Effect of solvent evaporation conditions on gas separation performance for asymmetric polysulfone membranes

Asymmetric polysulfone membranes were prepared by the phase inversion technique under different solvent evaporation conditions prior to the gelation step. The membranes were cast from the two component system of polymer and N,N‐dimethylacetamide in which the polymer concentration was changed from 25.0 to 30.0%. The solvent evaporation temperature was changed from 70 to 120°C, and the evaporation time was 0–15 min. Ethanol, water, or 2‐propanol was used as the gelation media. The membranes were characterized by the measurement of oxygen/nitrogen permeation with the lamination technique and by observation with scanning electron microscopy. With an increase in the solvent evaporation time, the oxygen permeance decreased and its selectivity over nitrogen increased; although the permeance was in the range of 1–2 GPU, the oxygen selectivity over nitrogen exceeded 8. A correlation between the permeation performance and the operational parameters involved in the solvent evaporation process was obtained. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1367–1374, 1999     

Preparation and gas separation performance of silicone-coated polysulfone membranes

Composite membranes (CM) were prepared by coating the dense surface of different asymmetric polysulfone flat membranes (AM) with a solution of silicone rubber polymer. The surface porosity (ε) of the dense skin AM samples varied between 4 × 10^?5 and 1·5 × 10^?8, with an average mean pore size between 0·10 and 0·07 μm. Scanning electron microscopy (SEM), gas permeation experiments (H₂, N₂, CH₄, CO₂) and a simple resistance model were used for the determination of structure-permeability relationships. This study indicates that the CM prepared with polysulfone AM having ε < 3 × 10^?7, coated with a concentration of 6% silicone solution and a contact time of 1 min, has the best gas separation performance, with selectivities very close to the intrinsic polysulfone selectivities.     

Performance of polysulfone/carboxylated polysulfone membranes

Membranes were made from miscible blends of polysulfone (PSf) and carboxylated polysulfone (CPSf) having an average of 0.45 and 0.87 ? COOH groups per repeated unit. Membranes made from PSf and CPSf alone showed low separation for NaCl, glucose, polyethylene glycol (PEG) of various molecular weights and bovine albumin, from aqueous solutions under an applied pressure of 50 psig and higher. Membranes made from PSf/CPSf of varied blend composition showed higher separation factors for the above solutes. Highest separation was observed in membranes made from an 80/20 wt% PSf/CPSf 0.45 blend, which yielded a separation factor of 0.60 for NaCl, 0.97 for glucose, 0.98 for PEG and 0.99 for bovine albumin under an applied pressure in the range 50–150 psig. This higher performance is believed to be a result of a synergism between PSf and CPSf 0.45 to give a membrane morphology unique among the PSf/CPSf membranes.     

Novel surface modifying macromolecules (SMMs) blended polysulfone gas separation membranes by phase inversion technique

In this article an attempt was made to fabricate defect‐free asymmetric polysulfone (PSf) membranes for the separation of oxygen and nitrogen. The approach is based on the enhanced delayed demixing by blending surface modifying macromolecules (SMMs) in the casting solution and by immersing the cast film in isopropanol for a certain period before it is immersed in water. Different SMMs, including hydrophobic and charged SMMs, were synthesized, characterized, and blended to the host PSf. It was found that the charged SMM could indeed contribute to the removal of defective pores from the skin layer and enhancement of oxygen/nitrogen selectivity. The experimental results were further interpreted based on the shift of the phase boundary line on the polymer/solvent/nonsolvent triangular diagram, which occurred when SMMs were blended to PSf, due to the change in the polymer/nonsolvent interaction. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of novel fluorinated block copolyimide membranes for gas separation

We synthesized novel fluorinated block copolyimides with various diamine compositions and block chain lengths by chemical imidization in a two‐pod procedure. We describe the gas‐transport properties of the novel block copolyimide membranes. We demonstrate that the gas‐transport properties of the copolyimide membranes strongly depended on the block chain lengths. The gas permeabilities of the copolyimide membranes increased with increasing block chain length, and the gas selectivities increased with decreasing lengths. We clarify that the gas diffusivity of the block copolyimide membrane dominated the gas‐transport properties. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2436–2442, 2006     

Surface modification of polyimide and polysulfone membranes by ion beam for gas separation

The surface carbonization of polyimide (PI) and polysulfone (PSf) by ion beam has been performed to adapt the carbon molecular sieve properties on the skin of the polymeric membranes without the deformation of the membrane structure. In order to control the structure of membrane skin and to improve gas transport properties, the irradiation conditions, such as the dosage and the source of ion beams, have been varied. The ideal separation factor of CO₂ over N₂ through the surface‐modified PI and PSf membranes increased threefold compared to those of the untreated, pristine membranes, whereas the permeability decreased with almost two orders of magnitude. This appears to be due to the fact that the structure of membrane skin has been changed to a barrier layer. The formation of barrier layer was confirmed by comparing the calculated values of a simple resistance model with the experimental results, and the estimated permeability of this barrier was 10⁻⁴ barrer. It was concluded that ion beam irradiation could provide a useful tool for improving selectivity for gas separation membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1554–1560, 2000     

