Permeability of hydrophilic and hydrophobic Shirasu-porous-glass (SPG) membranes to pure liquids and its microstructure

Morphological properties of hydrophilic and hydrophobic Shirasu-porous-glass (SPG) membranes were investigated over a wide range of mean pore sizes (0.252–20.3 μm) by liquid permeability measurements, scanning electron microscopy and Hg porosimetry. Hydrophobic modification of membrane surface was made by surface coating with silicone resin. The results are discussed using the non-uniform capillary bundle model of membrane permeability. The mean pore tortuosity of 1.28 was kept constant over the whole range of mean pore sizes investigated. The SEM images confirmed that the geometry of pore network was similar for all SPG membranes, irrespective of their mean pore size. The span of pore size distribution ranged from 0.28 to 0.68 and the number of pores per unit cross-sectional membrane area from 10⁹ to 10¹³ m⁻². The membrane resistance was unchanged after surface treatment with silicone resin, which means that the pores were not plugged by the resin, even in the submicron range of mean pore sizes.     

Effects of membrane hydrophilicity on the removal of a trihalomethane via micellar-enhanced ultrafiltration process

Micellar-enhanced ultrafiltration (MEUF) process was explored for obtaining pure water from an aqueous solution containing small amount of trihalomethanes (THMs). A homologous series of polyethylene glycol alkylether was used as nonionic surfactant. To understand effects of membrane hydrophilicity on the performance of MEUF process, membranes for the ultrafiltration were prepared from polysulfone blends containing various amount of a hydrophilic copolymer, poly(1-vinylpyrrolidone-co-acrylonitrile) (P(VP-AN)). An increase in the permeate flux was observed with an increase of the membrane hydrophilicity. The performance of MEUF process in removing THM and surfactant was shown to depend on the membrane characteristics, surfactant characteristics, and operating pressure. The rejections of THM and surfactant were increased with increasing hydrophobicity of surfactant and hydrophilicity of membrane. The rejections of THM examined with hydrophilic membranes were increased with increasing operating pressure, while those examined with hydrophobic membranes were decreased with increasing operating pressure. THM included in water could be removed up to 99% via MEUF process. The performance of MEUF examined with hydrophilic membranes could be explained with the rejection of micelles containing THM, while that examined with hydrophobic membranes could be explained with hydrophobic interactions between surfactant and membrane materials.     

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.     

Plasma-induced graft copolymerization of poly(methacrylic acid) on electrospun poly(vinylidene fluoride) nanofiber membrane

Electrospun nanofibrous membranes (ENM) which have a porous structure have a huge potential for various liquid filtration applications. In this paper, we explore the viability of using plasma-induced graft copolymerization to reduce the pore sizes of ENMs. Poly(vinylidene) fluoride (PVDF) was electrospun to produce a nonwoven membrane, comprised of nanofibers with diameters in the range of 200-600 nm. The surface of the ENM was exposed to argon plasma and subsequently graft-copolymerized with methacrylic acid. The effect of plasma exposure time on grafting was studied for both the ENM and a commercial hydrophobic PVDF (HVHP) membrane. The grafting density was quantitatively measured with toluidine blue-O. The degree of grafting increased steeply with an increase in plasma exposure time for the ENM, attaining a maximum of 180 nmol/mg after 120 s of plasma treatment. However, the increase in the grafting density on the surface of the HVHP membrane was not as drastic, reaching a plateau of 65 nmol/mg after 60 s. The liquid entry permeation of water dropped extensively for both membranes, indicating a change in surface properties. Field emission scanning electron microscopy micrographs revealed an alteration in the surface pore structure for both membranes after grafting. Bubble point measurements of the ENM reduced from 3.6 to 0.9 um after grafting. The pore-size distribution obtained using the capillary flow porometer for the grafted ENM revealed that it had a similar profile to that of a commercial hydrophilic commercial PVDF (HVLP) membrane. More significantly, water filtration studies revealed that the grafted ENM had a better flux throughput than the HVLP membrane. This suggests that ENMs can be successfully engineered through surface modification to achieve smaller pores while retaining their high flux performance.     

Poorly water-soluble drug nanoparticles via an emulsion-freeze-drying approach

In this paper, we examine, by dissipative particle dynamics (DPD) simulation, the interactions between nanoparticles and block copolymer bilayer membranes. The bilayer has a hydrophobic core and hydrophilic head groups on both sides of the core. Nanoparticles without or with a grafted homopolymer are considered. For the conditions investigated, the single nanoparticles and small aggregates are located at the interfaces of the membrane, namely the interfaces between the hydrophilic domains of the membrane and the solvent as well as at the interface between the hydrophobic and hydrophilic domains of the membrane. The large aggregates are located in the hydrophilic domains. By increasing the length of the homopolymer grafted on the nanoparticles, the size of the aggregates in the membrane decreases. At relatively short DPD step times, the particles aggregate in the solvent. As the time increases, the single particles and aggregates penetrate into the membrane.     

