PAN ultrafiltration membranes grafted with natural amino acids for improving antifouling property

In this report, antifouling polyacrylonitrile (PAN) ultrafiltration membranes were prepared from blends of PAN/polyglycidyl methacrylate (PGMA) via phase inversion method followed by the grafting of natural amino acids through epoxy ring-opening reaction. The grafted PAN membranes possessed highly stable hydrophilic surfaces as a result of the grafting of amino acids, which was adequately demonstrated in attenuated total reflectance–Fourier transform infrared spectroscopy (ATR/FTIR), X-ray photoelectron spectroscopy (XPS), and contact angle measurements. The results of tensile strength and scanning electron microscopy (SEM) images further proved that the surface modification had little effect on their mechanical properties, surface, and cross-sectional morphologies. Meanwhile, remarkable resistance against bovine serum albumin (BSA) and lysozyme (Lyz) fouling was observed for the neutral amino acid-based PAN membranes due to the formation of zwitterionic hydration layer on the membrane surface, while PAN membranes grafted with charged amino acids were able to prohibit the approach of like charged proteins with reduced deposition and provide the driving force for oppositely charged protein adsorption. Furthermore, the ultrafiltration and antifouling performance of PAN membranes were investigated by BSA filtration experiments. Compared with the pristine PAN membrane, all the modified PAN membranes exhibited higher pure water flux, better flux recovery ratio, lower rejection, less total permeation resistance, and preferable stability, having potential applications in protein separation and purification.     

Amine-Terminated PAN Membranes as Anion-Adsorber Materials

Anion-adsorbing membranes provide an interesting possibility to remove toxic arsenate and chromate from drinking water. A promising way to prepare anion-exchange materials is to introduce positively charged amine groups on polymers. In this study, polyacrylonitrile (PAN) ultrafiltration membranes were modified with amine functionalities on the membranes. The success of the modifications was demonstrated using infrared spectroscopy and zeta potential measurements. Additionally, the arsenate adsorption was analyzed. The modified membrane showed arsenate adsorption 5 times higher than the pristine PAN membrane.     

Study of the characteristics and the performance of self-made nanoporous polyethersulfone membranes

Polyethersulfone (PES) membranes were prepared in this study by using the DIPS technique (diffusion induced phase separation) in view of a better insight into the performance of commercial polyethersulfone membranes and a verification for the limited information given by the manufacturer. During this process, a lot of conditions influence the final membrane structure. Beside the choice of the solvent (dimethylformamide (DMF) or N-methyl-pyrrolidone (NMP)), it was shown that the concentration of the polymer and the relative air humidity are the most crucial ones. Optimizing these factors led to reproducible membranes, which were characterized for hydrophobicity, roughness, surface charge and molecular weight cut-off (MWCO). The performance was studied by doing cross-flow filtration experiments with aqueous solutions of uncharged and charged component. Although the self-made membranes were characterized by a larger MWCO in comparison with commercial polyethersulfone nanofiltration membranes, the retention for the self-made membranes was almost equal to or even higher than the commercial membranes in the case of filtrating negatively, respectively, positively charged component. The high retention of the self-made membranes for positively charged component can be explained by adsorption experiments or by surface charge measurements before and after filtration.     

Charged polyacrylonitrile membranes having amphiphilic quaternized ammonium groups for ultrafiltration

Four types of positively charged polyacrylonitriles having quaternized N,N-dimethylaminoethyl methacrylate (DAMA) were synthesized and were used to prepare ultrafiltration membranes by a phase-inversion method. The effect of aliphatic ethyl, octyl, and stearyl groups and the benzyl group, which covalently bind to the quaternary ammonium group, on filtration properties was studied by ultrafiltration under an applied pressure of 760 mmH₂O. Water permeability through the resultant membranes increased as the aliphatic chain length on the quaternary ammonium group increased. For a copolymer membrane having a benzyl group on the quaternary ammonium group, water permeability was lower than that for the ethyl type of copolymer membrane. The membrane permeability and pore size for the molecular size-exclusion effect were studied at various NaCl concentrations in the 0–0.15M region. The membranes having octyl and stearyl groups showed stable filtration behavior by increase of the NaCl concentration, while the membranes having an ethyl group and a benzyl group on the quaternary ammonium group showed a change of the water permeability due to a pore-size increase for the membrane by NaCl addition. Measurements of membrane potential indicated the shielding of positively charged sites of the membranes by salt addition. Further, the copolymer membranes showed a separation ability for water/2-butanol of low water content. The separation ability was attributed to the chemical structure of the membranes having different interaction characteristics with the mixture components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1821–1828, 1998     

