Amino acids functionalized graphene oxide for enhanced hydrophilicity and antifouling property of poly(vinylidene fluoride) membranes

Herein, functionalized graphene oxide (GO) was prepared by the covalent functionalization with amino acids (lysine, glycine, glutamic acid and tyrosine) in this study. Zeta potential results demonstrated that covalent functionalization of GO with amino acids was favourable for their homogeneous dispersion in water and organic solvents. Based on the higher absolute value of zeta potential and the better dipersion stability of GO-lysine, the PVDF/GO-lysine hybrid membranes were then prepared via the phase inversion induced by immersion precipitation technique. SEM images showed a better pore diameter and porosity distribution on the PVDF/GO-lysine membrane surface. The zeta potential absolute value of the PVDF/GO-lysine membrane surface was higher than that of the virgin PVDF membrane. Furthermore, the PVDF/GO-lysine membranes surface exhibited good hydrophilicity. The water flux of PVDF/GO-lysine membranes can reach to two times of that of the virgin PVDF membrane. And the BSA adsorbed amount on PVDF/GO-lysine surface was decreased to 0.82 mg/cm² for PVDF/GO-lysine-8% membrane. Filtration experiment results indicated that the fouling resistance was significantly improved for the PVDF/GO-lysine membranes. As a result, lysine functionalized GO will provide a promising method to fabricate graphene oxide based hybrid membranes with effective antifouling property and hydrophilicity.     

Photografted thin polymer hydrogel layers on PES ultrafiltration membranes: characterization, stability, and influence on separation performance

Highly fouling-resistant ultrafiltration (UF) membranes were synthesized by heterogeneous photograft copolymerization of two water-soluble monomers, poly(ethylene glycol) methacrylate (PEGMA) and N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl)ammonium betaine (SPE), with and without cross-linker monomer N,N'-methylene bisacrylamide (MBAA), onto a polyethersulfone (PES) UF membrane. The characteristics, the stability, and the UF separation performance of the resulting composite membranes were evaluated in detail. The membranes were characterized with respect to membrane chemistry (by ATR-IR spectroscopy and elemental analysis), surface wettability (by contact angle), surface charge (by zeta potential), surface morphology (by scanning electron microscopy), and pure water permeability and rejection of macromolecular test substances (including the "cutoff" value). The surface chemistry and wettability of the composite membranes did not change after incubating in sodium hypochlorite solution (typically used for cleaning UF membranes) for a period of 8 days. Changes in water permeability after static contact with solutions of a model protein (myoglobin) were used as a measure of fouling resistance, and the results suggest that PEGMA- and SPE-based composite membranes at a sufficient degree of graft modification showed much higher adsorptive fouling resistance than unmodified PES membranes of similar or larger nominal cutoff. This was confirmed in UF experiments with myoglobin solutions. Similar results, namely, a very much improved fouling resistance due to the grafted thin polymer hydrogel layer, were also obtained in the UF evaluation using humic acid as another strong foulant. In some cases, the addition of the cross-linker during modification could improve both permeate flux and solute rejection during UF. Overall, composite membranes prepared with an "old generation" nonfouling material, PEGMA, showed better performance than composite membranes prepared with a "new generation" one, the zwitterionic SPE.     

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.     

Hydrophilic modification of polyvinylidene fluoride membrane by blending amphiphilic copolymer via thermally induced phase separation

A new amphiphilic copolymer TD‐A is melt‐blended with polyvinylidene fluoride to fabricate hollow fiber membranes in order to improve the hydrophilicity and anti‐fouling property. Membrane samples with different blending ratios are prepared via thermally induced phase separation method. An optimum blending ratio of TD‐A (10 wt%) is determined by a series of characterizations to evaluate the effects of TD‐A contents on membrane properties. The hydrophilicity of the blended membrane samples increases with the increasing blending ratio, but excessive content of TD‐A in blended membranes can lead to structural defects and reduction of mechanical properties. TD‐A blended hollow fiber membrane with optimum blending ratio shows excellent bi‐continuous structure and high water flux. Membrane fouling is remarkably reduced due to the incorporation of TD‐A by static absorption and cyclic filtration tests of bovine serum albumin. Moreover, constant surface chemical compositions and stable flux during long‐term chemical cleaning demonstrate the hydrophilic stability of the blended membrane.     

