Preparation of poly(ether sulfone) hollow fiber UF membrane for removal of NOM

In this study, a high performance poly(ether sulfone) (PES) hollow fiber ultrafiltration (UF) membrane has been prepared for removal of natural organic matter (NOM). The membrane was spun from a dope solution containing PES/poly (vinyl pyrrolidone) (PVP 40K)/N‐methyl‐2‐pyrrolidone (NMP) by using a wet‐spinning process. Characterization of the membrane in terms of pure water flux, molecule weight cut‐off (MWCO), and retention for a model humic acid (HA) were conducted, and the fouling resistance was analyzed. The experimental results showed that the membrane had a pure water permeability of 20 × 10^?5 L m^?2 h^?1 Pa^?1 and a nominal MWCO of 6000 Da. The results also showed that the membrane retention for humic acid was over 97% and both productivity and selectivity for HA increased with increasing feed velocity. The PES membrane in this study exhibited a much lower fouling tendency than the commercial polysulfone membrane. SEM images revealed that the membrane had an outer dense skin and a porous inner surface. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 430–435, 2006     

Pertraction of cations in a hybrid membrane system containing soluble polymeric ionophores

A hybrid membrane system composed of two insoluble cation‐exchange membranes (Nafion) and a liquid membrane in between was studied. A series of organic and aqueous liquid membranes containing soluble polymers as macromolecular ionophores (macroionophores) was prepared and tested. The pertraction (membrane‐transport) characteristics of poly(ethylene glycol) and its ionizable derivatives, including as poly[poly(oxyethylene) phosphate] (PPOEP) and di‐[ω‐methoxy poly(oxyethylene)] phosphate, were measured and are discussed as dependent on the composition and molecular mass of a macroionophore. The liquid membrane composed of PPOEPs dissolved in dichloroethane combined the cation‐exchange properties with neutral coordination functionalities introduced by the poly(oxyethylene) backbone of this ionophore. The overall fluxes, facilitation factors, and the membrane system selectivity were measured in the carrier‐mediated pertraction of transient metal cations (Cu²⁺, Zn²⁺, Mn²⁺, Co²⁺, and Ni²⁺). PPOEP could facilitate the pertraction of Zn²⁺ and Cu²⁺ over Ni²⁺ and Co²⁺. In the case of an aquatic hybrid membrane system, high but nonselective ionic fluxes were observed. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 99–109, 2002; DOI 10.1002/app.10263     

Synthesis and characterization of PES/PSF/PEG by immersion precipitation for Mediterranean seawater desalination by FO membrane

In the present study, a simple, inexpensive, nontoxic, and environmentally friendly polyethylene glycol (PEG) polymer was used to enhance the hydrophilicity of the forward osmosis (FO) membrane using various PEG concentrations as a pore forming agent in the casting solution of polyethersulfone/polysulfone (PES/PSF) blend membranes. A nonwoven PES/PSF FO blend membrane was fabricated via the immersion precipitation phase inversion technique. The membrane dope solution was cast on polyethylene terephthalate (PET) nonwoven fabric. The results revealed that PEG is a pore forming agent and that adding PEG promotes membrane hydrophilicity. The membrane with 1 wt% PEG (PEG1) had about 27% lower contact angle than the pristine blend membrane. The PEG1 membrane has less tortuosity (which reduces from 3.4–2.73), resulting in a smaller structure parameter (S value) of 277 μm, due to the presence of open pores on the bottom surface structure, which results in diminished ICP. Using 1 M NaCl as the draw solution and distilled water as the feed solution, the PEG1 membrane exhibited higher water flux (136 L m⁻² h⁻¹) and lower reverse salt flux (1.94 g m⁻² h⁻¹). Also, the selectivity of the membrane, specific reverse salt flux, (J_s/J_w) showed lower values (0.014 g/L). Actually, the PEG1 membrane has a 34.6% higher water flux than the commercial nonwoven-cellulose triacetate (NW-CTA) membrane. By means of varied concentrations of NaCl salt solution (0.6, 1, 1.5, and 2 M), the membrane with 1 wt% PEG showed improved FO separation performance with permeate water fluxes of 108, 136, 142, and 163 L m⁻² h⁻¹. In this work, we extend a promising gate for designing fast water flux PES/PSF/PEG FO blend membranes for water desalination.     

