热致相分离法制备聚苯硫醚微孔膜

采用热致相分离法,以己内酰胺为溶剂,制备得到了聚苯硫醚微孔膜并对薄膜性能表征.聚苯硫醚-己内酰胺体系制膜的优点之一是溶剂己内酰胺是水溶性的,可以采用纯水作为后处理的萃取剂.选择了合适的浓度,利用压制成型法制备聚苯硫醚平板膜;研究了体系冷却时的相行为,并考察了降温速率、聚合物浓度等因素对微孔形态与薄膜性能的影响.研究表明,聚苯硫醚-己内酰胺体系以固液分相为主,萃取后形成球晶状的微孔结构.降温速率对薄膜的微孔形态、孔径以及连通性有重要影响;当体系以较低降温速率冷却时,多孔形态为枝叶状,形成了更多的开孔结构并获得了更大的孔径,这是获得高通量微孔膜的主要原因.通过控制降温速率可以制备纯水通量大于100 L/m2h,孔径约4～5μm且连通性良好的聚苯硫醚微孔膜;研究了聚合物浓度的影响,薄膜的纯水通量随着聚合物浓度的增大而减小,并且当聚苯硫醚浓度>50 wt%时,由于大于临界浓度而失去渗透性.     

醇／水混合液分离用聚乙烯醇复合膜的渗透汽化特性

制备了聚乙烯醇（ＰＶＡ）／聚丙烯睛（ＰＡＮ）渗透汽化复合膜，研究了交联剂用量、底膜结构、进料液组成、操作温度等因素对膜的渗透汽化性能的影响．发现ＰＶＡ／ＰＡＮ复合膜对水／醇混合液表现为水优先透过，进料液中乙醇浓度在６０～９９ｗｔ％的范围内，渗透通量Ｊｔ与温度之间符合Ａｒｒｈｅｎｉｕｓ关系，选择分离系数αＷ／Ｅ也随温度上升而增大．进料液为９５ｗｔ％的乙醇／水混合液时，７５℃下Ｊｔ高达３００～４５０ｇ／ｍ２ｈ，αＷ／Ｅ为８００～１１００．对异丙醇／水、异丁醇／水及甘油／水混合体系，复合膜显示出更为优秀的透过、分离性能．就膜的化学、物理结构与其渗透汽化性能间的关系进行了讨论．     

Synthesis and Characterization of Poly(ether-block-amide) Membranes

Poly(ether-block-amide) membranes were made via casting a solution on a nonsolvent (water) surface. In this research, effects of different parameters such as ratio of solvent mixture (n-butanol/isopropanol), temperature, composition of coagulation bath (water) and polymer concentration, on quality of the thin film membranes were studied. The mechanism of membrane formation involves solution spreading, solvent–nonsolvent exchange, and partial evaporation of the solvent steps. Solvent- nonsolvent exchange is the main step in membrane formation and determines membrane morphology. However, at higher temperature of polymeric solution greater portion of solvent evaporates. The results showed that type of demixing process (mutual affinity between solvent and nonsolvent) has important role in film formation. Also, addition of solvent to the nonsolvent bath is effective on membrane morphology. The film quality enhances with increasing isopropanol ratio in the solvent mixture. This behavior can be related to increasing of solution surface tension, reduction of interfacial tension between solution and nonsolvent and delayed solvent-nonsolvent demixing. Uniform films were made at a temperature rang of 60–80 °C and a polymer concentration of 4–7 wt%. Morphology of the membranes was investigated with scanning electron micrograph (SEM). Pervaporation of ethyl butyrate/water mixtures was studied using these membranes and high separation performance was achieved. For ethyl butyrate/water mixtures, It was observed that both permeation flux and separation factor increase with increasing ethyl butyrate content in the feed. Increasing temperature in limited range studied resulted in decreasing separation factor and increasing permeation flux.     

Preparation, characterization and effect of annealing on performance of cellulose acetate/sulfonated polysulfone and cellulose acetate/epoxy resin blend ultrafiltration membranes

Polymeric membranes based on cellulose acetate (CA)--sulfonated polysulfone blends at three different polymer compositions were prepared by solution blending and phase inversion technique, characterized and subjected to annealing at 70, 80 and 90 °C. The permeate water flux, separation of bovine serum albumin and its flux by the blend membranes before and after thermal treatment, have been compared and discussed. Similarly, CA and epoxy resin (diglycidyl ether of bisphenol-A) were blended in various compositions, in the presence and in the absence of polyethyleneglycol 600 as non-solvent additive, using N,N^′-dimethylformamide as solvent, and used for preparing ultraflltration membranes by phase inversion technique. The polymer blend composition, additive concentration, casting and gelation conditions were optimized. Blend membranes were characterized in terms of compaction, pure water flux, water content and membrane resistance. The effects of polymer blend composition and additive concentration on the above parameters were determined and the results are discussed.     

