Solution blown sulfonated poly(ether sulfone)/poly(ether sulfone) nanofiber‐Nafion composite membranes for proton exchange membrane fuel cells

A composite membrane of sulfonated poly(ether sulfone) (SPES)/poly(ether sulfone) (PES) nanofiber (NF) mat impregnated with Nafion was prepared and evaluated for its potential use as a proton conductor for proton exchange membrane (PEM) fuel cells. The supporting composite nanofibrous mat was prepared by solution blowing of a mixture of SPES/PES solution. The characteristics of the SPES/PES NF and the composite membrane, such as morphology, thermal stability, and performance of membrane as PEMs, were investigated. The performance of composite membranes was compared with that of Nafion117. The introduction of solution blown NFs to composite membranes modestly improved proton conductivity, water swelling, and methanol permeability. Therefore, composite membrane containing SPES/PES NFs can be considered as a novel PEM for fuel cell applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42572.     

Formation of multilayer poly(acrylic acid)/poly(vinylidene fluoride) composite membranes for pervaporation

Dual‐ and multilayer composite membranes, consisting of poly(acrylic acid) (PAA) and poly(vinylidene fluoride) (PVDF), were synthesized by the plasma‐induced polymerization technique. The dual‐layer membrane had a dense PAA layer grafted onto a microporous PVDF substrate, whereas in the multilayer membranes, the grafted PAA and the PVDF layers were arranged in an alternating sequence (e.g., PAA/PVDF/PAA and PAA/PVDF/PAA/PVDF/PAA). These membranes were used in a pervaporation process to separate ethanol–water solutions. For the dual‐layer membranes, the results indicated that the separation factor increased and the permeation flux decreased with increasing amounts of grafted PAA. For the case of grafting yield < 0.6 mg/cm², the composite membrane demonstrated poor separation. As the grafting yield reached 0.85 mg/cm², a sharp increase of the separation factor was observed. For the multilayer membranes, the pervaporation performances were very good, with high separation factors (on the order of 100) and reasonable permeation fluxes over a wide ethanol concentration range. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2266–2274, 2004     

Poly(ethylene glycol) crosslinked sulfonated polysulfone composite membranes for forward osmosis

Forward osmosis (FO) membranes were prepared by a coating method with poly(ethylene glycol) crosslinked sulfonated polysulfone (SPSf) as a selective layer. The poly(ether sulfone)/SPSf substrate was prepared by phase inversion. The composite membranes were characterized with respect to membrane chemistry (by attenuated total reflectance/Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy), hydrophilicity (by static contact angle measurement), and surface morphology (by scanning electron microscopy and atomic force microscopy). The FO performance was also characterized. The effects of the crosslinker concentration on the hydrophilicity and FO performance were investigated. The crosslinked membrane exhibited a high hydrophilicity with a lowest contact angle of 15.5°. Under FO tests, the membranes achieved a higher water flux of 15.2 L m^?2 h^?1 when used against deionized water as the feed solution and a 2 mol/L sodium chloride (NaCl) solution as the the draw solution. The membranes achieved a magnesium sulfate rejection of 96% and an NaCl rejection of 55% when used against a 1 g/L inorganic salt solution as the feed solution and a 2 mol/L glucose solution as the draw solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43941.     

Zirconium phosphate sulfonated poly (fluorinated arylene ether)s composite membranes for PEMFCs at 100-140 °C

Organic-inorganic hybrid composite membranes have been prepared and evaluated for polymer electrolyte membrane fuel cells (PEMFCs) at 100-140 °C. A series of synthesized poly (fluorinated arylene ether)s was sulfonated by fuming sulfuric acid (20% SO₃). The zirconium phosphate composite membrane was prepared by soaking the sulfonated poly (fluorinated arylene ether)s stepwise in 1 M zirconyl chloride solution and 1 M phosphoric acid solution. The chemical, thermal, and electrochemical properties of the composite membrane were investigated by thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and unit cell test. The cell performance of the zirconium phosphate sulfonated poly (fluorinated arylene ether)s composite membrane was superior to that of the starting membrane at intermediate temperature, 100-140 °C. And the cell performance with composite membrane indicated stable behavior during experimentation when operating temperature maintained at 120 °C, whereas sulfonated poly (fluorinated arylene ether)s membrane was irreversible degradation under the same condition.     