Influence of membrane surface properties on initial rate of colloidal fouling of reverse osmosis and nanofiltration membranes

Recent studies have shown that membrane surface morphology and structure influence permeability, rejection, and colloidal fouling behavior of reverse osmosis (RO) and nanofiltration (NF) membranes. This investigation attempts to identify the most influential membrane properties governing colloidal fouling rate of RO/NF membranes. Four aromatic polyamide thin-film composite membranes were characterized for physical surface morphology, surface chemical properties, surface zeta potential, and specific surface chemical structure. Membrane fouling data obtained in a laboratory-scale crossflow filtration unit were correlated to the measured membrane surface properties. Results show that colloidal fouling of RO and NF membranes is nearly perfectly correlated with membrane surface roughness, regardless of physical and chemical operating conditions. It is further demonstrated that atomic force microscope (AFM) images of fouled membranes yield valuable insights into the mechanisms governing colloidal fouling. At the initial stages of fouling, AFM images clearly show that more particles are deposited on rough membranes than on smooth membranes. Particles preferentially accumulate in the “valleys” of rough membranes, resulting in “valley clogging” which causes more severe flux decline than in smooth membranes.     

Salt‐Induced Fabrication of Superhydrophilic and Underwater Superoleophobic PAA‐g‐PVDF Membranes for Effective Separation of Oil‐in‐Water Emulsions

Conventional polymer membranes suffer from low flux and serious fouling when used for treating emulsified oil/water mixtures. Reported herein is the fabrication of a novel superhydrophilic and underwater superoleophobic poly(acrylic acid)‐grafted PVDF filtration membrane using a salt‐induced phase‐inversion approach. A hierarchical micro/nanoscale structure is constructed on the membrane surface and endows it with a superhydrophilic/underwater superoleophobic property. The membrane separates both surfactant‐free and surfactant‐stabilized oil‐in‐water emulsions under either a small applied pressure (<0.3 bar) or gravity, with high separation efficiency and high flux, which is one to two orders of magnitude higher than those of commercial filtration membranes having a similar permeation property. The membrane exhibits an excellent antifouling property and is easily recycled for long‐term use. The outstanding performance of the membrane and the efficient, energy and cost‐effective preparation process highlight its potential for practical applications.     

Synthesis and property of a novel sulfonated poly(ether ether ketone) with high selectivity for direct methanol fuel cell applications

A novel membrane material based on random copolymer composed of poly(acrylonitrile-([3-(methacryloylamino)propyl]-dimethyl(3-sulfopropyl) ammonium hydroxide)) (PAN–MPDSAH) was synthesized by the water phase suspension polymerization. The zwitterionic PAN-based membranes were prepared through blending PAN and PAN–MPDSAH copolymer by a phase inversion method. The zwitterionic PAN-based membranes have higher hydrophilicity and wettability, and lower protein adsorption in comparison with the control PAN membrane. Ultrafiltration experiments revealed that membrane fouling, especially irreversible membrane fouling, for the zwitterionic PAN-based membranes is remarkably reduced due to the incorporation of zwitterionic PMPDSAH segments on the membrane surfaces. Moreover, the reversible membrane fouling during ultrafiltration process can be easily washed away by simple water cleaning. The zwitterionic PAN-based membranes can run for a long time and be reused without significant decrease of separation performance.     

Humic acid fouling during microfiltration

A major factor limiting the use of microfiltration for surface water treatment is membrane fouling by natural organic matter. The extent and mechanisms of humic acid fouling during microfiltration have been examined using stirred cell filtration experiments and scanning electron microscopy. The extent of fouling was strongly dependent on both the source and preparation of the humic acid solutions. The large flux decline observed during constant pressure microfiltration was caused by the formation of a humic acid deposit located on the upper surface of the membrane. Prefiltration of the humic acid solutions dramatically reduced the rate of fouling through the removal of large humic acid aggregates. The initial fouling in this system was determined almost entirely by the convective deposition of these large particles/aggregates on the membrane surface. This initial deposit accelerated the subsequent rate of humic acid fouling, possibly serving as a nucleation site for deposition of macromolecular humic acids.     

Direct contact membrane distillation of humic acid solutions

Direct contact membrane distillation process has been conducted for the treatment of humic acid solutions using microporous polytetrafluoroethylene and polyvinylidene fluoride membranes. The membranes were characterized in terms of their non-wettability, pore size and porosity. Water advancing and receding contact angles on the top membrane surfaces were measured. Experiments were also carried out employing pure water as feed at different mean temperatures and the water vapor permeance of each membrane was determined. Different humic acid concentrations in the feed solution, pH values and transmembrane temperature difference were tested. The direct contact membrane distillation technique is more adequate for the treatment of humic acid solutions than the applied pressure-driven separation processes, as lower membrane fouling was detected.     

