聚偏氟乙烯膜的制备及其影响规律的研究

以聚偏氟乙烯(PVDF)为膜材料,LiCl为添加剂,NMP,DMF,DMAC为溶剂进行正交试验,确定不同的溶剂种类,聚合物浓度,添加剂浓度对膜结构和性能的影响,并通过正交实验分析出最佳的制膜液组成:18%PVDF/3%LiCl/DMAC,经表征后纯水通量为223.73L/m2h,对牛血清白蛋白(M=67000)截留率为78%,孔径为44nm。     

混合添加剂对TiO2/PVDF平板超滤膜性能和结构的影响

研究了不同比例的混合添加剂PEG600-LiCl、丙酮-LiCl、丙三醇-LiCl和PVP-LiCl对TiO2/PVDF平板超滤膜性能和结构的影响,并利用扫描电子显微镜( SEM)和接触角测量仪表征了复合膜的结构.结果表明,PEG600-LiCl、丙酮-LiCl、丙三醇-LiCl和PVP-LiCl 4种混合添加剂均可以改善膜性能,其中PEG600-LiCl、丙三醇-LiCl、PVP-LiCl3种混合添加剂加到铸膜液中,明显改善了PVDF膜表面的亲水性,可以将膜表面接触角降低至55°.当PVP与LiCl的质量比为1∶2时,膜的性能达到最优,孔隙率为82.5％,平均孔径为0.1 μm,水通量为100.5 L·m-2·h-1,截留率为95.4％.     

PVDF纺丝液流变性及其中空纤维膜纺制

以聚偏氟乙烯(PVDF)为原料,磷酸三乙酯(TEP)为稀释剂,纳米Al2O3为添加剂,采用旋转黏度计,探讨了纳米Al2O3和PVDF结晶对纺丝液的流变性与可纺性的影响,并对纺制的PVDF中空纤维膜进行了测试表征.结果表明:PVDF/TEP/Al2O3体系属于切力变稀流体,在添加剂质量分数为1.5％时,非牛顿性变弱,结构化程度最低,可纺性最好;随着温度的降低和时间的延长,PVDF结晶会促使纺丝液黏度急剧上升;采用热致相分离法纺制PVDF中空纤维膜微孔结构均匀一致,孔径分布窄,平均孔径19.3 nm,孔隙率60.668％.     

蒙皂石/PVDF与LiC1/PVDF微孔膜性能的异同

研究了蒙皂石(MMT)、LiCl两种成孔添加剂对PVDF膜性能的影响.无论哪种添加剂都会使铸膜液黏度增加,且有利于膜的成形.但PVDF/蒙皂石/DMAC黏度符合假塑性流体的特性,因而可改善材料的可加工性;PVDF/LiCl/DMAC黏度符合膨胀性流体的特性.从相图看,均改变了双节的位置,对非溶剂的容纳能力降低,Licl作为添加剂较MMT有更强的致凝胶作用;用正交试验证明了在10℃的凝胶浴温度下PVDF,MMT、LiCl分别为14%、7%、0%时对PEG20000的截留率最大可达95.23%;在25℃的凝胶浴温度下PVDF、MMT、LiCl分别为10%、0%、5%时对油水混合物的截留率最大可达90.56%;DSC测试表明,MMT为添加剂的PVDF膜结晶度低于LiCl为添加剂的PVDF膜,但从TG图知前者的质量分解量低于后者,说明它的热稳定性较强.     

混合溶剂对TiO2/PVDF平板超滤膜性能和结构的影响

采用N,N-二甲基乙酰胺(DMAC)和N-甲基吡咯烷酮(NMP)为混合溶剂制备PVDF超滤膜。考察了不同混合比例的DMAC和NMP对膜性能及膜结构的影响,同时利用扫描电子显微镜(SEM)对膜表面及断面结构进行分析,原子力学显微镜(AFM)对膜表面粗糙度进行了分析,利用接触角测量仪对膜表面接触角进行了测量。结果表明,使用混合溶剂对膜孔径和膜亚层结构影响较大,但混合溶剂对膜孔隙率和接触角基本没有影响。当混合溶剂DMAC/NMP为1:2时,膜性能达到最优,孔隙率为70%,平均孔径为0.24μm,水通量为373 L.m-2.h-1,截留率为88%。     

