氧化铝凝胶改性聚偏氟乙烯超滤膜的制备与表征

为提高聚偏氟乙烯超滤膜的亲水性,采用Al_2O_3凝胶对有机高分子聚偏氟乙烯膜进行改性,制备Al_2O_3凝胶改性聚偏氟乙烯超滤膜,并与非凝胶化无机纳米Al_2O_3颗粒改性进行对比。考察铸膜液中Al_2O_3凝胶加入量对改性聚偏氟乙烯超滤膜性能和结构的影响。采用扫描电镜、X射线能谱、傅里叶红外光谱和超滤实验等对超滤膜结构和性能进行表征,结果表明,Al_2O_3凝胶加入量1.0 g时,改性超滤膜水通量提高5.48倍;扫描电镜表明,改性超滤膜和未改性超滤膜均为典型的非对称结构,改性超滤膜表面孔数目明显增加,断面微观结构未发生改变;红外光谱及能谱分析表明,Al_2O_3凝胶与高分子聚偏氟乙烯之间为物理共混。Al_2O_3凝胶改性聚偏氟乙烯超滤膜,改善了膜表面亲水性,提高水通量,并保持较大截留率。     

温敏性PVDF/PGS-g-PNIPAM纳米复合超滤膜的制备和性能

通过化学接枝法将聚(N-异丙基丙烯酰胺)(PNIPAM)接枝聚合在凹凸棒石(PGS)纳米纤维表面,制备了系列接枝率的温敏性PGS-g-PNIPAM纳米颗粒,将其与聚偏氟乙烯(PVDF)共混制备温敏性纳米复合超滤膜,深入研究PNIPAM接枝率对膜结构和性能的影响。结果表明,凹凸棒石表面PNIPAM接枝率随溶液中NIPAM单体浓度增大而增加;PGS-g-PNIPAM使复合膜中PVDF晶核变小,数目增多,膜更为疏松多孔,PVDF/PGS-g-PNIPAM膜的平均孔径在20 nm左右,膜的平均孔径和最大孔径均随凹凸棒石表面PNIPAM接枝率的增加而增大;PVDF/PGS-g-PNIPAM膜具有温敏性,温敏开关系数随PNIPAM接枝率的增加先增强后减弱,当接枝率为21.33%时膜温敏开关系数最大,达到1.51,膜渗透通量也最大,对牛血清白蛋白具有良好的截留和抗污染性能。     

Preparation and characterization of polyvinylidene fluoride hollow fiber membranes for ultrafiltration

Polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared using the solvent spinning method. N,N-dimethylacetamide was the solvent and ethylene glycol was employed as non-solvent additive. The effect of the concentration of ethylene glycol in the PVDF spinning solution as well as the effect of ethanol either in the internal or the external coagulant on the morphology of the hollow fibers was investigated. The prepared membranes were characterized in terms of the liquid entry pressure of water measurements, the gas permeation tests, the scanning electron microscopy, the atomic force microscopy, and the solute transport experiments. Ultrafiltration experiments were conducted using polyethylene glycol and polyethylene oxides of different molecular weights cut-off as solutes. A comparative analysis was made between the membrane characteristic parameters obtained from the different characterization techniques.     

聚偏氟乙烯超滤膜亲水改性研究进展

膜污染会缩短超滤膜的使用寿命,增加由于水力清洗、化学清洗以及膜组件更换而产生的费用。为减少运行成本,有必要对膜污染加以控制。膜污染与原水中污染物的性质和膜本身的性质密切相关。亲水性膜具有水通量高、抗污染性能好的特点,因而提高超滤膜的亲水性是提高膜的水通量和控制膜污染的重要方法之一。简要介绍了具有良好化学稳定性、耐辐射性、耐热性的聚偏氟乙烯膜的表面亲水改性和共混亲水改性的研究进展,指出通过不同的改性方式,聚偏氟乙烯膜都能够实现亲水性的增强。     

Effect of hydrophilic poly(ethylene glycol) methyl ether additive on the structure,morphology, and performance of polysulfone flat sheet ultrafiltration membrane

