gas transport in vertically-aligned carbon nanotube/parylene composite membranes

Vertically-aligned carbon nanotube (VACNT) composite membranes were fabricated by impregnating carbon nanotube (CNT) forests with poly-para-xylylene (parylene-C) through room-temperature chemical vapor deposition (CVD). Transport properties of diverse gases through the CNT/parylene membranes were investigated. The gas permeances scaled inversely with their molecular weights in accordance with Knudsen model and the value of permeance was about 30 times higher than that predicted by the Knudsen diffusion kinetics, which was attributed to the atomically smooth interiors of CNTs. In addition, the gas permeance values in this work were higher than those reported for other VACNT membranes, due to the smaller membrane thickness and good crystallinity of the CNTs.     

Gas permselection properties in silicone-coated asymmetric polyethersulfone membranes

The gas permeation properties of H₂, He, CO₂, O₂, and N₂ through silicone-coated polyethersulfone (PESf) asymmetric hollow-fiber membranes with different structures were investigated as a function of pressure and temperature and compared with those of PESf dense membrane and silicone rubber (PDMS) membrane. The PESf asymmetric hollow-fiber membranes were prepared from spinning solutions containing N-methyl-2-pyrrolidone as a solvent, with ethanol, 1-propanol, or water as a nonsolvent-additive. Water was also used as both an internal and an external coagulant. A thin silicone rubber film was coated on the external surface of dried PESf hollow-fiber membranes. The apparent structure characteristics of the separation layer (thickness, porosity, and mean pore size) of the asymmetric membranes were determined by gas permeation method and their cross-section morphologies were examined with a scanning electron microscope. The results reveal that the gas pressure normalized fluxes of the five gases in the three silicone-coated PESf asymmetric membranes are nearly independent of pressure and did not exhibit the dual-mode behavior. The activation energies of permeation in the silicone-coated asymmetric membranes may be larger or smaller than those of PESf dense membrane, which is controlled by the membrane physical structure (skin layer and sublayer structure). Permselectivities for the gas pairs H₂/N₂, He/N₂, CO₂/N₂, and O₂/N₂ are also presented and their temperature dependency addressed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 837–846, 1997     

Gas transport properties of polybenzoxazinoneimides and their prepolymers

Three types of imide-containing polyamic acids (polybenzoxazinoneimide prepolymers), namely, a homopolymer, a copolymer, and a polymer-metal complex were synthesized and used for homogeneous membranes preparation. These membranes exhibited good physico-mechanical properties and also chemical and hydrolytical stability. Their gas separation properties were measured and analyzed by correlation with macromolecular packing density. Polybenzoxazinoneimide membranes were prepared by heating prepolymer membranes to 220 °C. Difference between gas separation properties of membranes based on polybenzoxazinoneimides and those of their prepolymers was estimated. Gas transport properties of all novel membranes were compared with those of known membranes by using Robeson's diagram. It was established that a polybenzoxazinoneimide membrane including a polymer-metal complex is the most effective among membranes studied here.     

Gas separation properties of new polyoxadiazole and polytriazole membranes

The gas separation properties of new aromatic poly-1,2,4-triazole and poly-1,3,4-oxadiazole membranes have been systematically investigated. Various functional groups were incorporated as pendent groups onto the polymer backbone of poly-1,2,4-triazoles. A wide permeability/selectivity spectrum was covered with the choice of functional groups incorporated into the polymer backbone of poly-1,3,4-oxadiazoles. High permeabilities were found for poly-1,3,4-oxadiazoles with a 1,1,3-trimethyl-3-phenylindane (PIDA-POD) and a 4,4′(2,2′-diphenyl)hexafluor propane (HF-POD) unit in the polymer backbone, while incorporation of a 4,4′-diphenyl ether unit (DPE-POD) results in a polymer with a low permeability but an extremely high selectivity. While the permeabilities vary over four orders of magnitude, the solubility remains almost constant and, therefore, the increase in permeability is mainly due to an increase in diffusivity. The permeability is discussed in terms of the polymer free volume.     

