Modified gas‐translation model for prediction of gas permeation through microporous organosilica membranes

A modified gas‐translation (GT) model was applied for the theoretical analysis of gas permeation through microporous organosilica membranes derived from bis(triethoxysilyl)ethane (BTESE) via a sol–gel method using different water/alkoxide molar ratios. The pore sizes of BTESE‐derived membranes were quantitatively determined by normalized Knudsen‐based permeance analysis, which was based on a modified‐GT model, using experimentally obtained permeances of He, H₂, N₂, C₃H₈, and SF₆. The pore sizes of BTESE‐derived membranes were successfully controlled from 0.65 to 0.46 nm by increasing the H₂O/BTESE ratio from 6 to 240. Furthermore, theoretical correlations of all possible pairs of permeance ratios were calculated based on the modified‐GT model. The experimental data were in good agreement with the theoretical correlation curves, indicating that the modified‐GT model can clearly explain gas permeation mechanisms through microporous membranes, and, thus, can be used to predict the gas permeation properties for these membranes. © 2014 American Institute of Chemical Engineers AIChE J 60: 4199–4210, 2014     

Development of ethanolamine‐based ionic liquid membranes for efficient CO2/CH4 separation

This study is focused on the development of ionic liquids (ILs) based polymeric membranes for the separation of carbon dioxide (CO₂) from methane (CH₄). The advantage of ILs in selective CO₂ absorption is that it enhances the CO₂ selective separation for the ionic liquid membranes (ILMs). ILMs are developed and characterized with two different ILs using the solution‐casting method. Three different blend compositions of ILs and polysulfone (PSF) are selected for each ILMs 10, 20, and 30 wt %. Effect of the different types of ILs such as triethanolamine formate (TEAF) and triethanolamine acetate (TEAA) are investigated on PSF‐based ILMs. Field emission scanning electron microscopy analysis of the membranes showed reasonable homogeneity between the ILs and PSF. Thermogravimetric analysis showed that by increasing the ILs loading thermal stability of the membranes improved. Mechanical analysis on developed membranes showed that ILs phase reduced the amount of plastic flow of the PSF phase and therefore, fracture takes place at gradually lower strains with increasing ILs content. Gas permeation evaluation was carried out on the developed membranes for CO₂/CH₄ separation between 2 bar to 10 bar feed pressure. Results showed that CO₂ permeance increases with the addition of ILs 10–30 wt % in ILMs. With 20–30 wt % TEAF‐ILMs and TEAA‐ILMs, the highest selectivity of a CO₂/CH₄ 53.96 ± 0.3, 37.64 ± 0.2 and CO₂ permeance 69.5 ± 0.6, 55.21 ± 0.3 is observed for treated membrane at 2–10 bar. The selectivity using mixed gas test at various CO₂/CH₄ compositions shows consistent results with the ideal gas selectivity. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45395.     

Effect of air gap on gas permeance/selectivity performance of BTDA‐TDI/MDI copolyimide hollow fiber membranes

Fabrication, morphology evaluation , and permeance/selectivity properties of three asymmetric BTDA‐TDI/MDI copolyimide hollow fiber membranes (HFM s ) are reported. The asymmetric HFM s were spun using the dry/wet phase inversion process. The effect of one of the major spinning parameters, the air gap, on the permeance/selectivity properties of the produced HFM was investigated. Scanning e lectron m icroscopy was used to evaluate the morphological characteristics and the macroscopic structure of the developed HFM. The permeance values of He, H₂, CH₄, CO₂, O₂, and N₂ gases were measured by the variable pressure method at different feed pressures and temperatures and the permselectivity coefficients were calculated. The higher selectivity values were evaluated for the Μ1 membrane and were found to be 49.33, 2.99, 5.13, 5.57 , and 9.61 for H₂/CH₄, O₂/N₂, CO₂/CH₄, CO₂/N₂ , and H₂/CO₂ gas mixtures , respectively. The selectivity experiments of H₂/CH₄, CO₂/CH₄ , and O₂/N₂ mixtures were performed at 25 ° C. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4490–4499, 2013     

