Effect of titanium dioxide nanoparticles on polydimethylsiloxane/polyethersulfone composite membranes for gas separation

Introducing inorganic nanoparticles into the structure of polymeric membranes is an interesting approach for the enhancement of physical, chemical, and separation properties of the membranes. In this article, the performance of a two‐layer nanocomposite membrane for gas separation was studied. Three different methods for embedding titanium dioxide (TiO₂) nanoparticle were employed for the membrane preparation. The techniques include blending TiO₂ in the polydimethylsiloxane (PDMS) coating layer, blending TiO₂ in the polyethersulfone (PES) support and dip coating of PES support with TiO₂ accompanied by PDMS coating. The aim of the current research was finding the optimum technique for introducing TiO₂ into the membrane to obtain superior performance for gas separation. The results indicated that PES support containing TiO₂ nanoparticles possessed favorable effect on gas separation capability. The optimum performance was obtained by PDMS‐coated membranes prepared with 7 wt% TiO₂‐embedded PES support. Carbon dioxide (CO₂) permeance, CO₂/nitrogen, and CO₂/methane selectivity were obtained as 188.7 GPU, 8.6, and 3.4, respectively. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Effect of coating method on gas separation by PDMS/PES membrane

In this study, polydimethylsiloxane (PDMS)‐coated polyethersulfone (PES) composite membrane was prepared for gas separation. “Film casting” and “dip‐coating” techniques were used for producing selective PDMS layer on the surface of the PES support. The effects of coating technique and conditions including coating solution concentration and curing temperature on permselectivity of CO₂, CH₄, and N₂ were investigated. The prepared PES support did not provide any selectivity to the gases. When the concentration of PDMS coating solution was increased, initially permeability of CO₂ was rapidly dropped and then gradually reached to an almost constant value. The optimum concentration of coating solution was 5 wt%. Curing temperature showed no pronounced effect on the CO₂ permeability and selectivity. In “film casting” method, double coating showed superior permeability and selectivity. However, triple “dip‐coating” was promising. The selectivity of composite membrane prepared by “dip‐coating” was higher than “film casting” method. CO₂/N₂ and CO₂/CH₄ selectivity of five sequential dip‐coated composite membranes was 45.5 and 9.3, respectively. POLYM. ENG. SCI., 2013. © 2013 Society of Plastics Engineers     

Fabrication of asymmetric polyethersulfone membranes for separation of carbon dioxide from methane using polyetherimide as polymeric additive

Polyetherimide (PEI) was used as a polymeric additive for preparing an asymmetric polyethersulfone (PES) membrane for the separation of CO₂ from CH₄. In pure gas experiments, the higher skin layer thickness and the lower porosity of the sub layer for the membrane prepared from the polymer blend with the composition of 98:2 lead to an increase in CO₂/CH₄ selectivity and a decrease in the CO₂ permeance in contrast with a pristine PES. For higher PEI contents, the higher fractional free volume of the membranes improves the gas permeance and reduces the CO₂/CH₄ selectivity. The incorporation of PEI in PES reduces the CO₂ sorption in PES via decreasing the non-equilibrium free volume and imparts antiplasticization properties to the membrane.     

Modification of PES/PU membrane by supercritical CO2 to enhance CO2/CH4 selectivity: Fabrication and correlation approach using RSM

Integrally skinned asymmetric gas separation membranes of polyethersulfone (PES)/polyurethane (PU) blend were prepared using supercritical CO₂ (SC-CO₂) as a nonsolvent for the polymer solution. The membrane consisted of a dense and a porous layer, which were conjoined to separate CO₂ from CH₄. The FTIR, DSC, tensile and SEM tests were performed to study and characterize the membranes. The results revealed that an increase in SC-CO₂ temperature causes an increment in permeance and a decrease in membrane selectivity. Furthermore, by raising the pressure, both permeance and selectivity increased. The modified membrane with SC-CO₂ had much higher selectivity, about 5.5 times superior to the non-modified membrane. This higher selectivity performance compared to previous works was obtained by taking the advantages of both using partial miscible blend polymer due to the strong polar–polar interaction between PU PES and SC-CO₂ to fabricate the membrane. The response surface methodology (RSM) was applied to find the relationships between several explanatory variables and CO₂ and CH₄ permeance and CO₂/CH₄ selectivity as responses. Finally, the results were validated with the experimental data, which the model results were in good agreement with the available experimental data.     

