凝胶相转化温度和空气预蒸发时间对PVDF超滤膜性能及结构的影响

利用非溶剂相转化法(NIPS),以聚偏氟乙烯(PVDF)/聚乙烯吡咯烷酮(PVP)/N,N-二甲基乙酰胺( DMAC)为铸膜液体系,水为凝固浴制备了大通量超滤膜.考察了铸膜液温度、凝胶浴温度、空气预蒸发时间等条件对超滤膜性能与结构的影响.研究结果显示,随着铸膜液和凝胶浴温度的提高,膜纯水通量增大,强度增强,截留率降低,膜的第一泡点压力减小,膜的孔隙率随铸膜液温度升高而增大,随凝胶浴温度升高先增大后减小,膜断面指状孔发育较为通透,海绵层致密.延长铸膜液在空气预蒸发时间,膜的第一泡点压力和孔隙率降低,超滤膜截留率提高,通量和强度变化不大.     

聚丙烯腈超滤膜成膜工艺的研究

本文根据吕勃-索里拉金(Loeb-Sourirajan)方法,制得了不对称结构的聚丙烯腈超滤膜。研究了不同制膜工艺条件对膜结构和性能的影响,其中包括:蒸发时间、聚合物浓度、沉淀浴温度、热处理温度,不同种类的溶剂及预压时间。     

低截留分子质量新型聚芳醚腈酮超滤膜的研制

以新型聚芳醚腈酮为膜材料 ,以N -甲基 - 2 -吡咯烷酮 (NMP)为溶剂 ,研究了聚合物浓度、添加剂种类及含量、凝胶浴温度等对超滤膜性能的影响。结果表明 ,聚合物质量分数以 1 2 %～ 1 3 %为合适的制膜浓度 ,以聚乙二醇PEG - 4 0 0为添加剂时获得了高截留率和高水通量的超滤膜。随着凝胶浴温度的升高 ,水通量明显增大 ,而截留率有所下降 ,而共聚物的浓度增加则有相反的效果。制得的超滤膜具有较低的截留分子量 (PEG- 2 0 0 0 ) ,将制得的超滤膜用于达旦黄、黄X-G等染料的分离 ,截留率均达 90 %以上     

CA／PAN-Al2O3有机-无机复合超滤膜的制备

以醋酸纤维素(CA)及聚丙烯腈(PAN)为膜材料,以纳米三氧化二铝(Al2O3)为添加剂,通过浸入-沉淀相转化法制备了有机-无机超滤膜,从凝固浴温度及组成两个方面考察成膜规律.试验结果表明,凝固浴温度及组成对膜性能有较大影响,综合膜水通量及截留率多方面进行考虑,凝固浴温度50℃较为适宜;凝固浴中加入表面活性剂,膜的水通量及截留率均得到改善.     

PVDF-PAN-纳米粘土杂化中空纤维超滤膜纺丝工艺研究

以聚偏氟乙烯和聚丙烯腈为主要膜材料、N,N-二甲基乙酰胺为溶剂、无水LiCl和有机纳米粘土为添加剂,采用干-湿相转化法纺丝工艺制备杂化中空纤维超滤膜,研究了干程、外凝胶浴温度、芯液温度和组成等纺丝工艺参数对杂化膜微观结构和分离性能的影响.SEM观察发现,中空纤维膜有较致密的外表面和多孔的内表面,干程对膜的横截面结构和表面形态都有影响:增加芯液含量有利于抑制大孔结构的产生,使孔径变小,结构致密,芯液为质量分数40%无水乙醇时,制得的膜对BSA截留率达到99%.试验结果表明,在较高的凝胶浴温度和较大的干程下制得的膜有较高的水通量和较低的截留率;凝胶浴温度升高,膜的力学性能加强,铸膜液中聚合物的质量分数为16%时,最大拉伸强度为3.16 MPa.     

杂萘联苯共聚醚砜中空纤维超滤膜的制备

以杂萘联苯共聚醚砜为膜材料、N,N-二甲基乙酰胺为溶剂、乙二醇甲醚(EGME)为添加剂,采用干-湿纺丝工艺制备新型中空纤维非对称超滤膜,考察了EGME含量、干纺程长度以及凝胶浴温度对杂萘联苯共聚醚砜中空纤维膜结构和性能的影响。结果表明,随着EGME含量的增加超滤膜的水通量增大,而对聚乙二醇10000的截留率基本不变,干纺程长度和凝胶浴温度对超滤膜的性能有较大影响,所制备的中空纤维超滤膜对聚乙二醇10000的截留率高于95%,水通量达到258 L/(m2.h)。     

聚丙烯腈/聚砜共混膜的制备及其结构表征

采用粘度法和红外光谱法研究聚丙烯腈(PAN)/聚砜(PS)的相容性,研究聚合物组成,共混物浓度,添加剂,凝胶浴等对PAN/PS共混膜的水通量和截留率的影响.采用扫描电镜分析PAN/PS共混膜的显微结构.结果表明:PAN/PS共混膜与PAN膜具有相似的化学稳定性,但较PAN膜具有更好的分离和透过特性.     

