Preparation of polysulfone hollow fiber affinity membrane modified with mercapto and its recovery properties. I. Synthesis and preparation of hollow fiber matrix membrane

Several kinds of chloromethyl polysulfones (CMPSF) with different chlorinity and reactive groups were synthesized by Friedel‐Crafts reaction, which could be utilized as reactively matrix membrane materials. The CMPSF hollow matrix membranes were prepared with phase inversion by utilization of the CMPSF/additive/DMAC casting solution and CMPSF as membrane materials. The rheological behavior of CMPSF/additives/DMAC spinning casting solution was studied. The experimental results showed that the spinning casting solution was a pseudoplastic fluid, the apparent viscosity of the spinning casting solution decreased with the increase of shearing rate, and the viscous flow activity energy of the spinning casting solution was inclined to unchange at high shearing rate. The effects of composition of spinning casting solution and process parameters of dry–wet spinning on the structure of CMPSF hollow fiber matrix membrane were investigated. The pore size, porosity, and water flux of membrane decreased with the increase of additive content, bore liquid, and dry spinning distance. With the increase of extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow fiber matrix membrane increased, but the pore size and water flux of the membrane decreased. It was also found that the effects of internal coagulant composition and external coagulant composition on the structure of CMPSF hollow fiber matrix membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of CMPSF hollow fiber matrix membrane and decrease the pore size, porosity, and water flux of the CMPSF hollow fiber matrix membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the CMPSF hollow fiber matrix membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 758–771, 2006     

Preparation of a heterogeneous hollow‐fiber affinity membrane having a mercapto chelating resin and its recovery of Hg2+ cations

A kind of heterogeneous hollow‐fiber affinity filter membrane with a high chelating capacity for Hg²⁺ was prepared by phase separation with blends of a mercapto chelating resin and polysulfone as the membrane materials, N,N‐dimethylacetamide as the solvent, and water as the extraction solvent. The adsorption isotherms of the hollow‐fiber affinity filter membrane for Hg²⁺ were determined. The heterogeneous hollow‐fiber affinity filter membrane was used for the adsorption of Hg²⁺ cations through the coordination of the mercapto group and Hg²⁺ cations, and the effects of the morphology and structure of the affinity membrane on the chelating properties were investigated. The chelating conditions, including the chelating resin grain size, pH value, concentration of the metallic ion solution, mobile phase conditions, and operating parameters, had significant effects on the chelating capacity of the hollow‐fiber affinity filter membrane. The results revealed that the greatest chelating capacity of the hollow‐fiber affinity filter membrane for Hg²⁺ was 1090 μg/cm² of membrane under appropriate conditions, and the adsorption isotherms of Hg²⁺ could be described by the Langmuir isotherm. The dynamic chelating experiments indicated that the hollow‐fiber affinity membrane could be operated at a high feed flow rate and that large‐scale removal of Hg²⁺ could be realized. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation and characterization of braided tube reinforced polyacrylonitrile hollow fiber membranes

Polyacrylonitrile (PAN) and polyester (PET) braided hollow tube that used as a special reinforcement are braided from their filaments via two‐dimensional weaving techniques. PAN braided tube reinforced homogeneous PAN hollow fiber membranes and PET braided tube reinforced heterogeneous PAN hollow fiber membranes are prepared by concentric circles squeezed‐coated spinning method. As for PAN hollow fiber membrane, the effects of PAN concentration on the performance of the prepared hollow fiber membranes are investigated in terms of pure water flux, protein rejection, mechanical strength, and morphology observations by a scanning electron microscope (SEM). The interfacial bonding state of the braided tube reinforced PAN hollow fiber membranes is studied by constant speed stretching method. Results show that the breaking strength of two‐dimensional braided tube reinforced PAN hollow fiber membranes is higher than 80 MPa. The structure of separation surface is similar to the structure of an asymmetric membrane. With the increase of polymer concentration, the membrane flux decreases while the retention rate of BSA increase. The membrane porosity and maximum pore size have the same decreasing tendency as the increase of PAN concentration. The results also show that the interfacial bonding state of the PAN two‐dimensional braided tube reinforced homogeneous PAN hollow fiber membranes is better than that of the PET two‐dimensional braided tube reinforced heterogeneous PAN hollow fiber membranes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41795.     