Preparation and characterization of nanoporous polysulfone membranes with high hydrophilic property using variation in CBT and addition of tetronic‐1107 surfactant

Asymmetric polysulfone (PSF) membranes were prepared from PSF, Tetronic‐1107, and 1‐methyl‐2‐pyrrolidone (NMP) via immersion precipitation. Pure water was used as the gelation media. The effects of coagulation bath temperature (CBT) (0 and 25°C), and addition of Tetronic‐1107 on the morphology, wettability, and pure water permeation flux (PWF) of the prepared membranes were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), contact angle measurements, and experimental set up. The contact angle measurements demonstrated that the hydrophilicities of the nanoporous PSF membranes were significantly enhanced by addition of a small amount of Tetronic‐1107 surfactant in the casting solution, along with using the lower CBT. It was also found that addition of Tetronic‐1107 in the casting solution along with increasing the CBT from 0 to 25°C incites formation of bigger pores on the top surface and results in formation of membranes with higher thickness and more porous structure in the sublayer. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tuning the gas separation performance of fluorinated and sulfonated PEEK membranes by incorporation of zeolite 4A

Mixed matrix membranes (MMMs) containing fluorinated‐sulfonated poly(ether ether ketone) (F‐SPEEK) and zeolite 4A filler, were prepared by solution casting. F‐SPEEK with a fixed degree of sulfonation (40%) was used for membrane synthesis. The SEM pictures showed good interfacial adhesion between filler particles and polymer, which was also confirmed by the increase in glass transition temperature of MMMs with increase in filler particles. Pure and mixed gas permeation experiments were carried out to investigate the potential of this membrane material. The results revealed that addition of zeolite 4A fillers enhanced both permeability and selectivity owing to the intrinsic nature of polymer and modified membrane morphology due to filler. The highest permeability obtained for CO₂ at 30% filler loading was 49.2 Barrer, while highest selectivities obtained for CO₂/CH₄ and CO₂/N₂ were 55 and 58 compared to 47 and 51 for the unfilled polymer, respectively. Intrinsic CO₂ solubility of F‐SPEEK was observed to be decreased from 10.7 to 1.9 (10^?2) cm³ (STP)/cm³ cmHg with the addition of Zeolite 4A. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45952.     

Review on the development of defect‐free and ultrathin‐skinned asymmetric membranes for gas separation through manipulation of phase inversion and rheological factors

Development of high‐performance asymmetric membranes is a major breakthrough in membrane technology. A comprehensive study on original concepts and new advances in membrane formation process is necessary to generate defect‐free and ultrathin‐skinned asymmetric membranes with superior performance for gas separation process. Correlation of rheological factors with primary‐phase inversion process is a novel approach in membrane research that provides a potential platform to improve membrane performance. The former controls general morphology of membrane, whereas the latter further affects molecular orientation in membrane. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 442–451, 2003     

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.     

Incorporation effects of fluorinated side groups into polyimide membranes on their physical and gas permeation properties

The effects of incorporation of fluorinated alkyl side groups into polyimide membranes were investigated in terms of their physical and gas permeation properties. Four polyimides with fluorinated side groups and four polyimides without the side groups were prepared by polycondensation of 2‐(perfluorohexyl)ethyl‐3, 5‐diamino benzoate (PFDAB) and m‐PDA with four aromatic dianhydrides (6FDA, ODPA, BTDA, and PMDA), respectively. It was found that the incorporation of fluorinated side groups into the polyimide membranes decreased their surface free energies (T_gs), solubility parameters, and fractional free volume (FFV)s and therefore, enhanced the permeabilities for CO₂, O₂, N₂, and CH₄ gases but reduced the selectivities for CO₂/ CH₄, O₂ /N₂, CO₂/N₂ gas pairs depending upon the structure of dianhydride monomers. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2756–2767, 2000     

含氟高分子表面活性剂的合成及其乳化性能的研究

以甲基丙烯酸十二氟庚酯(RfAA)、甲基丙烯酸(MAA)或2-丙烯酰胺-2-甲基丙磺酸(AMPS)、甲基丙烯酸聚乙二醇酯(PEGMA)为共聚单体,以亲氟-亲水-空间位阻的方式,合成了两种含氟高分子表面活性剂P(RfAA-PEGMA-MAA)和P(RfAA-PEGMA-AMPS)。考察了它们对RfAA的乳化性能,探讨了单体种类、单体含量、引发剂用量以及链转移剂用量对单体转化率和聚合物乳化性能的影响。结果表明,n(RfAA)∶n(MAA或AMPS)∶n(PEGMA)=5∶3∶2,引发剂用量为单体总质量的4%,链转移剂用量分别为单体总质量的3%、2%时,所合成的两种含氟高分子表面活性剂对RfAA均表现出了良好的乳化性能,它们的最低表面张力分别为56.3、49.1 mN/m,CMC均约为0.002 g/mL。     