Synthesis and characterization of multiblock copolymers based on hydrophilic disulfonated poly(arylene ether sulfone) and hydrophobic partially fluorinated poly(arylene ether ketone) for fuel cell applications

Sulfonated fluorinated multiblock copolymers based on high performance polymers were synthesized and evaluated for use as proton exchange membranes (PEMs). The multiblock copolymers consist of fully disulfonated poly(arylene ether sulfone) and partially fluorinated poly(arylene ether ketone) as hydrophilic and hydrophobic segments, respectively. Synthesis of the multiblock copolymers was achieved by a condensation coupling reaction between controlled molecular weight hydrophilic and hydrophobic oligomers. The coupling reaction could be conducted at relatively low temperatures (e.g., 105 °C) by utilizing highly reactive hexafluorobenzene (HFB) as a linkage group. The low coupling reaction temperature could prevent a possible trans‐etherification, which can randomize the hydrophilic‐hydrophobic sequences. Tough ductile membranes were prepared by solution casting and their membrane properties were evaluated. With similar ion exchange capacities (IECs), proton conductivity and water uptake were strongly influenced by the hydrophilic and hydrophobic block sequence lengths. Conductivity and water uptake increased with increasing block length by developing nanophase separated morphologies. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments revealed that the connectivity of the hydrophilic segments was enhanced by increasing the block length. The systematic synthesis and characterization of the copolymers are reported. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 214–222, 2010     

微乳液聚合耦合共混法构建聚偏氟乙烯共混杂化膜

以苯乙烯和甲基丙烯酸甲酯混合物作为油相, 采用反相微乳液法制备了AgCl纳米粒子; 通过微乳液原位聚合油相单体得到包含AgCl纳米粒子的聚合乳液; 将聚合乳液与聚偏氟乙烯(PVDF)通过共混法构建了包含AgCl纳米粒子的PVDF共混杂化膜. 紫外-可见光谱、 透射电子显微镜(TEM)及扫描电子显微镜(SEM)等表征结果和超滤实验结果表明, 聚合乳液加入的同时引入了亲水性聚合物和表面亲水的AgCl纳米粒子, 不仅改善了PVDF共混杂化膜的孔隙率和平均孔径, 还显著增强了PVDF共混杂化膜的极性和亲水性, 最终提升了膜的水通量和抗污染性能; 过量聚合乳液加入后不能与PVDF材料均匀共混, 而且AgCl纳米粒子也会在膜中形成团聚物堵塞膜孔隙, 从而削弱了膜的水通量和抗污染性能.     

Emulsion pathways to composite polymeric membranes for separation processes

A novel method for the preparation of selective composite membranes from emulsions is suggested. The dispersed phase is chosen to yield a polymer soluble in those components for which the membrane should be selective; the continuous phase, on the other hand, is selected to yield a polymer that is insoluble in any of the components of the mixture. Conventional emulsions (which have a maximum dispersed phase volume fraction of 0.74) or microemulsions can be employed to generate composites. However, concentrated emulsions which allow volume fractions as large as 0.99 are most suitable as precursors to selective and efficient membranes. These concentrated emulsions have the appearance of gels with a structure similar to that of foams. The relatively high permeabilities obtained with the resultant membranes are due to the small thickness of the films of the continuous phase. A concentrated emulsion of a hydrophobic (hydrophilic) monomer dispersed in a hydrophilic (hydrophobic) continuous phase is first prepared at room temperature, with suitable initiators in each phase for later polymerization, and with an appropriate dispersant in the continuous phase. To ensure the stability of the emulsion, the hydrophilic monomer is, in general, replaced by monomer plus water. On heating the gel at 50 °C, polymerization occurs in both phases and the emulsion transforms into a composite polymer membrane. As examples, composite membranes containing polystyrene as the dispersed phase and polyacrylamide as the continuous phase are used to separate toluene from cyclohexane, while other composite membranes containing acrylamide as the dispersed phase and a crosslinked polystyrene as the continuous phase are used to separate water from ethanol.Lecture presented at the Colburn Symposium, University of Delaware, October 19, 1988.     