Gas permeation and separation properties of sulfonated polyimide membranes

Permeability and selectivity of pure gas H₂, CO₂, O₂, N₂ and CH₄ as well as a mixture of CO₂/N₂ for sulfonated homopolyimides prepared from 1,4,5,8-naphthalene tetracarboxylic dianhydride (NTDA) and 2,2-bis[4-(4-aminophenoxy)phenyl] hexafluoro propane disulfonic acid (BAPHFDS) were measured and compared to those of the non-sulfonated homopolyimide having the same polymer backbone. The polyimide in a proton form (NTDA-BAPHFDS(H)) displayed higher selectivity of H₂ over CH₄ without loss of H₂ permeability. Strong intermolecular interaction induced by sulfonic acid groups decreased diffusivity of the larger molecules. The CO₂/N₂ (19/81) mixed gas permeation was investigated as a function of humidity. With increasing relative humidity from 0% RH to 90% RH, the CO₂ permeability for NTDA-BAPHFDS(H) polyimide increased by more than one order of magnitude, and the selectivity of CO₂/N₂ also increased twice or more. On the other hand, the gas permeability for the non-sulfonated polyimide slightly decreased with increasing humidity. NTDA-BAPHFDS(H) polyimide displayed a CO₂ permeability of 290×10⁻¹⁰ cm³ (STP) cm/(cm² s cmHg) and a separation factor of CO₂/N₂ of 51 at 96% RH, 50 °C and total pressure of 1 atm.     

高性能气体分离聚苯胺膜

系统论述了聚苯胺自支撑膜和复合膜对气体的分离性能。聚苯胺自支撑膜、聚苯胺 /尼龙、聚苯胺 /氧化铝复合膜经去掺杂尤其是二次掺杂后 ,气体分离系数会显著提高 ,而透气系数略有提高。二次掺杂态聚苯胺自支撑膜和复合膜都具有极高的氧氮分离性能 ,已超过了一般聚合物材料的上限 ,最优异的聚苯胺膜的氧氮选择分离系数可达 30 ,它在包括有高选择性能膜材料聚酰亚胺、聚吡咙、聚三唑等在内的所有聚合物膜中排行第一 ,对空气分离显示出极大优势。预计聚苯胺复合膜及纳米膜在医疗保健等领域具有很大应用潜力     

Preparation,characterization, and adsorption properties of cellulose acetate‐polyaniline membranes

Four lots of cellulose acetate (CA) membranes, modified with polyacrylic acid, using various plasticizers, and coated with polyaniline (PANI) were prepared. The morphology of the membranes was evaluated by using scanning electron microscopy, and the membranes showed larger pore size when the plasticizers were used. The electrical conductivity of the modified membranes and coated with PANI increased by two orders of magnitude when the plasticizer triphenyl phosphate was used. The strain at break improved by an order of magnitude and the glass transition temperature (T_g) showed an average decrease of 36°C when the membranes were plasticized. Finally, these membranes were tested as ion‐exchange materials of a gold‐iodide complex. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

聚乙烯胺/Cu3（BTC）2-MMT-NH2混合基质膜的制备及气体传递性能

采用阳离子交换与Cu₃(BTC)₂原位合成相结合制备Cu₃(BTC)₂-MMT,同时,借助3-氨基丙基三乙氧基硅烷(KH550)氨基功能化制备Cu₃(BTC)₂-MMT-NH₂杂化材料。然后,将杂化材料添加到聚乙烯胺(PVAm)基质中作为选择性涂层涂覆到聚砜(PSf)支撑体上,制备了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜。通过XRD和FTIR对杂化材料的晶态结构和化学结构进行了表征,同时采用ATR-FTIR证实了Cu₃(BTC)₂-MMT-NH₂杂化材料与PVAm基质之间存在氢键相互作用。系统性研究了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜中MMT阳离子交换量、Cu₃(BTC)₂-MMT与KH550的质量比、Cu₃(BTC)₂-MMT-NH₂的负载量、操作压力、湿膜厚度、操作温度以及混合气作为原料气对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：在纯气气氛,操作温度为25℃、操作压力为1 bar(1 bar=0.1 MPa)的条件下,当Cu₃(BTC)₂-MMT-NH₂负载量为3%(质量)时,膜的气体分离性能最优,CO₂渗透率为203 GPU(1GPU=10^-6 cm³·cm^-2·s^-1·cmHg^-1,1 cmHg=1333.22 Pa),CO₂/N₂选择性为100.7,远高于添加MMT、Cu₃(BTC)₂和MMT/Cu₃(BTC)₂混合物的混合基质膜。这是由于Cu₃(BTC)₂-MMT-NH₂具有层间快速传递通道且与聚合物基质有良好的相容性。此外,混合气测试条件下,混合基质膜运行360 h,仍能保持优异的CO₂分离性能稳定性。     