Preparation and properties of PVDF-fabric composite membrane for membrane distillation

The flat sheet PVDF-fabric composite membrane used for membrane distillation was prepared by coating and wet phase inversion process. The composite membrane consisted of a PVDF porous membrane layer and a fabric layer. The thin polyester filament woven fabric with water-and-oil repellent finish was used as the support of composite membrane. The effects of fabric texture, PVDF concentration in casting solution and functional finishing of fabric on the preparation and properties of the composite membrane were investigated. The experimental results showed that fabric texture, PVDF concentration and functional finishing of fabric had great influence on the preparation and properties of the composite membrane. When the PVDF concentration in casting solution was 10-12% and the support fabric, with 435 warps/10 cm and 273 wefts/10 cm and the area weight of 79 g/m², was finished with 2 g/L water-and-oil repellent agent FK-501, the prepared composite membrane exhibited better performance in tensile strength, peeling strength and water vapor permeability, with mean pore size of 0.63 μm and overall porosity of 57.6%.     

Sulfonated poly(ether ether ketone)‐induced porous poly(ether sulfone) blend membranes for the separation of proteins and metal ions

Asymmetric ultrafiltration (UF) membranes were prepared by the blending of poly(ether sulfone) (PES) and sulfonated poly(ether ether ketone) (SPEEK) polymers with N,N′‐dimethylformamide solvent by the phase‐inversion method. SPEEK was selected as the hydrophilic polymer in a blend with different composition of PES and SPEEK. The solution‐cast PES/SPEEK blend membranes were homogeneous for all of the studied compositions from 100/0 to 60/40 wt % in a total of 17.5 wt % polymer and 82.5 wt % solvent. The presence of SPEEK beyond 40 wt % in the casting solution did not form membranes. The prepared membranes were characterized for their UF performances, such as pure water flux, water content, porosity, and membrane hydraulic resistance, and morphology and melting temperature. We estimated that the pure water flux of the PES/SPEEK blend membranes increased from 17.3 to 85.6 L m^?2 h^?1 when the concentration of SPEEK increased from 0 to 40 wt % in the casting solution. The membranes were also characterized their separation performance with proteins and metal‐ion solutions. The results indicate significant improvement in the performance characteristics of the blend membranes with the addition of SPEEK. In particular, the rejection of proteins and metal ions was marginally decreased, whereas the permeate flux was radically improved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Actual air separation across multilayer composite membranes

Multilayer composite membranes are fabricated from six types of thin films as selective layers, an ethyl cellulose (EC) thin film as a flexible spacer, and poly(ether sulfone) (PES) with 15–45 nm pore size or 100–120 μm thickness as a porous support layer. The effects of the thin‐film type and its layer number, operating temperature, and transmembrane pressure difference, as well as the operational time on the actual air‐separation properties through the composite membranes, are investigated by a constant pressure‐variable volume method. The results show that a pure polystyrene thin‐film composite membrane exhibits poor actual air‐separation performance due to its brittleness, although it has a higher ideal oxygen over nitrogen separation factor. The oxygen‐enrichment air (OEA) flux through all of the composite membranes tested increases significantly with increasing operating temperature and pressure difference. The oxygen concentration in the OEA increases slightly with an increase in operating temperature, and the oxygen concentration through the polystyrene/cholesteryl oleyl carbonate blend, top layer composite membrane exhibits the maximal value. As the transmembrane pressure difference increases, the oxygen concentration in the OEA also exhibits the maximal value. The maximum oxygen concentration can reach 39.1%, which is achieved by the multilayer composite membrane consisting of a polystyrene/cholesteryl oleyl carbonate (95/5) monolayer, an EC single flexible spacer, and a PES support at 35°C and a transmembrane pressure difference of 550 kPa. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2396–2403, 2000     

Ethanol‐responsive characteristics of polyethersulfone composite membranes blended with poly(N‐isopropylacrylamide) nanogels