多孔堇青石中空纤维陶瓷膜的制备与表征(英文)

采用相转化和烧结法,通过一步成型制备了新颖的堇青石中空纤维陶瓷膜,并对制备的中空纤维膜微观结构、孔隙率和孔径分布、抗弯强度、纯净水通量和氮气渗透性等结构与性能进行了表征。结果表明:堇青石中空纤维膜为多孔非对称结构,由内部大孔层和外部海绵状多孔层组成。在1360℃保温2h制备的堇青石中空纤维膜孔隙率为39.2%,抗弯强度为76.5MPa。0.10MPa压差下的纯净水和氮气渗透性分别达到61.34m3/(m2·h·MPa)和7824m3/(m2·h·MPa)。实验证明,采用较大粒径的廉价工业级粉体为原料,可制备非对称的中空纤维陶瓷微滤膜。     

Temperature‐sensitive PVDF hollow fiber membrane fabricated at different air gap lengths

This article describes preparation of temperature‐sensitive poly(vinylidene fluoride) hollow fiber membranes using the dry‐wet spinning technique and investigates effects of air gap length on the structures and performances. In spinning these hollow fibers, N,N‐dimethyl formamide and poly(ethylene glycol) (10,000) were used as the solvent and pore‐forming agent, respectively. The prepared fiber membranes were characterized by scanning electron microscopy, pore size measurement, filtration experiments of pure water flux, and solutes with different molecular weights. The fiber membranes exhibit a quite asymmetric structures consisting of double skin layers situated on the fiber walls, two finger‐like layers near skin layers as well as macrovoids and sponge‐like structures at the center of the fiber cross‐sections. Remarkable changes of pure water flux and retention of solute are observed around 32°C, indicating an excellent temperature‐sensitive permeability. As the air gap length increases, the pore size of fiber membrane decreases, which results in decrease of pure water flux and allows small molecules to permeate through the fiber membrane. POLYM. ENG. SCI., 53:2519–2526, 2013. © 2013 Society of Plastics Engineers     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m^-1. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m^-2·h^-1 which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

Morphology and performance of polysulfone hollow fiber membrane

Polysulfone hollow fiber membranes were prepared via the dry-wet spinning process from dope solutions comprised of polysulfone, n-methyl-2-pyrrolidone, polyvinyl-2-pyrrolidone, and dodecylbenzene sulfonic acid, sodium salt. Morphology and performance of the membranes were affected by the compositions of coagulant and dope solution. Pore size and the water flux of the membrane increased by the addition of dodecylbenzene sulfonic acid, sodium salt to water in the coagulation bath, due to the changes of physicochemical properties of the outer coagulant. Addition of dodecylbenzene sulfonic acid, sodium salt to the dope solution also increased the pore size. The absence of polyvinyl-2-pyrrolidone, the pore forming agent, in the dope solution resulted in a remarkable decrease of pore size of the membrane. The distance between the spinneret and coagulation bath affected the membrane structure and performance. The membranes prepared in this study were suitable for hemofiltration in terms of molecular weight cut-off characteristics. © 1993 John Wiley & Sons, Inc.     

Improvement of porous polyvinylidene fluoride-co-hexafluropropylene hollow fiber membranes for sweeping gas membrane distillation of ethylene glycol solution

Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N₂ permeation, overall porosity, critical water entry pressure (CEP_w), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N₂ permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m⁻¹. CEP_w of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m⁻²·h⁻¹ which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.     