Positively charged hollow‐fiber composite nanofiltration membrane prepared by quaternization crosslinking

Poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) can be crosslinked by interfacial polymerization to develop a positively charged dense network structure. According to this mechanism, a positively charged hollow‐fiber composite nanofiltration (NF) membrane was prepared by quaternization to achieve a crosslinked PDMAEMA gel layer on the outer surface of polysulfone hollow‐fiber ultrafiltration (UF) membranes with a PDMAEMA aqueous solution as a coating solution and p‐xylylene dichloride as an agent. The preparation conditions, including the PDMAEMA concentration, content of additive in the coating solution, catalyzer, alkali, crosslinking temperature, and hollow‐fiber substrate membrane, were studied. Fourier transform infrared spectroscopy and scanning electron microscopy were used to characterize the structure of the membranes. This membrane had a rejection to inorganic salts in aqueous solution. The rejection of MgSO₄ (2 g/L aqueous solution at 0.7 MPa and 25°C) was above 98%, and the flux was about 19.5 L m^?2 h^?1. Moreover, the composite NF membranes showed good stability in the water‐phase filtration process. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and properties of negatively charged ultrafiltration membrane: Photografted sodium styrene sulfonate onto brominated polyacrylonitrile membrane

Charged ultrafiltration membranes were prepared by photografting sodium styrene sulfonate onto photosensitive polyacrylonitrile membrane containing bromine atoms. The degree of the photografting was characterized by contact angles of air or n-octane in water and FTIR spectra for the negatively charged membrane. Permeations of dextran and dextransulfate through the negatively charged membranes were studied by ultrafiltration in the aqueous solutions of both solutes. With an increase of photoirradiation, the permeability of the solutes decreased. Also, an electrostatic repulsion of the solute and the membrane was confirmed by direct comparison between the permeability of the solutes, dextran, and dextransulfate, each having similar molecular size.     

Development of energy-saving spinning membrane systemand negatively charged ultrafiltration membranes for recovering oil from waste machine cutting fluid

Membranes with hydrophobic surfaces have higher tendency for protein adsorption and bacteria attachment.As a result, these membranes foul rapidly in cross-flow filtration processes. Changing the membrane surface properties can slow down the membrane fouling process. For difficult membrane separation processes like oilwater emulsion separation, changing membrane properties alone cannot slow down the membrane fouling process. The ordinary cross-flow filtration system cannot be successfully employed for this kind of separation, and the spinning membrane disc system could be considered. The conventional spinning membrane disc system however is not energy efficient due to the centrifugal force acting against the permeate flow; this reduces the effective filtration pressure during the separation operation. Efforts were undertaken to develop a group of negatively charged ultrafiltration membranes, prepared from polyacrylonitrile-vinyl acetate-sodium p-sulfophenyl methallyl ether (CP-24) with polyacrylonitrile-vinyl acetate (CP-16), to be used in an energy-saving design of spinning membrane disc separation system. Our experimental results clearly demonstrate the energy saving benefit of our design; at filtration pressure of 276 kPa and at membrane disc spinning velocity of 1,000 rpm without sacrificing the oil rejection (>98% for 1,000 ppm oil-in-water) by our membrane, the permeate velocity was increased as high as 132% by our energy-saving system over conventional spinning membrane disc separation system.     

Separation of proteins by charged ultrafiltration membranes

The separation of a protein mixture by charged ultrafiltration membranes was studied. A negatively charged polymer was obtained by sulfonation of polysulfone, and a positively charged polymer was synthesized by chloromethylation of polysulfone and then by quaternization of the amino group. Then, the negatively and positively charged ultrafiltration membranes were cast from solutions of charged polymer/NMP(or DMF)/lithium nitrate. The molecular weight cut-off of the membranes were controlled by the changing casting conditions.

Single protein solutions were ultrafiltrated at the isoelectric point and at another pH level by the use of charged membranes. At the isoelectric point, rejection of the protein was low, while it was high at the pH level which gave the protein the same sign of charge as that of the membrane.

A protein mixture of myoglobin and cytochrome C was separated by the charged ultrafiltration membranes at the isoelectric point of one of the proteins. At the isoelectric point of cytochrome C, myoglobin has a negative charge. Thus myoglobin was rejected with a rejection of about 80% by the negatively charged membrane. At the same time, cytochrome C permeated completely through the membrane. Conversely, at the isoelectric point of myoglobin, cytochrome C has a positive charge and thus it was rejected with a rejection of about 20% by the positively charged membrane. The rejection of myoglobin here was almost zero.     