SYNTHESIS AND CHARACTERIZATION OF HYBRID PROTON CONDUCTING MEMBRANES OF POLY（VINYL ALCOHOL） AND PHOSPHOMOLYBDIC ACID

Hybrid proton conducting membranes of poly（vinyl alcohol） （PVA） and phosphomolybdic acid （PMA） were prepared by solution casting method. The effect of PMA doping and PVA crosslinking density on the membrane properties and proton conductivity were investigated. The crosslinking reaction between the hydroxyl group of PVA and the aldehyde group of glutaraldehyde （GA） was characterized by IR spectroscopy. Proton conductivity of the membranes increases with an increase in concentration of the doped PMA and also with an increase in crosslinking density of the membranes. Proton conductivity results indicate that a significant amount of PMA was maintained in the membranes even after several hours of immersion in water. A maximum conductivity of 0.0101 S cm^-1 was obtained for the membrane with 33.3 wt% PMA and crosslinking density of 5.825 mol%. X-ray diffraction studies were carried out to investigate the influence of PMA doping and crosslinking density on the nature of the membranes. These properties make them very good candidates for polymer electrolyte membranes for direct methanol fuel cell application.     

聚偏氟乙烯电纺膜及其电化学性能的研究

用电纺的方法制备了聚偏氟乙烯纳米纤维膜,它们具有多微孔结构,能够作为锂电池聚合物电解质.电纺中聚合物溶液的浓度对制备的电纺膜的结构形态有很大的影响,低浓度(10 wt%)时得到珠丝结构的膜,浓度15 wt%时则为纤维结构,而高浓度(18 wt%)时,电纺膜为交联的网状结构.用电纺法制备的聚偏氟乙烯纳米纤维微孔膜具有较高的孔隙率,而且它们与锂金属电极具有良好的界面稳定性;在25℃时吸液率最高可达340%,以这种膜制备的聚合物电解质室温电导率可达到1.57×10-3S.cm-1;由该电解质组装的扣式电池以0.5 mA.cm-2恒流充放电,25℃时50次循环后几乎无容量损失,具有良好的循环性能;即使60℃时,电池仍能保持良好的工作稳定性.     

Effect of Polyvinylpyrrolidone on Separation Performance of Cellulose Acetate-Polysulfone Blend Membranes

Blend membranes comprising cellulose acetate and polysulfone (CA/PSf) were prepared through a solution casting method using a different concentration of polyvinylpyrrolidone (PVP) as the pore former. Fourier transform infrared spectroscopy (ATR-FTIR) was used to investigate structural properties of membranes. Membranes morphology and its thermal properties were characterized by scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The strength of membranes was studied by mechanical stability. The effect of PVP concentration on separation performance of the prepared membranes was studied. The separation performance of prepared membranes was tested by using an aqueous solution of cadmium metal complexed with humic acid. The results showed that an increase in the PVP concentration in the cast film from 0 to 3 wt% increased the thermal stability, water content (%), pure water flux, and solute rejection. SEM results showed that the pore size decreased but the number of pores increased on an increase in the PVP concentration.     

Preparation and characterization of polyvinylidene fluoride (PVDF) hollow fiber membranes

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared by dry/wet and wet phase inversion methods. In spinning these PVDF hollow fibers, dimethylacetamide (DMAc) and polyvinyl pyrrolidone (PVP) were used as a solvent and an additive, respectively. Water was used as the external coagulant. Water or ethanol was used as the internal coagulants. The membranes were characterized in terms of water flux, molecular weight cut-off for the wet membranes. Gas permeation fluxes and effective surface porosity were determined by a gas permeation method for the dried membranes. The cross-sectional structures were examined by scanning electron microscopy. The effects of polymer concentration, air-gap, PVP molecular weight, PVP content in the polymer dope, and the internal coagulant on the permeation properties and membrane structures were examined. Highly permeable PVDF hollow fiber membranes could be prepared from a polymer dope containing low molecular weight PVP and using ethanol as the internal coagulant.     