Influence of membrane structure on fouling layer morphology during apple juice clarification

The flux behavior of 0.2 μm nylon, polysulfone (PS), polyvinylidene fluoride (PVDF) and polyethersulfone (PES) membranes was examined during dead-end microfiltration of commercial apple juice. On nylon membranes, a 0.1 μm thick surface fouling layer rapidly formed that acted as a secondary membrane. The colloidal particles retained by this surface layer aggregated to form a thick loose gel structure, producing an anisotropic fouling structure. In contrast, the 4 μm thick surface fouling layer of PES was slower to form and had a more open structure with a lower flux resistance per unit thickness. The morphology of the PES surface layer also did not differ dramatically from the loose gel structure that subsequently formed on top of this secondary membrane. The PS surface fouling layer was similar in structure to nylon whereas the PVDF layer more closely resembled that found with PES. The density of the surface fouling layer did not directly correlate to membrane surface hydrophobicity or pure water flux. Atomic force microscopy (AFM) indicated that surface roughness strongly influenced surface fouling layer morphology. The membrane surface appears to act as a template for the fouling process; therefore, smooth membranes (nylon and PS) produce a dense surface fouling layer whereas this same layer on rough membranes (PES and PVDF) is much more open. Consequently, the fluxes of PES and PVDF membranes are less affected by fouling formation.     

Hydrophilic modification of polyethersulfone membranes by low temperature plasma-induced graft polymerization

A complete and permanent hydrophilic modification of polyethersulfone (PES) membranes is achieved by argon plasma treatment followed by polyacrylic acid (PAA) grafting in vapor phase. Both Ar plasma treatment alone and post-PAA grafting rendered a complete hydrophilicity to the PES membranes. The hydrophilicity of the membranes treated with only the Ar plasmas is not, however, permanent. In contrast, the PES membranes treated with Ar plasma and subsequent acrylic acid (AA) grafting are permanently hydrophilic. High energy resolution X-ray photoelectron spectroscopy (XPS) confirmed the grafting of PAA to all surfaces of the membrane. Furthermore, water bubble point measurements remain unaffected. The pore sizes of the grafted membranes at higher grafting yield are slightly decreased. The modified membranes are less susceptible to protein fouling than the unmodified membranes and the pure water flux for the modified membranes was tremendously increased by plasma treatment. Furthermore, the modified membranes are easier to clean and required little caustic to recover permeation flux.     

Fouling of reverse osmosis membranes by biopolymers in wastewater secondary effluent: Role of membrane surface properties and initial permeate flux

Reverse osmosis (RO) is being increasingly used in treatment of domestic wastewater secondary effluent for potable and non-potable reuse. Among other solutes, dissolved biopolymers, i.e., proteins and polysaccharides, can lead to severe fouling of RO membranes. In this study, the roles of RO membrane surface properties in membrane fouling by two model biopolymers, bovine serum albumin (BSA) and sodium alginate, were investigated. Three commercial RO membranes with different surface properties were tested in a laboratory-scale cross-flow RO system. Membrane surface properties considered include surface roughness, zeta potential, and hydrophobicity. Experimental results revealed that membrane surface roughness had the greatest effect on fouling by the biopolymers tested. Accordingly, modified membranes with smoother surfaces showed significantly lower fouling rates. When Ca²⁺ was present, alginate fouled RO membranes much faster than BSA. Considerable synergistic effect was observed when both BSA and alginate were present. The larger foulant particle sizes measured in the co-existence of BSA and alginate indicate formation of BSA-alginate aggregates, which resulted in greater fouling rates. Faster initial flux decline was observed at higher initial permeate flux even when the flux was measured against accumulative permeate volume, indicating a negative impact of higher operating pressure.     

Cellulose acetate nanocomposite ultrafiltration membranes tailored with hydrous manganese dioxide nanoparticles for water treatment applications

Hydrous manganese dioxide (HMO) nanoparticles incorporated cellulose acetate (CA) composite ultrafiltration (UF) membranes are prepared with the aim of improving the water permeation and BSA contaminant removal. The HMO nanoparticles are synthesized from manganese ion and characterized by FT‐IR, XRD, and FESEM. The effect of variation of HMO on CA membranes is probed using FT‐IR, EDAX, contact angle, SEM, and AFM analysis to demonstrate their chemical functionality, hydrophilicity, and morphology. CA/HMO membranes are showing the enhancement in pure water flux (PWF), water uptake, porosity, hydrophilicity, fouling resistance, BSA rejection, and flux recovery ratio (FRR). CA‐1 membrane displayed higher PWF (143.6 Lm²h^?1), BSA rejection (95.9%), irreversible fouling (93.3%), and FRR (93.3%). Overall results confirmed that the CA/HMO nanocomposite UF membranes overcome the bottlenecks and shows potential for water treatment applications.     

