聚四氟乙烯中空纤维膜的多巴胺自聚表面改性及性能研究

通过多巴胺的自聚附着行为,对聚四氟乙烯(PTFE)中空纤维膜进行亲水改性。采用扫描电镜(SEM)、X射线光电子能谱(XPS)、红外光谱(FT-IR)和接触角(CA)对膜改性前后的表面形貌、化学组成和亲水性进行了表征。研究了改性条件对膜纯水通量的影响,并以牛血清蛋白(BSA)溶液为污染物考察了改性前后膜的抗污染性能。结果表明,多巴胺被成功引入PTFE膜表面,改性12 h时膜表面的F元素含量降低2.14%,O元素含量增加3.06%。膜的亲水性得到显著改善,水接触角由改性前的110°降低至改性后的80°。改性8 h时,纯水通量达原膜通量的1.5倍。改性前后膜孔径变化不大,但改性后的PTFE膜具有更好的抗污染性能,清水清洗后的通量恢复率在90%以上。     

丙烯酸接枝PVDF超滤膜亲水改性研究

采用自由基聚合方法将丙烯酸接枝到经过消去反应形成一定C=C含量的PVDF中空纤维超滤膜表面,改善了膜表面的亲水性。依据超滤膜的孔径结构要求,调控丙烯酸接枝链的长度。通过XPS、SEM和水通量实验分析效果表明,丙烯酸接枝改性PVDF中空纤维超滤膜表面引入了-COOH和-OH亲水基团,膜表面和孔壁形成的亲水层没有改变膜表面的孔径尺寸,水通量比改性前提高了280%以上。     

不同亲水基团亲水改性PTFE中空纤维膜

为改善PTFE中空纤维膜表面亲水性能,扩大其在污水处理领域中的运用,采用含有磺酸基、氨基、羟基、醛基、羧基的溶液浸渍预处理,利用低温等离子体法对PTFE中空纤维膜进行表面亲水改性。SEM、ATR-FTIR分析结果表明,PTFE中空纤维膜经过不同亲水基团改性后,磺酸基、氨基、羟基、醛基、羧基成功地接枝到PTFE膜表面。改性后的PTFE中空纤维膜的接触角和出水渗透压有较大幅度下降,其中经羧基改性后的PTFE中空纤维膜接触角最低下降为52°,出水渗透压下降为0.18MPa。5种亲水基团中,改性PTFE中空纤维膜最佳的亲水基团为羧基,最佳的预处理溶液为丙烯酸。     

PTFE中空纤维膜的亲水改性

利用氟碳表面活性剂、二氯甲烷为溶剂对聚四氟乙烯(PTFE)中空纤维膜进行亲水改性。研究了表面活性剂浓度及组装时间对中空纤维膜亲水性能的影响,确定了亲水改性的最佳条件为氟碳表面活性剂浓度为3g/L,PTFE中空纤维膜组装浸泡最佳时间4h,同时对亲水改性后PTFE中空纤维膜的污水处理效果进行了测试,结果表明其污水处理性能高于国家标准要求,化学需氧量去除率达到84.2%,氨氮去除率达到94.4%,悬浮物去除率达到99.0%。     

压力温度双敏性聚氨酯中空纤维膜通透性研究

以聚氨基甲酸酯(PU)为基质相,添加成孔剂及二氧化硅粒子,采用熔融纺丝法制得了具有对压力、温度刺激双重敏感的PU中空纤维膜;研究了膜的水通量随压力、温度的变化,对膜表面形貌进行了表征;并考察了中空纤维膜的截留性能。结果表明:制得的PU中空纤维膜为均质膜;膜孔径分布较窄,87.17%的孔集中在0.15～0.20μm。随着压力、温度上升或下降,膜的水通量相应增大或减小,水通量与压力、温度变化有着明显的相关性。经一次过滤,无机粒子清除率达98.52%～99.78%。     

聚四氟乙烯复合微滤膜的制备及性能表征

为解决聚四氟乙烯(PTFE)中空纤维膜大孔缺陷和表面亲水性差的问题,采用亲水性PTFE平板膜作过滤层,PTFE中空纤维膜作支撑层,通过裹缠的方法制备PTFE复合微滤膜。实验中最佳的拉伸倍率为300%～200%,在此拉伸倍率下,PTFE复合膜孔径分布均匀,最可几孔径为0. 35μm,最可几孔径占比为75. 9%,最大孔径小于0. 4μm,孔隙率大于80%,拉伸强度达到了9. 15 MPa,爆破强度大于0. 3 MPa,PTFE复合膜过滤层接触角为70°,纯水通量为1 107 L/(m2·h)。     