新型聚芳醚腈酮中空纤维超滤膜的研究

以含二氮杂萘酮结构聚芳醚腈酮(PPENK)为膜材料,N-甲基-2-吡咯烷酮(NMP)为溶剂,采用干-湿相转化法制备了中空纤维超滤膜.考察了聚合物浓度、添加剂含量以及纺丝过程中空气间隙、凝胶浴温度和纤维壁厚对膜结构及性能的影响.结果表明,当聚合物浓度为13%,添加剂EgOH含量α=0.9时,膜通量可达770 L·m-2·h-1,对BSA的截留率在90%以上;增大空气间隙可使膜的截留性能提高,但膜通量有所下降,最佳空气间隙为5～8cm;凝胶浴温度的升高增大了膜的通量,截留率下降幅度不大,凝胶浴温度宜控制在21～25℃范围内;纤维壁厚在0.15～0.18 mm时膜性能最佳.     

杂萘联苯聚醚砜超滤膜的研制

以杂萘联苯聚醚砜(PPES)为膜材料,N-甲基-2-吡咯烷酮(NMP)为溶剂,采用相转化法制备了非对称超滤膜.结果表明,聚合物浓度的变化、添加剂含量的变化、凝胶浴温度或停留蒸发时间的改变都会影响超滤膜的性能,所制得的PPES超滤膜在0.1 Mpa的操作压力下对PEG10000的截留率高于95%,纯水通量可达632 L·m-2·h-1.     

添加剂对PVDF平板超滤膜性能和结构的影响

分别以无水氯化锂(LiCl),磷酸(H_3PO_4)为添加剂,采用正交试验设计方法优化PVDF平板超滤膜制备条件.以去离子水为凝胶浴,考察了聚合物浓度、溶剂种类、添加剂含量对超滤膜平均孔径,孔隙率等膜结构特征殁膜纯水通量、BSA截留率的影响.结果表明,对于LiCl体系,影响膜孔隙率的制膜条件是:LiCl浓度>溶剂种类>PVDF浓度,制膜液组成为12% PVDF/DMAC/5%LiCl时孔隙率最高,达到86.42%;对于H_3PO_4体系,影响膜孔隙率的制膜条件是:溶剂种类>H_3PO_4浓度>PVDF浓度,制膜液组成为15%PVDF/NMP/5%H_3PO_4时孔隙率最高,达到85.86%;对于LiCl和H_3PO_4体系,影响膜孔径的因素均为:PVDF浓度>溶剂种类>添加剂浓度,最大孔径下的最佳制膜液组成为12%PVDF/NMP/3%添加剂.研究得出LiCl体系和H_3PO_4体系的最佳组合分别为18PVDF/NMP/3%LiCl和15%PVDF/NMP/5%H_3PO_4.     

Pore morphology control and hydrophilicity of polyacrylonitrile ultrafiltration membranes

The effects of different solvents (dimethyl formamide: DMF and dimethylsulfoxide: DMSO) on the solubility of polyacrylonitrile (PAN) were investigated by the phase diagrams of H₂O/DMF/PAN and H₂O/DMSO/PAN ternary systems through cloud‐point titration method at low polymer concentration. The influences of polymer concentrations and temperatures on the morphologies of PAN ultrafiltration membranes were elucidated. The morphologies of fabricated UF membranes were characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and the basic performance of ultrafiltration including pure water flux and rejection of BSA were explored. At 25°C, the pure water flux of ultrafiltration membranes at the lower PAN content (16 wt % PAN in 84 wt % DMSO) reached 213.8 L/m/bar and the rejection of BSA was 100%. Interestingly, the water flux of UF membranes dramatically decreased to 20.6 L/m/bar (20 wt %) and 2.9 L/m/bar (24 wt %) when increasing PAN concentrations in DMSO. On the other hand, the hydrophilicity of membranes can be enhanced by increasing coagulation temperatures and polymer concentrations which were characterized by static contact angle, fitting well with the variation tendency of roughness. Although there are many works concerning on the effects of phase inversion conditions on the performance of PAN UF membranes, to our best knowledge, there is seldom works focusing on investigating the membrane hydrophilicity trend by adjusting phase inversion conditions. To disclose the reason of the enhanced hydrophilicity, the water and glycol contact angles of various membranes were measured and the surface tensions were presented. The results illustrated that the enhanced hydrophilicity of PAN UF membranes fabricated at higher temperatures or higher polymer concentrations was due to the higher polarity on membrane surface. Since the vast majority of ultrafiltration membranes in labs and in industrial scale have been fabricated by immersion phase inversion method, this work can provide a guidance to obtain hydrophilic PAN UF membranes by adjusting the process of phase inversion. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41991.     