Recovery of alcohols from water using polydimethylsiloxane–silica nanocomposite membranes: Characterization and pervaporation performance

Different polydimethylsiloxane (PDMS) nanocomposite membranes were synthesized by incorporating various contents of nanosized silica particles to improve the PDMS pervaporation (PV) performance. A uniform dispersion of silica nanoparticles in the PDMS membranes was obtained. The nanocomposite membranes were characterized morphologically by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results showed that surface roughness increases by incorporating silica, and this decreases absorption of penetrants on the membrane. Swelling studies showed that the presence of silica nanoparticles into the PDMS membranes decreases degree of swelling, which can be attributed to rigidification of the PDMS matrix. Additionally, the results revealed that helium permeability decreases through the nanocomposite membranes, due to the more polymer chains packing. Effects of silica on recovery of isopropanol (IPA) from water mixtures were also investigated. Based on the results, incorporating silica nanoparticles promotes significantly the PDMS membrane selectivity because the polymer chains are rigidified and also the polymer free volume decreases. However, permeation flux decreases as diffusion of the penetrants reduces in the presence of silica nanoparticles within the PDMS membranes. As PV performance depends on operating conditions, effects of feed composition, and temperature were also studied. Moreover, recoveries of IPA, ethanol, and methanol from water mixtures were compared using the PDMS‐silica nanocomposite membranes. The results demonstrated that polarity and solubility of alcohols affect permeation flux and selectivity resulting in the higher permeation flux and selectivity for IPA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Cellulose triacetate/LUDOX-SiO2 nanocomposite for synthesis of pervaporation desalination membranes

A series of cellulose triacetate/Ludox-silica nancomposite pervaporation membranes was successfully prepared via solution casting, aiming to improve the performance of cellulose triacetate membranes for desalination. The fabricated nanocomposite membranes were characterized to study the membrane morphology, chemical composition, mechanical properties, and surface hydrophilicity. Furthermore, the desalination performance was investigated as a function of silica (SiO₂) loading (ranging from 1 to 4 wt%) and feed concentration at 30 and 60 g/L of sodium chloride (NaCl). Pervaporation experiments showed that incorporating 4 wt% SiO₂ into a cellulose triacetate (CTA) membrane increased the water flux by a factor 2.5 compared with pristine CTA (from 2.2 to 6.1 kg m⁻² h⁻¹) for a 30 g/L NaCl feed solution at 70°C, while the salt rejection remained above 99%. The CTA/4 wt% SiO₂ membrane was found to have only 21% flux reduction when tested with a 60 g/L NaCl feed solution, without changes in membrane selectivity. This suggests that the developed CTA/Ludox-SiO₂ nanocomposite pervaporation membrane is suitable for desalination.     

细乳液聚合制备改性硅溶胶／聚丙烯酸酯复合乳液

常温下一步法制备改性硅溶胶,并通过细乳液聚合制备改性硅溶胶／聚丙烯酸酯复合乳液。考查了温度对聚合速率和单体转化率的影响以及不同乳化剂含量下聚合过程中乳胶粒粒径的变化情况;测试了乳胶膜的吸水率,并用接触角法表征了乳胶膜的表面自由能。     

Preparation of hydrophobic flat sheet membranes from PVDF-HFP copolymer for enhancing the oxygen permeance in nitrogen/oxygen gas mixture