PREPARATION OF ASYMMETRIC POLYETHERKETONE FLAT AND HOLLOW FIBER MEMBRANES FOR GAS SEPARATION USING ACETIC ACID BASED COAGULANTS

Membranes for gas separation have developed significantly in the last twenty years,however,there is still a need for high temperature and chemically resistant membranes that exhibit good selectivity and gas permeability.Our study examines the fundamental properties of polyetherketone (PEK,a thermally stable and chemically resistant polymer) membranes prepared using concentrated sulphuric acid (98% H_2SO_4) as the solvent.Non-solvents used in the work included acetic acid,ethanol,methanol,glycerol,and wat...     

Electron-beam graft-modified membranes with externally controlled flux

Pre-irradiation grafting as a means to modify commerical poly(vinylidene fluoride) (PVDF) membranes has been studied. The membranes prepared were weak cation-exchange membranes (acrylic acid functionality), anion-exchange membranes (trimethyl ammonium functionality) and temperature-sensitive membranes (N-isopropyl amide functionality). Different graft loads were obtained by varying reaction time, radiation dose and in the case of acrylic acid the graft solution composition. The trimethyl ammonium chloride functionality was obtained by grafting vinyl benzyl chloride onto a PVDF membrane and aminating the benzyl chloride groups in a 45% trimethyl amine–water solution. For a membrane grafted with 9 wt% acrylic acid the flux increased approximately 70 times when the pH was decreased from 6 to 2. For a membrane with 5 wt% trimethyl ammonium functionality the flux increased both when pH was decreased below 3 and increased above 11. For a membrane grafted with 18 wt% N-isopropyl acrylamide a sharp increase of flux was observed when the temperature was raised above 32°C.     

THE INFLUENCE OF PEG MOLECULAR WEIGHT ON MORPHOLOGIES AND PROPERTIES OF PVDF ASYMMETRIC MEMBRANES

The preparation and properties of asymmetric poly(vinyldiene fluoride)(PVDF)membranes are described in this study.Membranes were prepared from a casting solution of PVDF,N,N-dimethylacetamide(DMAc)solvent and water- soluble poly(ethylene glycol)(PEG)additives by immersing them in water as coagulant medium.Experiments showed that when PEG molecular weight increased,the changes in the resultant membranes' morphologies and properties showed a transition point at PEG6000.This indicated that PEG with a relati...     

热诱导相分离法制备亲水性乙烯-丙烯酸共聚物微孔膜

选择 3种不同丙烯酸含量的乙烯 丙烯酸共聚物 (EAA)为原材料 ,二苯醚 (DPE)为稀释剂 ,采用热诱导相分离法 (TIPS)制备了亲水性高分子微孔膜 .接触角实验证明 ,EAA为亲水性高分子材料 .利用熔点仪根据浊度的变化测绘出 3种不同EAA/DPE体系的双结点线以及通过DSC得出相应 3体系的结晶温度曲线 .实验结果还表明 ,随着乙烯 丙烯酸共聚物中丙烯酸含量的增加 ,结晶温度曲线向低温方向移动 ,相对应的膜孔直径也增加 .此外 ,随着EAA DPE体系中EAA初始浓度的逐渐增加 ,膜孔直径逐渐变小 ,当体系中EAA初始浓度高于 5 0 %时 ,不再出现微孔结构     

ULTRAFILTRATION MEMBRANE FORMATION OF PES-C, PES AND PPESK POLYMERS WITH DIFFERENT SOLVENTS

Ultrafiltration membranes were prepared using phenolphthalein polyarylethersulfone (PES-C),polyethersulfone (PES) and poly(phthalazinone ether sulfone ketone) (PPESK) as polymers and NMP,DMAc,DMF and DMSO as solvents by immersion precipitation via phase inversion.Experimental data of thermodynamic properties of the polymer solutions and kinetic process of membrane formation were reported.For polymer solutions with good solvents,the sequence of the viscous flow activation energy (E_η) was coincident with ...     