Optimization of CO2–CH4 separation performance of integrally skinned asymmetric membranes prepared from poly(2,6‐dimethyl‐1,4‐phenylene oxide) by factorial design

Integrally skinned asymmetric flat sheet membranes were prepared from poly(2,6‐dimethyl 1,4‐phenylene oxide)(PPO) for CO₂–CH₄ separation. Various experiments were carried out to identify PPO membranes, which have good mechanical strength and gas separation abilities. Membrane strength and selectivity depend on the interplay of the rate of precipitation and the rate of crystallization of the PPO. The effects of major variables involved in the membrane formation and performance, including the concentration of the polymer, solvent, and additive, the casting thickness, the evaporation time before gelation, and the temperature of the polymer solution, were investigated. Factorial design experiments were carried out to identify the factor effects. The membrane performance was modelled and optimized to approach preset values for high CO₂ permeance and a high CO₂ : CH₄ permeance ratio. Membranes were prepared based on the optimum conditions identified by the model. Essentially, defect‐free membranes were prepared at these conditions, which resulted in a pure gas permeance of 9.2 × 10⁻⁹ mol/m² s Pa for CO₂ and a permeance ratio of 19.2 for CO₂ : CH₄. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1601–1610, 1999     

Quest for high performance carbon capture membranes: Fabrication of SAPO-34 and CNTs-doped polyethersulfone-based mixed-matrix membranes

Gas separation process is an effective method for capturing and removing CO₂ from post-combustion flue gases. Due to their various essential properties such as ability to improve process efficiency, polymeric membranes are known to dominate the market. Trade-off between gas permeability and selectivity through membranes limits their separation performance. In this study, solution casting cum phase separation method was utilized to create polyethersulfone-based composite membranes doped with carbon nanotubes (CNTs) and silico aluminophosphate (SAPO-34) as nanofiller materials. Membrane properties were then examined by performing gas permeation test, chemical structural analysis and optical microscopy. While enhancing membranes CO₂ permeance, SAPO-34 and CNTs mixture improved their CO₂/N₂ selectivity. By carefully adjusting membrane casting factors such as filler loadings. Using Taguchi statistical analysis, their carbon capture efficiency was improved. The improved mixed-matrix membrane with loading of 5 wt% CNTs and 10 wt% SAPO-34 in PES showed highly promising separation performance with a CO₂ permeability of 319 Barrer and an ideal CO₂/N₂ selectivity of 12, both of which are within the 2008 Robeson upper bound. A better mixed-matrix membrane with outstanding CO₂/N₂ selectivity and CO₂ permeability was produced as a result of the synergistic effect of adding two types of fillers in optimized loading.     

Enhanced gas separation performance of PSF membrane after modification to PSF/PDMS composite membrane in CO2/CH4 separation

Asymmetric polysulfone (PSF) membrane was developed and modified to PSF/polydimethylsiloxane (PSF/PDMS) composite membrane by dip coating technique. Effect of PDMS coating time on membrane properties was examined by scanning electron microscopy, thermogravimetric analysis, differential scanning calorimetry, attenuated total reflectance‐Fourier transform infrared, and water contact angle. The increase in PDMS coating time resulted in a decrement in the thermal strength of PSF membrane. Surface contact angle values revealed that increase in PDMS coating time had increased the surface hydrophobicity in membranes. CO₂/CH₄ separation performance of membranes was evaluated, and an increase in CO₂/CH₄ ideal selectivity was observed with the increase of PDMS coating time. At feed pressure of 10 bar, the selectivity of PSF has increased up to 65% after dip coating with PDMS for 30 min. Modification of polymeric membrane into composite membrane provided a way forward towards the enhancement of gas separation performance in polymeric membranes. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45650.     