Effect of pH on hydrophilicity and charge and their effect on the filtration efficiency of NF membranes at different pH

In this work the effect of pH on membrane structure, its permeability and retention was studied. In addition, we studied whether the possible changes in the membrane properties due to the pH change are reversible. This is important for understanding the performance of nanofiltration membranes at different conditions and for the selection of cleaning processes. Moreover, the results facilitate the choice of membrane for specific applications.

Several commercial NF membranes were studied at different pH values. Their retention and flux were explained by the charge and the hydrophilic characteristics of the membranes. The filtrations were made with uncharged sugar and salt solutions.

The lower the membrane contact angle (i.e., a more hydrophilic membrane) the higher was the change in apparent zeta potential when pH was increased from 4 to 7. As a result, the retention of ions with more hydrophilic membranes changed more than hydrophobic ones when the pH was increased in the feed solution. However, some membranes retained ions well at high pH although their apparent zeta potential or hydrophilicity was relatively low. These membranes had charge inside the pores and it was not detected by streaming potential measurement along the surface or by measuring the contact angle of the surface. Thus, the apparent zeta potential of the exterior membrane surface did not sufficiently describe the ionic transport through the membrane. In addition, some membranes became significantly more open at high pH (i.e., flux increased). This was explained by the chemical nature of the polymer chains in the membrane skin layer, i.e., dissociating groups in the polymer made the surface more hydrophilic and looser when charges of the polymer chains started to repel each other at elevated pH. Generally, the retention of uncharged glucose decreased more at high pH than the salt retention. The changes in permeabilities and retentions were found to be mostly reversible in the pH range studied (very slowly in some cases, however).     

Removal of aromatic compounds in the aqueous solution via micellar enhanced ultrafiltration: Part 1. Behavior of nonionic surfactants

The effects of nonionic surfactants having different hydrophilicity and membranes having different hydrophobicity and molecular weight cut-off on the performance of micellar-enhanced ultrafiltration (MEUF) process were examined. A homologous series of polyethyleneglycol (PEG) alkylether having different numbers of methylene groups and ethylene oxide groups was used for nonionic surfactants. Polysulfone membranes and cellulose acetate membranes having different molecular cut-off were used for hydrophobic membranes and hydrophilic membranes, respectively. The concentration of surfactant added to pure water was fixed at the value of 100 times of critical micelle concentration (CMC). The flux through polysulfone membranes decreased remarkably due to adsorption mainly caused by hydrophobic interactions between surfactant and membrane material. The decline of solution flux for cellulose acetate membranes was not as serious as that for polysulfone membranes because of hydrophilic properties of cellulose acetate membranes. The surfactant rejections for the cellulose acetate membranes increased with decreasing membrane pore size and with increasing the hydrophobicity of surfactant. On the other hand the surfactant rejections for polysulfone membranes showed totally different rejection trends with those for cellulose acetate membranes. The surfactant rejections for the polysulfone membranes depend on the strength of hydrophobic interactions between surfactant and membrane material and molecular weight of surfactants.     

Fabrication of nano-scale liposomes containing doxorubicin using Shirasu porous glass membrane

Nano-scale liposomes were successfully produced using a Shirasu porous glass (SPG) membrane emulsification technique. Primary liposomes prepared by a film-hydration method were treated using SPG membranes with different pore sizes (2.0, 1.0, 0.7, 0.5, and 0.2 μm) for control over the liposome size. The liposome sizes were evaluated using a dynamic light scattering method and their morphologies were observed by optical microscopy and transmission electron microscopy. As the passage number of liposomes through SPG membrane increased, the size and its distribution of the liposomes gradually decreased. A smaller pore size of the SPG membrane and a higher applied pressure resulted in liposomes with a smaller size. After the preparation of nano-scale liposomes containing ammonium sulfate (AS), doxorubicin (DOX) was encapsulated in the liposomes by a remote loading method, where AS served as a precipitant for DOX. The encapsulation efficiency of the DOX was maximized up to 94% when the concentrations of AS and DOX were 250 and 0.045 mM, respectively. We have obtained the release profiles of the liposomes with different sizes. As shown below, liposomes with smaller size exhibited a faster release profile of drug due to the large surface area. These nano-scale liposomes encapsulating an anti-cancer drug can potentially be employed as drug delivery vehicles for intravenous injection.     