溶剂/非溶剂体系对聚醚砜微孔膜性能和结构的影响

以N,N-二甲基乙酰胺(DMAc)、N-甲基吡咯烷酮(NMP)和N,N-二甲基甲酰胺(DMF)为溶剂,乙醇(EtOH)、异丙醇(IPA)、正丁醇(BuOH)、一缩二乙二醇(DegOH)、聚乙二醇400(PEG400)为非溶剂添加剂,研究了溶剂/非溶剂体系对聚醚砜(PES)膜的结构和性能的影响.改变铸膜液体系中的非溶剂含量对膜的结构和性能有很大影响,但是这种影响不是以非溶剂的绝对含量来衡量的,而取决于非溶剂/溶剂的比值.改变溶剂的组成和配比也改变了溶剂/非溶剂体系,体系的溶度参数越接近PES的溶度参数,与PES的相容性越好,但是膜的通量较小.实验结果表明,采用NMP(或DMAc)与DMF以适当比例混合作溶剂,比采用单一NMP(或DMAc)作为溶剂制得的膜通量要大.通过改变溶剂配比,可实现对膜的表面开孔率、孔径、断面结构等参数的微控.     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

聚间苯二甲酰间苯二胺平板膜的制备及其性能研究

以聚间苯二甲酰间苯二胺（PMIA）为制膜原料,氯化锂（LiCl）、聚乙二醇（PEG-400）和聚乙烯吡咯烷酮（PVP）为添加剂,通过非溶剂诱导相转化法制备了PMIA平板膜,系统考察了聚合物浓度、添加剂种类和含量对PMIA膜结构和性能的影响。结果表明,聚合物浓度和LiCl含量增加,铸膜液黏度增大,导致膜孔径减小,纯水通量降低。而PEG含量的增加,使得聚合物链呈现舒展状态,膜孔径增大,纯水通量升高,亲水性增强。随着PVP含量的增加,膜的纯水通量先升高后降低,膜的亲水性变差。当PMIA的质量分数为9%,LiCl的质量分数为2.8%,PVP的质量分数为1.2%时,膜的纯水通量高达1421.55 L·m^-2·h^-1·bar^-1,对牛血清蛋白（BSA）的截留率为80%,展现出较高的渗透性,为制备高性能膜材料提供了新的思路。     

聚偏氟乙烯有机膜的共混改性及性能研究

将聚偏氟乙烯和高分子聚合物共混,通过溶胶-凝胶相转化法研制综合性能良好的微孔膜,考察了铸膜液浓度、PVDF与共混添加剂的配比、凝胶浴温度、溶剂挥发时间和酸、碱、氧化处理对共混膜性能的影响.结果表明,随着铸膜液中聚合物总含量、膜液的黏度增加,纯水通量总体呈下降趋势,孔隙率先增加后减小,最后趋近平衡;随着共混添加剂在铸膜液中相对含量的增加,纯水通量先增加后减小,孔隙率可得到有效提高,平均孔径变化不大;凝胶浴温度对纯水通量没有较大影响;延长溶剂的挥发时间,使平均孔径减小;找到合适的共混添加剂并选择适当的膜液组成,能够使共混改性膜的纯水通量、孔隙率、抗酸、碱、氧化性能较改性前得到有效提高.其中纯水通量较改性前提高10％左右,孔隙率提高15％左右,说明共混化是一种改善PVDF膜性能的有效方法,具有极好的实用开发价值.     

不同铸膜液成分对PES/PVDF膜结构与性能影响的研究

采用浸没沉淀相转化法,以二甲亚砜(DMSO)、磷酸三乙酯(TEP)及二甲基乙酰胺(DMAC)作为铸膜溶剂,制备聚醚砜(PES)/聚偏氟乙烯(PVDF)共混膜,研究不同铸膜液成分对膜结构与性能的影响。通过膜的纯水通量、孔隙率、接触角等表征膜性能。利用有机添加剂N-甲基吡咯烷酮(NMP)、聚乙烯吡咯烷酮(PVP)改变PES/PVDF共混膜的性能,结果表明无机添加剂可增大其纯水通量和孔隙率并改善其亲水性。     

