离子液体微乳液合成纳米AgCl及AgCl/poly(MMA-co-St)杂化膜性能调控

在以离子液体氯化-1-十二烷基甲基咪唑(C12mimCl)为表面活性剂,甲基丙烯酸甲酯(MMA)与苯乙烯(St)混合物为油相介质的反相微乳液中合成AgCl纳米粒子,进而采用微乳液原位聚合法制备AgCl/poly(MMA-co-St)杂化膜。通过紫外可见光谱和透射电镜分析了微乳液组成(油相介质组成和增容水量ω)对纳米AgCl粒子形貌的影响。结合扫描电镜和苯、环已烷的溶胀实验探讨了微乳液组成对杂化膜性能的调控作用。结果发现,微乳液油相介质中St/MMA体积比增大有利于在微乳液和杂化膜中获得更多纳米AgCl粒子,增加了杂化膜的苯平衡溶胀吸附量(A∞,b)与苯/环已烷的平衡溶胀吸附选择性(αs,b/c)。在St/MMA体积比为1∶3时杂化膜的A∞,b和αs,b/c分别达到330 mg·g-1和19.21;但过多苯乙烯加入油相介质,其苯环中π键会破坏水核中AgCl粒子的稳定性而引起粒子团聚,从而降低了杂化膜的A∞,b和αs,b/c。反相微乳液中合成的纳米AgCl粒子量随ω增大而增多、粒径增大,杂化膜的A∞,b和αs,b/c随ω的增加而增大。但过高的ω导致微乳液中出现AgCl大粒子,从而引起杂化膜的A∞,b和αs,b/c下降。     

离子液体微乳液合成纳米AgCl及AgCl/poly(MMA-co-St)杂化膜性能调控

在以离子液体氯化-1-十二烷基甲基咪唑(C₁₂mimCl)为表面活性剂,甲基丙烯酸甲酯(MMA)与苯乙烯(St)混合物为油相介质的反相微乳液中合成AgCl纳米粒子,进而采用微乳液原位聚合法制备AgCl/poly(MMA-co-St)杂化膜。通过紫外可见光谱和透射电镜分析了微乳液组成(油相介质组成和增容水量ω)对纳米AgCl粒子形貌的影响。结合扫描电镜和苯、环已烷的溶胀实验探讨了微乳液组成对杂化膜性能的调控作用。结果发现,微乳液油相介质中St/MMA体积比增大有利于在微乳液和杂化膜中获得更多纳米AgCl粒子,增加了杂化膜的苯平衡溶胀吸附量(A_∞,b)与苯/环已烷的平衡溶胀吸附选择性(α_s,b/c)。在St/MMA体积比为1：3时杂化膜的A_∞,b和α_s,b/c分别达到330mg·g^-1和19.21;但过多苯乙烯加入油相介质,其苯环中π键会破坏水核中AgCl粒子的稳定性而引起粒子团聚,从而降低了杂化膜的A_∞,b和α_s,b/c。反相微乳液中合成的纳米AgCl粒子量随ω增大而增多、粒径增大,杂化膜的A_∞,b和α_s,b/c随ω的增加而增大。但过高的ω导致微乳液中出现AgCl大粒子,从而引起杂化膜的A_∞,b和α_s,b/c下降。     

F127反相微乳液中纳米AgCl粒子的可控合成和AgCl/F127-PMMA有机/无机杂化膜的研究

在大分子F127为表面活性剂的反相微乳液体系中,合成AgCl纳米粒子。然后通过聚合制备AgCl/F127-PMMA有机/无机杂化膜,用于苯/环己烷混合物的渗透汽化分离。利用电导率仪、紫外可见光谱及透射电镜研究微乳液的增溶水量(ω)对微乳液结构、胶束中AgCl粒子的生成和形貌的影响。结果表明:合成的AgCl粒子粒径小于10 nm;增加微乳液的ω,生成的AgCl粒子变大。聚合后制备的AgCl/F127-PMMA有机/无机杂化膜中,AgCl粒子能保持较好的分散性。50wt%苯/环己烷混合物的渗透汽化结果表明,在合适的ω下,所制备的AgCl/F127-PMMA有机/无机杂化膜能克服常规高分子膜的trade-off现象,表现出较好的分离性能。     