Green and feasible fabrication of loose nanofiltration membrane with high efficiency for fractionation of dye/NaCl mixture by taking advantage of membrane fouling

Loose nanofiltration membrane emerges as required recently, since it is hard for conventional nanofiltration membrane to fractionate mixture of dyes and salts in textile wastewater treatment. However, the polymeric membranes unavoidably suffer from membrane fouling, which was caused by the adsorption of organic pollutants (like dyes). Normally, the dye fouling layer will shrink membrane pore size, thus resulting in flux decline and rejection increase. It is thought that membrane fouling may be a double-edged sword and can be an advantage if properly utilized. Thereby, loose nanofiltration membranes were constructed here by a green yet effective method to fractionate dyes/salt mixture by taking advantage of membrane fouling without using poisonous ingredients. A commercially available polyacrylonitrile (PAN) ultrafiltration membrane with high permeability was chosen as the substrate, and dyes were used to contaminate PAN substrate and formed a stable barrier layer when adsorption of dyes reached dynamic equilibrium. The resultant PAN-direct red 80 (DR80) composite membranes displayed superior permeability (~128.4 L m⁻² h⁻¹) and high rejection (~99.9%) to DR80 solutions at 0.4 MPa. Moreover, PAN-DR80 membranes allowed fast fractionation of dyes/sodium chloride (NaCl) mixture, which maintained a negligible dye loss and a low NaCl rejection (~12.4%) with high flux of 113.6 L m⁻² h⁻¹ at 0.4 MPa. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47438.     

Novel thin-film nanocomposite membrane with water-soluble polyhydroxylated fullerene for the separation of Mg2+/Li+ aqueous solution

Despite the prosperity of membrane technology, the separation efficiency for Mg²⁺/Li⁺ mixture is still far from satisfactory. Herein, a novel thin-film nanocomposite (TFN) membrane was developed by loading polyhydroxylated fullerene (PHF) via interfacial polymerization. The effects of the PHF dosages on the as-developed membranes were investigated comprehensively by XPS, SEM, AFM, contact angle measurements, as well as nanofiltration tests. The results revealed the TFN membrane containing 0.01% (w/v) PHF exhibited the optimum performances. The membrane showed a pure water flux of 6.7 L·m⁻²·h⁻¹·bar⁻¹ and salt rejections with the order of Na₂SO₄ (95.6%) > MgSO₄ (93.6%) > MgCl₂ (89.9%) > NaCl (22.6%) > LiCl (16.3%). The membrane not only presented a separation factor of 13.1 in separating Mg²⁺/Li⁺ mixtures, but also demonstrated excellent antifouling ability, which enables membrane regeneration without operation break, suggesting its great potentials in the recovery of Li⁺ from brine or seawater. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48029.     

A hydrogel-coated membrane for highly efficient separation of microalgal bio-lipid

A cross-linked hydrogel-coated membrane was fabricated to achieve simple but highly efficient separation of bio-lipids directly from an aqueous microalgal culture medium. The membrane is composed of a stainless steel membrane coated conformally with a cross-linked hydrogel, poly(2-hydroxyethyl methacrylate) (pHEMA), synthesized by a photo-initiated chemical vapor deposition (piCVD) process. The pHEMA-coated membrane has hydrophilicity and underwater-oleophobicity for efficient separation of a bio-lipid-in-hexane/water mixture by gravity. The conformal pHEMA film-coated membrane enables extremely high oil rejection performance with intrusion pressure of 6.1 kPa and water permeation flux of 6.5×10³ L m^-2 h^-1, with excellent separation efficiency greater than 98.0%.     