Poly(vinyl chloride) hollow‐fiber membranes for ultrafiltration applications: Effects of the internal coagulant composition

Poly(vinyl chloride) (PVC) hollow‐fiber membranes were spun by a dry/wet phase‐inversion technique from dopes containing 15 wt % PVC to achieve membranes with different pore sizes for ultrafiltration (UF) applications. The effects of the N,N‐dimethylacetamide (DMAc) concentration in the internal coagulant on the structural morphology, separation performance, and mechanical properties of the produced PVC hollow fibers were investigated. The PVC membranes were characterized by scanning electron microscopy, average pore size, pore size distribution, void volume fraction measurements, and solubility parameter difference. Moreover, the UF experiments were conducted with pure water and aqueous solutions of poly(vinyl pyrrolidone) as feeds. The mechanical properties of the PVC hollow‐fiber membranes were discussed in terms of the tensile strength and Young's modulus. It was found that the PVC membrane morphology changed from thin, fingerlike macrovoids at the inner edge to fully spongelike structure with DMAc concentration in the internal coagulant. The effective pores showed a wide distribution, between 0.2 and 1.1 μm, for the membranes prepared with H₂O as the internal coagulant and a narrow distribution, between 0.114 and 0.135 μm, with 50 wt % DMAc. The results illustrate that the difference in the membrane performances was dependent on the DMAc concentration. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on preparation of heterogeneous polysulfone affinity filter membrane and its sorption properties for Hg2+

High quality heterogeneous polysulfone affinity flat filter membranes having chelating groups were prepared by phase separation by the use of blends of chelating resin and polysulfone as membrane materials, N,N‐dimethylacetamide as the solvent, and water as the extraction solvent. The effects of blending ratio, chelating resin grain size, and temperature of casting solution on the structure of affinity membranes were investigated. The sorption process of an affinity filter membrane for Hg²⁺, adsorbed under various chelating conditions such as chelating resin grain size, pH value, and the concentration of the metallic ion solution, was also studied. The results revealed that the greatest chelating capacity of an affinity filter membrane for Hg²⁺ was 1050 μg/cm² per membrane under appropriate conditions, and the sorption isotherms of Hg²⁺could be expressed by the Freundlich sorption model. Dynamic chelating experiments indicated that the Hg²⁺ could be extracted with the affinity filter membrane and reextracted under acidic conditions. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 908–915, 2003     

烧结温度对TiO2/不锈钢中空纤维复合膜结构和性能的影响

不锈钢中空纤维膜基膜孔径大,直接涂覆分离层容易产生表面缺陷。在二氧化钛悬浮液中加入聚乙烯醇作为黏结剂,通过真空辅助抽滤法在不锈钢中空纤维基膜表面形成一层均匀的分离层。通过高温烧结得到了TiO₂/不锈钢中空纤维复合膜,考察了烧结温度对于TiO₂/不锈钢中空纤维复合膜表面分离层形貌和结构的影响。不同烧结温度时,TiO₂/不锈钢中空纤维复合膜的表面形貌有所差异;随着烧结温度的升高,不锈钢复合膜的孔径和纯水通量均先升高再下降。当烧结温度为500℃时,表面涂层均匀,孔径分布集中,水通量较高。最后,以SPT-500膜测试了水包油乳液分离效果,分离效率达到99%以上,且具有良好的抗污染性能。     

Preparation and characterization of alumina hollow fiber membranes

With the rapid development of membrane technology in water treatment, there is a growing demand for membrane products with high performance. The inorganic hollow fiber membranes are of great interest due to their high resistance to abrasion, chemical/thermal degradation, and higher surface area/volume ratio therefore they can be utilized in the fields of water treatment. In this study, the alumina (Al₂O₃) hollow fiber membranes were prepared by a combined phase-inversion and sintering method. The organic binder solution (dope) containing suspended Al₂O₃ powders was spun to a hollow fiber precursor, which was then sintered at elevated temperatures in order to obtain the Al₂O₃ hollow fiber membrane. The dope solution consisted of polyethersulfone (PES), Nmethyl-2-pyrrolidone (NMP) and polyvinylpyrrolidone (PVP), which were used as polymer binder, solvent and additive, respectively. The prepared Al₂O₃ hollow fiber membranes were characterized by a scanning electron microscope (SEM) and thermal gravimetric analysis (TG). The effects of the sintering temperature and Al₂O₃/PES ratios on the morphological structure, pure water flux, pore size and porosity of the membranes were also investigated extensively. The results showed that the pure water flux, maximum pore size and porosity of the prepared membranes decreased with the increase in Al₂O₃/PES ratios and sintering temperature. When the Al₂O₃/PES ratio reached 9, the pure water flux and maximum pore size were at 2547 L/m²·h and 1.4 μm, respectively. Under 1600dgC of sintering temperature, the pure water flux and maximum pore size reached 2398 L/(m²·h) and 2.3 μm, respectively. The results showed that the alumina hollow fiber membranes we prepared were suitable for the microfiltration process. The morphology investigation also revealed that the prepared Al₂O₃ hollow fiber membrane retained its’asymmetric structure even after the sintering process.     