Formation of pore‐filled microfiltration membranes using a combination of modified interfacial polymerization and grafting

A novel method of fabricating pore‐filled membranes has been developed by coating a hydrophobic polyolefinic microfiltration membrane with polyethylenimine (PEI) to produce a chemically active surface. An evaporative coating technique was used to coat the internal surface of a polyolefinic membrane with PEI in chloroform (CHCl₃). The coated PEI was then crosslinked by naphthalene‐1,4‐disulfonyl chloride in carbon tetrachloride (CCl₄). The incorporation of the PEI coating changed the properties of the base membrane from hydrophobic to relatively hydrophilic; the nitrogens could be titrated, and the coating could not be washed out. 4,4′‐Azo‐bis(4‐cyanovaleryl chloride), a heat‐sensitive radical source, was incorporated into the coated membrane. The coated membrane, with incorporated azo compound, was heated to 75 °C in the presence of acrylic acid, 4‐(vinylpyridine), or styrene to give the corresponding grafted, pore‐filled membranes. The membranes exhibited hydraulic fluxes and pH valve effects consistent with molecular brushes grafted within the pores of the membranes. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 40: 242–250, 2002     

亲水膜的表面改性及在膜蒸馏中的应用

膜的微孔性和疏水性是水溶液膜蒸馏的两个基本条件,迄今人们均采用疏水性高分子材料制成疏水微孔膜用于膜蒸馏研究。本文采用辐照接枝聚合和等离子体表面聚合的方法,将亲水的醋酸纤维素微孔膜和硝酸纤维素微孔膜表面疏水化改性,成功地用于膜蒸馏研究,大大扩展了疏水微孔膜的材料来源。实验结果表明,亲水膜表面改性得到的疏水膜,其膜蒸馏性能不低于疏水材料制成的膜,尤其是等离子体聚合法可以实现多种特殊单体在多孔的材料表面聚合,成为制备高性能疏水微孔膜的有效手段,为膜蒸馏的深入发展和实用化创造了有利条件。     

Separation of cells and proteins from fermentation broth in a shear-enhanced cross-flow ultrafiltration module as the first step in the refinement of lactic acid

A shear-enhanced, cross-flow ultrafiltration module was used to separate cells and proteins from the fermentation broth. Three (fermented) media were studied: rich medium, rich medium with hydrolytic enzymes added after fermentation, and wheat flour hydrolysate. To find a membrane with as high a flux as possible, but still capable of separating cells and proteins from the lactic acid containing broth, the performance of three hydrophilic membranes of varying cutoffs (10,000, 20,000, and 30,000) and one hydrophobic membrane (cutoff 25,000) was investigated. The proteins produced by the lactic acid bacteria during fermentation and the hydrolytic proteins were retained by the hydrophilic membrane with a cutoff of 20,000, whereas wheat flour proteins were detected in the permeate. In the permeates from the hydrophobic membrane (cutoff 25,000), almost no proteins were detected. The flux of the whole-wheat flour hydrolysate was significantly lower than that of rich medium, for both the hydrophilic and the hydrophobic membranes. The flux was, in all cases, higher for the hydrophilic membrane (12–85 L/[m²·h], depending, on which medium was treated) than for the hydrophobic one (8–45 L/[m²·h]), even though the nominal cutoffs of the hydrophobic and hydrophilic membranes were almost the same. However, the difference in flux was smaller when the whole-wheat flour hydrolysate was processed (12 vs 8 L/[m²·h]) than when the rich medium was processed (85 vs 45 L/[m²·h]). Protein retention was higher for the hydrophobic membrane than for the hydrophilic membrane (cutoff 20,000) owing to blocking of the pores by proteins adsorbed on to the hydrophobic membrane surface.     

不同浸润性多孔电极表面的气泡行为

采用氢气模板法制备了具有多孔结构的电极; 通过改变电镀电流密度和电镀时间实现了电极表面多孔结构孔径和分布的控制; 通过改变表面化学组成有效调控了电极表面的浸润性质. 比较了具有不同微观结构和表面化学组成的电极在给定条件下电解水过程中气泡的产生及行为机制. 实验结果表明: 相对于亲水的多孔电极, 疏水的多孔电极表面能够黏附气泡, 更易倾向于形成稳定的气膜; 多孔结构对于亲水电极表面气泡行为的影响比对疏水电极表面气泡行为的影响更为显著; 与没有多孔结构的亲水电极相比, 具有多孔结构的亲水电极表面产生的气泡数量多, 速率快; 与较小孔径的多孔亲水电极相比, 较大孔径的多孔亲水电极表面产生气泡速率快且黏附气泡数量少. 该研究结果为微气泡减阻电极的设计提供了理论依据.     

