Antifouling ultrafiltration membrane composed of polyethersulfone and sulfobetaine copolymer

A new random copolymer was synthesized by reacting hydrophilic N,N-dimethyl-N-methacryloxyethyl-N-(3-sulfopropyl) (DMMSA) with hydrophobic butyl methacrylate (BMA) through a conventional radical polymerization. The as-prepared sulfobetaine copolymer (DMMSA–BMA) was blended with polyethersulfone (PES) to fabricate antifouling ultrafiltration membrane for BSA separation. The X-ray photoelectron spectroscopy analysis of blend membranes revealed concentration of sulfobetaine groups at the membrane surfaces that endowed the membrane with higher hydrophilicity and better antifouling property. For the membrane with 8.0 wt% DMMSA–BMA copolymer concentration (No. 5), irreversible fouling has been considerably reduced and the flux recovery rate of the blend membrane reached as high as 82.8%. Furthermore, the blend membrane could effectively resist BSA fouling in a wide pH range from 4.0 to 8.0.     

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.     

Protein-adsorption-resistance and permeation property of polyethersulfone and soybean phosphatidylcholine blend ultrafiltration membranes

Novel ultrafiltration membranes were prepared by simple blending of polyethersulfone (PES) and soybean phosphatidylcholine (SPC). X-ray photoelectron spectroscopy (XPS) and water contact angle measurements indicated SPC enrichment at the membrane surfaces. The immobilization and arrangement of PC groups at surfaces rendered the membranes more hydrophilic. BSA adsorption amount decreased from 56.2 μg/cm² for SPC-free PES membrane to 2.4 μg/cm² for PES/SPC blend membrane. The fouling-resistant property of the blend membranes was improved considerably with an increase of SPC content while the pure water permeation flux decreased remarkably. Using PEG/PVP mixture instead of PEG as pore-forming agent increased pure water flux of PES/SPC blend membrane to some extent.     

Effects of hypochlorite treatment on the surface morphology and mechanical properties of polyethersulfone ultrafiltration membranes

Polyethersulfone membranes are widely used for ultrafiltration and microfiltration especially in the dairy industry, but they are believed to degrade when exposed to the sodium hypochlorite solution that is used to sanitize the processing equipment. Such membranes were exposed to sodium hypochlorite for up to 25,000 ppm-day at 55 °C, and pH 9 and 12. Mechanical properties as measured by dynamic mechanical analysis and tensile strength did not change greatly, but surface properties measured by FTIR-ATR, field emission scanning electron microscopy and associated energy dispersive X-ray spectroscopy detected significant changes in the surface. Surface pitting was observed and was found to be most severe at pH 9. It was thought that pitting was the likely cause of degradation in performance of the membranes and that pits could act as stress raisers leading to cracking.     

The effect of heat treatment of PES and PVDF ultrafiltration membranes on morphology and performance for milk filtration

The flat sheet polyethersulfone (PES) and poly(vinylidene fluoride) (PVDF) membranes were prepared by immersion precipitation technique. The influence of hot air and water treatment on morphology and performance of membranes were investigated. The membranes were characterized by AFM, SEM, cross-flow filtration of milk and fouling analysis. The PES membrane turns to a denser structure with thick skin layer by air treatment at various temperatures during different times. This diminishes the pure water flux (PWF). However the milk permeation flux (MPF) was considerably improved at 100 °C air treatment for 20 min with no change in protein rejection. The smooth surface and slight decrease in surface pore size for air treated PES membrane at 100 °C compared to untreated membrane may cause this behavior for the membrane. The water treatment of PES membranes at 55 and 75 °C declines the PWF and MPF and increases the protein rejection. This is due to slight decrease in membrane surface pore size. The treatment of PES membrane with water at higher temperature results in a porous structure with superior performance. The fouling analysis of 20 min treated membrane indicates that the surface properties of 100 °C air treated and 95 °C water treated PES membranes are improved compared to untreated membrane. The SEM observation depicts that the morphology of air and water treated PVDF membranes was denser and smoother with increasing the heat treatment temperature. The 20 min air treated PVDF membranes at 100 °C and water treated at 95 °C exhibited the highest performance and antifouling properties.     