小孔径PVDF超滤膜的研制

本文主要研究了高通量小孔径ＰＶＤＦ超滤膜。分析了溶剂体系，添加剂种类无机盐含量及第二组分ＰＭＭＡ等对膜性能的影响，实验结果表明，选择合适的溶剂体系和致孔剂，可制得高通量的致密小孔径ＰＶＤＦ超滤膜，同时，在ＰＶＤＦ膜中共混入少量与之相容的ＰＭＭＡ可显著改善该类膜的亲水性，进一步提高膜的水通量。     

添加剂和凝结剂温度对用无溶剂致相位分离法生产高性能PVDF/聚醚F127混合中空光纤膜的影响(英文)

Poly(vinylidene fluoride)(PVDF) has become one of the most popular materials for membrane prepara-tion via nonsolvent induced phase separation(NIPS) process.In this study,an amphiphilic block copolymer,Plu-ronic F127,has been used as both a pore-former and a surface-modifier in the fabrication of PVDF hollow fiber membranes to enhance the membrane permeability and hydrophilicity.The effects of 2nd additive and coagulant temperature on the formation of PVDF/Pluronic F127 membranes have also been investigated.The as-spun hollow fibers were characterized in terms of cross-sectional morphology,pure water permeation(PWP),relative molecular mass cut-off(MWCO),membrane chemistry,and hydrophilicity.It was observed that the addition of Pluronic F127 significantly increased the PWP of as-spun fibers,while the membrane contact angle was reduced.However,the size of macrovoids in the membranes was undesirably large.The addition of a 2nd additive,including lithium chlo-ride(LiCl) and water,or an increase in coagulant temperature was found to effectively suppress the macrovoid for-mation in the Pluronic-containing membranes.In addition,the use of LiCl as a 2nd additive also further enhanced the PWP and hydrophilicity of the membranes,while the surface pore size became smaller.PVDF hollow fiber with a PWP as high as 2530 L?m?2?h?1?MPa?1,a MWCO of 53000 and a contact angle of 71° was successfully fabricated with 3%(by mass) of Pluronic F127 and 3%(by mass) of LiCl at a coagulant temperature of 25 °C,which shows better performance as compared with most of PVDF hollow fiber membranes made by NIPS method.     

Effect of additives concentration on the surface properties and performance of PVDF ultrafiltration membranes for refinery produced wastewater treatment

The aim of this study was to investigate the effect of pore-forming hydrophilic additives on the porous asymmetric polyvinylideneflouride (PVDF) ultrafiltration (UF) membrane morphology and transport properties for refinery produced wastewater treatment. PVDF ultrafiltration membranes were prepared via a phase inversion method by dispersing lithium chloride monohydrate (LiCl·H₂O) and titanium dioxide (TiO₂) nanoparticles in the spinning dope. The morphological and performance tests were conducted on PVDF ultrafiltration membranes prepared from a different additive content. The top surface and cross-sectional area of the membranes were observed using a field emission scanning electron microscope (FESEM) and energy dispersive X-ray (EDX) analysis. The surface wettability of porous membranes was determined by the measurement of a contact angle. The mean pore size and surface porosity were calculated based on the permeate flux. The results indicated that the PVDF/LiCl/TiO₂ membranes with lower TiO₂ nanoparticles loading possessed smaller mean pore size, more apertures inside the membrane with enhanced membrane hydrophilicity. LiCl·H₂O has been employed particularly to reduce the thermodynamic miscibility of dope which resulted in increasing the rate of liquid–liquid demixing process. The maximum flux and rejection of refinery wastewater using PVDF ultrafiltration membrane achieved were 82.50 L/m² h and 98.83% respectively at 1.95 wt.% TiO₂ concentration.     

BPAC-UF组合工艺对微污染原水处理效果及膜污染控制

采用生物粉末活性炭-超滤(BPAC-UF)分体式工艺的中试装置,探究该工艺对西氿微污染原水的处理效果,在此基础上对比研究聚偏氟乙烯(PVDF)和聚氯乙烯(PVC)两种材质超滤膜的膜污染情况。PVDF膜和PVC膜两种不同材质的膜组合工艺对浊度去除率均超过95%,超滤膜可保证出水浊度要求。PVDF膜对尺寸不超过2μm的颗粒物去除效果要略优于PVC膜。初期PAC未转化为BPAC时,工艺对氨氮和CODMn的去除主要靠活性炭吸附。当PAC转化为BPAC,BPAC-UF对氨氮的去除主要是通过生物作用,后期去除率稳定在80%以上,BPAC-UF对CODMn去除率不高,稳定在25%左右。在膜污染控制方面,PVDF膜和PVC膜的跨膜压差增长趋势相似,但PVC膜的跨膜压差增速要略高于PVDF膜。经过强化物理反冲洗和化学反冲洗后,PVDF膜和PVC膜的产水性能均能恢复至较优状态,且PVDF膜恢复程度略优于PVC膜。     