Ethanol‐responsive smart membranes with different microstructures are prepared from blends of polyethersulfone (PES) and poly(N‐isopropylacrylamide) (PNIPAM) nanogels by immersion precipitation phase inversion method in a convenient and controllable manner. The introduction of PNIPAM nanogels forms the microporous structures on the surface of the top skin layer and on the pore walls of the finger‐like porous sublayer of membranes. The ethanol‐responsive characteristics of the proposed PES composite membranes are systematically investigated. With increasing ethanol concentration in the range from 0 to 15 wt %, the trans‐membrane flux of ethanol solution increases. The microstructures and the resultant ethanol‐responsive characteristics of the composite membranes can be regulated by the content of PNIPAM nanogels blended in the membranes. The more the content of PNIPAM nanogels blended in the membranes, the more the number of the submicron pores is, and thus the better the ethanol‐responsive characteristics of the composite membranes. The proposed ethanol‐responsive smart membranes are expected to be combined with the traditional pervaporation membranes as a smart vavle to achieve continuous and highly efficient ethanol production during the biological fermentation. The preparation technique and results in this study provide valuable guidance for further design and the industrial‐scale fabrication of novel composite membranes for application in ethanol separation systems. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41032.     

Nanofibrous ultrafiltration membranes containing cross-linked poly(ethylene glycol) and cellulose nanofiber composite barrier layer

Nanofibrous ultrafiltration membranes based on the thin-film nanofibrous composite (TFNC) format with a nanocomposite barrier layer made of cross-linked poly(ethylene glycol) (PEG) matrix and ultra-fine cellulose nanofibers (CN, ∼5 nm in diameter) were demonstrated. Physical properties, including pore size, chemical composition, morphology, hydrophilicity and surface roughness of these membranes, were characterized by filtration test, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), water contact angle measurements and atomic force microscopy (AFM). It was found the cross-linked PEG/CN barrier layer was highly hydrophilic and had excellent anti-fouling properties, which were confirmed by short-term and long-term fouling tests using bovine serum albumin (BSA) solution (1 g/L). In addition, the membranes exhibited better anti-fouling properties and recovery ability than comparable commercial membranes (e.g., Pall Life Sciences omega membranes and Koch HFK 328 membranes). For example, the flux of the composite layer was about twice as high as that of commercial membranes during the long-term testing, while the rejection was maintained above 90%.     

Comparative behavior of PVA/PAN and PVA/PES composite pervaporation membranes in the pervaporative dehydration of caprolactam

Flat‐sheet composite membranes were developed by the traditional phase inversion technique using poly;(vinyl alcohol) (PVA). PVA composite pervaporation (PV) membranes were prepared with crosslinked PVA selective layer and porous polyacrylonitrile (PAN) and polyether sulfone (PES) substrate layer material as supports for separating heat sensitivity substance ε‐caprolactam (CPL) from CPL/water mixtures. Glutaraldehyde was used as crosslinking agent. The effect of the composition of glutaraldehyde on membrane stability and structure were investigated. The operating parameters, such as feed concentration and operating temperature, remarkably affected PV performance of the composite membranes. The composite membranes with PVA casted on PAN (PVA/PAN) showed superior PV performance than that casted on PES (PVA/PES). This study has also shown that the type of porous support plays an important role in the PV performance. As a result, this work has presented the information needed of the behavior of PV membranes for dehydration applications of industrial caprolactam. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 4005–4011, 2007     

An interpolymer anionic composite reverse osmosis membrane derived from poly(vinyl alcohol) and poly(styrene sulfonic acid)

An interpolymer anionic composite membrane for reverse osmosis was prepared from poly(vinyl alcohol) and poly(styrene sulfonic acid). The effects of composition of a casting solution, heat-curing periods, and casting thickness on the reverse osmosis performance of resulted membranes have been examined. A mixture of water and ethyl alcohol (12/7, wt %) was found to be a proper solvent for casting an interpolymer membrane on the supporter. The composite membrane was formed by casting the polymer solution in ultrathin film on a microporous polypropylene supporter, evaporating the solvent, and heat-curing at 120°C for a proper period. the optimum composition of a casting solution was as follows: wt % of poly(vinyl alcohol)/poly(styrene sulfonic acid)/solvent was 3/2/95. The membrane heat-cured at 120°C for 2 h has a good performance for reverse osmosis, viz., water flux of 9.1–28.4 L/m².h at salt rejection level of 88.1–93.4% under applied pressure of 80 kg/cm² with 0.5% NaCl aqueous solution. The formation mechanism of a water-insoluble membrane was discussed.     