聚乙烯胺/Cu3（BTC）2-MMT-NH2混合基质膜的制备及气体传递性能

采用阳离子交换与Cu₃(BTC)₂原位合成相结合制备Cu₃(BTC)₂-MMT,同时,借助3-氨基丙基三乙氧基硅烷(KH550)氨基功能化制备Cu₃(BTC)₂-MMT-NH₂杂化材料。然后,将杂化材料添加到聚乙烯胺(PVAm)基质中作为选择性涂层涂覆到聚砜(PSf)支撑体上,制备了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜。通过XRD和FTIR对杂化材料的晶态结构和化学结构进行了表征,同时采用ATR-FTIR证实了Cu₃(BTC)₂-MMT-NH₂杂化材料与PVAm基质之间存在氢键相互作用。系统性研究了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜中MMT阳离子交换量、Cu₃(BTC)₂-MMT与KH550的质量比、Cu₃(BTC)₂-MMT-NH₂的负载量、操作压力、湿膜厚度、操作温度以及混合气作为原料气对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：在纯气气氛,操作温度为25℃、操作压力为1 bar(1 bar=0.1 MPa)的条件下,当Cu₃(BTC)₂-MMT-NH₂负载量为3%(质量)时,膜的气体分离性能最优,CO₂渗透率为203 GPU(1GPU=10^-6 cm³·cm^-2·s^-1·cmHg^-1,1 cmHg=1333.22 Pa),CO₂/N₂选择性为100.7,远高于添加MMT、Cu₃(BTC)₂和MMT/Cu₃(BTC)₂混合物的混合基质膜。这是由于Cu₃(BTC)₂-MMT-NH₂具有层间快速传递通道且与聚合物基质有良好的相容性。此外,混合气测试条件下,混合基质膜运行360 h,仍能保持优异的CO₂分离性能稳定性。     

Enhanced transport properties of reverse osmosis membranes by chemical treatment

The performance of thin film composite (TFCL-LP^®) membranes that were treated with hydrofluoric acid (HF) improved and their flux increased significantly without any loss in ion-rejection properties. In contrast, DESAL3 membranes do not show any significant change in transport properties after similar treatment with HF. We used scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and contact angle measurements to determine why this difference in behavior occurs. The difference in microstructure, as described by the interstitial void model, seems to be responsible for their behavior after being exposed to chemicals like HF. Therefore, we attempt to correlate transport properties with the microstructural changes (smoothing of membrane ridge-valley structure or no change in density of spherulites) observed. This method of treatment seems to be very effective in simultaneously enhancing the flux and rejection of reverse osmosis membranes which have a typical ridge and valley structure. © 1996 John Wiley & Sons, Inc.     

Mixed gas and pure gas transport properties of copolyimide membranes

Copolyimides were synthesized from dianhydride of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride (6FDA) with various diamine contents of 4,4′‐oxydianiline (ODA) and 2,3,5,6‐tetramethyl‐1,4‐phenylenediamine (TeMPD) by chemical imidization in a two‐step procedure. Polyimides (PIs) were characterized using thermogravimetric analysis, Fourier transform infrared spectroscopy, differential scanning calorimetry, as well as specific volume and free volume. The gas transport properties for pure gas and blends of CO₂ and CH₄ for the homopolymers and 6FDA‐ODA/TeMPD copolymers were investigated at 35°C and 150 psi pressure. In pure gas permeation, permeability of CO₂ and CH₄ increased with increasing TeMPD content in the diamine moiety, whereas the ideal selectivity decreased with increasing TeMPD content. In the mixed gas permeation, permeabilities and separation factor were measured as a function of CO₂ feed molar fraction for five PI membranes. The behavior of pure gas and mixed gas permeabilities and separation factor of CO₂/CH₄ mixtures as the chemical nature of the diamine and the CO₂ molar fraction in the feed gas were varied and are discussed in detail. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013