Effects of coagulation bath temperature and polyvinylpyrrolidone content on flat sheet asymmetric polyethersulfone membranes

In this study, effects of coagulation bath temperature (CBT) and polyvinylpyrrolidone (PVP K15) concentration as a pore former hydrophilic additive on morphology and performance of asymmetric polyethersulfone (PES) membranes were investigated. The membranes were prepared from a PES/ethanol/NMP system via phase inversion induced by immersion precipitation in a water coagulation bath. The morphology of prepared membranes was studied by scanning electron microscopy (SEM), contact angle measurements, and mechanical property measurements. Permeation performance of the prepared membranes was studied by separation experiments using pure water and bovine serum albumin (BSA) solution as feed. The obtained results indicate that addition of PVP in the casting solution enhances pure water permeation flux and BSA solution permeation flux while reducing protein rejection. Increasing CBT results in macrovoid formation in the membrane structure and increases the membrane permeability and decreases the protein rejection. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

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.     

聚乙烯醇-二氧化硅/聚丙烯腈杂化复合膜渗透蒸发分离己内酰胺/水溶液

制备了以聚乙烯醇(PVA)填充纳米SiO2改性膜为活性层,聚丙烯腈(PAN)超滤膜为底膜的PVA-SiO2/PAN杂化复合膜,并用于己内酰胺(CPL)脱水。用FTIR,SEM,XRD,TGA分别对膜进行了表征,并考察了膜中纳米SiO2粒子的质量分数、进料组分质量分数和温度对复合膜分离性能的影响。结果表明,引入纳米SiO2后,杂化膜的热稳定性明显提高。当膜中纳米SiO2质量分数为1.0%时,复合膜渗透蒸发分离性能最佳。60℃下此复合膜用于分离质量分数为40%的CPL溶液时,其总通量和分离因子分别达到2 177 g/(m2.h)和349。     

PVPK30和Tween80对中空纤维超滤膜结构和性能的影响

通过考察添加剂-聚乙烯吡咯烷酮（PVPK30）和Tween80对杂萘联苯聚醚砜酮（PPESK）中空纤维超滤膜结构和分离性能的影响，发现：随高分子添加剂聚乙烯吡咯烷酮K30浓度的升高，膜水通量减小，截留率基本无变化，膜结构逐渐由指状结构转变成海绵状结构。有机大分子添加剂Tween80可以提高膜的水通量，但膜结构不随添加剂浓度而改变，均为指状结构。当Tween80浓度小于5wt％时，随Tween80浓度的增加，膜水通量升高，截留率下降。比较不同凝胶浴温度下的膜分离性能可以看到，凝胶浴温度提高可以显著提升膜的纯水通量。     

Preparation and characterization of PVDF-PFSA flat sheet ultrafiltration membranes

High performance polyvinylidene fluoride (PVDF) flat sheet ultrafiltration (UF) membranes have been prepared by an immersion precipitation phase inversion method using perfluorosulfonic acid (PFSA) as a pore former and as a hydrophilic component of the membranes and polyethylene glycol (M_w = 400) (PEG400) as a pore forming agent. The effects of the presence of PEG and the concentration of the PFSA on the phase separation of the casting solutions and on the morphologies and performance of UF membranes including their porosity, water flux, rejection of bovine serum albumin (BSA) protein, and anti-fouling property were investigated. Phase diagrams, viscosities and the phase separations upon exposure to water vapor showed that both PEG400 and PFSA promoted demixing of the casting solution. Scanning electron microscopy measurements showed that the PVDF-PFSA blend membranes had more macropores and finger-like structures than the native PVDF membranes. The PVDF-PFSA membrane (5 wt-% PEG400+ 5 wt-% PFSA) had a pure water flux of 141.7 L/m²·h, a BSA rejection of 90.1% and a relative pure water flux reduction (RFR) of 15.28%. These properties were greatly superior to those of the native PVDF membrane (pure water flux of 5.6 L/m²·h, BSA rejection of 96.3% and RFR of 42.86%).     