Improved protein-adsorption resistance of polyethersulfone membranes via surface segregation of ultrahigh molecular weight poly(styrene-alt-maleic anhydride)

A styrene-maleic anhydride (SMA) alternating copolymer with ultrahigh molecular weight (M_w > 10⁶) synthesized in super critical carbon dioxide (SC CO₂) medium was used as hydrophilic polymeric additive in the preparation of polyethersulfone (PES) membranes. The PES/SMA blend membranes were prepared by immersion precipitation process. X-ray photoelectronic spectroscopy (XPS) measurements confirmed that the hydrolyzed SMA preferentially segregated to membrane–coagulant interface during membrane formation. For the PES/SMA blend membranes, no big change was observed in the cross-sectional structure and the mechanical properties were well maintained after SMA addition except that a thicker top layer was formed. The surface morphology analysis by atomic force microscopy (AFM) showed that the membrane surface roughness increased with the added SMA amount. The results of water contact angle, water absorbance measurements and static protein adsorption experiments revealed that the surface enrichment of SMA endowed PES/SMA blend membranes with significantly improved surface hydrophilicity and protein-adsorption resistance.     

Modification of polyethersulfone membranes using terpolymers engineered and integrated antifouling and anticoagulant properties

In this study, random terpolymers of methoxy poly(ethylene glycol)‐poly(sodium styrene sulfonate‐co‐methyl methacrylate) (MPEG‐P(SSNa‐co‐MMA)) integrated with antifouling and anticoagulant properties were synthesized by atom transfer radical polymerization (ATRP) for the first time and confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), and gel permeation chromatography (GPC). The terpolymers with desired antifouling and anticoagulant segments were then used as amphiphilic additives to modify polyethersulfone membranes by an engineering blended approach. Water contact angle (WCA) results indicated that the surface hydrophilicity of the modified membranes enhanced. Protein ultrafiltration experiments showed that the antifouling ability of the modified membranes increased. In addition, the modified membranes showed decreased protein adsorption (bovine serum albumin, BSA), suppressed platelet adhesion, and prolonged activated partial thromboplastin time (APTT). Copyright © 2013 John Wiley & Sons, Ltd.     

Enhanced antifouling and anticoagulant properties of grafted biomolecule polyethersulfone membranes

Polyethersulfone (PES) has been widely used in membrane technology and used to purify water in water treatments application or as a dialyzer to purify blood in hemodialysis. In this work, PES was chemically modified by separately grafting two biomolecules, 4‐aminobenzenesulfonamide (ABS), and 4‐amino‐N‐(5‐methylisoxazol‐3‐yl)benzenesulfonamide (AMBS), on PES backbone, and these modified membranes were blended to unmodified PES, in 1:1 ratio, in order to obtain PES‐b‐PES‐ABS and PES‐b‐PES‐AMBS membranes. The first aim of this study is to measure the anticoagulant properties of the modified membrane by measuring the activated partial thromboplastin time (APTT) and prothrombin time (PT). The second aim of the study is to evaluate the antifouling properties of the modified PES membranes by examining its antimicrobial activity against two Gram‐negative bacteria, which are Pseudomonas aeruginosa (P. aeruginosa) and Escherichia coli (E. coli); two Gram‐positive bacteria, which are Bacillus subtilis (B. subtilis) and Staphylococcus aureus (S. aureus); and a fungus, which is Candida albicans (C. albicans). The results showed that grafting of ABS and AMBS improved overall the hydrophilicity properties of the modified PES membranes. PES‐b‐PES‐ABS membranes showed better anticoagulant properties with 13 seconds for PT and 38 seconds for APPT, in comparison with the control sample (pure plasma), which showed 12 seconds for PT and 30 seconds for APPT. For antimicrobial tests, both PES‐b‐PES‐ABS and PES‐b‐PES‐AMBS membranes did not show any antibacterial activity, but when zinc oxide (ZnO) nanoparticles were added to the modified PES membranes in concentrations between 3% to 5% w/w, PES‐b‐PES‐ABS‐ZnO (M‐4 and M‐5), and PES‐b‐PES‐AMBS‐ZnO (M‐8 and M‐9) nanocomposite membranes showed antibacterial activity against P. aeruginosa and S. aureus.     

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.     