ZrO2纳米粒子原位杂化PVDF膜的制备及其抗污染性能

针对传统聚合物膜抗污染性差的问题,本文从杂化膜结构设计出发,提出将ZrO2纳米粒子的原位制备和聚偏氟乙烯(PVDF)相转化成膜过程有机结合的制膜新方法.该方法将阴离子交换树脂引入到N,N-二甲基甲酰胺(DMF)中,以氧氯化锆为原料,利用阴离子交换树脂提供的―OH与无机盐的阴离子进行交换,得到ZrO2纳米粒子均匀分散的N,N-二甲基甲酰胺溶胶体系.随后将PVDF聚合物溶解到所得的N,N-二甲基甲酰胺溶胶体系中,获得均一、透明的铸膜液.利用X射线光电子能谱(XPS)和透射电子显微镜(TEM)对杂化膜中锆的存在状态和分散性能进行了表征.结果表明,ZrO2纳米粒子均匀分散在PVDF基体中,并且形成的纳米粒子的粒径约为10-20 nm.通过粘度、分相速度和膜形态的测定,研究了成膜机理.结果表明,ZrO2纳米粒子的引入加速了铸膜液成膜过程的分相速度.杂化膜的亲水性能通过接触角测定仪进行了评价.并选择以牛血清蛋白为代表模拟污染物,考察了杂化超滤膜的抗污染性能.结果表明,原位形成的ZrO2纳米粒子显著提高了膜的亲水性,减少了膜对蛋白质的吸附.这种将ZrO2纳米粒子的原位制备和PVDF相转化成膜过程有机结合的制膜新方法在有机-无机杂化膜的制备领域具有显著意义.     

反相微乳液模板原位聚合制备纳米氯化银/聚甲基丙烯酸甲酯及其结构表征

用甲基丙烯酸甲酯(MMA)作油相,反相胶束微乳液作为模板,制备了纳米氯化银(AgCl)粒子,再进行原位聚合制备了纳米氯化银/聚甲基丙烯酸甲酯(AgCl/PMMA)复合材料.透射电镜(TEM)分析表明,纳米AgCl的尺寸为20～80 nm.扫描电镜(SEM)测试表明纳米AgCl粒子均匀地存在于PMMA基材中.红外分析证明,胶束中水和表面活性剂AOT的羰基在MMA聚合后微观环境发生变化,纳米粒子同聚合物之间有吸附行为.动态力学(DMTA)分析复合材料,发现纳米AgCl粒子与聚合物之间存在强烈相互作用,形成了中间相层(interphase layer),改变了聚合物的动态力学性能.     

反相微乳液中AgCl纳米粒子的可控合成与AgCl/GMA-MMA-AMPS共聚物有机-无机杂化膜的研究

以2-丙烯酰胺基-2-甲基丙磺酸(AMPS)为表面活性剂,在甲基丙烯酸缩水甘油酯(GMA)和甲基丙烯酸甲酯(MMA)混合物为油相的反相微乳液体系中合成了AgCl纳米粒子,然后通过微乳液聚合制备了AgCl/GMA-MMA-AMPS共聚物有机-无机杂化膜,并用于苯/环己烷混合物的渗透气化分离.利用紫外-可见光谱及透射电子显...     

抗污染PVA/PVDF电纺纳米纤维复合超滤膜的制备及过滤性能

以聚对苯二甲酸二醇酯(PET)无纺布为基底,聚偏氟乙烯(PVDF)纳米纤维为支撑层,聚乙烯醇(PVA)纳米纤维膜为分离层,采用静电纺丝法制备超滤膜,并用水/丙酮混合溶液对复合纳米纤维膜表面进行溶液处理,再加入戊二醛交联改性得到致密分离层.采用扫描电子显微镜(SEM)和红外光谱(FTIR)表征了复合超滤膜的表面,用水接触角(WCA)表征复合超滤膜的亲水性.在0.02 MPa恒压下死端过滤油/水乳液,测试复合超滤膜的过滤性能.结果表明,最优条件下制备的复合超滤膜死端过滤油/水乳液的通量为(42.50±4.78)L/(m~2·h),截留率达到(95.72±0.33)%;循环使用5次后,依然具有较好的过滤性能,常压下死端过滤复合超滤膜的纯水通量为(3469±28)L/(m~2·h).     