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     

A high CO2 permselective mesoporous silica/carbon composite membrane for CO2 separation

Ordered mesoporous silica/carbon composite membranes with a high CO₂ permeability and selectivity were designed and prepared by incorporating SBA-15 or MCM-48 particles into polymeric precursors followed by heat treatment. The as-made composite membranes were characterized by high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and N₂ adsorption, of which the gas separation performance in terms of gas permeability and selectivity were evaluated using the single gas (CO₂, N₂, CH₄) and gas mixtures (CO₂/N₂ and CO₂/CH₄, 50/50 mol.%). In comparison to the pure carbon membranes and microporous zeolite/C composite membranes, the as-made mesoporous silica/C composite membranes, and the MCM-48/C composite membrane in particular, exhibit an outstanding CO₂ gas permeability and selectivity for the separation of CO₂/CH₄ and CO₂/N₂ gas pairs owing to the smaller gas diffusive resistance through the membrane and additional gas permeation channels created by the incorporation of mesoporous silicas in carbon membrane matrix. The channel shape and dimension of mesoporous silicas are key parameters for governing the gas permeability of the as-made composite membranes. The gas separation mechanism and the functions of porous materials incorporated inside the composite membranes are addressed.     

Effect of gas permeation temperature and annealing procedure on the performance of binary and ternary mixed matrix membranes of polyethersulfone,SAPO‐34, and 2‐hydroxy 5‐methyl aniline

This study investigated the effect of annealing time and temperature on gas separation performance of mixed matrix membranes (MMMs) prepared from polyethersulfone (PES), SAPO‐34, and 2‐hydroxy 5‐methyl aniline (HMA). A postannealing period at 120°C for a week extensively increased the reproducibility and stability of MMMs, but for pure PES membranes no post‐annealing was necessary for stable and reproducible performance. The effect of operation temperature was also investigated. The permeabilities of H₂, CO₂, and CH₄ increased with increasing permeation temperature from 35°C to 120°C, yet CO₂/CH₄ and H₂/CH₄ selectivities decreased. PES/SAPO‐34/HMA ternary and PES/SAPO‐34 binary MMMs exhibited the highest ideal selectivity and permeability values at all temperatures, respectively. For H₂/CO₂ pair, when temperature increased from 35°C to 120°C, selectivity increased from 3.2 to 4.6 and H₂ permeability increased from 8 to 26.5 Barrer for ternary MMM, demonstrating the advantage of using this membrane at high temperatures. The activation energies were in the order of CH₄ > H₂ > CO₂ for all membranes. PES/SAPO‐34/HMA membrane had activation energies higher than that of PES/SAPO‐34 membrane, suggesting that HMA acts as a compatibilizer between the two phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40679.     

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.     

Facile CO2 Separation in Composite Membranes

CO₂ emission from anthropogenic sources has raised worldwide environmental concerns and hence proficient energy paradigm has tilted towards CO₂ capture. Membrane technology is one of the efficient technologies for CO₂ separation since it is environmentally friendly, inexpensive, and offers high surface areas. Various approaches are discussed to improve membrane performance focusing mainly on permeability and selectivity parameters. Different types of fillers are incorporated to reach the Robeson's upper bound curve. In this review, polymer‐inorganic nanocomposite membranes for the separation of CO₂, CH₄, and N₂ from various gas mixtures are comprehensively discussed. Metal organic frameworks (MOFs) and ionic liquid (ILs) mixed‐matrix membranes are also considered.     

Polydimethylsiloxane/postmodified MIL‐53 composite layer coated on asymmetric hollow fiber membrane for improving gas separation performance

Composite layer containing postmodified MIL‐53 (P‐MIL‐53) was exploited to be coated on as‐fabricated asymmetric hollow fiber membrane for improving gas separation performance. The morphology and pore size distribution of P‐MIL‐53 particles were characterized by SEM and N₂ adsorption isotherm. The EDX mapping and FTIR spectra were performed to confirm the presence of P‐MIL‐53 deposited on the outer surface of hollow fiber membranes. The results of pure gas permeation measurement indicated that incorporation of P‐MIL‐53 particles in coating layer could improve permeation properties of hollow fiber membranes. By varying coating times and P‐MIL‐53 content, the membrane coated with PDMS/15%P‐MIL‐53 composite by three times achieved best performance. Compared to pure PDMS coated membrane, CO₂ permeance was enhanced from 29.96 GPU to 40.24 GPU and ideal selectivity of CO₂/N₂ and CO₂/CH₄ also increased from 23.28 and 26.95 to 28.08 and 32.03, respectively. The gas transport through composite membrane was governed by solution‐diffusion mechanism and CO₂ preferential adsorption of P‐MIL‐53 contributed to considerable increase of CO₂ solubility resulting in accelerated permeation rate. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44999.     