Nanostructured polyethersulfone membranes for dye and protein separation: Exploring antifouling role of holmium (III) molybdate nanosheets

Nanostructured polymer membranes are nowadays of crucial importance in achieving antifouling properties. Nanomaterials with tunable composition, size, and morphology, surface modification and functionality offer unprecedented opportunities for efficient wastewater treatment. In this work, the effect of holmium (III) molybdate (Ho₂MoO₆) nanomaterial as a new nanofiller on preparation of nanostructured polyethersulfone (PES) mixed matrix membranes was examined in terms of hydrophilicity, membrane morphology, permeability, dye and protein separation and antifouling property. The Ho₂MoO₆ nanosheets were synthesized and characterized by FTIR, XRD, and FESEM and used in different amounts in PES matrix. The pore size and the membrane porosity increased with Ho₂MoO₆ loading. The nanocomposite membranes showed enhancement in hydrophilicity, antifouling properties, dye rejection and permeability. The remarkably pure water flux (195 L/m²h at 3 bar) and 92.3% flux recovery after bovine serum albumin (BSA) filtration were obtained for the membrane mixed with 2 wt% Ho₂MoO₆ compared to 95 L/m²h and 75.2% obtained for the bare PES, respectively. Moreover, significantly high rejection of Acid Red 125 (95 ± 1%) was achieved. Thus, the experimental results established the potential efficiency of the novel nanocomposite membrane for the separation applications.     

Chiral separation of phenylalanine in ultrafiltration through DNA-immobilized chitosan membranes

Ultrafiltration experiments for the chiral separation of racemic phenylalanine were performed with DNA-immobilized chitosan membranes having various pore sizes. Atomic analysis on the membranes showed that the chitosan membranes covalently bound six times more DNA than the cellulose membranes used in our previous study [A. Higuchi, Y. Higuchi, K. Furuta, B.O. Yoon, M. Hara, S. Maniwa, M. Saitoh, K. Sanui, Chiral separation of phenylalanine by ultrafiltration through immobilized DNA membranes, J. Membr. Sci. 221 (2003) 207–218]. d-Phenylalanine preferentially permeated through DNA-immobilized chitosan membranes with a pore size <6.4 nm [molecular weight cut-off (MWCO) <67,000]. The binding affinity of a specific enantiomer due to the pore size of the DNA-immobilized membranes regulated the preferential permeation of the enantiomer through the membranes. l-Phenylalanine was adsorbed on the DNA-immobilized chitosan membranes with a pore size <6.4 nm (MWCO < 67,000), while there was little difference between the adsorption of d-phenylalanine and l-phenylalanine on the membranes with a pore size >6.4 nm (MWCO > 67,000). The DNA-immobilized chitosan membranes were categorized as channel type membranes.     

An enzymatic approach to the cleaning of ultrafiltration membranes fouled in abattoir effluent

Membrane fouling severely curtails the economical and practical implementation for the purification of biologically related process streams such as abattoir effluent (Jacobs, WRC Report no. K5/362, 1991, Pretoria, South Africa [1]). Mechanical and chemical removal of foulants usually lead to membrane damage and additional pollution. Enzymes, specific for the degradation of proteins and lipids, were tested as key components of biological cleaning regimes for membranes fouled in abattoir effluent. Fouling of polysulphone membranes was assessed as previously described by Maartens et al. (J. Membrane Sci., 119 (1996) 1 [2]) and optimal enzyme concentrations and incubation times were determined for the different preparations. The ability of each cleaning agent to remove adsorbed protein and lipid material, as well as their ability to restore the water-contact angle and the pure-water flux of the fouled membranes, were determined and compared. These variables were also used to compare the cleaning efficiency of enzymatic cleaning agents with conventional chemical agents under optimal conditions. The enzymes and enzyme detergent mixtures were effective cleaning agents and the pure-water flux of statically fouled membranes could be restored by treatment with these agents.     

Modification of polysulfone membranes 4. Ammonia plasma treatment

The effect of NH₃ and NH₃/Ar plasma on ultrafiltration polysulfone membranes have been studied. Results of contact angle, FTIR-ATR and X-ray photoelectron spectroscopy experiments clearly showed that both plasmas introduced hydrophilic, nitrogen- and oxygen-containing moieties on the polymer surface and that NH₃/Ar plasma was more efficient. That plasma was also more aggressive--signs of strong etching could be seen on the SEM pictures. Redeposition of etched material seemed to take place inside the pores. On the contrary, ammonia plasma was soft and caused cleaning the surface and pores enlargement. Performance of ammonia plasma modified membranes was greatly improved and independent on solution pH. The last observation proved amphoteric character of the surface. NH₃/Ar plasma treatment gave membranes of acidic surface and filtration indices not so good as for ammonia plasma.     