In this work, effects of hydrophilic poly(ethylene glycol) methyl ether (PEGME) 5000 additive on the structure, morphology, and performance of polysulfone (PSF) membrane have been investigated. The membranes are prepared with direct blending of PEGME5000 (0–9 wt %) with two compositions of PSF (12 and 15 wt %) into N-methyl-2-pyrrolidone and further characterized in terms of morphology, structure, fouling, and ultrafiltration performance. The ternary phase diagram is plotted to investigate the thermodynamic stability of the system. Moreover, protein adsorption tests are conducted using bovine serum albumin (BSA) to see the effect of PEGME5000 on surface hydrophilicity. The ultrafiltration experiments are performed using humic acid (HA) solution and oil-in-water (o/w) emulsion. The result showed that, the contact angle decreased from 64° to 46° and from 67.6° to 49° for 12M and 15M membranes, respectively, indicating an improved hydrophilicity. The 12M and 15M membranes with 9 wt % of PEGME5000 have the lowest BSA adsorption due to highest antifouling property. The maximum permeability was obtained 0.72 and 0.51 L/m² h kPa for 12M5 and 15M3, respectively, due to maximum porosity which is also supported by the morphological result. In HA permeation, 12M5 and 15M3 achieved a maximum Flux _RR around 0.95 and 0.91, respectively, which was remarkably higher compared to 0.61 and 0.62 Flux _RR of 12M0 and 15M0. Also, PEGME5000 significantly affected the structure and morphology of the membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47163.     

Preparation and characterization of metal-complex imprinted PVDF hollow fiber membranes

Using nickel-2,2′-dipyridyl complex as a template, N-vinyl-2-pyrrolidone as the metal coordination functional monomer, and ethylene glycol dimethacrylate as the crosslinker, polyvinylidene fluoride (PVDF) hollow fiber ultrafiltration membrane as the supported membrane, metal complex imprinted polymeric membranes were prepared. The association constant of template-monomer interaction in the prepolymerization solution was estimated to be 4.38 × 10⁴ (L/mol)² by spectrophotometric titration analysis. The attenuated total reflection Fourier transform infrared spectroscopy and scanning electron micrograph characterization indicated that the surface of the support PVDF membrane was completely coated by the imprinted polymer layer after modification. The imprinted membranes exhibited the selective permeability for the template in certain nickel acetate solution. The molecularly imprinted membranes gave higher permeation separation factors at about pH 6, whereas increasing pressure would lower the separation ability. The effects of ion concentration, cations and counterions, ligand selectivity, pH, and trans-membrane pressure were investigated and the permeation performances of the imprinted membranes could be regarded as facilitated transport mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of antibacterial polyvinylidene fluoride (PVDF) ultrafiltration membranes with direct addition of N-halamine polymers

In this study, novel antibacterial ultrafiltration polyvinylidene fluoride (PVDF) flat sheet membranes were produced with addition of synthesized N-halamine polymers. The ternary phase diagrams of PVDF and the synthesized polymers with N-methyl-2-pyrrolidone and water systems were prepared. The water flux and BSA rejection performances of the produced membranes were assessed both with and without PVP addition, and compared with a commercial membrane. The produced membranes were characterized with FTIR, XPS, DSC, and SEM analysis. Addition of N-halamine polymers to the membrane structure significantly improved the biocidal performance of the produced membranes against Staphylococcus aureus and Escherichia coli (10⁵ CFU).     

Polyurethane and carboxylated polysulfone blend ultrafiltration membranes. I. Preparation and characterization

Polysulfone was functionalized by carboxylation and blended with polyurethane (ether type). Blend membranes were prepared in the presence and absence of the additive poly(ethylene glycol) 600 and subjected to ultrafiltration characterizations such as compaction, pure water flux, water content, and hydraulic resistance. Morphological studies of the membranes were performed with scanning electron microscopy. The effects of the polymer composition and additive concentrations on the above parameters were analyzed and the results compared. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1307–1315, 2005     

Cellulose acetate and sulfonated polysulfone blend ultrafiltration membranes. I. Preparation and characterization

Modification of polymeric membrane materials by incorporation of hydrophilicity results in membranes with low fouling behavior and high flux. Hence, Polysulfone was functionalized by sulfonation and ultrafiltration membranes were prepared based on sulfonated polysulfone and cellulose acetate in various blend compositions. Polyethyleneglycol 600 was employed as a nonsolvent additive in various concentrations to the casting solution to improve the ultrafiltration performance of the resulting membranes. The total polymer concentration, cellulose acetate, and sulfonated polysulfone polymer blend composition, additive concentration, and its compatibility with polymer blends were optimized. The membranes prepared were characterized in terms of compaction, pure water flux, membrane resistance, and water content. The compaction takes place within 3–4 h for all the membranes. The pure water flux is determined largely by the composition of sulfonated polysulfone and concentration of additive. Membrane resistance is inversely proportional to pure water flux, and water content is proportional to pure water flux for all the membranes. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1749–1761, 2002     

聚砜超滤膜的制备及结构性能研究

实验以低分子量的PEG作为添加剂制备聚砜超滤膜,通过不同低分子量和不同含量的PEG加入,改变了膜结构性能。制膜液由聚砜(PSf)/二甲基乙酰胺(DMAc)/聚乙二醇(PEG)组成。通过水通量、截留率和电镜图来评价添加剂对膜的性能结构影响。     

Preparation of hydrophobic flat sheet membranes from PVDF-HFP copolymer for enhancing the oxygen permeance in nitrogen/oxygen gas mixture