In this study, poly(vinilydene fluoride-co-hexafluoropropylene)(PVDF-HFP) was used for preparation of hydrophobic membranes using non-solvent induced phase inversion(NIPS) technique. PVDF-HFP copolymer with concentrations of 10 wt% and 12 wt% was prepared to investigate the effect of polymer concentration on pore structure,morphology, hydrophobicity and performance of prepared membranes. Besides, the use of two coagulation baths with the effects of parameters such as coagulant time, polymer type and concentration, and the amount of nonsolvent were studied. The performance of prepared membranes was evaluated based on the permeability and selectivity of oxygen and nitrogen from a gas mixture of nitrogen/oxygen under operating conditions of feed flow rate(1–5 L·min~(-1)), inlet pressure to membrane module(0.1–0.5 MPa) and temperatures between 25 and 45 °C. The results showed that the use of two coagulation baths with different compositions of distillated water and isopropanol,coagulant time, polymer type and concentration, and the amount of non-solvent additive have the most effect on pore structure, morphology, thickness, roughness and crystallinity of fabricated membranes. Porosity ranges for the three fabricated membranes were determined, where the maximum porosity was 73.889% and the minimum value was 56.837%. Also, the maximum and minimum average thicknesses of membrane were 320.85 μm and115 μm. Besides, the values of 4.7504 × 10~(-7) mol· m~(-2)· s~(-1)· Pa~(-1), 0.525 and 902.126 nm were achieved for maximum oxygen permeance, O_2/N_2 selectivity and roughness, respectively.     

Polysulfone/zinc oxide nanoparticle mixed matrix membranes for CO2/CH4 separation

Preparation and characterization of novel polysulfone/zinc oxide (PSf/ZnO) mixed matrix membranes (MMMs) with different ZnO loadings for high selective CO₂/CH₄ separation were aimed in this study. Scanning electron microscopy photographs demonstrated that spongy and small tear like pores in plain PSf membrane (0 wt % of ZnO) replaced with large tear like pores close to surface layer by increasing ZnO content up to 0.1 and 1 wt %. In contrast, a dense and less free volume structure was obtained in membranes having 3 and 5 wt % of ZnO. Membrane porosity increased from 28.68 to 50.51% with increasing ZnO content from 0 to 1 wt %. Then, a reduction in porosity was observed for membranes containing 3 and 5 wt % of ZnO. Atomic force microscopy images presented variation in membrane surface roughness. Surface roughness decreased from 67.64 nm for plain PSf to 47.86 nm for membrane containing 1 wt % of ZnO. While, surface roughness increased and reached to 115.5 and 122.4 nm for MMMs having 3 and 5 wt % of ZnO. Gas separation properties of PSf/ZnO MMMs were examined and CO₂/CH₄ selectivity of MMMs containing 3 and 5 wt % of ZnO were 22.29 and 54.29, respectively, in 1 bar feed pressure. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39745.     

A new technique for preparation of PDMS/ceramic nanocomposite membrane for gaseous hydrocarbons separation

A novel composite membrane using polydimethylsiloxane (PDMS) as a top active layer and ceramic nanocomposite as the support layer was developed for the gaseous hydrocarbons separation. For the fabrication of hybrid membranes, nanocomposite technology applied for manufacturing ceramic supports with controllable microstructures. Also, a new method was used for coating a uniform and no penetrated polymeric layer. Top layer of ceramic support with nanocomposite microstructures was fabricated using 5 wt % α‐Al₂O₃‐SiO₂ bidispersed suspensions with optimum weight fraction of second phase (SiO₂) based on the fractional collision frequency theory. PDMS selective layer was coated on the outer surface of the porous ceramic nanocomposite support by dip‐coating method. In this respect, the effect of several parameters such as pretreatment temperature, PDMS solution concentration, and number of coated polymeric layers on prepared layers morphology and hybrid membrane performance in the separation of condensable hydrocarbons (iso and n‐butane) from hydrogen were investigated. The results showed that the membranes fabricated at 140°C as pretreatment temperature and three polymeric layers by 7, 15, and 15 wt % PDMS concentration, respectively, had a high selectivity (>25 at 2 bar)) in C₄H₁₀/H₂ separation. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Nano-silica/polysulfone asymmetric mixed-matrix membranes (MMMs) with high CO2 permeance in the application of CO2/N2 separation

Nano-sized silica/polysulfone (PSf) flat sheet asymmetric MMMs with high CO₂ permeance for CO₂/N₂ separation were fabricated by dry/wet phase inversion method using N, N-dimethylacetamide (DMAc) and tetrahydrofuran (THF) as solvents and ethanol as additives. The results indicated that the addition of nano-silica on the polymer matrix resulted on reduced membrane performance due to void formation and particle agglomeration. Optimum membrane performance was obtained at the following fabrication parameters: 22 wt.% PSf, 31.8 wt.% DMAc, 31.8 wt.% THF, 14.4 wt.% ethanol, 20 s evaporation time, and 0 wt.% silica loading, with CO₂/N₂ selectivity of 15.6 and CO₂ permeance of 14.2 GPU.     

