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.     

Modification of porous poly(vinylidene fluoride) membrane using amphiphilic polymers with different structures in phase inversion process

Three kinds of amphiphilic polymers, including the tri-block copolymer of (polyethylene oxide)–(polypropylene oxide)–(polyethylene oxide) (I, EPTBP), the comb-like copolymer of polysiloxane with polyethylene oxide and polypropylene oxide side chains (II, ACPS) and the hyperbranched star copolymer of polyester-g-methoxyl polyethylene glycol (III, HPE-g-MPEG), were blended with PVDF to fabricate porous membranes via a phase inversion process, respectively, and the effects of the different structures of the amphiphilic polymers on the properties of the blend membranes were compared. The membranes were characterized by scanning electron microscopy (SEM), elemental analysis, X-ray photoelectron spectroscopy (XPS) analysis, mercury porosimetry, water contact angle measurements, etc. The anti-fouling properties of the prepared membranes were evaluated by static and dynamic bovine serum albumin (BSA) adsorptions. Specially, the stabilities of these amphiphilic polymers in the final membranes were estimated by continuous leaching tests. At the same time, the properties of the membranes using the amphiphilic polymers as modifiers were compared with those of the membrane using poly(ethylene glycol) (PEG) as modifier.     

Enhanced separation performance of PVDF/PVP-g-MMT nanocomposite ultrafiltration membrane based on the NVP-grafted polymerization modification of montmorillonite (MMT)

A novel hydrophilic nanocomposite additive (PVP-g-MMT), coupling of hydrophilic modifier, self-dispersant, and pore-forming agent (porogen), was synthesized by the surface modification of montmorillonite (MMT) with N-vinylpyrrolidone (NVP) via "grafting from" polymerization in the presence of H(2)O(2)-NH(3)·H(2)O as the initiator, and then the nanocomposite membrane of poly(vinylidene fluoride) (PVDF) and PVP-g-MMT was fabricated by wet phase inversion onto clean glass plates. The existence and dispersion of PVP-g-MMT had a great role on structures, morphologies, surface composition, and chemistry of the as-prepared nanocomposite membranes confirmed by varieties of spectroscopic and microscopic characterization techniques, all of which were the correlated functions of PVP-g-MMT content in casting solution. By using the dead-end filtration of protein aqueous solution, the performance of the membrane was evaluated. It was seen that all of the nanocomposite membranes showed obvious improvement of water flux and proper BSA rejection ratio, compared to the control PVDF membrane. Meanwhile, dynamic BSA fouling resistance and flux recovery properties were also greatly enhanced due to the changes of surface hydrophilicity and morphologies. All the experimental results indicated that the as-prepared PVDF nanocomposite membranes showed better separation performances than the control PVDF membrane. Hopefully, the demonstrated method of hydrophilic nanocomposite additive synthesis would be applied for commonly hydroxyl group-containing inorganic nanoparticles, which was favorable to fabricate hydrophilic nanoparticle-enhanced polymer membranes for water treatment.     

Effect of poly(ethylene glycol) 200 on the formation of a polyetherimide asymmetric membrane and its performance in aqueous solvent mixture permeation

To investigate the effect of poly(ethylene glycol) (PEG) 200 on membrane performance, asymmetric polyetherimide (PEI) membranes with a small pore size were prepared by dry/wet-phase inversion from the casting solution containing N-methyl-2-pyrrolidone as a solvent and poly(ethylene glycol) 200 as an additive. Our experiment revealed that the addition of PEG 200 has an influence on the casting solution properties, permeation properties, and resulting membrane structures. Moreover, a drying process also affects the formation of a dense skin layer. Increasing the amount of PEG 200 drastically improved the solute rejection rate. The drying process improved the rejection rate. We also observed the effect of the mixed solvent (water/ethanol) on permeation through the membranes with various pore sizes. In the case of the membrane with a dense skin layer, the solvent permeation showed relationships with solution viscosity, surface tension, and membrane-solvent interaction.     

HBPE-g-PVDF/PVDF blend nanofiltration membrane: preparation and characterization

Hyperbranched polyester-grafted poly(vinylidene fluoride) (HBPE-g-PVDF) was synthesized and used as additive in preparation of PVDF blend membranes. HBPE-g-PVDF copolymer was characterized with FTIR and TGA techniques. The prepared membranes were also characterized with SEM, AFM and contact angle measurement. The performance of prepared membranes as nanofiltration membrane was studied by pure water flux (PWF), salt rejection, dynamic and static fouling tests. The results showed that hydrophilicity of prepared membranes greatly increased after blending, and their pore size and pore size distribution and so PWF of blend membranes increased.     