海藻酸钠/聚砜复合纳滤膜的制备与性能研究

以海藻酸钠(SA)水溶液为活性层铸膜液,分别以聚砜( PSF)、聚丙烯腈(PAN)为基膜,采用涂敷、热处理、交联剂交联的方法制备了荷负电复合纳滤膜,考察了海藻酸钠浓度、基膜、交联剂浓度等对膜性能的影响,制膜条件优化结果为,以聚砜超滤膜为基膜,海藻酸钠铸膜液质量分数为3％,交联剂为质量分数0.5％的硫酸和质量分数1％的戊...     

湿式催化氧化/膜过滤组合工艺膜过滤机理

采用湿式催化氧化/膜过滤组合工艺,以Mo-Zn-Al-O粉末作为催化剂降解阳离子红GTL模拟染料废水,探讨在膜过滤过程中平均孔径为0.1 μm的微滤和0.022 μm的超滤聚偏氟乙烯(PVDF)中空纤维膜的过滤机理。实验结果表明,两种膜过滤组合工艺对染料的降解效果均优于单独湿式催化氧化,0.01 MPa恒压条件下运行120 min后微滤和超滤的膜通量分别衰减了26.63%和16.48%,其原因是粉末催化剂可在微滤膜孔内部沉积形成中间阻塞过滤,后在表面形成滤饼层;而在超滤膜表面仅形成滤饼层。通过实验结果对膜阻力进行计算,可知在相同反应过程后微滤膜产生的不可逆阻力大于超滤膜。在不同反应条件下,催化剂的沉积量与膜阻力呈现线性相关。     

聚丙烯微孔膜荷负电表面的构建与阻抗蛋白质吸附性能

报道一种有效构建聚丙烯微孔膜(PPMM)荷负电表面的新方法.组合大气压介质阻挡放电等离子体预处理和界面交联技术,制得表面荷正电的PPMM;通过动态静电自组装技术将阴离子聚电解质固定到膜表面,从而获得荷负电的PPMM,ATR-FTIR,XPS和FESEM分析确证了修饰过程中膜表面化学组成与形貌的变化.静态水接触角和纯水通...     

PAN超滤膜的常压介质阻挡放电等离子体亲水改性

利用常压介质阻挡放电（DBD）等离子体技术,在非对称聚丙烯腈（PAN）超滤膜的表面接枝含有亲水基团的丙烯酸（AA）和聚乙二醇甲基丙烯酸酯（PEG360OHMA）,采用衰减全反射傅立叶变换红外光谱仪（ATR-FTIR）、水接触角测定仪和扫描电镜（SEM）表征膜的表面性质,牛血清蛋白（BSA）溶液过滤实验考察膜的抗生物污染性能。结果表明,常压DBD等离子体亲水改性的超滤膜具有良好的抗生物污染性能。     

紫外辐照接枝制备荷正电纳滤膜

通过在PEK-C微孔膜表面紫外辐照接枝甲基丙烯酰氧乙基三甲基氯化铵（DMC）制备了一种表面荷正电的纳滤膜。通过测定膜的纯水通量和对不同盐溶液截留率的变化,系统研究了接枝条件对膜分离性能的影响。结果表明,采用该方法制成的纳滤膜对高价阳离子盐溶液MgCl2的截留率和渗透通量都较高。     

Effect of Conditioning Ultrafiltration Membranes on their Performances in Electrodialysis with Ultrafiltration Membrane

Abstract

A recent alternative method based on ultrafiltration membrane stacked in an electrodialysis cell was recently used for the separation of bio‐active high added value charged molecules, such as peptides and polyphenols. However, the ultrafiltration membranes which are uncharged membranes present lower electrical conductivity, in comparison with conventional ion‐exchange membranes. The purpose of this study was to evaluate the effect of conditioning ultrafiltration membranes of different molecular weight cut‐off (MWCO) (10, 20, 50, and 100 kDa) in solution with different ionic strength (distilled water and 0.1 M NaCl_(aq)) on their electrodialytic properties. It appeared that the conditioning solution could have a major impact on the electrical conductivity value of an ultrafiltration membrane and that the final conductivity value after soaking increased with an increase in molecular weight cut‐off. However, the soaking period and solution had no effect on membrane thickness. Furthermore, the electrical conductivity of the membrane was increased after an electrodialysis with ultrafiltration membranes process of a salt solution.     