A new route for the fabrication of TiO2 ultrafiltration membranes with suspension derived from a wet chemical synthesis

Titania ultrafiltration membranes were successfully fabricated by a new route, which was directly derived from the nanoparticles suspension that was the intermediate product prior to dry and calcine in the synthesis of nanoparticle by a wet chemical method. The morphology and the crystal structure of the prepared membrane were analyzed by SEM and XRD. The effect of various dipping time on the membrane thickness was investigated. The rejection of the bovine serum albumin (BSA, 67,000 Da) was used to evaluate the separation characteristics of these membranes, and the relationship between the dipping time and the optimization thickness of the membrane was built on the base of the data of the pure water flux. SEM images showed that the surface of the membrane was defect-free and XRD revealed that the titania crystalline phase was pure anatase. The membrane thickness increased linearly with the square root of the dipping time and the dipping time of 30 s was necessary to form a defect-free titania layer on the top of supports. The titania layer derived from the dipping time of 30 s could be of thickness of 5.9 μm and an average pore size of 60 nm. The pure water permeability of the membrane was 860 × 10⁻⁵ L/(m² h Pa) (860 L/(m² h bar)), and the BSA rejections of the membranes prepared reached to 90% after 20 min running.     

The effects of flow angle and shear rate within the spinneret on the separation performance of poly(ethersulfone) (PES) ultrafiltration hollow fiber membranes

The effects of dope flow rate and flow angle within a spinneret during spinning hollow fiber membranes on the morphology, water permeability and separation performance of poly(ethersulfone) ultrafiltration hollow fiber membranes were investigated. For this purpose, two spinnerets with different flow angles were designed and used. The dope solution, containing polyethersulphone (PES)/N-methyl-2-pyrrolidone (NMP)/diethylene glycol (DG) with a weight ratio of 23/41/36, which was very close to its cloud point (binodal line), was used in order to speed up the coagulation of nascent fibers so that the relaxation effect on molecular orientation was reduced. The wet-spinning process was purposely chosen to fabricate the hollow fibers without extra drawing. Therefore, the effects of gravity and elongation stress on fiber formation could be significantly reduced and the orientation induced by shear stress within the spinneret could be frozen into the wet-spun fibers. Experimental results suggest that higher dope flow rates (shear rates) in the spinneret produce UF hollow fiber membranes with smaller pore sizes and denser skin layers due to the enhanced molecular orientation. Hence, the pore size and the water permeability decrease, but the solute separation increases. Hollow fibers spun from a conical spinneret have smaller mean pore sizes with larger geometric standard deviations, thus exhibiting lower water flux and greater solute separation than hollow fibers spun from a traditional straight spinneret. In addition, SEM studies indicate macrovoids response differently for the 90° straight and 60° conical spinnerets when increasing the dope flow rate. Macrovoids can be significantly suppressed and almost disappear in the 90° spinneret at high dope flow rates. This phenomenon cannot be observed for the 60° conic spinneret.     

Simulation of an ultrafiltration process of bovine serum albumin in hollow-fiber membranes

This work presents a numerical simulation of an ultrafiltration process of bovine serum albumin in solution, using hollow-fiber membranes. Such membranes are constituted of tiny polymer cylinders disposed in a tube-and-shell arrangement. The concentrate flows through the interior of the fibers and the pure solvent is recovered in the shell, assuming perfect solute rejection. In modeling the process, the flow of concentrate inside the fibers was considered to be laminar, with constant density, viscosity and solute diffusivity. Axial diffusion and angular effects were ignored. The model combines the effect of concentration polarization and adsorption, which are the two main limiting phenomena in ultrafiltration processes. The pressure on the shell side was considered constant and inside the fibers a linear pressure profile, dependent on the axial position, was adopted. The solution of the problem was achieved with the method of orthogonal collocation, with adequate choice of the weight function in the radial direction. In the axial direction, a finite-difference method was used. The numerical results were compared with experimental data available in the literature.     

