添加剂和凝结剂温度对用无溶剂致相位分离法生产高性能PVDF/聚醚F127混合中空光纤膜的影响(英文)

Poly(vinylidene fluoride)(PVDF) has become one of the most popular materials for membrane prepara-tion via nonsolvent induced phase separation(NIPS) process.In this study,an amphiphilic block copolymer,Plu-ronic F127,has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fiber membranes to enhance the membrane permeability and hydrophilicity.The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F127 membranes have also been investigated.The as-spun hollow fibers were characterized in terms of cross-sectional morphology,pure water permeation(PWP),relative molecular mass cut-off(MWCO),membrane chemistry,and hydrophilicity.It was observed that the addition of Pluronic F127 significantly increased the PWP of as-spun fibers,while the membrane contact angle was reduced.However,the size of macrovoids in the membranes was undesirably large.The addition of a 2nd additive,including lithium chlo-ride(LiCl) and water,or an increase in coagulant temperature was found to effectively suppress the macrovoid for-mation in the Pluronic-containing membranes.In addition,the use of LiCl as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes,while the surface pore size became smaller.PVDF hollow fiber with a PWP as high as 2530 L?m?2?h?1?MPa?1,a MWCO of 53000 and a contact angle of 71° was successfully fabricated with 3%(by mass) of Pluronic F127 and 3%(by mass) of LiCl at a coagulant temperature of 25 °C,which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.     

TIPS behavior for IPP/nano-SiO2 blend membrane formation and its contribution to membrane morphology and performance

In the present work, the TIPS behavior of isotactic polypropylene(iP P)/di-n-butyl phthalate(DBP)/dioctyl phthalate(DOP)/nano-SiO_2 system and the competition relation between liquid–liquid phase separation and polymer crystallization are successfully adjusted by adding nano-SiO_2. The liquid–liquid phase separation temperature of the system increases with increasing nano-SiO_2 content. Besides, iP P crystallization temperature is also changed after adding nano-SiO_2. IPP/nano-SiO_2 blend hollow fiber microporous membrane is prepared via TIPS method. SEM photos show that the membrane exhibits mixed morphology combining cellular structure relating to liquid–liquid phase separation and branch structure originating from polymer crystallization. The relative weight of cellular structure first decreases and then increases with the increase of nano-SiO_2 content. Furthermore, porosity, connectivity among pores and pure water flux of the membrane first increase and then decrease with increasing nano-SiO_2 content. However, mechanical performance of the membrane is improved at all times with increasing nano-SiO_2 content.     

Scale-up of NaA zeolite membranes onα-Al2O3 hollow fibers by a secondary growth method with vacuum seeding

NaA zeolite membranes were prepared by secondary growth method on the outer surface ofα-Al2O3 hollow fiber supports. Vacuum seeding method was used for planting zeolite seeds on the support surfaces. Hydrother-mal crystallization was then carried out in a synthesis solution with molar ratio of Al2O3:SiO2:Na2O:H2O=1:2:2:120 at 100 °C for 4 h. Effects of seeding conditions on preparation of hollow fiber NaA zeolite membranes were extensively investigated. Moreover, hollow fiber membrane modules with packing membrane areas of ca. 0.1 and 0.2 m2 were fabricated to separate ethanol/water mixture. It is found that the thickness of seed layer is obviously affected by seed suspension concentration, coating time and vacuum degree. Close-packing seed layer is required to obtain high-quality membranes. The optimized seeding conditions (seed suspension mass concentration of 0.5%–0.7%, coating time of 5 s and vacuum degree of 10 kPa) lead to dense NaA zeolite layer with a thickness of 6–8μm. Typically, an as-synthesized hollow fiber NaA zeolite membrane exhibits good pervaporation performance with a permeation flux of 7.02 kg·m?2·h?1 and separation factor N 10000 for sepa-ration of 90%(by mass) ethanol/water mixture at 75 °C. High reproducibility has been achieved for batch-scale production of hollow fiber NaA zeolite membranes by the hydrothermal synthesis approach.     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA), MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmenthanol =350g.m-2.h-1 and separation factor a > 400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Fabrication and characterization of novel foaming polyurethane hollow fiber membrane