水凝胶涂层法用于PTFE平板膜的亲水改性研究

采用戊二醛和O-羧甲基壳聚糖(OCMCS)、聚乙烯醇(PVA)在聚四氟乙烯(PVDF)平板膜内进行交联形成一层水凝胶涂层,从而对PTFE平板膜进行亲水改性。考察了反应条件对膜亲水性能的影响和膜的抗污染性能,并对膜表面进行表征。结果表明,水凝胶涂层附着在PTFE纤维表面使膜原纤维变粗,随着PVA含量的增加,改性膜的水通量先增加后减少,接触角先减小后增大,并且当PVA与OCMCS的质量比为1:1,反应时间为6 h、温度为50℃时,膜的性能为优,此时水通量(4 481±80) L/(m~2·h)、接触角57.48°。由于改性膜的表面含有羟基和氨基等官能团,使膜具备良好的抗蛋白质吸附能力;PVA与OCMCS交联形成的物质分子量大,粘附力强,使亲水涂层不易脱落。     

两亲性聚合物沉积法聚四氟乙烯中空纤维膜的亲水改性研究

以具有两亲结构的两亲性聚合物脂肪醇聚氧乙烯醚，通过回旋振荡涂覆法对疏水的聚四氟乙烯(PTFE)中空纤维膜改性处理制备亲水性聚四氟乙烯膜，在膜表面形成亲水沉积层，并研究了两亲性聚合物浓度、涂覆时间、热处理时间和热处理温度对PTFE中空纤维膜亲水性能的影响。结果表明，两亲性聚合物浓度为5%,涂覆时间2 h,热处理时间和温度分别为16 h和40℃条件下制备的聚四氟乙烯中空纤维膜，纯水通量可达2 482 L/(m²·h)。     

助剂配比对聚四氟乙烯中空纤维膜性能的影响

混料—挤出—拉伸—烧结工艺可用来制备聚四氟乙烯(PTFE)中空纤维膜。混料是该工艺的首要工序,通过选择不同助剂和调整助剂配比,可制得具有不同性能的中空纤维膜。本文选取溶剂油Isopar H作为助剂,对按照不同配比制得的PTFE中空纤维膜从宏观和微观层面进行了测试和表征。结果表明,当溶剂油与PTFE分散树脂配比为19:100时,通过扫描电子显微镜(SEM)观察到微孔孔径分布均匀,利用孔径分析仪测得的最大孔径和平均孔径均最小,没有大孔缺陷出现,而且孔隙率和纯水通量均较高,力学性能优良。因此,溶剂油Isopar H与PTFE分散树脂较佳配比为19:100。     

PTFE平板微孔膜用于渗透蒸馏浓缩茶多酚的研究

采用"挤出-压延-拉伸"法,通过改变纵向拉伸倍数,制备出平均孔径为0.25～0.80μm,孔隙率为46.9%～78.3%的4种疏水PTFE平板微孔膜。制备得到的PTFE平板微孔膜具有"纤维-结点"的网状微孔结构。随着纵向拉伸倍数的增加,微孔膜结构中的结点变小,纤维变细,孔径和孔隙率增大,孔隙分布更均匀。分别以茶多酚水溶液和CaCl2溶液为进料液和渗透液,进行渗透蒸馏浓缩实验。研究了膜孔径、渗透液和进料液的浓度、流速等对渗透通量和截留率的影响。结果表明,增大PTFE平板微孔膜孔径、提高渗透液的浓度以及进料液和渗透液的流速可提高渗透通量。整个实验过程中,4种PTFE平板微孔膜对茶多酚的截留率均能保持在99.9%以上,且不受操作条件的影响。     

Performance Evaluation of Alkaline Treated Poly(vinylidene fluoride) Membranes

A poly(vinylidene fluoride) (PVDF) hollow fiber membrane surface was modified by alkaline treatment in this study. This subject was selected with the aim to confirm the mechanisms of alkaline degradation of PVDF membranes, characterize the variations of membrane surface morphology (e.g., average pore size, pore size distribution, porosity, etc.), and estimate the membrane fouling potential by a bench-scale test with synthetic surface water. The conditions of the alkaline treatment covered various concentrations, temperature, and processing time. The results of this study indicate that the hydrophilic PVDF membranes can be obtained after appropriate treatment without loss of integrity of the membrane surface. All factors, including the concentration of NaOH, temperature, and processing time affect membrane properties. The surface images and air flow rate of unmodified and modified membranes showed difference in their average pore size and pore size distribution. In general, the increase of the processing time decreases the average pore size at constant concentration and temperature; the increase of the NaOH concentration in solution and temperature fastens the degradation process. Membrane pure water flux decreased after alkaline treatment. This can be attributed to the decrease of pore size. However, the membrane anti-fouling potential increased after alkaline treatment due to the enhancement of hydrophilic property of membrane surface.     

