Modification of polysulfone hollow fiber ultrafiltration membranes using hyperbranched polyesters with different molecular weights

A series of hyperbranched polyesters (HBPEs) using trimethylolpropane (TMP) as a core were synthesized via an esterification reaction, and the molecular weights of these HBPEs were 1600, 2260, 3370, and 5170 g/mol, respectively. Then, these HBPEs were added into dope solutions to prepare PSf hollow fiber membranes via a wet‐spinning method. When the HBPE molecule weight increased from 1600 to 5170 g/mol, the initial viscosities of the PSf–HBPE–PEG400–DMAc dope solutions increased, and the shear‐thinning phenomenon of these dope solutions became increasingly obvious. When these dope solutions were immersed into the deionized water, the demixing rate increased with an increase in the HBPE molecule weight at first and then decreased; this results in the increase of membrane porosity and the coexistence of finger‐like and sponge‐like structures. With the addition of HBPE, the start pure water contact angle and the mean effective pore size of the membranes decreased, and the J_w increased. For the mechanical properties of the membranes, the breaking strength and the elongation of the membranes also increased. Copyright © 2015 John Wiley & Sons, Ltd.     

Modification of polysulfone ultrafiltration membranes with UV irradiation and hydrophilicity increasing agents

Hydrophobic polysulfone UF membranes were modified with UV irradiation and hydrophilicity increasing agents. The modifications were tested with 0.5% whey-protein solution and 0.05% lysozyme solution at pH 6 and with 0.05% bovine serum albumin solution at various pH values. UV irradiation increased flux and the hydrophilicity of the membranes. The flux increases obtained varied with pH and modification agents used and could be more than 400% compared to unmodified conditions without any loss in retention. The best retentions were obtained at pH values, where both the protein and the membrane had the same charge, and a strong electrostatic repulsion was obtained. The pores enlarged to fixed sizes, which depended on the sizes of the proteins and the range of double layer forces between proteins and membranes at different states of charge density.     

Preparation and properties of polysulfone/TiO2 composite ultrafiltration membranes

The influence of inorganic filler TiO₂ nanoparticles on the morphology and properties of polysulfone (PS) ultrafiltration membranes was investigated. PS/TiO₂ composite membranes were prepared by a phase‐inversion method. TiO₂ nanoparticles modified by sodium dodecyl sulfate were uniformly dispersed in an 18 wt % PS casting solution. The addition of TiO₂ resulted in an increase in the pore density and porosity of the membrane skin layer. The pore size distribution changed from the log‐normal distribution to the bimodal distribution because of the presence of TiO₂ nanoparticles, and some large pores were observed when the concentration of the filler was over 3 wt %. The skin layer was gradually thickened; meanwhile, the morphology sublayer changed from macrovoids to spongelike pores, in comparison with PS membranes without the filler. The addition of TiO₂ also induced increases in the hydrophilicity, mechanical strength, and thermal stability. The ultrafiltration experiments showed when the concentration of TiO₂ was less than 2 wt %, the permeability and rejection of the membrane was enhanced and then decreased drastically with a higher filler concentration (>3%). © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 879–887, 2006     

Effect of type of solvent and non‐solvents on morphology and performance of polysulfone and polyethersulfone ultrafiltration membranes for milk concentration

Polysulfone (PS) and polyethersulfone (PES) ultrafiltration membranes were manufactured from a casting solution of the polymer, polyvinylpyrrolidone (PVP) in various solvents [N,N‐dimethylacetamide (DMAc), N,N‐dimethylformamide (DMF) and 1‐methyl‐2‐pyrrolidone (NMP)] by immersing the prepared films in different non‐solvents [water, 2‐butanol, mixture of water and 2‐butanol, mixture of water and 2‐propanol (IPA) and mixture of water and 1‐butanol]. The influences of various solvents and non‐solvents on morphology and performance of the prepared membranes were analyzed by scanning electron microscopy (SEM) and separation experiments using milk as the feed. Copyright © 2005 John Wiley & Sons, Ltd.     

Rapid characterization of ultrafiltration membranes by scanning electron microscopy

Physicochemical properties of ultrafiltration membranes were studied by scanning electron microscopy. The membrane elemental composition (carbon, oxygen, and sulfur) was determined by energy dispersion analysis. The elements were shown to be homogeneously distributed along the membrane. A homogeneous pore distribution on the membrane surface was found after covering it with a thin gold layer. The pore sizes are 50 nm. The topographic analysis of the permeate-side of the membrane indicated its anisotropy.     