紫外键联马来酸酐表面改性聚丙烯腈超滤膜

采用紫外光法将马来酸酐（MAH）单体键联到聚丙烯腈（PAN）超滤膜表面,考察了紫外光强度、辐射时间、光敏剂浓度以及单体浓度对MAH反应率的影响。采用衰减全反射-傅里叶红外光谱（ATR /FT-IR）、扫描电镜（SEM）和水接触角（CA）对改性膜和原膜进行表征,结果表明单体MAH已成功键联到PAN膜表面,膜表面的亲水性得到提高。蛋白质静态污染以及超滤实验表明马来酸酐键联改性对PAN膜水通量影响不大,但抗污染性能得到明显提高,且由于MAH含有酸酐基团,使PAN膜的可反应性大大提高,使PAN膜易于进一步改性。     

水解聚丙烯腈超滤膜的制备与性能

以水解改性聚丙烯腈(HPAN)为膜材料,采用相转化法成功制备了HPAN超滤膜。通过孔隙率测试、水接触角测试和动态污染试验等方法,研究了PAN水解时间对HPAN超滤膜结构形态和性能的影响。结果表明:随着PAN水解时间的增加,HPAN超滤膜的亲水性提高,孔的贯通性改善,孔隙率增加,纯水通量得到明显提升;但较长的水解时间会导致HPAN降解以及HPAN超滤膜截留性能下降。水解时间为2 h时,HPAN超滤膜具有优异的透水性,对牛血清白蛋白有较高的截留能力(93%)以及良好的防污能力。     

Solvent‐resistant nanofiltration membranes based on multilayered polyelectrolytes deposited on silicon composite

Alternating deposition of oppositely charged polyelectrolyte complexes (PECs) on inorganic–organic composite membranes can efficiently overcome the drawback of microcracks induced by inorganic particles. Different bilayers of Poly (diallyldimethylammonium, chloride)/sulfonated poly(ether ether ketone) (PDDA/SPEEK) were first deposited on the charged silicon composite with hydrolyzed polyacrylonitrile (PAN‐H) support and evaluated for solvent resistant nanofiltration membranes (SRNF) application. The morphology of the membranes was studied in detail via SEM and AFM. Because of Donnan exclusion, the multilayered PEC silicon composite membranes showed very high retentions up to 99% for negatively charged solutes (Rose Bengal (RB), 1017 Da) in the pressure driven filtration of isopropanol (IPA) solutions. For the first time, PEC‐based silicon composite membranes were also applied in the filtration of organic solvents, where they were found to combine a remarkable stability in polar solvents with high fluxes and retentions. Compared with silicon composite membranes, the introduction of multilayered PDDA/SPEEK can efficiently improve the membrane performance and overcome the drawback induced by inorganic fillers. PEC‐based silicon composite membranes thus show excellent prospective use in SRNF. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Permeation behavior of dextrans by charged ultrafiltration membranes of polyacrylonitrile photografted with ionic monomers

Charged copolymers, polyacrylonitrile, having grafts of quaternized poly(N,N-dimethylaminoethylmethacrylate) and poly(sodium p-styrenesulfonate), were synthesized by photograft-polymerization. The charged ultrafiltration membranes, which had heterogeneous porous structures, were prepared by casting graft polymer solution containing poly(vinyl alcohol) into water. The permeation of nonionic dextran and anionic dextransulfate through the charged membranes was studied by ultrafiltration in aqueous solution. The molecular weight cutoff characteristics of the charged membrances were obtained using dextrans of various molecular sizes. The permeation behavior was discussed in terms of the charge effect of the graft polymers and electrostatic interaction between the polymers and the solute molecules.     

流动电位法研究聚烯烃微孔膜在电解质溶液中的动电现象

对NaCl、KCl、MgCl2、Na2SO4、MgSO4等5种电解质溶液中2种不同微孔膜(管式聚乙烯微滤膜和管式聚丙烯腈超滤膜)的流动电位进行了实验研究。考察了电解质浓度、离子种类和价态对膜的流动电位的影响。根据Helmholtz-Smoluchowski方程和Gouy-Chapmann理论算出2种膜的微孔表面zeta电位和电荷密度。结果表明，两种微孔膜均由于离子的吸附而带有负电荷，电解质浓度、离子种类及价态对膜的流动电位、表面zeta电位和电荷密度均具有重要的影响。     

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