PVDF膜改性的方法研究

本文介绍了目前国内外聚偏氟乙烯(PVDF)超滤膜改性中常用的膜表面改性方法和膜材料改性方法。PVDF膜表面改性主要通过膜表面的物理改性、磺化改性、表面接枝改性、光化学改性、低温等离子体改性等方法来实现;而PVDF膜材料的改性主要是通过PVDF与亲水性高分子材料或小分子无机粒子的共混以及膜材料本体的化学改性来实现。改性PVDF膜的亲水性增强,使水通量增加,提高了机械性能,改善了抗污染性,增加了膜的使用寿命。     

PVDF膜改性方法研究进展

本文介绍了目前国内外聚偏氟乙烯(PVDF)超滤膜改性中常用的膜表面改性方法和膜材料改性方法。PVDF膜表面改性主要通过膜表面的物理改性、磺化改性、表面接枝改性、光化学改性、低温等离子体改性等方法来实现;而PVDF膜材料的改性主要是通过PVDF与亲水性高分子材料或小分子无机粒子的共混以及膜材料本体的化学改性来实现。改性PVDF膜的亲水性增强,使水通量增加,提高了机械性能,改善了抗污染性,增加了膜的使用寿命。     

Cu-BTC/PVDF杂化膜的原位掺杂制备及增强的染料吸附性能

将Cu-BTC颗粒与聚偏氟乙烯(PVDF)溶液共混,原位掺杂制备了Cu-BTC/PVDF杂化膜,利用扫描电子显微镜(SEM)、X射线衍射仪、热重分析仪和傅里叶变换红外光谱仪等对杂化膜的结构进行了表征,并对杂化膜的亲/疏水性质、膜孔隙率以及膜水通量进行了测定,探讨了Cu-BTC的掺杂量对杂化膜结构和性质的影响.结果表明,Cu-BTC的存在使PVDF薄膜的成核机理发生改变,降低了PVDF膜孔尺寸,提高了膜表面亲水性和水通量.在对刚果红(CR)的吸附实验中,Cu-BTC/PVDF杂化膜表现出显著增强的吸附活性,且随着Cu-BTC掺杂量的增加,Cu-BTC/PVDF对CR的吸附性能逐渐增强.吸附热动力学拟合结果表明,吸附过程以Langmuir单分子层吸附和化学吸附为主要特征.     

Fabrication,characterization, and performance evaluation of polyethersulfone/TiO2 nanocomposite ultrafiltration membranes for produced water treatment

In the present work, development of neat and nanocomposite polyethersulfone membranes composed of TiO₂ nanoparticles is presented. Membranes are fabricated using nonsolvent phase inversion process with the objective of improving antifouling, hydrophilicity, and mechanical properties for real and synthetic produced water treatment. Membranes are characterized using scanning electron microscopy, Fourier‐transform infrared, contact angle, porosity measurement, compaction factor, nanoparticles stability, and mechanical strength. The performance of prepared membranes was also characterized using flux measurement and oil rejection. Fourier‐transform infrared spectra indicated that noncovalence bond formed between Ti and polyethersulfone chains. The contact angle results confirmed the improved hydrophilicity of nanocomposite membranes upon addition of TiO₂ nanoparticles owing to the strong interactions between fillers and water molecules. The increased water flux for nanocomposite membranes in comparison with neat ones can be due to coupling effects of improved surface hydrophilicity, higher porosity, and formation of macrovoids in the membrane structure. The membrane containing 7 wt% of TiO₂ nanoparticles was the best nanocomposite membrane because of its high oil rejection, water flux, antifouling properties, and mechanical stability. The pure water flux for this membrane was twice greater than that of neat membrane without any loss in oil rejection. The hydrophilicity and antifouling resistance against oil nominates developed nanocomposite membranes for real and synthetic produced water treatment applications with high performance and extended life span.     

F127反相微乳液的组成对AgCl纳米粒子形成及AgCl/F127-PMMA杂化膜结构和性能的影响

以F127为表面活性剂构成的反相微乳液制备AgCl纳米粒子和AgCl/F127-PMMA杂化膜,通过紫外可见光谱(UV-visible)、透射电镜(TEM)研究了微乳液的增容水量(ω)和盐浓度(Csalt)对AgCl粒子形成与形貌的影响;结合表面ζ电位测定、扫描电镜(SEM)分析和溶胀实验等考察了AgCl/F127-PMMA杂化膜的结构和性能。研究结果表明,低ω下盐浓度增加,胶束中AgCl反应速率增大,导致大量小粒径AgCl粒子的形成;高ω下盐浓度增加,将加快AgCl粒子的生长,从而导致胶束中的AgCl粒子粒径增大;各种ω下盐浓度的增加,都会引起胶束中单质Ag的形成。杂化膜的SEM分析显示,AgCl粒子粒径越小,在杂化膜中的分散性越好,膜表面的ζ电位也越高,膜在苯中的溶胀性能也越高;单质Ag的出现和AgCl粒子数目的增多,杂化膜中将显现明显的粒子团聚现象,这极大地影响了杂化膜在苯中的溶胀性能;而杂化膜在环己烷中的溶胀性能较低,且随ω和盐浓度的变化极小。     