Antifouling ultrafiltration membrane fabricated from poly (arylene ether ketone) bearing hydrophilic hydroxyl groups

A new kind of membrane formation polymer, cardo poly(arylene ether ketone) bearing hydrophilic hydroxyl groups (PEK‐OH) was synthesized from the biphenol monomer 2‐(2‐hydroxyethyl)‐3, 3‐bis (4‐hydroxyphenyl)‐isoindolin‐1‐one (PPH‐OH), and 4, 4′‐difluorodiphenylketone. PEK‐OH asymmetric ultrafiltration membranes were prepared using the immersion coagulation phase inversion method. The PEK‐OH membrane prepared using the optimized conditions exhibited a pure water flux of 516 ± 18 L·m^?2·h^?1 and a 99.1 ± 1.4% rejection of bovine serum albumin (BSA) at an operating pressure of 0.1 MPa. The contact angle of PEK‐OH membrane was 66.0 ± 2.4 lower than these of the PEK‐C membrane (87.0 ± 2.8°, prepared from polymer PEK‐C under the same membrane formation condition as PEK‐OH membrane) and the UE50 membrane (84.0 ± 1.6°, a commercial PES ultrafiltration membrane). The amount of BSA protein adsorbed to the PEK‐OH membrane under static condition was measured to be 3.12 μg·cm^?2, which was greatly lower than that of 88.71 μg·cm^?2 and 74.40 μg·cm^?2 for the PEK‐C and the UE50 ultrafiltration membranes, respectively. Under dynamic filtration of BSA experiments, the PEK‐OH ultrafiltration membrane showed a 78.3% water flux recovery ratio, while only a 39.7% for the PEK‐C membrane and 46.5% for UE50 membrane were detected in the first cycle. After three cycles of BSA and LYZ filtration, the flux recovery ratio of PEK‐OH ultrafiltration membrane changed to be stable at 75% and 73%, while that of PEK‐C and UE50 ultrafiltration membranes remained declining gradually. Thus, hydrophilic PEK‐OH improves antifouling membrane property. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42809.     

凝固浴组成对SMA/CPVC共混超滤膜的结构与性能影响

通过非溶剂致相分离（NIPS）法制备了苯乙烯-马来酸酐共聚物（SMA）/氯化聚氯乙烯（CPVC）共混超滤膜,探讨了凝固浴中不同溶剂（DMAc）含量对其超滤膜表面酸酐基团偏析程度、微观结构、亲水性、水通量、截留率和抗污染的影响。结果表明：凝固浴中溶剂含量的增加抑制了酸酐基团向膜表面的偏析,导致亲水性减弱;同时,铸膜液中溶剂与水分子之间扩散速率的变小引起延迟分相,使得膜表面孔径变小和分布变窄。当溶剂质量分数为3%时,超滤膜对牛血清白蛋白（BSA）截留率提升至98.10%、通量恢复率为96.82%,且不可逆污染率降为3.77%,表明凝固浴中适量的溶剂可进一步提高超滤膜抗污染性能。     

掺杂石墨相氮化碳高通量芳香聚酰胺超滤膜制备

以聚间苯二甲酰间苯二胺(PMIA)为膜材料,石墨相氮化碳(g-C3N4)为添加剂,通过相转化法制备了PMIA/g-C3N4超滤膜。分别探讨了不同添加量的g-C3N4对超滤膜的水通量、分子截留性能等影响。结果表明,与不含gC3N4的超滤膜相比,改性后的超滤膜的结构和性能发生了显著变化,添加一定比例的g-C3N4纳米粒子可以有效增加膜的通量和亲水性,但过量的添加会影响膜的分离性能。研究发现,当添加的g-C3N4的量相对于PMIA的质量分数为5%时,膜的整体性能最佳,此添加量的膜的纯水通量达到了542 L/(m^2·h),截留分子量Mm为133.3×10^3,表面纯水接触角为48.36°,孔隙率为67.10%,裂解温度为360℃。     

Polyamide/polyacrylonitrile thin film composites as forward osmosis membranes

Thin film composites (TFCs) as forward osmosis (FO) membranes for seawater desalination application were prepared. For this purpose, polyacrylonitrile (PAN) as a moderately hydrophilic polymer was used to fabricate support membranes via nonsolvent‐induced phase inversion. A selective thin polyamide (PA) film was then formed on the top of PAN membranes via interfacial polymerization reaction of m‐phenylenediamine and trimesoyl chloride (TMC). The effects of PAN solution concentration, solvent mixture, and coagulation bath temperature on the morphology, water permeability, and FO performance of the membranes and composites were studied. Support membranes based on low PAN concentrations (7 wt %), NMP as solvent and low coagulation bath temperature (0 °C) demonstrated lower thickness, thinner skin layer, more porosity, and higher water permeability. Meanwhile, decreasing the PAN solution concentration lead to higher water permeance and flux and lower reverse salt flux, structural parameter, and tortuosity for the final TFCs. Composites made in N,N‐dimethylformamide presented lower permeance and flux for water and salt and higher salt rejection, structural parameter, and tortuosity. FO assay of the composites showed lower water permeance values in saline medium comparing to pure water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44130.