Transport of Iron and Cobalt Complex Ions through Liquid Membrane Mediated by Methyltrioctylammonium Ion with the Aid of Redox Reaction

Abstract

A new type of carrier-mediated metal transport through liquid membrane is presented. The system involves redox reactions rather than acid-base reactions which have often been utilized in metal transport systems. Iron ion was selectively transported and concentrated through the membrane via a chloride complex by use of a lipophilic quaternary ammonium ion, methyltrioctylammonium (MTOA, Q⁺), as a carrier. The two aqueous solutions of different redox potentials were separated by a polymer-supported liquid membrane in which MTOA · chloride (Q⁺·CI^?) was dissolved as the carrier. Iron(III) ion in hydrochloric acid media formed a FeCl₄ ^? type complex which was readily extracted to the organic membrane phase as an ion-pair complex Q⁺·FeCl₄ ^?. On contact with a reducing agent on the other side of the membrane, iron(III) was reduced to iron(II) and liberated into aqueous solution; the chloride complexes of iron(II) are too hydrophilic to stay in the membrane phase. On the other hand, cobalt ion was transported via nitrilotriacetic acid (NTA) complex by MTOA carrier in a similar manner to the iron transport. The nature of the transport reactions was studied under various operational conditions (redox agents, carrier and ligand concentration, pH, coexisting metals, etc.). The extension of these transport reactions to a water-in-oil-in-water type emulsion system as well as to a photoassisted transport system was studied.     

The determination of diffusion coefficients of counter ion in an ion exchange membrane using electrical conductivity measurement

Electrical conductivity experiments were carried out in a bi-ionic (chloride-nitrate) electrolyte with and without a permselective anion exchange membrane (ACS of Tokuyama Soda) at variable chloride/nitrate concentration. Diffusion coefficients of counter ions (Cl⁻ and NO₃⁻) in the membrane were determined from a mathematical model based on the Nernst-Planck diffusion-convection theory: the mean diffusion coefficients in the membrane were obtained by fitting the (conductivity vs. concentration) curves with the Nernst-Planck equation.     

Enhanced the antifouling and antibacterial performance of PVC/ZnO-CMC nanoparticles ultrafiltration membrane

Inorganic nanoparticles (NPs) have been employed in modification for polyvinyl chloride (PVC) membrane intrinsic hydrophobicity. Carboxymethyl chitosan (CMC), a natural organic matter, was used to relieve the agglomeration of zinc oxide (ZnO) NPs in the membrane matrix. In this paper, ZnO-CMC NPs were successfully prepared via co-precipitation approach, blended with PVC membranes, and the effect of ZnO-CMC NPs for the membrane properties was studied. The SEM and EDX confirmed excellent dispersion of ZnO-CMC NPs on the membrane surface. The enhanced hydrophilicity, porosity and inter-connected finger-like strcture of modified membranes confirmed by water contact angle and SEM. In addition, pure water flux of PVC/ZnO-CMC composite membrane was 107.36 L m⁻² h⁻¹ (PVC/ZnO-CMC (0.25 wt%)), which was higher than that of neat PVC membrane (83.11 L m⁻² h⁻¹). Importantly, the modified membranes exhibits lower static BSA adsorbtion because of the improved hydrophilicity, and a higher flux recovery rate (>90%) after three sequential filtration cycles. The antibacterial behavior of PVC/ZnO-CMC membrane was tested simply using Escherichia coli, and the results indicated that all composite membranes possess excellent antibacterial properties. Our work presents PVC/ZnO-CMC NPs composite membrane a promising future in wastewater treatment and antibacterial application.     

Permeability of poly-L-methionine membrane and its oxidized membrane to water vapor

The permeability of poly-L -methionine (PLM) membrane and its oxidized form to water vapor was studied. Permeability coefficients of the PLM membrane were large, of the order of 10^?7 cm³ (S.T.P.)·cm/cm²·sec·cm Hg. The sorption and permeation behavior of the PLM membrane was hydrophobic. The oxidized membrane was prepared by treating one or both sides of the PLM membrane with an aqueous solution of hydrogen peroxide. The membrane oxidized from one side is probably not layered but has a gradient of composition from one surface to the other. The amounts of water sorbed by the modified membrane increased with increase in oxidation time. The permeability coefficients of water vapor through the modified membrane were of the order of 10^?6 cm³ (S.T.P.)·cm/cm²·sec·cm Hg.     