Enhanced antifouling performance of ZnS/GO/PVDF hybrid membrane by improving hydrophilicity and photocatalysis

In order to improve the antifouling performance of PVDF membrane, a novel zinc sulfide/graphene oxide/polyvinylidene fluoride (ZnS/GO/PVDF) composite membrane was prepared by immersed phase inversion method. The surface morphology, crystal structure, photocatalytic activity, and antifouling property of the as‐prepared membranes were systematically studied. Results showed that the ZnS/GO/PVDF hybrid membranes were successfully fabricated with uniform surface. The hybrid membrane surface possessed higher hydrophilicity with water contact angle decreasing from 77.1° to 62.2°. The permeability of the hybrid membrane was therefore enhanced from 222.9 to 326.1 L/(m² hour). Moreover, bovine serum albumin (BSA) retention experiment showed that the hybrid membrane separation was also promoted by 7.2%. The blending of ZnS and GO enhanced the hydrophilic and photocatalytic performances of PVDF membrane, which mitigated the membrane fouling effectively. This novel hybrid membrane could accelerate the practical application of photocatalytic technology in membrane separation process.     

Fabrication of Cu(OH)_2 Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu(OH)_2 nanowires were prepared and incorporated into poly(vinylidene fluoride)(PVDF) to fabricate Cu(OH)_2-PVDF ultrafiltration(UF) membrane via immersion precipitation phase inversion process. The effect of Cu(OH)_2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy(XPS), Fourier transform infrared(FTIR) spectroscopy, atomic force microscopy(AFM), scanning electron microscopy(SEM) and X-ray diffraction(XRD) measurements. The results showed that all the Cu(OH)_2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity, smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)_2 nanowires. In addition, water flux and bovine serum albumin(BSA) rejection were also measured to investigate the filtration performance of membranes. The results indicated that all the Cu(OH)_2-PVDF membranes had high water flux, outstanding BSA rejection and excellent antifouling properties. It is worth mentioning that the optimized performance could be obtained when the Cu(OH)_2 nanowires content reached 1.2 wt%. Furthermore, the membrane with 1.2 wt% Cu(OH)_2 nanowires showed outstanding oil-water emulsion separation capability.     

Fabrication of Cu(OH)<Subscript>2</Subscript> Nanowires Blended Poly(vinylidene fluoride) Ultrafiltration Membranes for Oil-Water Separation

Cu(OH)2 nanowires were prepared and incorporated into poly(vinylidene fluoride) (PVDF) to fabricate Cu(OH)2-PVDF ultrafiltration (UF) membrane via immersion precipitation phase inversion process.The effect of Cu(OH)2 nanowires on the morphology of membranes was investigated by X-ray photoelectron spectroscopy (XPS),Fourier transform infrared (FTIR) spectroscopy,atomic force microscopy (AFM),scanning electron microscopy (SEM) and X-ray diffraction (XRD) measurements.The results showed that all the Cu(OH)2-PVDF membranes had wider fingerlike pore structure and better hydrophilicity,smoother surface than pristine PVDF membrane due to the incorporation of Cu(OH)2 nanowires.In addition,water flux and bovine serum albumin (BSA) rejection were also measured to investigate the filtration performance of membranes.The results indicated that all the Cu(OH)2-PVDF membranes had high water flux,outstanding BSA rejection and excellent antifouling properties.It is worth mentioning that the optimized performance could be obtained when the Cu(OH)2 nanowires content reached 1.2 wt％.Furthermore,the membrane with 1.2 wt％ Cu(OH)2 nanowires showed outstanding oil-water emulsion separation capability.     