两亲性梳状聚醚硅氧烷对相转化法聚偏氟乙烯多孔膜的共混改性作用研究

以聚醚链段为侧链的两亲性梳状聚醚硅氧烷(ACPS)为改性剂,研究了相转化法制备聚偏氟乙烯(PVDF)多孔膜的改性效果与机理.采用SEM、XPS、接触角、水通量等考察了ACPS对膜结构与性能的影响.研究发现,ACPS在相转化成膜过程中不流失,随着制膜液中ACPS含量的增加,相分离速度降低,膜中微孔由指状结构向蜂窝状结构发展,膜强度提高,亲水性显著提高.提出了ACPS在膜表面的富集现象和在膜中的稳定性机理和模型.结果表明,两亲性梳状聚醚硅氧烷在原理上是一类适合于相转化法制备聚合物微孔膜表面亲水化改性的有效物质.     

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.     

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.     

Fabrication of Hydrophilic and Sponge-like PVDF/Brush-like Copolymer Blend Membranes Using Triethylphosphate as Solvent简

Porous PVDF blend membranes with good hydrophilicity and a symmetric structure were prepared by the phase inversion method using amphiphilic brush-like copolymers, P（MMA-r-PEGMA）, as hydrophilic additive and triethylphosphate （TEP） as solvent. P（MMA-r-PEGMA） was synthesized by radical polymerization in TEP. Then the obtained amphiphilic copolymer solution was mixed with PVDF and TEP to prepare the dope solution. The effects of P（MMA-r-PEGMA） content and coagulation composition on membrane morphologies were investigated using scanning electron microscopy （SEM）. The results demonstrated that, even blended with amphiphilic copolymers, a symmetric structure can be formed. Hollow fiber membranes with a mainly symmetric structure were also fabricated. The dry hollow fiber membranes showed good hydrophilicity, high flux and good rejection performance because of their hydrophilic surface and pores wall.     

Porous poly(vinylidene fluoride) membrane modified with hyperbranched poly(amine‐ester)

Poly(vinylidene fluoride) (PVDF) membranes were hydrophilic modified with hydroxyl group terminated hyperbranched poly(amine‐ester) (HPAE). Fourier transform infrared spectroscopy (FT‐IR) was used to study the chemical change of PVDF membranes. X‐ray photoelectron spectroscopy (XPS) indicated that some HPAE molecules were retained in PVDF membrane through polymer chain coiling. The presence of HPAE would improve the hydrophilicity of PVDF membrane. Scanning electron microscopy (SEM) was employed to characterize the morphology of different membranes. The thermodynamic stability for PVDF/DMAc/HPAE/Water system was characterized by the determination of the gelation values. Precipitation kinetics for PVDF/DMAc/HPAE/Water system was studied by precipitation time measurement. The water contact angle indicated that the hydrophilicity and the biocompatibility corresponding to protein adsorption of PVDF membrane were improved significantly after blending with hydrophilic HPAE molecules. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication and characterization of a novel TiO2 nanoparticle self-assembly membrane with improved fouling resistance

A novel TiO₂ nanoparticle self-assembly membrane was prepared based on ultrahigh molecular weight poly(styrene-alt-maleic anhydride)/poly(vinylidene fluoride) (SMA/PVDF) blend membrane. TiO₂ nanoparticle solution was beforehand prepared via the controlled hydrolysis of titanium tetraisopropoxide. The diameter (10 nm or less) and anatase crystal structure were analyzed using transmission electron microscopy (TEM) and X-ray diffraction (XRD). The SMA/PVDF blend membranes prepared by the phase inversion method were immersed into the TiO₂ nanoparticle solution for a week to produce TiO₂ self-assembly membranes. The chemical compositions in membrane surface were analyzed by X-ray photoelectron spectroscopy (XPS). The membrane morphologies were measured by scanning electron microscopy (SEM). Finally, the membrane hydrophilicity, protein anti-fouling property and the molecular weight cutoff (MWCO) were characterized by water contact angle measurement, static protein absorption and filtration experiments, respectively. It is demonstrated that, in comparison to PVDF/SMA blend membrane, the permeability and anti-fouling ability of TiO₂ self-assembly membranes were significantly improved.     