Facilitated transport of olefin through solid PAAm and PAAm-graft composite membranes with silver ions

Solid poly(acrylamide) (PAAm) composite membranes containing silver ions have been investigated for olefin/paraffin separation. The propylene permeance increased significantly for a solid PAAm/AgBF₄ composite membrane with increasing loading amount of silver ions. Silver ions in solid PAAm form reversible complexes with propylene, resulting in the facilitated transport of propylene. The propylene selectivity of 100 over propane was obtained when the mole ratio of silver ions to acrylamide unit was 1. This high separation performance would be obtained predominantly because of the high loading of the propylene carrier, silver ions. PAAm-graft/AgBF₄ composite membranes were prepared in order to improve the gas permeance. Introduction of PAAm grafts on a polysulfone microporous membrane surface was confirmed by FT-IR spectroscopy. The propylene permeance was increased through the PAAm-graft/AgBF₄ membranes compared to that through of the PAAm/AgBF₄ composite membranes, indicating the formation of ultra-thin top layer.     

1-正辛基-3-甲基咪唑六氟磷酸盐离子液体对聚砜分离膜的结构控制及其作用机理

以1-正辛基-3-甲基咪唑六氟磷酸盐[C8mim][PF6]作为膜结构控制剂,采用相转化法制备具有不同孔结构的聚砜分离膜.随着[C8mim][PF6]含量的增大,聚砜膜的孔结构从典型的不对称指状孔结构、高度拉长的大孔结构、典型的大空穴,变化至海绵状孔结构,离子液体[C8mim][PF6]在聚砜膜制备中表现出孔结构控制、增塑作用.通过能谱分析表明,[C8mim][PF6]在所制备的聚砜膜中存在部分的保留,通过水与聚砜膜表面接触角的测定,[C8mim][PF6]在聚砜膜中的残留提高了膜的亲水性能.基于相分离过程的基本理论,探讨了疏水性[C8mim][PF6]在铸膜液相分离过程中孔结构形成的作用机理.研究表明,[C8mim][PF6]在铸膜液中含量越高,对于相分离的延时效应越大,体系更易发生延时分相.     

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography

Hydrophobic interaction membrane chromatography has gained interest due to its excellent performance in the purification of humanized monoclonal antibodies. The membrane material used in hydrophobic interaction membrane chromatography has typically been commercially available polyvinylidene fluoride. In this contribution, newly developed inverse colloidal crystal membranes that have uniform pores, high porosity and, therefore, high surface area for protein binding are used as hydrophobic interaction membrane chromatography membranes for humanized monoclonal antibody immunoglobulin G purification. The capacity of the inverse colloidal crystal membranes developed here is up to ten times greater than commercially available polyvinylidene fluoride membranes with a similar pore size. This work highlights the importance of developing uniform pore size high porosity membranes in order to maximize the capacity of hydrophobic interaction membrane chromatography.     

Negatively charged poly(vinylidene fluoride) microfiltration membranes by sulfonation

Negatively charged PVDF microfiltration membranes were prepared using direct sulfonation with chlorosulfonic acid. The effect of sulfonation on the surface chemical properties, morphology, pore size distribution, hydrophilicity, water uptake, pure water flux, fouling and rejection were investigated. As the sulfonation reaction time was furthered, the degree of sulfonation and ion-exchange capacity increased and the membranes became more hydrophilic due to introduction of sulfonyl groups to the membrane surface. Using X-ray photoelectron spectroscopy, the composition of sulfonyl group with respect to sulfur concentration increased with time. From the SEM and porosity measurements, both the untreated and treated membranes did not reveal a substantial change in its morphology. The pure water flux increased significantly having a decreasing intrinsic resistance trend with degree of sulfonation. Both fouling phenomena and rejection were enhanced, with fouling of charged poly(styrene sulfonic acid) molecules on the surface-modified membrane decreased and rejection values increased with increasing degree of sulfonation mainly due to the effective electrostatic repulsion between the negatively charged PSSA and the negatively charged membrane.     

The polymerization of acrylic acid in the presence of copolymers containing interacting and non-interacting groups

There has been a kinetic examination of the polymerization of acrylic acid in dilute aqueous solution in the presence of copolymers of vinyl pyrrolidone with acrylamide or styrene. In general, the characteristics of the polymerizations are very similar to those found in the presence of polyvinyl pyrrolidone homopolymer, but the definite differences, taken in conjunction with gravimetric data on the polymer complexes, can be explained by the fact that acrylamide is hydrophilic while styrene is hydrophobic. The use of the copolymers has permitted an assessment of the effect of dilution of monomer adsorbed on the interacting polymer.