Micellar enhanced ultrafiltration of phenol in synthetic wastewater using polysulfone spiral membrane

The micellar enhanced ultrafiltration (MEUF) of phenol in synthetic wastewater using two polysulfone spiral membranes of 6- and 10-kDa molecule weight cut-off (MWCO) and cetylpyridinium chloride (CPC) as cationic surfactant was studied. The effects on the permeate flux, permeate and retentate concentrations of phenol and CPC of various factors in the practical application of MEUF were studied, including surfactant and phenol concentrations, retentate flux, operating pressure, temperature and electrolyte. It was found that these two membranes could adsorb free phenol so the concentration of permeate phenol was lower than that of free phenol. The retentate phenol concentration kept increasing, then decreased slightly with the increase of the feed CPC concentration. Retentate flux and temperature had great effect on the performance of MEUF, and operating pressure did not. The addition of sodium carbonate (Na₂CO₃) could increase the retentate phenol concentration and decrease the permeate concentrations of phenol and CPC significantly.     

Gas permeation properties of asymmetric carbon hollow fiber membranes prepared from asymmetric polyimide hollow fiber

Asymmetric carbon hollow fiber membranes were prepared by pyrolysis of an asymmetric polyimide hollow fiber membrane, and their mechanical and permeation properties were investigated. The carbon membrane had higher elastic modulus and lower breaking elongation than the polyimide membrane. Permeation experiments were performed for single gases such as H₂, CO₂, and CH₄, and for mixed gases such as H₂/CH₄ at high feed pressure ranging from 1 to 5 MPa with or without toluene vapor. The permeation properties of the carbon membranes and the polyimide membrane were compared. There was little change in the properties of the carbon membranes with a passage of time. The properties were hardly affected by the feed pressure, whether the feed was accompanied with the toluene vapor or not, because the carbon membranes were not affected by compaction and plasticization.     

Solvent-induced morphological change of microporous hollow fiber membranes

Microporous polyethylene hollow fiber membranes (EHF-1 and EHF-2) were subjected to solvent treatment, and the effects of this treatment on membrane morphology and permeating properties were studied. Membranes treated with various organic solvents exhibited enhanced permeability, enlarged pore size, and increased shrinkage in the longitudinal direction. These phenomena were found to depend on the surface tension of the solvent: the higher the surface tension of the solvent, the larger the change in morphology and permeation of the membrane. A mechanism to account for the effects of solvent treatment on the morphology of the membrane is proposed taking into consideration the influence of the type of solvent used for treatment. The enhanced morphological and permeation changes are ascribed to the formation of liquid bridges between two microfibrils of the membrane during drying followed by the deformation and adhesion of the adjacent microfibrils based on the surface tension of the solvent.     

Hemocompatibility and ultrafiltration performance of PAN membranes surface‐modified by hyperbranched polyesters

Maleic anhydride was grafted onto a polyacrylonitrile (PAN) membrane surface via ultraviolet irradiation. Then, hyperbranched polyester, with varying numbers of hydroxyl end‐groups (H20, H30, and H40), was grafted onto the PAN membrane surface by the reaction of hydroxyl groups with anhydride groups of maleic anhydride. The modified membranes were characterized by scanning electron microscopy, static water contact angle, and attenuated total reflectance‐Fourier transform infrared spectroscopy measurements. The modified membranes showed a higher water flux and better antifouling properties than pristine PAN membranes, and their hydrophilicity was significantly improved. Membrane biocompatibility was characterized by platelet adhesion, and the results indicate that the modified membranes exhibited good biocompatibility. Copyright © 2016 John Wiley & Sons, Ltd.     

Electrokinetic and permeation characterization of hydrolyzed polyacrylonitrile (PAN) hollow fiber ultrafiltration membrane

PAN membrane and hydrolyzed PAN membranes with the same pore size were used to investigate the relationship between the electrokinetic property and permeation performance by streaming potential measurement and ion exchange technology. SEM and FT-IR/ATR spectra were employed to analyze the reaction and the presence of the amide groups. The thickness of the polyacrylic acid (PAA) layer on the membrane surface measured by ion-exchange titration technology increased with the reaction time, and that on membrane hydrolyzed for 50 min could reach 10.8 nm. Streaming potential measurement was used to study the influence of the carboxylic and nitrile group on the membrane surface on their separation property. Zeta potential measured in pure water had close relationship with the permeation property. This measurement also proved that there was a maximum zeta potential between zero and the concentration tested. For the ionization or dissociation of the carboxylic group on the membrane surface, treated membranes had a more flexible zeta potential range than that of the untreated membrane in the pH range of 3–9. They were all negative in pure water and 1 g·L⁻¹ KCl solution, while the membranes hydrolyzed for 30 min and 50min had IEPs at pH 5.5 and 6.1 in 1 g·L⁻¹ MgCl₂ solution. Special inflection points of all the membranes were observed in AlCl₃ solution for the positive colloid structure of Al(OH)₃.     