应用于膜蒸馏过程的F26微孔膜的初步研究

以N-甲基吡咯酮作为溶剂 ,丙酮为溶胀剂 ,聚乙二醇 4 0 0为添加剂利用相转换法制备出偏氟乙烯 六氟丙烯共聚物 (F2 6 )的疏水微孔膜并且应用在膜蒸馏过程中 .研究了丙酮以及N 甲基吡咯酮 丙酮体系对膜参数以及结构的影响 .通过SEM观察了膜的微观结构 ,发现用N 甲基吡咯酮 丙酮体系制得的微孔膜兼具指状孔和海绵状孔结构 .无添加剂条件下制得的F2 6膜其对蒸馏水的接触角比相同条件下制备的PVDF膜大 .在用相转换法制备的F2 6和PVDF的疏水膜中 ,选择具有适当孔径结构的微孔膜用于膜蒸馏实验 ,F2 6膜的膜蒸馏系数比PVDF膜来得大 ,相同操作条件下的膜蒸馏通量也比PVDF膜高 .     

Effect of PEG additive on membrane formation by phase inversion

This study investigates the effect of PEG additive as a pore-former on the structure formation of membranes and their permeation properties connected with the changes of thermodynamic and kinetic properties in phase inversion process. The membranes were prepared by using polysulfone (PSf)/N-methyl-2-pyrrolidone (NMP)/poly(ethylene glycol) (PEG) casting solution and water coagulant. The resulting membranes prepared by changing the molecular weight of PEG additive and the ratio of PEG to NMP were characterized by scanning electron microscope observations, measurements of water flux and PEG rejection. The thermodynamic and kinetic properties of membrane-forming system were studied through coagulation value, light transmittance and viscosity. The correlations between the final membrane structure/permeation properties and thermodynamic/kinetic properties of membrane forming system are discussed extensively.     

Effect of the preparation conditions on the formation of asymmetric poly(vinylidene fluoride) hollow fibre membranes with a dense skin

Integrally skinned asymmetric poly(vinylidene fluoride) hollow fibre membranes were prepared and characterized. The effects of phase inversion methods (dry-wet or wet) and spinning conditions, such as the type of solvent (NMP, DMAc), the concentration of polymer in dope solution, temperature of the external coagulation bath and the composition of the inner coagulant on the morphology and on the formation of a dense skin layer were investigated. The structure of the membranes was analyzed by scanning electron microscopy and the gas permeation properties with six different gases (He, H₂, N₂, O₂, CH₄ and CO₂) were measured at 25 °C to confirm the integrity of the selective skin layer. Under the proper conditions highly selective and permeable PVDF hollow fibre membranes were thus obtained by dry-wet spinning of a 30 wt.% PVDF solution in DMAc, using hot water (50 °C) as the external coagulant and a bore fluid of pure water as the internal coagulant. The best membrane had a selective outer skin with an effective thickness of approximately 0.2 μm. The ideal selectivity of the hollow fibres approached or even exceeded the intrinsic ideal selectivity of a dense PVDF film, for instance the selectivity for He over N₂ was 86.2 for the hollow fibre, whereas it was 83.5 for a dense PVDF reference film. DSC and FT-IR/ATR analysis indicated a higher fraction of the β-crystal phase in the selective skin and a high overall crystallinity than in the melt-processed film. The latter explains the relatively high selectivity and low permeability of the membranes. Intrinsic polymer properties make the membranes also suitable for vapour transport than for gas separation.     

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...     

PSSA pore-filled PVDF membranes by simultaneous electron beam irradiation: Preparation and transport characteristics of protons and methanol

Polystyrene sulfonic acid (PSSA) pore-filled poly(vinylidene fluoride) (PVDF) membranes have been prepared using simultaneous electron irradiation method. Porous PVDF films were grafted by pre-swelling in styrene solution and subsequent irradiation with an electron beam (EB) under nitrogen atmosphere and at ambient temperature. The grafted films i.e. polystyrene (PS) pore-filled PVDF were subsequently sulfonated with a diluted mixture of chlorosufonic acid. The effects of the reaction parameters on the content of PS grafted in the pores of PVDF films were investigated. The chemical and morphological properties of the membranes in comparison with their un-grafted and grafted counterparts were studied by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). The transport properties of these membranes such as ionic conductivity and methanol permeability were evaluated and correlated with the content of PS grafted in the pores of the PVDF films. The PSSA pore-filled PVDF membranes with PS content in the pores of 40% and above showed superior performance characteristics compared to Nafion 117 membrane and therefore can be potential alternatives to improve the performance of direct methanol fuel cell (DMFC).     