Cellulose acetate and polyethersulfone blend ultrafiltration membranes. Part I: Preparation and characterizations

The overall objective of this investigation is to achieve high‐performance membranes with respect to flux and rejection characteristics, with an interplay of blending polymers having desired qualities. Thus, cellulose diacetate and polyethersulfone as candidate materials, in the presence of polyethylene glycol 600 as a pore forming agent, were blended in 100/0, 95/5, 90/10, 85/15, 80,20 and 75/25% compositions using N,N′‐dimethylformamide as solvent and membranes were prepared by the phase inversion technique. Polymer blend composition, additive concentration, and casting and gelation conditions were standardized for the preparation of asymmetric membranes with various pore statistics and morphology. These blend membranes were characterized for compaction in ultrafiltration experiments at 414 kPa pressure in order to attain steady state flux and is reached within 4–5 hr. The pure water flux was measured at 345 kPa pressure and is determined largely by the composition of polyethersulfone and additive concentration. The flux was found to reach the highest values of 66.5 and 275 1/(cm² hr) at 0 and 10 wt% additive concentrations respectively, at 25% SPS content of the blend. Membrane hydraulic resistance derived by measuring water flux at various transmembrane pressure and by using an algorithm was found to be inversely proportional to pure water flux. Water content is estimated by simple drying and weighing procedures and found proportional to pure water flux for all the membranes. The molecular weight cut‐offs (MWCOs) of different membranes were determined with proteins of different molecular weights and found to vary from 20–69 kDa (globular proteins) depending on the PEG and SPS content in the casting dope. Skin surface porosity of the membranes were analyzed by scanning the frozen membrane samples using scanning electron microscopy (SEM) at different magnifications. The surface porosity is in direct correlation to the MWCO derived from solute retention experiments. Copyright © 2004 John Wiley & Sons, Ltd.     

Study on preparation and performances of cellulose acetate forward osmosis membrane

Cellulose acetate (CA) forward osmosis (FO) membranes were prepared via a phase inversion process. CA was used as membrane material for FO. Acetone and 1,4-dioxane were employed as solvent. Polyvinylpyrrolidone (PVP), maleic acid, and methanol were applied as additives. An orthogonal experiment was performed to optimize the ratio of every component in the casting solution. The membrane with best performance was selected to concentrate an anthocyanin solution. Saturated sucrose solution (about 60°Brix) was fit for using as draw solution in the concentration experiment. Water flux, porosity, and rejection rate were measured to evaluate the membrane properties. Reverse water rinsing was used in cleaning membrane that was fouled by anthocyanin solution. Results showed that under membrane thickness of 100 μm, coagulation temperature at room temperature, and evaporation time of 30 s, the optimum components in casting solution were 13% CA, 45% 1,4-dioxane, 31% acetone, 2% maleic acid, 3% PVP, and 6% methanol. In the concentration experiment, the prepared FO membrane showed water flux of 2.04 L m^?2 h^?1 and rejection rate of 98.61%. In the membrane cleaning experiment, the water flux of the FO membrane recovered 87.51% after rinsing for 1 h. The prepared membranes and previously published membranes were compared which showed the prepared membrane could significantly improve the rejection rate for anthocyanin solution.     

PREPARATION AND CHARACTERIZATION OF POLYSULFONE AND POLYETHERSULFONE MEMBRANES FOR CALCIUM (Ca2+) AND MAGNESIUM (Mg2+) SEPARATION BY COMPLEXATION ULTRAFILTRATION

ABSTRACT

Asymmetric ultrafiltration membranes were synthesized from locally available polysulfone and polyethersulfone polymers using aprotic solvents and organic additives by the phase inversion method. The membranes were characterized in terms of pure water permeability, separation behavior with respect to polyethylene glycols of various molecular weights and electrolytes. The suitability of using polyethyleneimine (PEI) for selective removal of calcium and magnesium salts by an ultrafiltration process was studied in terms of optimum polymer loading at reasonable permeate flux, irreversible adsorptive fouling of the macromolecular ligand on the polymer as functions of solution pH and ionic strength, and metal ion separation as a function of concentration and pressure. Direct electron microscopic observation of fresh, as well as fouled, membranes are presented.     

Composite membranes prepared from glutaraldehyde cross-linked sulfonated cardo polyetherketone and its blends for the dehydration of acetic acid by pervaporation