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.     

Asymmetric polysulfone gas separation membranes treated by low pressure DC glow discharge plasmas

Asymmetric polysulfone (PSF) gas separation membranes were prepared at different conditions such as non‐solvent concentration, evaporation time (ET) and coagulation bath temperature (CBT). In addition, effects of low‐pressure DC glow discharge plasma on the characteristics of PSF membranes were investigated. PSF membranes both before and after plasma treatment were characterized by several techniques, including contact angle measurement, scanning electron microscope (SEM), dynamic mechanical thermal analysis (DMTA), and atomic force microscopy (AFM). Furthermore, the performance of membranes was evaluated in terms of permeability of CO₂, CH₄, O_2, and N₂ gases. The ideal selectivity of CO₂/CH₄ and O₂/N₂ and surface free energy was calculated. Results showed that the EtOH concentration, ET and CBT affect the morphology of PSF membranes. For membranes prepared from a casting solution consisting of PSF 26.0, NMP 28.0, THF 28.0, and EtOH 18.0 wt % and ET for 3 min, the maximum selectivity of untreated membrane is about 69.76 and 12.59 for CO₂/CH₄ and O₂/N₂, respectively. After plasma treatment, the ideal selectivity is receded; however, the CO₂/CH₄ is still higher than 40.41 at pressure of 5 bars. Finally, preparation conditions and DC glow discharge plasmas have significant effects on the characteristics of the PSF membranes and result in an increase of the gas permeation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42116.     

Membranes for CO2 /CH4 and CO2/N2 Gas Separation

Membrane technology has emerged as a leading tool worldwide for effective CO₂ separation because of its well-known advantages, including high surface area, compact design, ease of maintenance, environmentally friendly nature, and cost-effectiveness. Polymeric and inorganic membranes are generally utilized for the separation of gas mixtures. The mixed-matrix membrane (MMM) utilizes the advantages of both polymeric and inorganic membranes to surpass the trade-off limits. The high permeability and selectivity of MMMs by incorporating different types of fillers exhibit the best performance for CO₂ separation from natural gas and other flue gases. The recent progress made in the field of MMMs having different types of fillers is emphasized. Specifically, CO₂/CH₄ and CO₂/N₂ separation from various types of MMMs are comprehensively reviewed that are closely relevant to natural gas purification and compositional flue gas treatment     

Fabrication and modification of cellulose acetate based mixed matrix membrane: Gas separation and physical properties

[Cellulose acetate (CA)-blend-multi walled carbon nano tubes (MWCNTs)] mixed matrix membranes (MMMs), [CA/polyethylene glycol (PEG)/MWCNTs] and [CA/styrene butadiene rubber (SBR)/MWCNTs] blend MMMs were prepared by solution casting method for gas separation applications using Tetrahydrofuran (THF) as solvent. Both raw-MWCNTs (R-MWCNTs) and functionalized carboxylic-MWCNTs (C-MWCNTs) were used in membrane preparation. The MWCNTs loading ratio and pressure effects on the gas separation performance of prepared membranes were investigated for pure He, N₂, CH₄ and CO₂ gases. Results indicated that utilizing C-MWCNT instead of R-MWCNTs in membrane fabrication has better performance and (CO₂/CH₄) and (CO₂/N₂) selectivity reached to 21.81 and 13.74 from 13.41 and 9.33 at 0.65 wt% of MWCNTs loading respectively. The effects of PEG and SBR on the gas transport performance and mechanical properties were also investigated. The highest CO₂/CH₄ selectivity at 2 bar pressure was reached to 53.98 for [CA/PEG/C-MWCNT] and 43.91 for [CA/SBR/C-MWCNT] blend MMMs at 0.5 wt% and 2 wt% MWCNTs loading ratio respectively. Moreover, increase of feed pressure led to membrane gas permeability and gas pair selectivity improvement for almost all prepared membranes. The mechanical properties analysis exhibited tensile modules improvement with increasing MWCNTs loading ratio and utilizing polymer blending.     

