pH‐ and temperature‐sensitive microfiltration membranes from blends of poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) and poly(N‐isopropylacrylamide)

The copolymer poly(vinylidene fluoride)‐graft‐poly(4‐vinylpyridine) (PVDF‐g‐P4VP) was prepared through the graft copolymerization of poly(vinylidene fluoride) with 4‐vinylpyridine. Through the blending of the PVDF‐g‐P4VP copolymer with poly(N‐isopropylacrylamide) (PNIPAm) in an N‐methyl‐2‐pyrrolidone solution, PVDF‐g‐P4VP/PNIPAm membranes were fabricated by phase inversion in aqueous media. Elemental analyses indicated that the blend concentration of PNIPAm in the blend membranes increased with an increase in the blend ratio used in the casting solution. Scanning electron microscopy revealed that the membrane surface tended to corrugate at a low PNIPAm concentration and transformed into a smooth morphology at a high PNIPAm concentration. The surface morphology and pore size distribution of the microfiltration membranes could be regulated by the blend concentration of the casting solution, temperature, pH, and ionic strength of the coagulation bath. X‐ray photoelectron spectroscopy revealed a significant enrichment of PNIPAm on the membrane surface. The flux of aqueous solutions through the blend membranes exhibited a pH‐ and temperature‐dependent behavior. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4089–4097, 2006     

Comparative study of composite membranes from nano‐metal‐oxide‐incorporated polymer electrolytes for direct methanol alkaline membrane fuel cells

A series of six composite membranes was prepared with two polymer electrolytes and three inorganic fillers, namely, silica, titania, and zirconia by a solution casting method. Two polymer electrolytes, that is, anion‐exchange membranes, were prepared from polystyrene‐block‐poly(ethylene‐ran‐butylene)‐block‐polystyrene (PSEBS) and polysulfone by chloromethylation and quaternization. A preliminary characterization of the ionic conductivity, methanol permeability, and selectivity ratio was done for all of the prepared composite membranes to check their suitability to work in direct methanol alkaline membrane fuel cells (DMAMFCs). The DMAMFC performance was analyzed with an in‐house fabricated single cell unit with a 25‐cm² area. Maximum performance was achieved for the composite membrane quaternized PSEBS/7.5% TiO₂ and was 74.5 mW/cm² at 60°C. For the comparison purposes, a commercially available anion‐exchange membrane (Anion Membrane International‐7001) was also investigated throughout the study. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Charged polyacrylonitrile membranes having amphiphilic quaternized ammonium groups for ultrafiltration

Four types of positively charged polyacrylonitriles having quaternized N,N-dimethylaminoethyl methacrylate (DAMA) were synthesized and were used to prepare ultrafiltration membranes by a phase-inversion method. The effect of aliphatic ethyl, octyl, and stearyl groups and the benzyl group, which covalently bind to the quaternary ammonium group, on filtration properties was studied by ultrafiltration under an applied pressure of 760 mmH₂O. Water permeability through the resultant membranes increased as the aliphatic chain length on the quaternary ammonium group increased. For a copolymer membrane having a benzyl group on the quaternary ammonium group, water permeability was lower than that for the ethyl type of copolymer membrane. The membrane permeability and pore size for the molecular size-exclusion effect were studied at various NaCl concentrations in the 0–0.15M region. The membranes having octyl and stearyl groups showed stable filtration behavior by increase of the NaCl concentration, while the membranes having an ethyl group and a benzyl group on the quaternary ammonium group showed a change of the water permeability due to a pore-size increase for the membrane by NaCl addition. Measurements of membrane potential indicated the shielding of positively charged sites of the membranes by salt addition. Further, the copolymer membranes showed a separation ability for water/2-butanol of low water content. The separation ability was attributed to the chemical structure of the membranes having different interaction characteristics with the mixture components. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 1821–1828, 1998     

Polyethylenimine–polyepichlorohydrin interpolymer for chelating ion-exchange membrane

Polyethylenimine membranes consisting of linear polyethylenimine (PEI) and polyepichlorohydrin (PECH) were prepared by casting and heating an N,N-dimethylformamide solution of the two polymers under nitrogen at 100°C for 60 min. The membrane was also prepared by a heat-press method in a conventional manner. The cast membrane obtained was transparent. The membrane has a crosslinked structure due to the reaction between the secondary amino groups in PEI and the chloromethyl groups in PECH. Although a larger feed ratio of PEI/PECH gave membranes with a larger adsorption capacity for Cu²⁺ ions, the optimum ratio was 40/100 with respect to mechanical properties. A belt conveyor system using the PEI membrane was able to transport Cu²⁺ ions from one bath to another. In a diffusion dialysis against 1N HCl, the PEI membrane crosslinked rather tightly showed a specific ion-selective transfer character. For example, in Cu²⁺–Ca²⁺ system the permeability ratio P_cu/P_ca was about 3.8. The selectivity arises from the difference between affinities (extractabilities) of PEI toward metal ions. The selectivity was changed depending on the pH value.     