Enhancing the antifouling property of polyethersulfone ultrafiltration membranes through surface adsorption-crosslinking of poly(vinyl alcohol)

An adsorption-crosslinking process of poly(vinyl alcohol) (PVA) was introduced to modify the surface of polyethersulfone (PES) ultrafiltration membranes for enhancement of their antifouling property. XPS and water contact angle measurement confirmed the obvious enhancement of surface hydrophilicity. Ultrafiltration results showed that the spreading of PVA chains over the hydrophobic membrane surface caused substantial but acceptable decrease on membrane flux. The fouling type analysis indicated that PVA adsorption effectively improved the antifouling property of PES membranes. With a PVA concentration of 0.5 wt% and three cycles of alternative adsorption-crosslinking, the total and irreversible fouling ratio of modified membranes were 0.38 and 0.22, respectively, much lower than those of control PES membrane (0.61 and 0.47), and the flux recovery ratio was increased accordingly. The long-term ultrafiltration experiment demonstrated the improvement of recycling property and the reliability of adsorption-crosslinking process.     

Preparation and characterization of modified polyphenylsulfone membranes with hydrophilic property for filtration of aqueous media

In the present research, the low water flux of polyphenylsulfone membranes was addressed, and a novel improvement in their water permeation and fouling resistance was achieved using polyethylene glycol (PEG) as the hydrophilic additive. Scanning electron microscopy and field emission scanning electron microscopy, atomic force microscopy, attenuated total reflection Fourier‐transform infrared spectroscopy, thermogravimetric analysis, and tensile test were applied for the investigation of membrane morphology, surface topography, surface chemical structure, thermal stability, and mechanical properties, respectively. Moreover, the relative hydrophilicity/hydrophobicity of the membranes was assessed via determination of membrane water uptake capacity and water contact angle. The membrane performance was studied and compared by determination of pure water flux and filtration of canned beans production wastewater as well as bovine serum albumin solution. The filtration results indicated a remarkable pure water flux and 100% turbidity rejection provided by the polyphenylsulfone/PEG 20 000 membrane. In addition, it was confirmed that the amount of residual PEG within the membrane was increased with increasing PEG molecular weight and concentration.     

Preparation of high density polyethylene/polyethylene-block-poly(ethylene glycol) copolymer blend porous membranes via thermally induced phase separation process and their properties

<正>High density polyethylene(HDPE)/polyethylene-block-poly(ethylene glycol)(PE-b-PEG) blend porous membranes were prepared via thermally induced phase separation(TIPS) process using diphenyl ether(DPE) as diluent.The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry(DSC).By varying the content of PE-b-PEG,the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy(SEM) and wide angle X-ray diffraction(WAXD). The chemical compositions of whole membranes and surface layers were characterized by elementary analysis,Fourier transform infrared spectroscopy-attenuated total reflection(FTIR-ATR) and X-ray photoelectron spectroscopy(XPS).Water contact angle,static protein adsorption and water flux experiments were used to evaluate the hydrophilicity,antifouling and water permeation properties of the membranes.It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes.In the investigated range of PE-b-PEG content,the PEG blocks could not aggregate into obviously separated domains in membrane matrix.More importantly,PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation,but also enrich at the membrane surface layer.Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity,protein absorption resistance and water permeation properties,which would be substantially beneficial to HDPE membranes for water treatment application.     

Preparation and characterisation of novel polysulfone membranes modified with Pluronic F-127 for reducing microalgal fouling

In this study, hydrophilic and fouling-resistant polysulfone (PS) membranes were fabricated using the phase inversion method to reduce membrane fouling caused by microalgal culture. The Pluronic F-127 polymer, which is used as a hydrophilic co-polymer, was added to the membranes to improve the membrane properties. Characteristic specifications of the fabricated membranes, such as morphology, surface roughness, chemical structures and hydrophobicity/hydrophilicity, were studied using scanning electron microscopy, atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDS), attenuated total reflection-fourier infrared (ATR-FTIR) spectroscopy and contact angle devices. According to the results obtained, it was observed that, with the increase of the Pluronic F-127 concentration in the membranes, the surface roughness of the membranes decreased and hydrophilicity and permeation fluxes increased notably. Furthermore, it was observed that the addition of the Pluronic F-127 polymer into the membranes reduced reversible/irreversible membrane fouling. Additionally, a characterisation of the fouled membranes was performed for the purpose of comprehensively understanding the membrane fouling mechanism caused by microalgal culture.     