Cardo polyetherketone (PEK-C) composite membranes were prepared by casting glutaraldehyde (GA) cross-linked sulfonated cardo polyetherketone (SPEK-C) or silicotungstic acid (STA) filled SPEK-C and poly(vinyl alcohol) (PVA) blending onto a PEK-C substrate. The compatibility between the active layer and PEK-C substrate is improved by immersing the PEK-C substrate in a GA cross-linked sodium alginate (NaAlg) solution and using water–dimethyl sulfoxide (DMSO) as a co-solvent for preparing the STA-PVA-SPEK-C/GA active layer. The pervaporation (PV) dehydration of acetic acid shows that permeation flux decreased and separation factor increased with increasing GA content in the homogeneous membranes. The permeation flux achieved a minimum and the separation factor a maximum when the GA content increased to a certain amount. Thereafter the permeation flux increased and the separation factor decreased with further increasing the GA content. The PV performance of the composite membranes is superior to that of the homogeneous membranes when the feed water content is below 25 wt%. The permeation activation energy of the composite membranes is lower than that of the homogeneous membranes in the PV dehydration of 10 wt% water in acetic acid. The STA-PVA-SPEK-C-GA/PEK-C composite membrane using water–DMSO as co-solvent has an excellent separation performance with a flux of 592 g m⁻² h⁻¹ and a separation factor of 91.2 at a feed water content of 10 wt% at 50 °C.     

Effect of preparation variables on morphology and pure water permeation flux through asymmetric cellulose acetate membranes

In this study, cellulose acetate (CA) ultrafiltration (UF) membranes were prepared using the phase inversion method. Effects of CA and polyethylene glycol (PEG) concentrations in the casting solution and coagulation bath temperature (CBT) on morphology of the synthesized membranes were investigated. Based on L₉ orthogonal array of Taguchi experimental design 18 membranes were synthesized (with two replications) and pure water permeation flux through them were measured. It was found out that increasing PEG concentration in the casting solution and CBT, accelerate diffusional exchange rate of solvent 1-methyl-2-pyrrolidone (NMP) and nonsolvent (water) and consequently facilitate formation of macrovoids in the membrane structure. Increasing CA concentration, however, slows down the demixing process. This prevents instantaneous growth of nucleuses in the membrane structure. Hence, a large number of small nucleuses are created and distributed throughout the polymer film and denser membranes are synthesized. Rate of water flux through the synthesized membranes is directly dependent on the size and number of macrovoids in the membrane structure. Thus, maximum value of flux is obtained at the highest levels of PEG concentration and CBT (10 wt.% and 23 °C, respectively) and the lowest level of CA concentration (13.5 wt.%). Analysis of variance (ANOVA) showed that all parameters have significant effects on the response. However, CBT is the less influential factor than CA and PEG concentrations on the response (flux).     

Effect of solution extrusion rate on morphology and performance of polyvinylidene fluoride hollow fiber membranes using polyvinyl pyrrolidone as an additive

<正>Polyvinylidene fluoride(PVDF) hollow fiber membranes prepared from spinning solutions with different polyvinyl pyrrolidone(PVP) contents(1%and 5%) at different extrusion rates were obtained by wet/dry phase process keeping all other spinning parameters constant.In spinning these PVDF hollow fibers,dimethylacetamide(DMAc) and PVP were used as a solvent and an additive,respectively.Water was used as the inner coagulant.Dimethylformamide(DMF) and water(30/70) were used as the external coagulant.The performances of membranes were characterized in terms of water flux,solute rejection for the wet membranes.The structure and morphology of PVDF hollow fiber were examined by BET adsorption,dry/wet weight method and scanning electron microscopy(SEM).It is found that the increase in PVP content and extrusion rate of spinning solution can result in the increase of water flux and decrease of solute rejection.The improvements of interconnected porous structure and pore size are induced by shear-thinning behavior of spinning solution at high extrusion rates,which could result in the increase of water flux of hollow fiber membranes.The increase of extrusion rate also leads to the increase of membrane thickness due to the recovery effect of elastic property of polymer chains.     

BPU/PLLA/DO体系的热力学性质对成膜过程及共混膜结构的影响

利用浸沉凝胶相转化法制备医用聚氨酯(BPU)/聚乳酸(PLLA)微孔膜,讨论了BPU/PLLA不同配比时聚合物/1,4-二氧六环/水三元体系的凝胶特性及其对共混膜结构和性能的影响,并初步探讨成膜机理.研究结果表明,随着BPU/PLLA质量比例由90/10变为75/25、50/50、25/75、10/90,聚合物/溶剂/非溶剂三元体系的热力学稳定性增强,凝胶值增大,但是共混溶液的黏度增大;并且,共混膜的孔隙率、膜厚、平均孔径、水蒸汽透过速率及吸水率先增加后降低.这主要是由于随着BPU/PLLA质量比例的变化,动力学扩散过程控制成膜速度转变为成膜体系热力学性质控制成膜速度;成膜过程由延时分相转变为瞬时分相,后又转变为延时分相.