Potential of DMSO as greener solvent for PES ultra‐ and nanofiltration membrane preparation

In this article, the performance of polyethersulfone (PES) ultra‐ and nanofiltration membranes, prepared with the non‐toxic solvent dimethyl sulfoxide (DMSO), was investigated. The membranes were prepared by immersion precipitation via phase inversion. Experimental results proved that DMSO is a better alternative to N‐methyl‐2‐pyrrolidone (NMP) as solvent for PES ultrafiltration membranes as the membranes had a higher permeability and rejection of bovine serum albumin (BSA). An explanation was found based on experimental cloud point data and scanning electron microscopy images showing the morphology. The rejection of BSA and rose Bengal (RB) was proportional to the polymer concentration. On the contrary, the permeability decreased with increasing polymer concentration. For a casting thickness of 250 µm, an optimal balance between permeability and rejection of macromolecules for ultrafiltration was found at 24 wt % PES. The permeability was inversely proportional to the casting thickness, but a small decrease in rejection was observed when lowering the thickness. A good balance between permeability and rejection of RB was found, using a reference nanofiltration membrane of 28.5 wt % PES with 150 µm casting thickness. This membrane achieved a RB rejection of 95.3% and a pure water flux of 2.03 L m^?2 h^?1 bar^?1. The membrane thickness and polymer concentration did not have a clear influence on the hydrophilicity of the membranes. It can be concluded that DMSO is a benign alternative as compared to traditional solvents such as NMP and also results in better PES membrane performances. DMSO is a perfectly suitable solvent for ultrafiltration applications and has potential to be used for nanofiltration applications. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46494.     

Studies on chitin 3—effect of coagulants and annealing on the preparation and the properties of chitin membrane

Chitin membrane was prepared by casting a N,N-dimethyl acetamide, N-methyl 2-pyrrolidone and lithium chloride (DMA-NMP-LiCl)solution of chitin and coagulating with several media. The effect of the coagulants on membrane formation was studied. 2-Propanol was found to be more favourable than methanol, ethanol, acetone and mixtures of 2-propanol and water. The membrane obtained in 2-propanol was subjected to annealing. Annealing made the membrane dense and strong. The tensile strength of the membrane annealed at 145°C for 2hr was about twice that of an unannealed membrane. The solute permeability of the annealed membranes was lower than that of the original one. These phenomena could be clearly interpreted in terms of crystallinity.     

Poly(ether-b-amide)/Tween20 Gel Membranes for CO2/N2 Separation

Poly(ether-b-amide) (PEBA)/Tween20 gel membranes containing from 0 wt% to 65 wt% of Tween20 in PEBA2533, PEBA3533, and PEBA4033 were prepared by solvent casting method for CO₂/N₂ separation. The gas separation properties of the polymeric gel membranes were tested for single gases of CO₂ and N₂ at 25°C with the feed pressure of 0.6 atm. For all pure PEBA membranes, CO₂ and N₂ permeability decreased as the amount of polyamide block increased, but CO₂/N₂ selectivity increased. For PEBA/Tween20 gel membranes, both the CO₂ permeability and CO₂/N₂ selectivity were greatly enhanced with the increase of Tween20 content. For the membrane of PEBA4033/Tween20-65, CO₂/N₂ selectivity, and CO₂ permeability reached 54 and 146 Barrer, respectively, which is very interesting for potential application in CO₂ removal from flue gas.     

Proton exchange membranes based on poly(vinylidene fluoride) and sulfonated poly(ether ether ketone)

Blend membranes were obtained by solution casting from poly(vinylidene fluoride) (PVDF) and sulfonated poly(ether ether ketone) (SPEEK) in N,N-dimethylacetamide (DMAc). DSC and XRD were used to characterize the structure of the blend membranes. The effect of PVDF content on the membrane properties was investigated. The methanol permeability, water uptake and the swelling ratio of blend membranes decreased with the increase of PVDF content. Though the proton conductivity decreased upon the addition of PVDF, they were still comparable to that of Nafion^® 117 membrane. Higher selectivities were also found for most blend membranes in comparison with Nafion^® 117 membrane. The effect of methanol concentration on solution uptake, swelling ratio and methanol permeability of the blend membranes was also studied.     