PREPARATION OF HIGH DENSITY POLYETHYLENE/POLYETHYLENE-ΒLOCK- POLY(ETHYLENE GLYCOL) COPOLYMER BLEND POROUS MEMBRANES VIA THERMALLY INDUCED PHASE SEPARATION PROCESS AND THEIR PROPERTIES

High density polyethylene (HDPE)/polyethylene-Wock-poly(ethylene glycol) (PE-b-PEG) blend porous membranes were prepared via thermally induced phase separation (TIPS) process using diphenyl ether (DPE) as diluent. The phase diagrams of HDPE/PE-b-PEG/DPE systems were determined by optical microscopy and differential scanning calorimetry (DSC). By varying the content of PE-b-PEG, the effects of PE-b-PEG copolymer on morphology and crystalline structure of membranes were studied by scanning electron microscopy (SEM) and wide angle X-ray diffraction (WAXD). The chemical compositions of whole membranes and surface layers were characterized by elementary analysis, Fourier transform infrared spectroscopy-attenuated total reflection (FTIR-ATR) and X-ray photoelectron spectroscopy (XPS). Water contact angle, static protein adsorption and water flux experiments were used to evaluate the hydrophilicity, antifouling and water permeation properties of the membranes. It was found that the addition of PE-b-PEG increased the pore size of the obtained blend membranes. In the investigated range of PE-b-PEG content, the PEG blocks could not aggregate into obviously separated domains in membrane matrix. More importantly, PE-b-PEG could not only be retained stably in the membrane matrix during membrane formation, but also enrich at the membrane surface layer. Such stability and surface enrichment of PE-b-PEG endowed the blend membranes with improved hydrophilicity, protein absorption resistance and water permeation properties, which would be substantially beneficial to HDPE membranes for water treatment application.     

Membrane formation mechanism and permeation properties of a novel porous polyimide membrane

The transport properties of a novel porous fluorinated polyimide membrane fabricated by a wet phase inversion process were studied with a stirred dead‐end filtration cell. The porous membrane‐forming solvents were tetrahydrofuran (THF), acetone, N,N‐dimethylacetamide (DMAc), N‐methylpyrrolidone (NMP), N,N‐dimethylformamide (DMF), and dimethylsulfoxide (DMSO). The phase separation phenomena in a ternary system of polyimide/solvent/water were investigated from cloud point curves by a titration method and binary interaction parameters. Solvent–water demixing in the system has been found to play very important roles in determining the structure and surface morphology of the polyimide membrane. The porous fluorinated polyimide membranes showed pore sizes from 4 to 500 nm and permeation properties from ultrafiltration to a microfiltration range. In this study, we particularly focused on fouling of the polyimide membranes, because fouling decreases the flux and increases the resistance. Interestingly, the porous polyimide membrane showed excellent water flux recovery after water cleaning compared with that of the polyethersulfone (PSf) membrane, which suggest that for a 6FDA‐6FAP membrane, the protein–membrane and protein–protein interaction was not so strong compared with those in a PSf membrane. Copyright © 2002 John Wiley & Sons, Ltd.     

Surface modification of phenolphthalein poly(ether sulfone) ultrafiltration membranes by blending with acrylonitrile-based copolymer containing ionic groups for imparting surface electrical properties

Asymmetric ultrafiltration membranes were fabricated from the blends of phenolphthalein polyethersulfone (PES-C) and acrylonitrile copolymers containing charged groups, poly(acrylonitrile-co-acrylamido methylpropane sulfonic acid) (PAN-co-AMPS). From the surface analysis by XPS and ATR-FTIR, it was found that the charged groups tend to accumulate onto the membrane surface. This result indicated that membrane surface modification for imparting surface electrical properties could be carried out by blending charged polymer. Furthermore, with the help of a relatively novel method to measure membrane conduction, the true zeta potentials calculated on the basis of the streaming potential measurements were used to reflect the charge state of membrane surface. In addition, it was noteworthy that, from the profiles of zeta potential versus pH curves and the magnitude of zeta potentials, the determination of zeta potential was dependent not only on the electrical properties of membrane surface but also on its hydrophilicity. At last, based on a relatively elaborate study on the electrostatic interaction between the membrane surface and protein, it was found that these charged membranes could meet different demands of membrane applications, such as resisting protein fouling or protein separation, through adjusting solution pH value.