酸性气体分离膜的研究现状及进展

当前,气体分离膜是一种环保绿色的分离技术,本文概括了目前用于去除CO2的商业膜材料(醋酸纤维素、聚酰亚胺和含氟聚合物),对不同膜的物理化学性质,气体渗透特性等进行了介绍。     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

金属-有机骨架材料在气体膜分离中的研究进展

金属-有机骨架材料(metal-organic frameworks,MOF)由于具有高比表面积、大孔隙率、功能性孔道结构以及种类多样性等特征,在储气、分离、催化、载药和光学等领域受到重视。其中,制备纯MOF膜或基于MOF的混合基质膜(mixed matrix membranes,MMMs)并用于气体分离,被认为具有潜在的应用前景。目前为止,实验合成的MOF材料种类已有两万种,为了快速筛选出合适的MOF材料作为膜材料,计算化学的方法可以极大地缩减MOF膜的研究周期,并有助于指导实验合成高效膜分离材料。本文分别从计算和实验两方面介绍了MOF膜在气体分离中的研究进展,分析表明,MOF膜的研究总体上向功能性更强、稳定性更高的方向发展,但是利用计算方法建立MOF膜的构效关系还存在一定的难度。因此,建立MOF膜的结构与性能表征的新概念、新方法,并利用MOF膜的结构-性能关系指导实验合成高稳定性、低成本的膜材料将是未来MOF膜的发展方向。     

聚砜/改性碳纳米管复合膜的制备及亲水性能

利用浸没沉淀相转化法,以聚砜(PSF)为膜材料,羧基化碳纳米管(MWCNTs-COOH)为添加剂,聚乙烯吡咯烷酮(PVP)为致孔剂,N,N-二甲基乙酰胺(DMAc)为溶剂,制备了聚砜/多壁碳纳米管复合膜,系统研究了制备复合膜时碳纳米管的添加量、预挥发时间以及凝固浴组成对其结构和性能的影响。实验结果表明,添加MWCNTs-COOH后,复合膜的亲水性能和抗污性能显著提高,同时复合膜的力学性能也明显增强。复合膜的 SEM 照片显示,随预挥发时间的延长和凝固浴中DMAc 质量分数的增加,复合膜断面由指状孔结构向海绵状孔结构过渡;复合膜的水通量下降,截留率上升。     

Effect of preparation parameters on performance of dense homogeneous polycarbonate gas separation membranes

The aim of this study is to determine the effect of preparation parameters on the membrane permeation mechanism and separation performances of dense homogeneous poly(bisphenol A carbonate) (PC) membranes. Blade‐casting and drop‐casting techniques are used for casting films from solutions with varying concentrations. Chloroform and methylene chloride are used to determine the effect of the properties of the casting solvent. Permeation measurements are done with Ar, N₂, O₂, CH₄, CO₂, and H₂ gases. The selectivity values of dense homogeneous membranes with a PC composition of 7% (w/v chloroform) are 1.7 for Ar/N₂, 1.1. for CH₄/N₂, 18 for CO₂/N₂, 26 for H₂/N₂, and 9.7 for O₂/N₂. These values with a PC composition of 15% (w/v methylene chloride) are 2.7, 1.3, 25, 44, and 13 for the same gases, respectively. In addition to the importance of the solvent type and composition, the casting type and thermal history also affects the performance of the membrane. Increasing the annealing period enhances the selectivity while decreasing the permeability for both casting solvents, yet this thermal history effect strongly depends on the solvent type because of solvent–polymer interactions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 776–785, 2003     

面向气体分离膜应用的多孔陶瓷基体研究

在众多基体材料中,多孔陶瓷由于化学和热稳定性较好而成为气体分离膜基体材料的首选,但一般陶瓷基体表面粗糙并存在裂纹、针孔等缺陷,增加了气体分离膜的制备难度,并对分离膜的性能产生不利的影响。笔者采用溶胶—凝胶法对多孔陶瓷基体表面进行修饰,有效地降低了表面粗糙度,同时把基体渗透率调整到适宜值,以得到面向气体分离膜应用的多孔陶瓷基体。     

Development of light‐induced functionalized asymmetric polysulfone membranes

The introduction of functionality into asymmetric polysulfone membranes has widened their applicability. They are modified with acrylic acid with a light‐induced technique. Fourier transform infrared, contact‐angle, porometry, and atomic force microscopy studies have been carried out to characterize the membranes. The performance of the modified membranes has been investigated with permeation measurements. The salt rejection (NaCl and Na₂SO₄) performance of the modified membranes shows evidence of functionalization on them. The modification of the membranes also develops the retention of small organic molecules (glucose and 2,4‐dichlorophenol). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

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