Polysulfone Membranes. III. Performance Evaluation of Polyethersulfone—PVP Membranes

Abstract

The performance of membranes produced from casting solutions consisting of polyethersulfone (PES), poly-(N-vinyl-pyrrolidone) (PVP), and N-methyl-2-pyrrolidinone (NMP) were systematically studied. Zero-shear casting solution viscosities for these polymer solutions were determined as a function of PES and PVP concentrations. Ultrafiltration membranes were then cast using the phase inversion technique and characterized by separation experiments using polyethylene glycols of various molecular weights as test solutes. A pore flow model was fitted to the resulting separation data to provide estimates of the average pore radius and membrane porosity. These parameters were used to compare laboratory results for this membrane casting solution system with performance data for commercially available polyethersulfone membranes.     

The effect of casting solvent and water on gas permeability of poly(γ-methyl L-glutamate) membrane

Gas permeability of poly(γ-methyl L-glutamate) (PMLG) membranes prepared by using dichlorethane, trifluoroacetic acid, and formic acid as solvents was studied. The membranes prepared by casting dichloroethane and trifluoroacetic acid solutions of the polymer, designated as PMLG—DCE and PMLG—TFA, respectively, had α-helical structures according to infrared absorption spectra, while the membranes prepared by allowing the PMLG—TFA membranes to swell in formic acid, designated as PMLG—FA, had mainly a β-sheet structure. The diffusion coefficients of each gas studied for PMLG—DCE, PMLG—TFA, and PMLG—FA decreased in that order, and the apparent activation energies of diffusion increased in that order. The apparent heats of solution for Ne,O₂, N₂, and CO₂ were negative in PMLG—FA. These results were discussed in connection with the molecular conformations of PMLG in the membranes. It is suggested that the diffusion of gases in PMLG—DCE takes place in the side-chain regions between helices, while in PMLG—FA the diffusion occurs across the polymer main chain whose mobility is depressed by the intermolecular hydrogen bonds. The effect of water on oxygen permeability of PMLG—DCE was small; on the contrary that of PMLG—FA was very large. Furthermore, it is assumed that the random-coil conformation partly exists in PMLG—TFA.     

Miscibility and morphological properties of quaternized polysulfone blends with polystyrene and poly(4‐vinylpyridine)

Quaternized polysulfones were synthesized by the quaternization reaction of chloromethylated polysulfone with different tertiary amines −N,N‐dimethylethylamine (DMEA) and N,N‐dimethyloctylamine (DMOA), respectively. New blends from these quaternized polysulfones (PSF‐DMEA or PSF‐DMOA) with polystyrene (PS) or poly(4‐vinylpyridine) (P4VP) were prepared by the solution casting method. Pure quaternized polysulfones, in N,N‐dimethylformamide (DMF)/methanol (MeOH) and DMF/water solvent/nonsolvent mixtures, and their blends with PS and P4VP, as well, were investigated by shear viscometry and viscoelasticity, atomic force microscopy, differential scanning calorimetry, and surface properties. The results obtained revealed that the blends have good miscibility. Surface morphology is characterized by roughness and nodules formations, depending on the alkyl radical lengths, composition of the polymer mixtures, including specific electron‐donor or electron‐acceptor characteristics of polymers. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Hydrophilic interpolymer membranes from crosslinked blends of poly(vinylalcohol), poly(styrene sodium sulfonate) and poly(vinyl methyl ether–alt–maleic anhydride)

Interpolymer ion exchange membranes were prepared from a compatible casting solution that contained poly(styrene sodium sulfonate), poly(vinyl methyl ether–alt–maleic anhydride), and poly(vinyl alcohol). Crosslinking of the films was accomplished through the formation of ester linkages that were stable in aqueous environments. Membrane properties (water content, capacity, concentration potential, equivalent conductivity) were measured over a wide range of membrane compositions. Ultrafiltration was carried out with a feed solution that was 0.01N in KCI and 15 ppm in erythrosin. Rejection and hydraulic permeability data were reported as a function of membrane composition.     