Foam-like materials had attracted great interest as promising absorbent. In this study, thermoplastic polyurethane(TPU) block sponge was synthesized. Polyester(PET) braid tubular reinforced polyurethane(PU) spongy hollow fiber membrane was prepared by a concentric circular spinning method. The method was woven from an outer coated water-blown PU separation layer and inner PET braid tubular. We have developed a simple and useful preparation technique for the PU spongy hollow fiber membrane. For the first time, the PU spongy hollow fiber membrane was prepared using a coating and controlled foaming technique. The influence of toluene isocyanate index on the physical properties, morphology, and structure of flexible PU sponge was discussed in terms of water contact angle(CA), pure water flux(PWF), Fourier Transform Infrared Analysis(FTIR),pressure-responsive property, and pull-out strength. The morphologies of the membranes were investigated by scanning electron microscopy. We have characterized the foams from an intuitive point of view and demonstrated that the dimensional morphology of the membrane was closely related to isocyanate index. The result showed that the surface cell size of the PU sponge hollow fiber membrane gradually decreased with an increase of the isocyanate index. Due to the elasticity of PU at room temperature, the pressure responsive characteristic of the membrane was prepared. When isocyanate index was 1.05, the interface bonding strength of PU spongy hollow fiber membranes reached as high as 0.37 MPa, porosity and PWF were 71.5% and 415.5 L·m~(-2)·h~(-1),respectively.     

CO2/CH4 separation using inside coated thin film composite hollow fiber membranes prepared by interfacial polymerization

Carbon dioxide(CO_2) is greenhouse gas which originates primarily as a main combustion product of biogas and landfill gas. To separate this gas, an inside coated thin film composite(TFC) hollow fiber membrane was developed by interfacial polymerization between 1,3–cyclohexanebis–methylamine(CHMA) and trimesoyl chloride(TMC). ATR-FTIR, SEM and AFM were used to characterize the active thin layer formed inside the PSf hollow fiber. The separation behavior of the CHMA-TMC/PSf membrane was scrutinized by studying various effects like feed gas pressure and temperature. Furthermore, the influence of CHMA concentration and TMC concentration on membrane morphology and performance were investigated. As a result, it was found that mutually the CHMA concentration and TMC concentration play key roles in determining membrane morphology and performance. Moreover, the CHMA-TMC/PSf composite membrane showed good CO_2/CH_4 separation performance. For CO_2/CH_4 mixture gas(30/70 by volume) test, the membrane(PD1 prepared by CHMA 1.0% and TMC 0.5%) showed a CO_2 permeance of 25 GPU and the best CO_2/CH_4 selectivity of 28 at stage cut of 0.1. The high CO_2/CH_4 separation performance of CHMA-TMC/PSf thin film composite membrane was mostly accredited to the thin film thickness and the properties of binary amino groups.     

Preparation and properties of hollow fibre nanofiltration membrane with continuous coffee-ring structure

Polyamide(PA)hollow fibre composite nanofiltration(NF)membranes with a coffee-ring structure and beneficial properties were prepared by adding graphene oxide(GO)into the interfacial polymerization process.The presentation of the coffee-ring structure was attributed to the heterogeneous,finely dispersed multiphase reaction system and the“coffee-stain”effect of the GO solution.When the piperazine concentration was 0.4 wt-%,the trimesoyl chloride concentration was 0.3 wt-%,and the GO concentration was 0.025 wt-%,the prepared NF membranes showed the best separation properties.The permeate flux was 76 L·m^?2·h^?1,and the rejection rate for MgSO4 was 98.6%at 0.4 MPa.Scanning electron microscopy,atomic force microscopy,and attenuated total reflectance-Fourier transform infrared spectroscopy were used to characterize the chemical structure and morphology of the PA/GO NF membrane.The results showed that GO was successfully entrapped into the PA functional layer.Under neutral operating conditions,the PA/GO membrane showed typical negatively charged NF membrane separation characteristics,and the rejection rate decreased in the order of Na2SO₄>MgSO₄>MgCl₂>NaCl.The PA/GO NF membrane showed better antifouling performance than the PA membrane.     

MASS TRANSFER IN MEMBRANE ABSORPTIONDESORPTION OF AMMONIA FROM AMMONIA WATER

Hydrophobic membrane can provide fast mass transfer for absorption-desorption of gasesform liquid to absorbent.The removal of ammonia from ammonia water and absorption with dilutesulphuric acid was studied in a pilot plant with polypropylene hollow fiber column,The removalrate and influences of operation temperature,flow rate and concentration on mass transferperformances were discussed mathematically.Experimental results and computer calculation show thatthe ammonia removal rate is not affected by the feed concentration for a given system.Both partialand overall mass transfer coefficients vary along the axis of the fiber,and the mass transfer for themembrane process is controlled by membrane resistance.     

MATHEMATICAL AND EXPERIMENTAL ANALYSIS OF AIR SEPARATION BY HOLLOW FIBER MEMBRANES

Approximate solutions for gas separation by hollow fiber membranes have been developedby several investigators.However,there are few reports of experimental verification of the models forhigh stage cut separations.In this work,an approximate mathematical model was developed and wasexperimentally verified for high stage cut air separation.Both countercurrent and cocurrent now pat-terns were used.In addition,the applicability of feed-inside mode for low stage cut air separation byhollow fiber membrane was examined.It was found that feed-inside mods was more advantageousthan feed-outside mode when used for the generation of oxygen-enriched air.     