Structure formation and characterization of PVDF hollow fiber membranes by melt‐spinning and stretching method

Melt‐spinning and stretching (MS‐S) method was proposed for preparing poly(vinylidene fluoride) (PVDF) hollow fiber membranes with excellent mechanical properties. The morphology and properties of PVDF fibers and membranes were investigated by small angle X‐ray scattering (SAXS), differential scanning calorimeter (DSC), field emission scanning electron microscope, mercury porosimeter, and tensile experiment. SAXS results indicated that the stacked lamellar structure aligned normal to the fiber axis was separated and deformed when the fibers were strained, and the long period of the strained fibers increased accordingly. Factors affecting the membrane properties were mainly spin‐draw ratio, annealing temperature, time, and stretching rate. Experimental results showed that the average pore size, porosity, and N₂ permeation of the membranes all increased with the increasing spin‐draw ratios and annealing temperatures. Annealing the nascent PVDF hollow fibers at 145°C for 12 h was suitable for attaining membranes with good performance. In addition, the amount and size of the micropores of the membrane increased obviously with stretching rate. Tensile experiment indicated PVDF hollow fiber membranes made by MS‐S process had excellent mechanical properties. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of Coagulant Temperature and On-Line Drawing on the Mechanical Properties and Permeation Performance of Cellulose Acetate Hollow Fibers

Cellulose acetate (CA) ultrafiltration hollow fibers were prepared via the dry–wet spinning technique. In the spinning process, the coagulant temperature was varied, and hence the on-line draw ratio was affected. The results revealed that the maximal draw ratio increased with the increase of coagulant temperature up to 55 ^○C and then leveled off. The inner diameters, outer diameters and thickness of the hollow fiber decreased with the increase of the draw ratio. The tensile properties of the resulting hollow fibers were measured, and the breaking tensile stress increased with the increase of draw ratio. When the coagulant temperature was increased from 25 to 70 ^○C, the porosity increased, the pore size was slightly enlarged in the outer skin, the hydraulic permeability increased, and the percentage of retention R decreased. In summary, by increasing the coagulant temperature, the maximal draw ratio can be increased, and hence the mass transfer properties and the other properties of drawn CA hollow fiber can be varied.     

后处理对改性聚氨酯系中空纤维膜压力响应行为的影响

采用熔融纺丝制得改性聚氨酯系中空纤维膜,通过测试水通量随压力的变化研究了拉伸、热处理温度和热处理时间对改性聚氨酯系中空纤维膜压力响应行为的影响。结果表明,所得膜可发生明显的压力响应行为,且拉伸倍数越大,膜的强度越大,压力响应行为越精确;随热处理温度升高,膜的支撑性变差,压力响应行为变弱;随热处理时间延长,膜形变回复率变低,压力响应行为减弱。     

Porous polyethersulfone hollow fiber membrane in gas–liquid contacting processes

Porous polyethersulfone hollow fiber membranes were fabricated via dry–wet phase inversion method with the polymer concentration in the spinning dope either 13 wt% or 15 wt%. The fabricated hollow fiber membranes were characterized by different test methods and the performance of membranes in contactor applications was tested by CO₂ absorption. The mean pore size, effective surface porosity and membrane porosity decreased while the membrane density and Liquid Entry Pressure (LEPw) increased as polymer concentration increased. The CO₂ absorption flux of the fabricated membranes was measured in two cases; i.e. when the absorbent, distilled water, was in the lumen side or in the shell side. The CO₂ flux for the membrane, fabricated from 13 wt% PES solution, was compared with some commercial and in-house made membranes. The former membrane had 111% higher flux than a commercial PTFE membrane.     