Application and development of synthetic polymer membranes. VI. Pervaporation of aqueous ethanol solution through quaternized poly[3-(N′,N′-dimethyl) aminopropylacrylamide-co-acrylonitrile] membranes

Membranes obtained from polymers, quaternized poly[3-(N′,N′-dimethyl) aminopropylacrylamide-co-acrylonitrile]s, showed selective separation of water from aqueous ethanol solution by pervaporation. The separation factor toward water reached over 15,000. Membrane performance showed a good correlation to membrane polarity. Differential scanning calorimetric melting endotherms of the water-swollen membranes were studied to clarify the state of water in the membranes. The results suggested that there are two states of water in the membrane: bound and free. The higher the fraction of bound water in the membrane, clearly, the more preferentially was water permeated.     

Hemodialysis membrane prepared from cellulose/N‐methylmorpholine‐N‐oxide solution. II. Comparative studies on the permeation characteristics of membranes prepared from N‐methylmorpholine‐N‐oxide and cuprammonium solutions

Two kinds of regenerated cellulose membranes for hemodialysis were prepared from casting solutions of N‐methylmorpholine‐N‐oxide (NMMO) and cuprammonium (denoted NMMO membranes and cuprammonium membranes, respectively). The concentration of cellulose in the casting solution investigated was 6–8 wt %. The permeation characteristics of both membrane series were compared in terms of the ultrafiltration rate (UFR) of pure water, the sieving coefficient (SC) of dextran, and the solute permeabilities of urea, creatinine, and vitamin B₁₂. The UFR and SC of the NMMO membranes were strongly affected by the cellulose concentration of the casting solution, and NMMO was a preferable solvent for the production of cellulose membranes with high performance; the cuprammonium solution gave low‐performance membranes. The pore structures of both types of membranes were estimated with the Hagen–Poiseuille law. The results showed that the NMMO membranes had larger pore radius and smaller pore numbers than the cuprammonium membranes. The differences in the membrane pore structures led to the differences in the performance between the two membrane series. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 333–339, 2003     

Effect of molecular weight parameters on gas transport properties of poly(2,6-dimethyl-1,4-phenylene oxide)

The gas permeability of O₂ and N₂ for homogeneous and composite membranes prepared from poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) samples with different molecular weight parameters was investigated. Temperature dependencies of gas permeability coefficients and permselectivity were determined for homogeneous membranes. It was established that gas permeability coefficients of homogeneous membranes depend on molecular weight of the polymers used. The gas permeability of composite membranes with a PPO selective layer was investigated as a function of PPO intrinsic viscosity [η] and its casting solution concentration (c). It was shown that under the condition [η]·c = const it is possible to obtain composite membranes with the same transport properties by using polymers with different molecular weight parameters. © 1996 John Wiley & Sons, Inc.     

Removal of nitrite ions from aqueous solutions by poly(N,N‐dimethylamino ethylmethacrylate) hydrogels

Removal of nitrite ions from aqueous solutions by protonated poly(N,N‐dimethylamino ethylmethacrylate) hydrogels (P(DMAEMA)) was investigated. We have shown that polycationic and pendant secondary amine group containing P(DMAEMA) hydogels is very efficient and highly selective for the removal of nitrite ions from aqueous solutions at even in very high concentrations. Adsorption studies have shown that pH of the nitrite solution has influence on the nitrite ion uptake capacity of P(DMAEMA) hydrogels. The adsorption capacity of hydrogels had been increased up to 3100 mg NO/g dry gel, by changing pH of the solution. The results of the adsorption studies showed that the interaction between nitrite ions and quaternized amine groups agree with the Langmuir‐type isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6023–6027, 2006     

Quest for high performance carbon capture membranes: Fabrication of SAPO-34 and CNTs-doped polyethersulfone-based mixed-matrix membranes

Gas separation process is an effective method for capturing and removing CO₂ from post-combustion flue gases. Due to their various essential properties such as ability to improve process efficiency, polymeric membranes are known to dominate the market. Trade-off between gas permeability and selectivity through membranes limits their separation performance. In this study, solution casting cum phase separation method was utilized to create polyethersulfone-based composite membranes doped with carbon nanotubes (CNTs) and silico aluminophosphate (SAPO-34) as nanofiller materials. Membrane properties were then examined by performing gas permeation test, chemical structural analysis and optical microscopy. While enhancing membranes CO₂ permeance, SAPO-34 and CNTs mixture improved their CO₂/N₂ selectivity. By carefully adjusting membrane casting factors such as filler loadings. Using Taguchi statistical analysis, their carbon capture efficiency was improved. The improved mixed-matrix membrane with loading of 5 wt% CNTs and 10 wt% SAPO-34 in PES showed highly promising separation performance with a CO₂ permeability of 319 Barrer and an ideal CO₂/N₂ selectivity of 12, both of which are within the 2008 Robeson upper bound. A better mixed-matrix membrane with outstanding CO₂/N₂ selectivity and CO₂ permeability was produced as a result of the synergistic effect of adding two types of fillers in optimized loading.     