Dispersion of "guava-like" silica/polyacrylate nanocomposite particles in polyacrylate matrix

A series of “guava-like” silica/polyacrylate nanocomposite particles with close silica content and different grafting degrees were prepared via mini-emulsion polymerization using 3-(trimethoxysilyl)propyl methacrylate (TSPM) modified silica/acrylate dispersion. The silica/polyacrylate composite particles were melt-mixed with unfilled polyacrylate (PA) resin to prepare corresponding silica/polyacrylate molded composites and the dispersion mechanism of these silica particles from the “guava-like” composite particles into polyacrylate matrix was studied. It was calculated that about 110 silica particles were accumulated in the bulk of every silica/polyacrylate composite latex particle. Both the solubility tests of silica/polyacrylate composite latex particles in tetrahydrofuran (THF) and the section transmission electron microscope (TEM) micrographs of silica/polyacrylate molded composites indicated that the grafting degree of silica particles played a crucial role in the dispersion of silica/polyacrylate composite particles into the polyacrylate matrix. When the grafting degree of polyacrylate onto silica was in a moderate range (ca. 20%–70%), almost all of silica particles in these “guava-like” composite particles were dispersed into the polyacrylate matrix in a primaryparticle-level. However, at a lower grafting degree, massive silica aggregations were found in molded composites because of the lack of steric protection. At a greater grafting degree (i.e., 200%), a cross-linked network was formed in the silica/polyacrylate composite particles, which prevented the dispersion of composite particles in THF and polyacrylate matrix as primary particles.     

Evaluation of interfacial layer properties in the polystyrene/silica nanocomposite

Processing conditions and final mechanical properties of polymer nanocomposites are affected by their interfacial layers behavior. However, it is impossible to determine directly the properties of these layers by dynamic rheometry tests. In this work, the interfacial layers properties are evaluated for polystyrene containing silica nanoparticles by the concept of glass‐transition temperature shift. The samples were prepared via solution‐mixing method and dynamic rheometry was used to determine the viscoelastic behavior of filled polymers in the melt state. This initial step showed that addition of silica particles increased the glass‐transition temperature. By preference, decrease in the filler particle size lead to a drastic increase in the glass‐transition temperature and interfacial layer volume fraction due to relatively high surface area of the small filler particles. Then, in the next step, the viscoelastic properties of interfacial layer have been evaluated on the basis of the properties of neat polystyrene using temperature‐frequency superposition law. For this purpose, the shift factor was calculated from the glass‐transition temperature of the sample with maximum filler content. Finally, the effect of immobilized interfacial layer on the viscoelastic properties of the polymer nanocomposite samples has been estimated. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Polyurethane/polyethersulfone dual-layer anisotropic membranes for CO2 removal from flue gas

Removing CO₂ from flue gas streams has been a permanent challenge regarding environmental issues. Membrane technology is a solution for this problem but more efficient membranes are required. The fabrication of dual-layer polyurethane/polyethersulfone membrane by the co-casting technique is undertaken and the effects of previous evaporation time and coagulation water bath temperature on membrane morphology are explored. Uniform layers with excellent adhesion are obtained. The effect of feed pressure and temperature on membrane permeability and selectivity for CO₂, N₂, and O₂ are studied. Increasing the pressure from 1 to 8 bar results in a reduction of CO₂ permeability and CO₂/N₂ ideal selectivity from 19.6 to 13.0 barrer, and from 66 to 60, respectively. Temperature in the range of 25–45°C enhances CO₂ permeability from 19.6 to 28.9 barrer, although CO₂/N₂ selectivity decreases from 66 to 43, yet showing good potential for applications.     