Preparation of a heterogeneous hollow‐fiber affinity membrane modified with a mercapto chelating resin

A high‐quality, heterogeneous hollow‐fiber affinity membranes modified with mercapto was prepared through phase separation with blends of a chelating resin and polysulfone as membrane materials, poly(ethylene glycol) as an additive, N,N‐dimethylacetamide as a solvent, and water as an extraction solvent. The effects of the blending ratio and chelating resin grain size on the structure of the hollow‐fiber affinity membrane were studied. The effects of the composition of the spin‐cast solution and process parameters of dry–wet spinning on the structure of the heterogeneous hollow‐fiber affinity membrane were investigated. The pore size, porosity, and water flux of the hollow‐fiber affinity membrane all decreased with an increase in the additive content, bore liquid, and dry‐spinning distance. With an increase in the extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow‐fiber affinity membrane all increased, but the pore size and water flux of the hollow‐fiber affinity membrane decreased. It was also found that the effects of the internal coagulant composition and external coagulant composition on the structure of the heterogeneous hollow‐fiber affinity membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of the heterogeneous hollow‐fiber affinity membrane and decrease the pore size, porosity, and water flux of the heterogeneous hollow‐fiber affinity membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the heterogeneous hollow‐fiber affinity membrane. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

聚偏氟乙烯中空纤维膜的制备

本丈研究了聚偏氟乙烯（PVDF）中空纤维微滤膜的制备。采用亲水聚合物材料（如PMMA、改性聚醚硅油等）对聚偏氟乙烯材料进行共混改性,显著提高了膜材料的亲水性;同时由于材料性质的改变,导致膜材料在成膜时的凝胶特性和相转化发生变化,所成膜的孔径、通水量、孔隙率、表面性能等也发生改变。通过选择合适的共混体系,可制备出高性能、高孔隙率、表面亲水的聚偏氟乙烯中空纤维膜。     

烧结温度对TiO2/不锈钢中空纤维复合膜结构和性能的影响

不锈钢中空纤维膜基膜孔径大,直接涂覆分离层容易产生表面缺陷。在二氧化钛悬浮液中加入聚乙烯醇作为黏结剂,通过真空辅助抽滤法在不锈钢中空纤维基膜表面形成一层均匀的分离层。通过高温烧结得到了TiO₂/不锈钢中空纤维复合膜,考察了烧结温度对于TiO₂/不锈钢中空纤维复合膜表面分离层形貌和结构的影响。不同烧结温度时,TiO₂/不锈钢中空纤维复合膜的表面形貌有所差异;随着烧结温度的升高,不锈钢复合膜的孔径和纯水通量均先升高再下降。当烧结温度为500℃时,表面涂层均匀,孔径分布集中,水通量较高。最后,以SPT-500膜测试了水包油乳液分离效果,分离效率达到99%以上,且具有良好的抗污染性能。     

Stability of acrylic acid grafted poly(vinylidene fluoride) hollow fiber membrane prepared by high‐energy electron beam

In this article, poly(vinylidene fluoride) (PVDF) hollow fiber membrane and acrylic acid (AA) were co‐irradiated by high‐energy electron beam to introduce hydrophilic carboxylic groups on the membrane surface. Thermal capability, mechanical performance, pore size, and permeation property were investigated to determine the stability of the membrane pore structure before and after irradiation polymerization. The decomposition temperature, melting point, glass transition temperature, and breaking force of the PVDF‐g‐AA membrane increased slightly because of irradiation grafting polymerization. After 15 months of storage, the pore size distribution of the PVDF‐g‐AA membrane became smaller and more dispersive. The pure water flux and the rejection to bovine serum albumin of the PVDF‐g‐AA membrane increased significantly with the increase in hydrophilicity and decrease in pore size. The results indicated that the structure and properties of the PVDF hollow fiber membrane were stable after high‐energy electron beam irradiation grafting polymerization, even after 15 months of storage. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41165.     