In this study, poly(vinilydene fluoride-co-hexafluoropropylene)(PVDF-HFP) was used for preparation of hydrophobic membranes using non-solvent induced phase inversion(NIPS) technique. PVDF-HFP copolymer with concentrations of 10 wt% and 12 wt% was prepared to investigate the effect of polymer concentration on pore structure,morphology, hydrophobicity and performance of prepared membranes. Besides, the use of two coagulation baths with the effects of parameters such as coagulant time, polymer type and concentration, and the amount of nonsolvent were studied. The performance of prepared membranes was evaluated based on the permeability and selectivity of oxygen and nitrogen from a gas mixture of nitrogen/oxygen under operating conditions of feed flow rate(1–5 L·min~(-1)), inlet pressure to membrane module(0.1–0.5 MPa) and temperatures between 25 and 45 °C. The results showed that the use of two coagulation baths with different compositions of distillated water and isopropanol,coagulant time, polymer type and concentration, and the amount of non-solvent additive have the most effect on pore structure, morphology, thickness, roughness and crystallinity of fabricated membranes. Porosity ranges for the three fabricated membranes were determined, where the maximum porosity was 73.889% and the minimum value was 56.837%. Also, the maximum and minimum average thicknesses of membrane were 320.85 μm and115 μm. Besides, the values of 4.7504 × 10~(-7) mol· m~(-2)· s~(-1)· Pa~(-1), 0.525 and 902.126 nm were achieved for maximum oxygen permeance, O_2/N_2 selectivity and roughness, respectively.     

界面增强型PVDF/PET膜的制备及性能

通过对支撑材料进行表面改性处理和浸入凝胶法制备了界面增强型聚偏氟乙烯/聚对苯二甲酸乙二醇酯（PVDF/PET）超滤膜。用电导率在线测量法确定了硅烷偶联剂 3-氨丙基三乙氧基硅烷（KH550）水解液的制备条件,考察了改性处理条件对PVDF/PET膜的界面性能和力学性能的影响。通过180°剥离试验测试PVDF膜与支撑层间的剥离强度,用扫描电镜观察PET无纺布及PVDF膜破坏底面的微观形貌,用傅里叶红外光谱仪表征PET表面化学组成。结果表明,水解液中KH550用量较少时（≤3%）,处理时间延长,PVDF/PET间的剥离强度增大,水解液中KH550用量较多时（>3%）,处理时间延长,PVDF/PET间的剥离强度先增大后减小;PVDF/PET膜的拉伸强度随水解液中KH550用量的增加或处理时间的延长先增大后略减小。改性前后PVDF/PET膜的分离与透过性能对比表明,PET表面改性后,PVDF膜的牛血清白蛋白（BSA）截留率几乎不受影响,水通量略增。     

Effects of mixed solvents and PVDF types on performances of PVDF microporous membranes

Polyvinylidene fluoride (PVDF) microporous flat membranes were cast with different kinds of PVDFs and four mixed solvents [trimethyl phosphate (TMP)–N,N‐dimethylacetamide (DMAc), triethyl phosphate (TEP)–DMAc, tricresyl phosphate (TCP)–DMAc, and tri‐n‐butyl phosphate (TBP)–DMAc]. The effects of different commercial PVDFs (Solef® 1015, FR 904, Kynar 761, Kynar 741, Kynar 2801) on membrane morphologies and membrane performances of PVDF/TEP–DMAc/PEG200 system were investigated. The membrane morphologies were examined by scanning electron microscopy (SEM). The membrane performances in terms of pure water flux, rejection, porosity, and mean pore radius were measured. The membrane had the high flux of 143.0 ± 0.9 L m^?2 h^?1 when the content of TMP in the TMP–DMAc mixed solvent reached 60 wt %, which was 2.89 times that of the membrane cast with DMAc as single solvent and was 3.36 times that of the membrane cast with TMP as single solvent. Using mixed solvent with different solvent solubility parameters, different morphologies of PVDF microporous membranes were obtained. TMP–DMAc mixed solvent and TEP–DMAc mixed solvent indicated the stronger solvent power to PVDF due to the lower solubility parameter difference of 1.45 MPa^1/2 and the prepared membranes showed the faster precipitation rate and the higher flux. The less macrovoids of the membrane prepared with TEP (60 wt %)–DMAc (40 wt %) as mixed solvent contributed to the higher elongation ratio of 96.61% ± 0.41%. Therefore, using TEP(60 wt %)–DMAc (40 wt %) as mixed solvent, the casting solution had the better solvent power to PVDF, and the membrane possessed the excellent mechanical property. The microporous membranes prepared from casting solutions with different commercial PVDFs exhibited similar morphology, but the water flux increased with the increment of polymer solution viscosity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

聚丙烯腈超滤膜的制备

为了得到高性能的超滤膜,采用相转化法,以聚丙烯腈(PAN)为原料,N-甲基-吡咯烷酮(NMP)为溶剂,制备了聚丙烯腈超滤膜.采用纯水通量以及膜对牛血清蛋白(BSA)的截留率作为评价标准,并使用扫描电镜对膜结构进行表征.研究了聚合物质量分数、添加剂种类、凝胶浴温度、凝胶浴种类对膜性能的影响.研究发现:在一定范围内提高聚合...     