In situ preparation of Al-containing PVDF ultrafiltration membrane via sol-gel process

Recently, inorganic nanoparticles blended within polymeric membranes have shown improved antifouling performance in wastewater treatment. However, agglomeration of nanoparticles remains as one of the major obstacles for generating a uniform surface. In this study, a new method for in situ preparation of Al-containing PVDF ultrafiltration membranes to improve the dispersion of nanoparticles is reported. The strategy of this method is to combine sol-gel process with traditional immersion precipitation process. Al sol was synthesized by the addition of anionic exchange resin in N,N-dimethylformamide (DMF) solvent containing aluminum chloride. Homogeneous Al-containing PVDF casting solution was then obtained by dissolving PVDF polymer in the Al sol. The membrane formation mechanism was investigated by precipitation kinetics and morphology. Results indicate that the addition of Al species can accelerate phase inversion of casting solution. Scanning electron microscopic images show that a typical transition from sponge-like structure to finger-like structure occurred with increasing Al species content. The existence and dispersion states of Al species in the resultant membrane matrix were further examined by transmission electron microscope and X-ray photoelectron spectrometer. The results indicate the Al species nanoparticles were well dispersed throughout PVDF matrix. Dynamic BSA fouling resistance experiments demonstrate the Al-containing PVDF membranes possess improved separation performances over the pure PVDF membranes.     

Versatility of hydrophilic and antifouling PVDF ultrafiltration membranes tailored with polyhexanide coated copper oxide nanoparticles

Hydrophilic poly(vinylidene fluoride) (PVDF) nanocomposite ultrafiltration (UF) membranes with excellent antifouling and antibiofouling characteristics are fabricated by employing polyhexanide coated copper oxide nanoparticles (P–CuO NPs). The presence of P–CuO NPs is played a significant role in altering the PVDF membrane matrix and probed by XRD, FTIR, FESEM and contact angle analysis. The PVDF/P–CuO nanocomposite membranes exhibited an outstanding antifouling performance indicated by the superior pure water flux, effective foulant separation and maximum flux recovery ratio during UF experiments as a result of the formation of the hydrophilic and more porous membrane due to the uniform distribution of P–CuO NPs. Particularly, the PVDF/P–CuO-3 membrane showed higher PWF of 152.5 ± 2.4 lm⁻²h⁻¹ and porosity of 64.5% whereas the lower contact angle of 52.5°. Further, it showed the higher rejection of 99.5 and 98.4% and the flux recovery ratio of 99.5 and 98.5% respectively for BSA and HA foulants, demonstrated its increased water permeation, foulant separation and antifouling behavior. Further, the decent antibacterial activity is showed by the PVDF/P–CuO nanocomposite membranes with the formation of halo-zone around the membrane when exposed to the bacterial medium demonstrated that, by this process an antibacterial water treatment membrane can be developed by simple phase inversion technique with good membrane stability.     

Porous poly(vinylidene fluoride) membrane modified with hyperbranched poly(amine‐ester)

Poly(vinylidene fluoride) (PVDF) membranes were hydrophilic modified with hydroxyl group terminated hyperbranched poly(amine‐ester) (HPAE). Fourier transform infrared spectroscopy (FT‐IR) was used to study the chemical change of PVDF membranes. X‐ray photoelectron spectroscopy (XPS) indicated that some HPAE molecules were retained in PVDF membrane through polymer chain coiling. The presence of HPAE would improve the hydrophilicity of PVDF membrane. Scanning electron microscopy (SEM) was employed to characterize the morphology of different membranes. The thermodynamic stability for PVDF/DMAc/HPAE/Water system was characterized by the determination of the gelation values. Precipitation kinetics for PVDF/DMAc/HPAE/Water system was studied by precipitation time measurement. The water contact angle indicated that the hydrophilicity and the biocompatibility corresponding to protein adsorption of PVDF membrane were improved significantly after blending with hydrophilic HPAE molecules. Copyright © 2011 John Wiley & Sons, Ltd.     

Structure and pH‐sensitive properties of poly (vinylidene fluoride) membrane changed by blending poly (acrylic acid) microgels

pH‐sensitive poly (vinylidene fluoride) (PVDF)/poly (acrylic acid) (PAA) microgels membranes are prepared by phase inversion of the N, N‐dimethylformamide solution containing PAA microgels and PVDF in aqueous solution. The composition and structure of the blend membrane are investigated by Fourier transform infrared spectra, X‐ray photoelectron spectroscopy measurements, thermo gravimetric analysis, field‐emission scanning electron microscope and atomic force microscope. The results indicate the surface and cross section of the blend membranes have a porous structure with PAA microgels immobilized inside the pore and on the membrane surface. The blend PVDF membranes exhibit pH‐sensitive water flux, with the most drastic change in permeability observed between pH 3.7 and 6.3. The blend membranes are fouled by bovine serum albumin, and their antifouling property is enhanced by increasing PAA microgels, mainly derived from the improved hydrophilic property. Copyright © 2013 John Wiley & Sons, Ltd.