Chemical and mechanical degradation of sulfonated poly(sulfone) membranes in vanadium redox flow batteries

A sulfonated poly(sulfone) (S-Radel^®) membrane with high proton conductivity and low vanadium ion permeability showed high initial performance in a vanadium redox flow battery (VRFB) but suffered mechanical and chemical degradation during charge/discharge cycling. The S-Radel membrane showed different degradation behavior in flow cell cycling and ex-situ vanadium ion immersion tests. When the membrane was immersed in aqueous V⁵⁺ solution, the sample cracked into small pieces, but did not degrade to any measurable extent in V⁴⁺ solution. During charge/discharge cycling in the VRFB cell, the membrane underwent internal delamination, preferentially on the side of the membrane that faced the positive electrode. A vanadium-rich region was observed near the membrane surface that experienced delamination and Raman spectroscopic analysis of the degraded surface indicated a slightly depressed 1026 cm^?1 band corresponding to a loss in the sulfonate SO₂ stretch intensity. Even though the S-Radel membrane underwent severe mechanical damage during the flow cell cycling, significant chemical degradation was not obvious from the spectroscopic analyses. For the VRFB containing an S-Radel membrane, an increase in membrane resistance caused an abnormal voltage depression during the discharge cycle. The reversible increase in membrane resistance and severe mechanical degradation of the membrane during cycling may be attributed to repeated formation and dissolution of particles inside the membrane. The mechanical stresses imposed by the particles coupled with a small amount of chemical degradation of the polymer by V⁵⁺ ions, are likely degradation mechanisms of the S-Radel membrane in VRFBs under high state-of-charge conditions.     

Preparation and characterization of chitosan/PEG/gelatin composites for tissue engineering

Chitosan scaffolds have gained much attention in tissue engineering. However, brittleness and low biodegradability limit scaffolds application, especially in use as guided tissue regeneration membranes (GTRm) in surgical operations. The first objective of this work is to improve the brittleness of the chitosan membrane, which is not desired for use via adding polyethylene glycol (PEG) to chitosan, and the second objective is to accelerate the degradation rate by blending gelatin with the binary chitosan‐PEG mixture. The addition of PEG softened the blend membrane in vision and in touch. The tensile compliant increased from 7.87 × 10^?3 (MPa^?1) for chitosan membrane to 3.63 × 10^?1 (MPa^?1) for chitosan‐PEG‐gelatin (CPG) membrane. Degradation results in vitro indicated that CPG membrane degraded faster and weight loss increased more significantly than chitosan membrane and the lowest tensile strength of CPG membrane could meet the requirement of the application. CPG membrane showed significant improvement in degradation and flexibility in comparison with the chitosan membrane. Cell adhesion, viability, and proliferation onto the external surface of CPG membrane with C2C12 cell had been evaluated in vitro and quantified by a methyl thiazolyl tetrazolium (MTT) reduction assay. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Separation of FFA from Partially Hydrogenated Soybean Oil Hydrolysate by Means of Membrane Processing

Different types of commercial porous and non-porous polymeric membranes have been investigated for their capabilities to separate free fatty acids (FFA) from hydrolysate of partially hydrogenated soybean oil. A regenerated cellulose (RC, PLAC) membrane exhibited the most prominent difference in rejection between FFA and glycerides and the highest flux (27 kg h⁻¹ m⁻²) in hydrolysate ethanol solution. The results also showed that, besides the pore size of membrane, the membrane flux depended largely on the property matching between membrane and solvent, as observed (40 kg h⁻¹ m⁻²) flux was achieved with methanol but no flux detected with hexane for PLAC. The polyvinyl alcohol (PVA, NTR-729 HF) and Polyamide (PA, NTR-759HR) membranes gave the second and third highest flux (10.1 and 5.7 kg h⁻¹ m⁻², respectively), where solute rejections for NTR-759HR were 95.9% for triacylglycerols (TG), 83.3% for diacylglycerols (DG); 87.7% for monoacylglycerols (MG) and 22.9% for FFA, respectively. A discontinuous membrane filtration using an RC membrane with ethanol changed the composition of hydrolysate from 32.2:34.2:7.9:25.7 TG/DG/MG/FFA to 47.8:36.0:10.2:6.0. The results from this work proved that FFA can be efficiently separated from a hydrolysis mixture of oil using an RC membrane in methanol and ethanol.     