Polysulfone/poly(ether sulfone) blended membranes for CO2 separation

Polymer blending as a modification technique is a useful approach for augmenting the gas‐separation and permeation properties of polymeric membranes. Polysulfone (PSF)/poly(ether sulfone) (PES) blend membranes with different blend ratios were synthesized by conventional solution casting and solvent evaporation technique. The synthesized membranes were characterized for miscibility, morphology, thermal stability, and spectral properties by differential scanning calorimetry (DSC), field emission scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared (FTIR) spectroscopy, respectively. The permeation of pure CO₂ and CH₄ gases was recorded at a feed pressure of 2–10 bar. The polymer blends were miscible in all of the compositions, as shown by DSC analysis, and molecular interaction between the two polymers was observed by FTIR analysis. The thermal stability of the blend membranes was found to be an additive property and a function of the blend composition. The morphology of the blend membranes was dense and homogeneous with no phase separation. Gas‐permeability studies revealed that the ideal selectivity was improved by 65% with the addition of the PES polymer in the PSF matrix. The synthesized PSF/PES blend membranes provided an optimized performance with a good combination of permeability, selectivity and thermal stability. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42946.     

The preparation of SPEEK/phosphate salts membranes and application for CO2/CH4 separation

SPEEK/phosphate salts membranes were prepared and utilized for CO₂/CH₄ separation. SPEEK with abundant –SO₃H groups and EO groups on polymer chains would be beneficial for CO₂ transport. The doped phosphate salts (NaH₂PO₄, Na₂HPO₄ and Na₃PO₄) with different acid‐base properties increased the water content in the membrane, and water was expected to increase both the solubility and diffusivity of CO₂ in the membrane. All membranes were characterized by FTIR, TGA, and XRD. The CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄ membranes were higher than that of SPEEK/NaH₂PO₄ and SPEEK/Na₂HPO₄ membranes. Compared to the pure SPEEK membrane, the CO₂ permeability and CO₂/CH₄ selectivity of SPEEK/Na₃PO₄?10 membrane were increased by 144% and 65%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43399.     

Amine-impregnated natural zeolite as filler in mixed matrix membranes for CO2/CH4 separation

Flat mixed matrix membranes (MMMs) comprising polysulfone and clinoptilolite-type natural zeolite were prepared by casting. Zeolite was modified with three alkylamines: ethanolamine (EA), bis(2-hydroxypropyl)amine (BHPA), and polyethylenimine (PEI) by the impregnation method. Impregnated zeolite samples were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, and N₂ adsorption–desorption. The alkylamine loading extent determined by thermogravimetric analysis was 5.2, 4.8, and 8.5% for EA, BHPA, and PEI, respectively. Analyses of MMMs showed that the incorporation of impregnated zeolite affected the glass-transition temperature (T_g) and mixed-gas transport properties. In this regard, a decreasing trend of the T_g values from 185.5 °C for the polymeric membrane up to 176.6 °C for Clino-EA-based MMM was recorded. In addition, the gas separation performance was evaluated at two different feed pressures. At 50 psi, MMMs showed an enhancement up to 30% on the CO₂ permeability (22.79 Barrer) and 55% on the CO₂/CH₄ selectivity (45.78) in comparison with the polymeric membrane (CO₂ permeability 17.34 Barrer; CO₂/CH₄ selectivity 29.38). These values varied depending on the alkylamine, BHPA being the most selective. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48286.     