截留分子质量和材质对浸没式超滤膜过滤性能的影响

针对截留分子质量和材质对浸没式超滤膜处理微污染地表水过滤性能的影响问题,研究了两者对膜去除水中颗粒物和有机污染物的特性及其对膜污染的影响。结果表明,随着膜截留分子质量的减小,超滤膜对浊度和各有机物指标的去除率逐渐升高,但超滤膜对溶解性有机物的去除率较低;不同材质的超滤膜对有机物的去除率存在差异。不同截留分子质量和材质的超滤膜过滤原水时的污染程度不同,截留分子质量较小的超滤膜污染程度较轻,但容易引起不可逆膜污染;聚砜(PS)膜抗污染的能力要强于聚偏氟乙烯(PVDF)和聚氯乙烯(PVC)膜,在实际应用中应根据不同水质特点合理选择超滤膜的截留分子质量和材质。     

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。     

Removal of Benzene/Toluene from Water by Vacuum Membrane Distillation in a PVDF Hollow Fiber Membrane Module

Abstract

Asymmetric polyvinylidene fluoride (PVDF) hollow fiber membranes were prepared by a phase inversion method using dimethylacetamide (DMAc) and a mixture of water/LiCl as solvent and a nonsolvent additive, respectively. The prepared membranes were characterized by scanning electron microscopy (SEM) for observing its microstructures and by a gas permeation method for measuring its surface porosity, pore size, and pore size distribution. Wetting pressures of the dry hollow fiber membranes were also measured. Using the prepared PVDF hollow fiber membranes, a membrane module was fabricated for removal of benzene/toluene from water. Effects of various operating parameters such as downstream vacuum levels, feed temperatures, and feed flow rates on performances of the module were investigated experimentally. The benzene/toluene removal was achieved over 99% under an optimal operating condition. Mass transfer of benzene or toluene removal is controlled not only by the liquid phase resistance but also by the membrane and gas phase resistances. Benzene and toluene can be removed from water simultaneously with no adverse coupling effects.     

超滤法除农药草甘膦水剂中悬浮物

本文小试选择了改性ＰＶＤＦ超滤膜，现场运行确定超滤过程的最佳工艺参数及膜管的清洗维护方法。结果表明超滤法除去农药草甘膦水剂中悬浮物是一种可行有效的方法，并已投入工业化生产。     

Fabrication and characterization of hydrophobic PVDF hollow fiber membranes for desalination through direct contact membrane distillation

The mixture of inorganic salt LiCl and soluble polymer polyethylene glycol (PEG) 1500 as non-solvent additive was introduced to fabricate hydrophobic hollow fiber membrane of polyvinylidene fluoride (PVDF) by phase inversion process, using N,N-dimethylacetamide (DMAc) as solvent and tap water as the coagulation medium. Compared with other three membranes from PVDF/DMAc, PVDF/DMAc/LiCl and PVDF/DMAc/PEG 1500 dope solution, it can be observed obviously by scanning electron microscope (SEM) that the membrane spun from PVDF/DMAc/LiCl/PEG 1500 dope had longer finger-like cavities, ultra-thin skins, narrow pore size distribution and porous network sponge-like structure owing to the synergistic effect of LiCl and PEG 1500. Besides, the membrane also exhibited high porosity and good hydrophobicity. During the desalination process of 3.5 wt% sodium chloride solution through direct contact membrane distillation (DCMD), the permeate flux achieved 40.5 kg/m² h and the rejection of NaCl maintained 99.99% with the feed solution at 81.8 °C and the cold distillate water at 20.0 °C, this performance is comparable or even higher than most of the previous reports. Furthermore, a 200 h continuously desalination experiment showed that the membrane had stable permeate flux and solute rejection, indicating that the as-spun PVDF hollow fiber membrane may be of great potential to be utilized in the DCMD process.