Permeation of vanadium cations through anionic and cationic membranes

The permeability of four commercially available ion-exchange membranes, the cationic Nafion 125 (duPont) and Selemion CMV (Asahi Glass) membranes and the anionic Selemion AMV and DMV membranes, to vanadyl, VO²⁺, and vanadic, VO ₂ ⁺ , ions was studied. The results show that two important variables determine the usefulness of a membrane as a membrane separator in a redox cell. These are selectivity and membrane-electrolyte resistance. Only the DMV membrane was considered to meet the requirements of low permeability to vanadium cations and at the same time permitting H⁺ ions to go through the membrane, thereby providing a very low membrane-electrolyte resistance in the redox fuel cell.     

Sulfonated polyimide/chitosan composite membrane for vanadium redox flow battery: Membrane preparation,characterization, and single cell performance

A novel sulfonated polyimide/chitosan (SPI/CS) composite membrane was prepared from self‐made SPI (50% of sulfonation degree) through an immersion and self‐assembly method, which was successfully applied in vanadium redox flow battery (VRB). The proton conductivity of SPI/CS composite membrane is effectively improved compared to the plain SPI membrane. The VO²⁺ permeability coefficient across SPI/CS composite membrane is 1.12 × 10^?7 cm² min^?1, which is only one tenth of that of Nafion® 117 membrane. Meanwhile, the proton selectivity of SPI/CS composite membrane is about eight times higher than that of Nafion® 117 membrane. In addition, the oxidative stability SPI/CS composite membrane is superior to that of pristine SPI membrane. The VRB single cell using SPI/CS composite membrane showed higher energy efficiency (88.6%) than that using Nafion® 117 membrane, indicating that SPI/CS composite membrane is a promising proton conductive membrane for VRB application. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

EB‐crosslinked Polymer Electrolyte Membranes Based on Highly Sulfonated Poly(ether ether ketone) and Poly(vinylidene fluoride)/Triallyl Isocyanurate

In this study, crosslinked polymer electrolyte membranes for polymer electrolyte membrane fuel cell (PEMFC) applications are prepared using electron beam irradiation with a mixture of sulfonated poly(ether ether ketone) (SPEEK), poly(vinylidene fluoride) (PVDF), and triallyl isocyanurate (TAIC) at a dose of 300 kGy. The gel‐fraction of the irradiated SPEEK/PVDF/TAIC (95/4.5/0.5) membrane is 87% while the unirradiated membrane completely dissolves in DMAc solvent. In addition, the water uptake of the irradiated membrane is 221% at 70 °C while that of the unirradiated membrane completely dissolves in water at above 70 °C. The ion exchange capacity and proton conductivity of the crosslinked membrane are 1.57 meq g⁻¹, and 4.0 × 10⁻² S cm⁻¹ (at 80 °C and RH 90%), respectively. Furthermore, a morphology study of the membranes is conducted using differential scanning calorimetry and X‐ray diffractometry. The cell performance study with the crosslinked membrane demonstrates that the maximum power density is 518 mW cm⁻² at 1036 mA cm⁻² and the maximum current density at applied voltage of 0.4 V is 1190 mA cm⁻².     