Pebax/a-MoS2/MIP-202混合基质膜的制备及CO2分离性能

为了获得高性能的CO₂/N₂分离膜,把空气中氧刻蚀的二硫化钼（a-MoS₂）和金属有机框架材料MIP-202通过机械力化学反应制备的双功能填料作为分散相,聚醚嵌段酰胺（Pebax-1657）作为连续相,采用溶液浇铸法制备了Pebax/a-MoS₂/MIP-202混合基质膜。采用FT-IR表征了填料的化学结构,借助ATR-FTIR、SEM、TG和力学性能测试表征了混合基质膜的化学结构、微观形貌结构、热稳定性和物理力学性能。研究了水含量、双功能填料配比、含量、膜两侧压差和操作温度对膜气体分离性能的影响,并考察了模拟烟道气（CO₂/N₂体积比15/85）条件下混合基质膜的长时间运行稳定性。结果表明：在温度为25℃、膜两侧压差为0.1 MPa的操作条件下,a-MoS₂与MIP-202质量比为5∶5和双功能填料含量为6%（质量）时,膜的气体分离性能达到最优,CO₂渗透性和CO₂/N₂选择性分别为380 Barrer和124.7,超过了2019年McKeown等提出的上限值。连续测试360 h后,混合基质膜的性能没有明显降低,其平均CO₂渗透性和CO₂/N₂选择性分别为358 Barrer和120.1。这主要是由于a-MoS₂和MIP-202协同提高了膜的气体分离性能。     

Pebax/a-MoS2/MIP-202混合基质膜的制备及CO2分离性能

为了获得高性能的CO₂/N₂分离膜,把空气中氧刻蚀的二硫化钼（a-MoS₂）和金属有机框架材料MIP-202通过机械力化学反应制备的双功能填料作为分散相,聚醚嵌段酰胺（Pebax-1657）作为连续相,采用溶液浇铸法制备了Pebax/a-MoS₂/MIP-202混合基质膜。采用FT-IR表征了填料的化学结构,借助ATR-FTIR、SEM、TG和力学性能测试表征了混合基质膜的化学结构、微观形貌结构、热稳定性和物理力学性能。研究了水含量、双功能填料配比、含量、膜两侧压差和操作温度对膜气体分离性能的影响,并考察了模拟烟道气（CO₂/N₂体积比15/85）条件下混合基质膜的长时间运行稳定性。结果表明：在温度为25℃、膜两侧压差为0.1 MPa的操作条件下,a-MoS₂与MIP-202质量比为5∶5和双功能填料含量为6%（质量）时,膜的气体分离性能达到最优,CO₂渗透性和CO₂/N₂选择性分别为380 Barrer和124.7,超过了2019年McKeown等提出的上限值。连续测试360 h后,混合基质膜的性能没有明显降低,其平均CO₂渗透性和CO₂/N₂选择性分别为358 Barrer和120.1。这主要是由于a-MoS₂和MIP-202协同提高了膜的气体分离性能。     

Effect study of hexagonal mesoporous silica/polyaniline nanocomposite on the structural properties of polysulfone membranes and its heavy metal removal efficiency

New mixed matrix membranes of polysulfone were synthesized by different content of hexagonal mesoporous silica coated by polyaniline and used for nickel and lead ion removal. The membranes were characterized by FESEM, XRD, BET, TGA, and FTIR, and zeta potential measurements. The results showed that PANi/HMS particles enhanced the membrane porosity and permeability. These effects were explained according to an increase of the membrane hydrophilicity due to the formation of new functional groups during membrane casting. The results showed that metal ion rejection was performed by a filtration–adsorption mechanism, resulting in fixation of metal ions on the active sites of membranes.     

Mixed substituent ether-containing polyphosphazene/poly(bis-phenoxyphosphazene) blends as membranes for CO2 separation from N2

Polyphosphazenes gain much of their physical and chemical properties from the substituents attached to the phosphorus atoms in the backbone. Poly(phosphazenes) that have short-chain polyether containing substituents, such as, 2-(2-methoxyethoxy)ethanol, have high CO₂ permeability and selectivity over N₂ as well as resistance to degradation under humidification at 60°C. However, the principal shortcomings of this polymer are the poor mechanical and surface characteristics. Blending of an example of this polyphosphazene (MEEP-80) with poly(bis-phenoxyphosphazene) (PPOP) has yielded more durable materials that have a non-adhesive surface. In this work, the blended polymer membranes were found to have increased CO₂ permeability with higher selectivity over N₂. Thermal analysis and the application of transport models support a structure of the blends that is not either an intimate blend or phase separated bulk structure, but one where PPOP domains retain their crystallinity and are dispersed within an amorphous MEEP-80 phase.