Functional membranes prepared by layer‐by‐layer assembly and its metal ions adsorption property

PVDF/(PEI‐C/PAA)_n functional membranes were prepared by layer‐by‐layer (LbL) assembly, and their heavy metal ions adsorption capability was investigated. The changes in the chemical compositions of membrane surfaces were determined by X‐ray photoelectron spectroscopy (XPS). XPS results show that the surface of the PVDF membrane can be alternatively functionalized by PEI‐C and PAA. The membrane surface hydrophilicity was evaluated through water contact angle measurement. Contact angle results show that the surface hydrophilicity of the membrane surface depends on the outermost deposited layer. Morphological changes of membrane surfaces were observed by scanning electron microscopy (SEM). The water fluxes for these membranes were elevated after modification. The performances of the PVDF/(PEI‐C/PAA)_n membranes on the adsorption of copper ions (Cu²⁺) from aqueous solutions were investigated by inductively coupled plasma (ICP). The results indicate that the PVDF/(PEI‐C/PAA)_n functional membranes show high copper ions adsorption ability. Copyright © 2010 John Wiley & Sons, Ltd.     

Improving hydrophilicity and protein resistance of poly(vinylidene fluoride) membranes by blending with amphiphilic hyperbranched-star polymer

To endow hydrophobic poly(vinylidene fluoride) (PVDF) membranes with reliable hydrophilicity and protein resistance, an amphiphilic hyperbranched-star polymer (HPE-g-MPEG) with about 12 hydrophilic arms in each molecule was synthesized by grafting methoxy poly(ethylene glycol) (MPEG) to the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent and blended with PVDF to fabricate porous membranes via phase inversion process. The chemical composition changes of the membrane surface were confirmed by X-ray photoelectron spectroscopy (XPS), and the membrane morphologies were measured by scanning electron microscopy (SEM). Water contact angle, static protein adsorption, and filtration experiments were used to evaluate the hydrophilicity and anti-fouling properties of the membranes. It was found that MPEG segments of HPE-g-MPEG enriched at the membrane surface substantially, while the water contact angle decreased as low as 49 degrees for the membrane with a HPE-g-MPEG/PVDF ratio of 3/10. More importantly, the water contact angle of the blend membrane changed little after being leached continuously in water at 60 degrees C for 30 days, indicating a quite stable presence of HPE-g-MPEG in the blend membranes. Furthermore, the blend membranes showed lower static protein adsorption, higher water and protein solution fluxes, and better water flux recovery after cleaning than the pure PVDF membrane.     

PVDF亲水复合膜的制备及表征

聚偏氟乙烯(PVDF)膜材料存在强疏水性的缺陷,亲水化改性是解决该问题的主要途径。以PVDF为基膜材料、聚乙烯醇(PVA)为共混材料、N,N-二甲基乙酰胺(DMAc)为溶剂,采用相转化法制备PVDF/PVA复合膜。考察了复合膜的PVDF/PVA共混比、固含量、低分子化合物添加剂、聚合物添加剂等非溶剂添加剂对复合膜接触角的影响。结果表明,当PVDF/PVA共混比为7/3,固含量为13%时,制备的复合膜接触角为22.92°;当添加剂为无水氯化锂、纳米二氧化硅、聚乙烯吡咯烷酮(PVP)时,复合膜接触角分别从53.12°、30.51°和41.89°都降低到了0°,亲水性提高,其中纳米二氧化硅作为添加剂时复合膜亲水性最好;当添加剂为丙三醇、PMMA、PEG时,复合膜接触角都增大,亲水性变差。     

Preparation and characterization polyvinylidene fluoride membranes from water and ethanol coagulants via in situ free radical polymerization

In this present study, the facile approaches of coagulants and in situ free radical polymerization method for modulating configurations and performances of polyvinylidene fluoride (PVDF) membranes are investigated. Configuration images show that the supramolecular aggregates of PVDF‐P(PEGMA‐r‐MMA) caused by in situ polymerization act as “template” of the tuned configurations of the resultant PVDF membranes. During delay demixing process (ethanol coagulant), the confine of the aggregates resulted in shift of the cauliflower nanograins to the stripe‐type nanograins. On the other hand, for the membranes prepared from the instantaneous demixing process in water coagulant, the aggregates contributed to the formation of the confined finger‐like structures and the globule agglomerates that constructed the whole thickness of the membrane bulk. Furthermore, those narrow distribution supramolecular aggregates and variation coagulants (water and ethanol) also yield the tuned performances. The membranes' improved mechanical properties and limited hydrophilicity improvement are attributed to the strong interconnection between the aggregates. Because of the fore‐forming of the P(PEGMA‐r‐MMA) aggregates with narrow distribution, all PVDF membranes prepared from the two coagulants possess enlarged flux, narrow distribution mean effective pore size (μ), and molecular weight cut‐off. The delay demixing process contributes to the narrower μ and molecular weight cut‐off, as well increased flux. Copyright © 2014 John Wiley & Sons, Ltd.