Preparation and recovery of polysulfone affinity membrane with mercapto as chelating group for Hg2+ cations

Highly qualified homogeneous poly(benzylsulfone) plate affinity membrane with mercapto group (PSF‐SH) was prepared successively through reactions between chloromethyl polysulfone matrix membrane and thiourea, and then alkalic hydrolysis. The mercapto‐functionalized polysulfone affinity membrane was utilized for the adsorption of Hg²⁺ cations through the coordination of the mercapto group and Hg²⁺ cations, in which the effects of the morphological and the structure of the affinity membrane on the chelating properties were investigated. The chelating conditions, including concentration of Hg²⁺, and temperature and pH of the introductory solution had significant influence on the chelating capacity of PSF‐SH affinity membrane. The highest static and dynamic chelating capacity of PSF‐SH plate membrane for Hg²⁺ cations were 398 and 403 μg/cm² per membrane, respectively, which demonstrated that the resultant polymer membrane was a highly efficient affinity chromatography for Hg²⁺. The affinity membrane containing mercapto group can be conveniently recovered by dilute hydrochloric acid for coordination of Hg²⁺ cations, which would have wide application for the treatment of waste water containing heavy metal cations. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2514–2522, 2007     

Preparation of a modified crosslinked chitosan/polyvinyl alcohol blended affinity membrane for purification of His-tagged protein

Based on a crosslinked chitosan (CS)/polyvinyl alcohol (PVA) matrix membrane, an immobilized metal ion affinity membrane (IMAM) using Cu²⁺ and Ni²⁺ ions as affinity ligands was prepared for purification of the His-tagged recombinant protein. The affinity membrane possessed a favorable membrane structure including 1.39 μm average pore size and 0.33 mL·cm⁻²·s⁻¹ water flux under 0.08 MPa pressure at 25 °C. The Cu²⁺ and Ni²⁺ ions capacities immobilized on the IMAM were 155.6 and 137.3 μmol·disk⁻¹, respectively. The IMAM had an excellent specific affinity to His-tagged protein. About 10-fold purification factor for the model protein was obtained in a batch adsorption, and serine hydroxymethyl transferase could be purified to a single band in sodium dodecyl sulfate–polyacrylamide gel electrophoresis analysis from its crude extract solution with an affinity membrane cartridge by a dynamic purification process. This work provides a promising IMAM for the purification of His-tagged recombinant proteins. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47347.     

Preparation of crosslinked alginate composite membrane for dehydration of ethanol–water mixtures

The purpose of this article was to develop new membranes with a high selectivity and permeation rate for separation of an alcohol/water system. Crosslinked alginate composite membranes were prepared by casting an aqueous solution of alginate and 1,6‐hexanediamine (HDM) onto a hydrolyzed microporous polyacrylonitrile (PAN) membrane. The influence of hydrolysis of the support membrane and crosslinking agent content in a dense layer on the selectivity and flux was studied and it was shown that both could improve the separation performance of the composite membrane greatly. The countercation of alginate coatings as a dense separating layer also influenced the separation properties of the membrane, which was better for K⁺ than for Na⁺. This novel composite membrane with K⁺ as a counterion has a high separation factor of 891 and a good permeation rate of 591 g m⁻² h⁻¹ for pervaporation of a 90 wt % ethanol aqueous solution at 70°C. At the same time, SEM micrographs showed that the pore structure of the PAN microporous membrane is changed by hydrolysis. The reason for the influence of the preparation conditions on the separation performance of the novel membrane is discussed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3054–3061, 2000     

碳纳米管填充PDMS膜的渗透汽化性能

将碳纳米管（CNTs）填充到PDMS中制备出CNTs/PDMS杂化膜,并将其用于乙醇/水体系的分离,发现由多壁碳纳米管制备的膜分离性能优于单壁碳纳米管填充膜,在40℃下,进料乙醇浓度为5%（质量分数）时,膜的分离因子可由8.3提高到10.0,渗透通量为206.2 g·（m²·h）^-1;采用十二烷基三氯硅烷对多壁碳纳米管进行修饰,并对修饰前后碳纳米管的性能进行表征,研究表明修饰后碳纳米管表面形成疏水层,碳纳米管的疏水性增强;将修饰后的碳纳米管填充到PDMS中,可进一步提高杂化膜对乙醇的选择性,膜的分离因子可提高到11.3,渗透通量为130.9 g·（m²·h）^-1。