Effect of chemical functionalization on the mechanical properties of polypropylene hollow fiber membranes

Chemical treatment of polymeric hollow fiber membranes (HFMs) is used to prepare their exterior surfaces for coatings. Typical treatments can cleave both C? C and C? H bonds of polypropylene, leading to lower mechanical strength of the fibers. This study evaluated the yield strength, maximum strain, ultimate tensile strength, and burst strength of HFMs treated with each of three common oxidizing reagents: ozone as a gas phase system, aqueous solutions of potassium persulfate, and ammonium persulfate for liquid phase systems. The yield strength and ultimate tensile strength of HFMs decreased continuously with increasing ozonation time. Batch treatments with aqueous oxidizing systems showed limiting values of the yield and ultimate tensile strengths with time. Swelling the hollow fibers with methanol prior to oxidation caused less reduction of the mechanical properties after persulfate treatment. Fibers pretreated with methanol showed lower losses of mechanical properties strength with aqueous oxidation systems. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1366–1373     

Downstream processing of lactic acid-whey permeate fermentation broths by hollow fiber ultrafiltration

Membrane filtration is a suitable method for cell harvesting and clarification of fermentation broths. Hollow fiber ultrafilters gave essentially 100% rejection ofL. bulgaricus cells from a whey permeate fermentation broth. A combination of low pressures and high velocity generally gave the best permeate flux. Fermentation media components (in this case, from the whey permeate) contributed significantly to fouling. Considering the pressure limitations of the current generation of asymmetric hollow fiber modules and the changes in physical properties of the fermentation broths, a cell concentration of 100–150 g/L could be obtained with the flux still relatively high (above 20LMH), although the chemical compatibility of the membrane module itself under long-term exposure to high acid conditions should be considered.     

The fabrication of hollow fiber membranes with double-layer mixed-matrix materials for gas separation

The concept of fabricating hollow fibers with double-layer mixed-matrix materials using the same polymeric matrix has been demonstrated for gas separation. Polyethersulfone (PES)–beta zeolite/PES–Al₂O₃ dual-layer mixed-matrix hollow fiber membranes with enhanced separation performance have been fabricated. This study presents an innovative approach of utilizing low cost PES and Al₂O₃ to replace expensive polyimides as the supporting medium for dual-layer mixed-matrix hollow fibers and eliminating interlayer de-lamination problems. The incorporations of 20 wt% beta zeolite in the outer selective layer and 60 wt% Al₂O₃ in the inner layer coupled with spinning at high elongational draw ratios yield membranes with an O₂/N₂ selectivity of 6.89. The presence of Al₂O₃ particles enables the membrane to retain its porous substructure morphology in the course of annealing above the glass transition temperature of PES. Moreover, spinning at high elongational draw ratios results in the re-distribution of Al₂O₃ particles towards both edges of the inner layer. Not only do the permeance and selectivity of the fibers increase, but also greater mechanical properties and lower degree of shrinkages are obtained. Therefore, the combination of PES–beta zeolite and PES–Al₂O₃ nanoparticles with a reasonable draw ratio may be another promising approach to produce hollow fibers with double-layer mixed-matrix materials.     

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.     

Microscopic behavior of polyvinylpyrrolidone hydrophilizing agents on phase inversion polyethersulfone hollow fiber membranes for hemofiltration

In some biomedical applications, hollow fiber membranes are highly demanded with desirably asymmetric structures, characterized by a dense selective inner skin with which the blood is in contact and supported by porous outer-layer. In this work, such membranes have been successfully prepared by appropriately adjusting membrane manufacturing parameters. Different molecular weights of polyvinylpyrrolidones (PVPs) were used as the hydrophilizing additives for membrane spinning in order to examine their underlying effects on membrane physicochemical properties, morphological structure, solute rejection behavior and hemofiltration performance. Numerous state-of-the-art characterizations on the resultant membranes showed that the hollow fiber membranes spun with the PVP having a molecular weight of 360K as the additive have the most hydrophilic, smooth and highly net negative charged inner surfaces. These membranes also exhibit the best hemofiltration performance in terms of the characteristically least fouling behavior with a normalized flux above 90%, the highest retention of serum albumin for more than 90%, and the best clearance for the simulated β₂-microglobulin toxin in blood waste.     