Preparation of PVDF hollow‐fiber membranes via immersion precipitation

Porous polyvinylidene fluoride (PVDF) hollow‐fiber membranes with high porosity were fabricated using the immersion precipitation method. Dimethylacetamide (DMAc) and N‐methyl‐2‐pyrrolidone (NMP) were used as solvent, respectively. In addition, polyvinylpyrrolidone (PVP), lithium chloride, and organic acids were employed as nonsolvent additives. The effects of the internal and external coagulation mediums on the resulting membrane properties were also investigated. The resulting hollow‐fiber membranes were characterized in terms of maximum pore radius, mean pore radius, effective surface porosity as well as wetting pressure. The structures of the prepared hollow fibers were examined using a scanning electron microscope. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 1643–1653, 2001     

Acrylonitrile copolymers: Synthesis,characterization, and formation of ultrafiltration membranes

A variety of poly(acrylonitrile‐co‐acrylamide) polymers of different compositions were synthesized by free radical copolymerization. Thin films were cast from polymer solutions, and coagulated into ultrafiltration membranes. The effect of preparative parameters on membrane gel structure was investigated. For nonsupported membranes, concentrated polymer solutions produce fine pore membranes with a lower flux; extending the drying time causes a diminution in membrane thickness, swelling index, and fluxes; the membrane thickness, swelling index, and permeate flux all increased with increasing coagulation bath temperature. For supported membranes, dilute polymer casting solutions, small casting gate opening, and added polyvinylpyrrolidone to the casting solution all increased the permeate flux. The membranes containing acrylamide were more hydrophilic, and had a smaller dispersion force component of the surface free energy than those prepared from the polyacrylonitrile homopolymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1271–1277, 1999     

Preparation and characterization of microporous polyethylene hollow fiber membranes

Microporous polyethylene (PE) hollow fiber membrane with a porosity of 43% and N₂ permeation of 4.96 cm³ (STP)/cm² s cmHg was prepared by melt‐spinning and cold‐stretching method. It was found that PE with a density higher than 0.96 g/cm³ should be used for the preparation of microporous PE hollow fiber membranes. By increasing the spin–draw ratio, both the porosity and the N₂ permeation of the hollow fiber membranes increased. Annealing the nascent hollow fiber at 115°C for 2 h was suitable for attaining membranes with good performance. By straining the hollow fiber to higher extensions, the amount and size of the micropores in the hollow fiber wall increased, and the N₂ permeation of the membranes increased accordingly. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 203–210, 2002; DOI 10.1002/app.10305     

等离子体改性聚偏氟乙烯超滤膜的研究

为了改善聚偏氟乙烯(PVDF)超滤膜的亲水性,采用等离子体技术对PVDF粉料进行功能化改性,使其表面带有功能化基团,以达到提高其水通量,进而改善抗污染能力的目的。实验结果表明:采用等离子体改性PVDF粉料,可以在PVDF粉料表面接上亲水性基团羟基和羰基,从而改善PVDF的亲水性。     

Preparation of soluble polyimides and ultrafiltration membrane performances

Various soluble polyimides with bis[4‐(3‐aminophenoxy)phenyl]sulfone and three kinds of dianhydrides were prepared in a polar N‐methyl‐2‐pyrrolidone solvent by the traditional chemical two‐step method. All the polymers synthesized had good solubilities in polar solvents and excellent thermal properties. Wide‐angle X‐ray diffraction studies showed that all polyimides were amorphous. Polyimide ultrafiltration asymmetric membranes were successfully prepared by the traditional phase‐inversion method. The cross sections of the polyimide ultrafiltration membranes showed a very thin surface layer and a porous sublayer. The pure water flux was very high and the solute rejection rate at poly(ethylene glycol) of MW 20,000 was above 90%. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1–9, 2000     

纳米SiO2-聚乙烯醇复合超滤膜的制备及应用

以水为溶剂，以聚乙二醇（PEG）为致孔剂，并通过向聚乙烯醇（PVA）溶液中添加纳米SiO2构成铸膜液。凝固浴为Na2SO4/KOH/N2O溶液。采用相转化过程制备纳米SiO2－PVA复合超滤膜。实验表明，膜孔径对压力是敏感的。考察了SiO2含量和PEG含量对膜性能的影响。该膜在含油废超滤实验中表现良好的抗污染性及稳定性。