聚砜中空纤维超滤膜制备条件的考察

考察了膜液温度，内外凝胶温度和膜液出喷丝头的剪切速度对聚砜中空纤维超滤膜性能的影响。结果表明，保持其它条件一定时，膜液温度升高或凝胶温度降低时，最终膜孔径变小，并用制膜体系三元相图进行了分析，当膜液出喷丝头的剪切速度达到某一极限值时（不同膜液体系，此极限值不同），获得了压密性能优良的聚砜中空纤维超滤膜。     

Structure and performance of temperature‐sensitive poly(vinylidene fluoride) hollow fiber membrane fabricated at different take‐up speeds

Graft copolymer (PVDF‐g‐PNIPAAm) having poly(vinylidene fluoride) (PVDF) backbones and poly(N‐isopropylacrylamide) (PNIPAAm) side chains was synthesized via radical copolymerization and its hollow fiber membrane was fabricated from dry–wet spinning technique with N, N‐dimethylformamide as the solvent and poly(ethylene glycol) (10,000) as the additive. The effects of spinning condition (take‐up speeds) on the structures and performances of resulting fiber membranes were systematically considered. The structures and performances of fiber membranes were characterized by element analysis, X‐ray photoelectron spectroscopy, water contact angle measurement, scanning electron microscope, atom force microscope, and filtration experiments. The results indicate that PNIPAAm side chains tended to enrich on the membrane surface and pore surface and especially tended to aggregate on the inner surface due to the effect of bore fluid. The hollow fiber membrane exhibits an obvious temperature‐sensitive property. The pure water flux increases remarkably around 32°C, while the retention of albumin egg decreases accordingly, when the permeation temperature rises from 20 to 45°C. As the take‐up speed increases, both the inner and outer diameters of fiber membranes decrease. A higher take‐up speed favors higher pure water permeation flux, which allows larger molecules to permeate through the fiber membrane. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes for pervaporation separation of ethanol/water solution

Polysulfone (PSF) hollow fiber membranes were spun by phase‐inversion method from 29 wt % solids of 29 : 65 : 6 PSF/NMP/glycerol and 29 : 64 : 7 PSF/DMAc/glycol using 93.5 : 6.5 NMP/water and 94.5 : 5.5 DMAc/water as bore fluids, respectively, while the external coagulant was water. Polyvinyl alcohol/polysulfone (PVA/PSF) hollow fiber composite membranes were prepared after PSF hollow fiber membranes were coated using different PVA aqueous solutions, which were composed of PVA, fatty alcohol polyoxyethylene ether (AEO₉), maleic acid (MAC), and water. Two coating methods (dip coating and vacuum coating) and different heat treatments were discussed. The effects of hollow fiber membrane treatment methods, membrane structures, ethanol solution temperatures, and MAC/PVA ratios on the pervaporation performance of 95 wt % ethanol/water solution were studied. Using the vacuum‐coating method, the suitable MAC/PVA ratio was 0.3 for the preparation of PVA/PSF hollow fiber composite membrane with the sponge‐like membrane structure. Its pervaporation performance was as follows: separation factor (α) was 185 while permeation flux (J) was 30g/m²·h at 50°C. Based on the experimental results, it was found that separation factor (α) of PVA/PSF composite membrane with single finger‐void membrane structure was higher than that with the sponge‐like membrane structure. Therefore, single finger‐void membrane structure as the supported membrane was more suitable than sponge‐like membrane structure for the preparation of PVA/PSF hollow fiber composite membrane. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 247–254, 2005     

压力温度双敏性聚氨酯中空纤维膜通透性研究

以聚氨基甲酸酯(PU)为基质相,添加成孔剂及二氧化硅粒子,采用熔融纺丝法制得了具有对压力、温度刺激双重敏感的PU中空纤维膜;研究了膜的水通量随压力、温度的变化,对膜表面形貌进行了表征;并考察了中空纤维膜的截留性能。结果表明:制得的PU中空纤维膜为均质膜;膜孔径分布较窄,87.17%的孔集中在0.15～0.20μm。随着压力、温度上升或下降,膜的水通量相应增大或减小,水通量与压力、温度变化有着明显的相关性。经一次过滤,无机粒子清除率达98.52%～99.78%。