DMFCs用磺化聚醚醚酮/磺化酚酞型聚醚砜共混质子交换膜

A sulfonated poly(ether ether ketone) (SPEEK) membrane with fairly high degree of sulfonation (DS) swells excessively and even dissolves at high temperature. To solve these problems, sulfonated phenolphthalein poly(ether sulfone) (SPES-C, DS 53.7%) is blended with the SPEEK matrix (DS 55.1%, 61.7%) to prepare SPEEK/SPES-C blend membrane. The decrease in swelling degree and methanol permeability of the membrane is dose-dependent. Pure SPEEK (DS 61.7%) membrane dissolves completely in water at 70ºC, whereas the swelling degree of the SPEEK (DS 61.7%)/SPES-C (40%, by mass) membrane is 29.7% at 80ºC. From room temperature to 80ºC, the methanol permeability of all SPEEK (DS 55.1%)/SPES-C blend membranes is about one order of magnitude lower than that of Nafion®115. At higher temperature, the addition of SPES-C polymer increases the dimensional stability and greater proton conductivity can be achieved. The SPEEK (DS 55.1%)/SPES-C (40%, by mass) membrane can withstand temperatures up to 150ºC. The proton conductivity of SPEEK (DS 55.1%)/SPES-C (30%, by mass) membrane approaches 0.16 S•cm－1, matching that of Nafion115 at 140ºC and 100% RH, while pure SPEEK (DS 55.1%) membrane dissolves at 90ºC. The SPEEK/SPES-C blend membranes are promising for use in direct methanol fuel cells because of their good dimensional stability, high proton conductivity, and low methanol permeability.     

Preparation and characterization of several types of polyvinyl butyral hollow fiber membranes by thermally induced phase separation

Hollow fiber membranes were prepared by thermally induced phase separation from three types of polyvinyl butyral (PVB) and a blend of two of these polymers. Although the difference in the chemical composition of the PVB polymers used was not remarkable, their respective membrane performances were quite different. With a high phase separation temperature the pore size of the prepared membrane was large, because structure growth occurred for a long time. Water permeability tests of the wet membranes showed the results that corresponded to the pore sizes of the membranes. By contrast, the results for the dried membrane appeared to be related to the hydrophilicity of the PVB polymer and independent of pore size in the wet condition. Although the membrane with high wettability had low mechanical strength, the membrane from the polymer blend of two different PVB polymers showed adequate wettability and mechanical strength. This produced a hollow fiber membrane with favorable characteristics for application in water treatment. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Structure control of asymmetric poly(vinyl butyral)‐TiO2 composite membrane prepared by nonsolvent induced phase separation

Poly(vinyl butyral) (PVB)‐TiO₂ composite hollow fiber membranes were prepared via nonsolvent induced phase separation (NIPS). The membrane had a skin layer on both the outer and inner surface at the initial stage after membrane preparation. However, the outer surface became porous with the passage of time, as the polymer in the membrane's outer surface was decomposed by the photocatalysis of TiO₂. The initial water permeability increased with the increase of TiO₂ content. Furthermore, for all the membranes, as time elapsed the water permeabilities increased and became constant after about 15 days, which was in accordance with the alteration on the membrane's outer surface. Despite decomposition of the polymer on the outer surface, particle rejection hardly changed because the inner surface kept the original structure. Thus, addition of TiO₂ to the membrane is a useful way to improve water permeability while maintaining particle rejection. The clear asymmetric structure with both porous structure at the outer surface and skin layer at the inner surface was achieved by the addition of TiO₂. Therefore, the addition of TiO₂ is a new method for achieving the high porosity at the outer surface of the hollow fiber membrane. In addition, tensile strength and elasticity kept constant over time and were higher than those of original PVB membranes. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

用于脱除C5及MTBE中甲醇的渗透汽化膜研究

Several pervaporation membranes, cellulose acetate (CA), polyvinylbutyral (PVB), poly(MMA-co-AA),MMA-AA-BA, CA/PVB blend and CA/poly(MMA-co-AA) blend, were prepared, and their pervaporation properties were evaluated by separation of methanol/C5 or methanol/MTBE (methyl tert-butyl ether). The results shows that the CA composite membrane has a high separation performance (flux Jmethanol = 350 g.m-2.h-1 and separation factor α＞400) for methanol/C5 mixtures, and the pervaporation characteristics of MMA-AA-BA copolymer membranes changes with the ratio of copolymer. For CA/poly(MMA-co-AA) blend membrane, the pervaporation performance is improved in comparison with CA or poly(MMA-co-AA) membrane. From the experiment of CA/PVB blend membranes for methanol/MTBE mixture, it is found that the compatibility of blends may affect the separation features of blend membrane.     