多孔堇青石中空纤维陶瓷膜的制备与表征(英文)

采用相转化和烧结法,通过一步成型制备了新颖的堇青石中空纤维陶瓷膜,并对制备的中空纤维膜微观结构、孔隙率和孔径分布、抗弯强度、纯净水通量和氮气渗透性等结构与性能进行了表征。结果表明:堇青石中空纤维膜为多孔非对称结构,由内部大孔层和外部海绵状多孔层组成。在1360℃保温2h制备的堇青石中空纤维膜孔隙率为39.2%,抗弯强度为76.5MPa。0.10MPa压差下的纯净水和氮气渗透性分别达到61.34m3/(m2·h·MPa)和7824m3/(m2·h·MPa)。实验证明,采用较大粒径的廉价工业级粉体为原料,可制备非对称的中空纤维陶瓷微滤膜。     

不同中空纤维膜材料对烟气中二氧化硫的吸收性能影响

膜法烟气脱硫能耗低、传质面积大、分离效率高，可以有效地解决传统塔器内的液泛、漏液、夹带等问题。本文采用自制的中空纤维膜接触器，通过改变烟气流量、水流量和水温对比了聚四氟乙烯（PTFE）、聚偏氟乙烯（PVDF）和聚丙烯（PP）这3种中空纤维膜对烟气中二氧化硫的吸收性能，并通过电镜和接触角仪表征，对比了3种膜的参数和疏水性。结果表明：在不同烟气流量、水量和水温下，3种膜的吸收性能都表现为PTFE＞PP＞PVDF，120min时二氧化硫吸收浓度，PTFE最大，是PP的1.68倍，是PVDF的4.62倍；烟气流量的改变对二氧化硫的吸收浓度有显著影响，当烟气流量由60mL/min提高到140mL/min时，120min时PTFE膜二氧化硫的吸收浓度提高了2.14倍；影响膜性能的主要因素为疏水性，PTFE浸泡前后的表面接触角为105°和97°，疏水性远大于PP和PVDF。PTFE中空纤维膜孔径大、孔隙率高，具有极强的疏水性，在烟气脱硫及相关吸收过程中表现出较好的应用前景。     

Enhanced forward osmosis from chemically modified polybenzimidazole (PBI) nanofiltration hollow fiber membranes with a thin wall

To develop high-flux and high-rejection forward osmosis (FO) membranes for water reuses and seawater desalination, we have fabricated polybenzimidazole (PBI) nanofiltration (NF) hollow fiber membranes with a thin wall and a desired pore size via non-solvent induced phase inversion and chemically cross-linking modification. The cross-linking by p-xylylene dichloride can finely tune the mean pore size and enhance the salt selectivity. High water permeation flux and improved salt selectivity for water reuses were achieved by using the 2-h modified PBI NF membrane which has a narrow pore size distribution. Cross-linking at a longer time produces even a lower salt permeation flux potentially suitable for desalination but at the expense of permeation flux due to tightened pore sizes. It is found that draw solution concentration and membrane orientations are main factors determining the water permeation flux. In addition, effects of membrane morphology and operation conditions on water and salt transport through membrane have been investigated.     

Preparation of polysulfone hollow fiber affinity membrane modified with mercapto and its recovery properties. I. Synthesis and preparation of hollow fiber matrix membrane

Several kinds of chloromethyl polysulfones (CMPSF) with different chlorinity and reactive groups were synthesized by Friedel‐Crafts reaction, which could be utilized as reactively matrix membrane materials. The CMPSF hollow matrix membranes were prepared with phase inversion by utilization of the CMPSF/additive/DMAC casting solution and CMPSF as membrane materials. The rheological behavior of CMPSF/additives/DMAC spinning casting solution was studied. The experimental results showed that the spinning casting solution was a pseudoplastic fluid, the apparent viscosity of the spinning casting solution decreased with the increase of shearing rate, and the viscous flow activity energy of the spinning casting solution was inclined to unchange at high shearing rate. The effects of composition of spinning casting solution and process parameters of dry–wet spinning on the structure of CMPSF hollow fiber matrix membrane were investigated. The pore size, porosity, and water flux of membrane decreased with the increase of additive content, bore liquid, and dry spinning distance. With the increase of extrusion volume outflow, the external diameter, wall thickness, and porosity of the hollow fiber matrix membrane increased, but the pore size and water flux of the membrane decreased. It was also found that the effects of internal coagulant composition and external coagulant composition on the structure of CMPSF hollow fiber matrix membrane were different. The experimental results showed that thermal drawing could increase the mechanical properties of CMPSF hollow fiber matrix membrane and decrease the pore size, porosity, and water flux of the CMPSF hollow fiber matrix membrane, and the thermal treatment could increase the homogeneity and stability of the structure of the CMPSF hollow fiber matrix membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 758–771, 2006