Hybrid sol–gel membranes of polyacrylonitrile–tetraethoxysilane composites for gas permselectivity

Sol–gel reaction of tetraethoxysilane (TEOS) with fumed silica–polyacrylonitrile (PAN) membrane was carried out to prepare hybrid gas permeable membranes for oxygen and nitrogen separation. Various amounts of fumed silica microparticles with a few μm diameters were compounded in PAN–dimethylsulfoxide (DMSO) solution. After casting of the viscous compound solution on a flat sheet with 100 μm thickness, DMSO was evacuated under vacuum at 80°C. Then, the silica–PAN composite membranes were treated with TEOS for 1 day at 40°C in methanol. Air permeation was examined and compared in silica–PAN composite membranes with and without TEOS treatment. The latter hybrid membranes showed selective oxygen permeability, which depended on amounts of fumed silica in the membrane. The TEOS hybrid PAN membranes have a high ability of oxygen permselectivity for O₂/N₂ gas mixture with α(O₂/N₂) = 13–17, when the silica content was in the range of 13–20 wt %. This is attributed to siloxane network formation in hybrid silica–PAN composite membranes. Favorable siloxane network formation resulted in high oxygen permeability of the hybrid composite membranes. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1752–1759, 2003     

Synthesis and characterization of homogeneously sulfonated poly(ether ether ketone) membranes: Effect of casting solvent

Poly(ether ether ketone) (PEEK) was homogeneously sulfonated to have various degrees of sulfonation from 48 to 83%. The sulfonated PEEK (sPEEK) membranes were prepared by a solvent casting method using a few solvents such as N,N‐dimethyl formamide, N,N‐dimethyl acetamide, and 1‐methyl‐2‐pyrrolidinone. The effect of casting solvent on the membrane morphology and properties was investigated. The sulfonation degree and ion exchange capacity were determined by a back titration method, and the morphology of membrane by SEM. It has been demonstrated that the surface morphology and properties of sPEEK membranes, such as water uptake, methanol permeability, ion conductivity, and mechanical strength, were considerably affected by the type of solvent, where the DMAC‐sPEEK system showed the best performance in the polymer electrolyte membrane application for DMFC. This solvent effect on the membrane morphology and properties was caused by interaction strength (hydrogen bonding) between polymer and solvent. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Pebax membrane for CO2/CH4 separation: Effects of various solvents on morphology and performance

In this study, the effects of different solvents on the morphology and permeation of poly(ether‐block‐amide) (Pebax‐1657) membranes were investigated. Pebax membranes were fabricated via a solution casting method with five different solvents, that is, N,N‐dimethyl formamide (DMF), N,N‐dimethyl acetamide (DMAc), N‐methyl‐2‐pyrrolidone (NMP), formic acid, and a mixture of ethanol (EtOH) with water (H₂O). Cross‐sectional scanning electron microscopy analysis of the membranes was performed to investigate the morphology of the prepared membranes. X‐ray diffraction and Fourier transform infrared analysis were also carried out to characterize the membranes. The interactions of the polymer and various solvents were evaluated with Hansen solubility parameters. Permeation experiments for CO₂ and CH₄ gases were performed to study the effects of the solvents on the permeation properties of the membranes. The solvent properties, such as the molar volume, boiling point, and solubility parameters, were investigated as were the membranes characteristics, such as the crystallinity, d‐spacing, and fractional free volume. The results obtained from the experiments show that the CO₂ permeability for the membranes prepared with different solvents followed this order: NMP > DMF > Formic acid > DMAc > H₂O/EtOH mixture. With increasing molar volume, the gas permeability increased for all of the membranes, except for DMAc, which showed a lower permeability because of its highly crystalline structure. DMF showed a higher CO₂/CH₄ ideal selectivity compared to the other membranes and, consequently, could be introduced as the best solvent from all aspects for the Pebax‐1657 membrane. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44531.