Self-assembly of inner skin hollow fiber polyelectrolyte multilayer membranes by a dynamic negative pressure layer-by-layer technique

In the past studies, electrostatic layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes (PEMMs). Till now, this method was mainly used to assemble flat sheet and tubular membranes. Since hollow fiber membrane has some advantages such as high-packing density, self-contained mechanical support and hence the consequent economical superiority, this study therefore seeked to assemble inner skin hollow fiber PEMMs by using a dynamic LbL adsorption technique. The assembly process was successfully accomplished by alternatively dynamically filtrating polyacrylic acid (PAA) and polyethyleneimine (PEI) on a hydrolyzed hollow fiber polyacrylonitrile (PAN) membrane under a negative pressure condition. In the case of pervaporation separation of 95 wt.% ethanol–water mixture (50 °C), the membrane obtained with only 4.5 and 6.5 bilayers had separation factor of 245 and 1338 while the permeate fluxes were 290 and 120 g/(m² h), respectively. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol were also investigated. Finally, scanning electron microscopy and atomic force microscopy clearly confirms a uniform and defect-free layer formed on the inner surface of hollow fiber support. Since different polyelectrolyte pairs could be used to assemble PEMMs for different uses, it was expected that the dynamic negative pressure LbL adsorption technique could also potentially be used to prepare many types of PEMMs in other fields.     

Performance optimization of hollow fiber reverse osmosis membranes. Part II. Comparative study of flow configurations

Sensitivity evaluation of overall performance of hollow fiber membranes was performed to study the effects of such operating parameters as pressure, packing density, and fiber diameter. It is shown that in a wide range of operating conditions, fiber productivity and selectivity as dependent upon hollow fiber length exhibit a similarity property. This is demonstrated in all three flow configurations of concurrent, countercurrent, and flow inside hollow fibers.     

Molecular elucidation of morphology and mechanical properties of PVDF hollow fiber membranes from aspects of phase inversion, crystallization and rheology

This study explores the fundamental science of fabricating poly(vinylidene fluoride) (PVDF) hollow fiber membranes as well as elucidates the correlation among membrane morphology, crystallinity and mechanical properties as functions of non-solvent additives and dope rheology in the phase inversion process. A series of non-solvents (i.e. water, methanol, ethanol, isopropanol) are used either as non-solvent additives in the dope or as a component in the external coagulant. Depending on the strength of the non-solvent, the phase inversion of semi-crystalline PVDF membranes is dominated by liquid–liquid demixing or solid–liquid demixing accompanying crystallization. As a result, the membrane morphology transforms from an interconnected-cellular type to an interconnected-globule transition type with lower mechanical strengths when adding water, methanol, ethanol, or isopropanol into the spinning dopes or into the coagulation bath. The crystallinity and size of spherulitic globules in the morphology are controlled by the amounts of non-solvents presented in the systems. The rheological behavior of dope solutions is explored and the relationship between elongation viscosity and mechanical properties has been elaborated. Analytical methods and molecular dynamics simulations are employed to provide insights mechanisms from the views of thermodynamic and kinetic aspects as well as the state of polymer chains involved in the phase inversion process.     

Separation and determination of seleno amino acids using gas chromatography hyphenated with inductively coupled plasma mass spectrometry after hollow fiber liquid phase microextraction

A new derivatization–extraction method for preconcentration of seleno amino acids using hollow fiber liquid phase microextraction (HF‐LPME) was developed for the separation and determination of seleno amino acids in biological samples by gas chromatography–inductively coupled plasma mass spectrometry (GC–ICP‐MS). Derivatization was performed with ethyl chloroformate (ECF) to improve the volatility of seleno amino acids. Parameters influencing microextraction, including extraction solvent, pH of sample solution, extraction time, stirring speed, and inorganic salt concentration have been investigated. Under the optimal conditions, the limits of detection (LODs) obtained for Se‐methyl‐selenocysteine (SeMeCys), selenomethionine (SeMet), and selenoethionine (SeEth) were 23, 15, and 11 ng Se l⁻¹, respectively. The relative standard deviations (RSDs) were 14.6%, 16.4%, and 19.4% for SeMeCys, SeMet, and SeEth (c = 1.0 ng ml⁻¹, n = 7), respectively, and the RSDs for SeMeCys, SeMet could be improved obviously if SeEth was utilized as the internal standard. The proposed method was applied for the determination of seleno amino acids in extracts of garlic, cabbage, and mushroom samples, and the recoveries for the spiked samples were in the range of 96.8–108% and 93.4–115% with and without the use of SeEth as internal standard. The developed method was also applied to the analysis of SeMet in a certified reference material of SELM‐1 yeast and the determined value is in good agreement with the certified value. Copyright © 2008 John Wiley & Sons, Ltd.