Preparation and characterization of polyvinylchloride based mixed matrix membrane filled with multi walled carbon nano tubes for carbon dioxide separation

Poly vinyl chloride/multi wall carbon nano tubes (PVC/MWCNTs) mixed matrix membranes (MMMs) were prepared for gas separation. Raw and functionalized MWCNTs (R-MWCNTs and C-MWCNTs) were utilized in membranes preparation. The C-MWCNT shows better performance compared to raw ones. Membrane (CO₂/CH₄) selectivity was increased from 39.21 to 52.18 at 2 bar pressure by MWCNT loading ratio. The modified membranes with styrene butadiene rubber (SBR-MMMs) showed 63.52 and 34.70 selectivity for (CO₂/CH₄) and (CO₂/N₂) at 2 bar pressure. Mechanical properties analysis exhibited tensile module improvement utilizing blending modification. Increase of feed pressure led to membrane gas permeability decreasing. But gas pair selectivity follows a nearly constant behavior for MMMs and increasing behavior for blend MMMs.     

Transport properties of gases through integrally skinned asymmetric composite membranes prepared from date pit powder and polysulfone

Studies were conducted on transport properties and separation performance of date pit/polysulfone composite membranes for CO₂, CH₄, N₂, He, and H₂ gases. Date seeds were obtained and processed into powder. Asymmetric flat sheet membrane was prepared by solvent casting method with 2–10 wt % date pit powder. Membrane characterization was done using high pressure gas permeation, X‐ray diffraction, thermogravimetric, and scanning electron microscope analyses. The separation performance and the plasticization resistance property were evaluated in terms of gas permeability, selectivity, and plasticization pressure, respectively. Time dependent performance properties were evaluated up to a pressure of 40 bar for 75 days. Results obtained showed the highest selectivity values of 1.54 (He/H₂), 3.637 (He/N₂), 2.538 (He/CO₂), 2.779 (He/CH₄), 3.179 (H₂/N₂), 3.907 (H₂/CO₂), 1.519 (CH₄/N₂), 1.650 (CO₂/N₂), and 1.261 (CO₂/CH₄) at 10 bar and 35 °C feed pressure and temperature, respectively. The resulting composite membrane showed about 39.50 and 66.94% increase in the selectivity of He/N₂ and CO₂/CH₄, respectively, as compared to the pure polysulfone membrane. Thus, the membrane composites possess some potentials in membrane gas separation. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43606.     

Development and tuning of Matrimid membrane oxygenators with improved biocompatibility and gas permeance by plasma treatment

In this study, a commercial polyimide is examined in the capacity of membrane oxygenator. The effects of polymer concentration, cosolvent, and nonsolvent additives in dope solution on the performance and morphology of membranes are investigated. In order to improve the performance, surface modification is carried out by using plasma-enhanced chemical vapor deposition. The obtained results reveal that CO₂ permeance decreased from 495 to 78 GPU upon increasing Matrimid concentration at constant tetrahydrofuran (THF) and ethanol (EtOH) concentrations. It was also found that increasing nonsolvent concentration as well as decreasing cosolvent concentration in dope led to increase in membrane gas permeance. According to morphological characterizations, increase in polymer concentration resulted in transformation of membranes from porous into spongy like microstructure with formation of a denser skin layer. In addition, membrane porosity and mean pore size reduced by increasing THF and decreasing EtOH concentrations. On the other hand, plasma treatment successfully introduced fluorine groups onto the membrane surface which promoted biocompatibility of the membranes. Energy-dispersive X-ray spectroscopy results revealed that fluorination of membrane surface was attained up to 23% and contact angle of membrane enhanced up to 120°. Membrane permeance was also increased slightly upon modification. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48824.