Surface modification of polyethersulfone membranes by blending triblock copolymers of methoxyl poly(ethylene glycol)-polyurethane-methoxyl poly(ethylene glycol)

The surface of polyethersulfone (PES) membrane was modified by blending triblock copolymers of methoxyl poly(ethylene glycol)-polyurethane-methoxyl poly(ethylene glycol) (mPEG-PU-mPEG), which were synthesized through solution polymerization with mPEG Mns of 500 and 2000, respectively. The PES and PES/mPEG-PU-mPEG blended membranes were prepared through spin coating coupled with liquid-liquid phase separation. FTIR and (1)H NMR analysis confirmed that the triblock copolymers were successfully synthesized. The functional groups and morphologies of the membranes were studied by ATR-FTIR and SEM, respectively. It was found that the triblock copolymers were blended into PES membranes successfully, and the morphologies of the blended membranes were somewhat different from PES membrane. The water contact angles and platelet adhesion were decreased after blending mPEG-PU-mPEG into PES membranes. Meanwhile, the activated partial thromboplastin time (APTT) for the blended membranes increased. The anti-protein-fouling property and permeation property of the blended membranes improved obviously. SEM observation and 3-(4, 5-Dimethylthiazol-2-yl)-2, 5-diphenyl tetrazolium bromide (MTT) assay proved the surfaces of the blended membranes promoted human hepatocytes adhesion and proliferation better than PES membrane.     

Preparation and characterization of polyaniline/polysulfone nanocomposite ultrafiltration membrane

Novel nanocomposite membrane was prepared through the filtration of polyaniline (PANI) nanofiber aqueous dispersion with polysulfone (PS) ultrafiltration (UF) membrane. Scanning electron microscope (SEM) images showed that PANI nanofiber layer was formed on the PS membrane surface. Atomic force microscopy (AFM) analysis indicated that the nanocomposite membrane had rougher surface than the PS substrate membrane. Compared with the PS substrate membrane, the nanocomposite membrane had much better permeability for the good hydrophilicity of PANI nanofiber layer, and had almost the same rejection performance. In addition, the nanocomposite membrane had positive surface potential under acidic condition because PANI could be protonated easily by acid. During the filtration of BSA solution, the nanocomposite membrane showed much better antifouling performance than the substrate membrane for the hydrophilicity and steric hindrance effect of its nanofiber layer. Moreover, under acidic solution condition, strong electrostatic repulsion between PANI nanofibers and BSA existed and improved membrane antifouling performance further.     

Spatial distribution of foulants on membranes during ultrafiltration of protein mixtures and the influence of spacers in the feed channel

Using matrix assisted laser desorption ionisation mass spectrum (MALDI-MS), this study reports the observations of the fouling distribution and composition along the membrane channel after the membranes were subjected to ultrafiltration of protein mixture solution in a crossflow module with and without spacer. In the fouling layer on a fully retentive membrane, the protein components with high molecular weight has higher presentation after 2 h of filtration and the presentation reduced to be lower than the smaller components after 6 h of filtration due to protein exchange and displacement phenomena in deposition layer caused by the differences in structure and diffusivity of different components. The protein exchange and replacement in the deposition layer was also observed on partial retentive membrane using a sequential fouling procedure. Fouling distribution along the membrane channel with spacer inserted in the module was more uniform and the flux was higher than that without spacer despite higher protein deposition observed in some cases.     

Use of atomic force microscopy and fractal geometry to characterize the roughness of nano-, micro-, and ultrafiltration membranes

Membrane surface roughness alters the surface area accessible to foulants and may influence macroscopic properties, such as zeta potential. It is usually quantified by atomic force microscopy (AFM) at a single scan size. This would be appropriate if roughness is independent of scale. This study shows that the root-mean-square roughness, R_RMS, is scale (or scan size, L × L) dependent through the power law R_RMS = AL^3−D. The coefficient, A, is the roughness at a scan size of 1² μm². D is the fractal dimension that relates the increase in roughness to the increase in scan size. Values for A and D were determined for a range of micro- and ultrafiltration membranes using an AFM scan series covering at least three orders of magnitude in L. They were also determined for nanofiltration membranes by re-analysis of data in the literature. The results suggest that using the power law expression allows potentially greater discrimination among membrane types and provides a way to quantify membrane roughness over a range of scales. It was further observed that the coefficients A and D of PVDF membranes showed positive and negative correlations, respectively, with the molecular weight cut-off. Additionally, zeta potentials of PVDF membranes measured by the tangential streaming potential method became more negative with increasing A and more positive with increasing D, suggesting possible significant influence of roughness on hydrodynamic transport of ions.