Preparation and properties of PVDF/PVA hollow fiber membranes

On principle of polymer blend phase separation, PVDF/PVA hollow fiber membranes were prepared using phase inversion method. The membrane morphology and performance varied with the blending ratio. The PVDF/PVA blends showed incompatibility by the results of dynamic mechanical analysis (DMA) and infrared attenuated total reflection (FTIR-ATR) sampling technique. Based on bursting pressure and tensile strengths results, we suggest that the mechanical properties of PVDF/PVA blend membranes are worse than that of PVDF membrane. PVA can improve the hydrophilicity of PVDF/PVA hollow fiber membranes, which could be illuminated by the decrease in contact angle, the increase in equilibrium water content (EWC) and the variety in dynamic moisture regain. The pure water flux increases while the rejection ratio decreases with PVA content increasing. Moreover, PVA can improve the anti-fouling property of PVDF/PVA hollow fiber membranes, which could be illuminated by the result of increase coefficient of resistance.     

中空纤维PVA/PAN复合膜填料的乙醇水溶液精馏性能

以乙醇/水溶液为分离对象,中空纤维PVA/PAN复合膜作为精馏填料,考察了不同膜组件的传质分离效率。实验结果表明:各种组件的分离效率均随塔釜加热功率的增加而减小;和大多数中空纤维膜接触器一样,其总传质系数Ky随中空纤维膜组件填充密度φ的增加而减少;相比于传统精馏填料而言,用中空纤维膜做精馏填料分离乙醇水溶液的分离效果更好,可以在常规填料不能操作的液泛线以上进行操作。当塔釜加热功率为120 W,45根中空纤维膜封装在内径为1.6 cm玻璃管中的传质单元高度(HTU)为5.64 cm。     

共混比及聚合物浓度对PVC/PVB相容性及超滤膜性能结构的影响

通过混合焓的计算,对不同共混比和聚合物浓度的聚氯乙烯(PVC)/聚乙烯醇缩丁醛(PVB)共混比体系的相容性进行预测,并通过稀溶液黏度(DSV)法、运动黏度法和目视法进行相应验证;以N,N-二甲基乙酰胺(DMAc)为溶剂,通过湿相转换法(NIPS)制备PVC/PVB共混平板超滤膜,并对超滤膜的性能和结构进行测试,系统地研究了PVC/PVB共混铸膜液的组成对平板超滤膜的结构及其分离性能的影响,为通过PVB共混改性PVC膜材料制备超滤膜提供了理论依据。     

HDPE hollow‐fiber membrane via thermally induced phase separation. II. Factors affecting the water permeability of the membrane

Some major factors of the melt spinning of high‐density polyethylene (HDPE) and a liquid paraffin (LP) blend, which affect the water permeability of HDPE hollow‐fiber membrane obtained therefrom, were investigated. The water permeability of the membrane was found to increase as the membrane thickness decreases and as the melt‐flow‐rate value of HDPE and the LP content of the blend increases. The dependence of the water permeability on the major factors is also discussed in connection with the morphology of the membrane. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1235–1242, 2000     

Aloe vera gel influence on the micellization behavior of copolymer Pluronic F127: A potential photosensitizer carrier for topical application

This work describes the influence of aloe vera gel on Pluronic F127 triblock copolymer (F127) micellization behavior. Aloe vera gel was obtained from aloe vera mucilage found in leaf pulp. F127 (20% w/w) gel and the aloe vera/F127 blend gel were obtained by using the cold method. Fourier transform infrared spectroscopy and X‐ray diffraction analyses of lyophilized samples did not show any important copolymer interaction between aloe vera gel and F127. However, in aqueous medium, the dynamic light scattering data showed that there was an important reduction in micelle size with increasing temperature of the aloe vera/F127 blend hydrogel. The differential scanning calorimetry results indicate that the aloe vera/F127 blend has a higher micellization temperature, affected by the lower dehydrating effect of the poly(propylene oxide) blocks during the micelle formation in comparison to F127 gel. The texture analyses (hardness and adhesiveness) showed that the addition of aloe vera gel did not change the Pluronic F127 gel texture properties. The photosensitizer zinc phthalocyanine (ZnPC) was incorporated into the aloe vera/F127 blend, and the results suggest that this formulation is suitable as a ZnPC delivery system for photodynamic therapy. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46191.