Preparation, morphology and performance evaluation of polyvinylalcohol (PVA)/polyethersulfone (PES) composite nanofiltration membranes for pulp and paper wastewater treatment

In this study, thin film composite PVA/PES nanofiltration membranes were fabricated for the treatment of pulp and paper industrial wastewater. Phase separation induced by immersion precipitation was used to prepare the PES support membrane. PVA/PES composite nanofiltration membranes were prepared by dipping the support PES membrane in the PVA and cross-linking solutions at different conditions. Maleic acid (MA) was used as cross-linking agent. PVA and MA have concentrations of 0.5?C2 and 0.05?C1 wt%, respectively. Morphological studies were carried out by means of scanning electron microscopy (SEM) as well as atomic force microscopy (AFM) techniques. In addition, the hydrophilicity of membranes was examined by contact angle measurements. Permeability and ability of PVA/PES composite nanofiltration membranes to reduce COD of the wastewater were evaluated by a cross flow filtration system. SEM images indicated that the PVA layer was uniformly formed on the PES support membrane. AFM images showed that the surface roughness, porosity and pore sizes of PES support membrane were reduced after formation of PVA layer on the support surface. Moreover, the hydrophilicity of the membranes was significantly increased. Experimental results demonstrated that the PVA/PES composite nanofiltration membranes were able to reduce the COD of wastewater. Optimum conditions for preparation of PVA/PES composite membrane are consisted of PVA concentration: 1 wt%, MA concentration: 0.5 wt%, cross-linking time: 3?min and curing time: 3?min.     

Effects of casting solution composition on performance of poly(ether sulfone) membrane

Flat-type poly(ether sulfone) (PES) membranes for ultrafiltration were prepared by the traditional phase-inversion technique. The effects of the concentration of PES and the combination of two solvents, dichloromethane (DCM) and N-methyl-2-pyrrolidone (NMP), with differences in volatility and solvating power on membrane performance were examined in terms of pure water flux (PWF) and solute rejection (SR) against poly(ethylene glycol) (PEG, MW 20,000). Changing the thermodynamic quality of PES/NMP casting solution by combining DCM, a volatile and weak solvent, affected the PWF of the resulting membrane. The SR of PES/DCM–NMP membrane, however, was more likely dependent upon the effect of evaporating the volatile solvent from the casting solution/air interface rather than the effect of changing the thermodynamic quality of the casting solution. Combining DCM in PES/NMP casting solution transformed the fingerlike macrovoids of PES/NMP membrane prepared without DCM into the isolated macrovoids. PES/DCM–NMP membrane prepared with PVP, a water soluble poreforming agent, showed an increased PWF while maintaining SR of over 90%, even under the reduced feeding pressure of 1 kg/cm². It is necessary to measure molecular weight cutoff of membrane for demonstrating the potential of PVP for improving the membrane permeability without losing the selectivity.© 1996 John Wiley & Sons, Inc.     

Morphological and electrochemical characterization of a poly(3-methylthiophene)/PVDF composite

Composite electrodes were prepared via electrochemical polymerization of 3-methylthiophene in porous PVDF membranes of various thicknesses. The electrochemical properties were determined by cyclic voltammetry and charge-discharge tests and the possible correlation of the results with the morphology of the host membranes was examined. The best definition of n- and p-doping/undoping processes and the biggest capacitance (82 F g⁻¹) were obtained with a 27.5 μm-thick composite. Further characterization of this composite using electrochemical impedance spectroscopy revealed three behaviors associated with variation in the oxidation state of poly(3-methylthiophene) during transition from the n-undoping to p-doping states. The behavior of the charge transfer resistance and the double layer capacitance as a function of the applied potential were also determined.     

Effect of support layer on gas permeation properties of composite polymeric membranes

PES/Pebax and PEI/Pebax composite membranes were prepared by coating the porous PES and PEI substrate membranes with Pebax-1657. The morphology and performance of the prepared membranes were investigated by SEM and CO₂ and CH₄ permeation tests. The CO₂ permeances of 28 and 52 GPU were achieved for PES/Pebax and PEI/Pebax composite membranes, respectively, with CO₂/CH₄ selectivities almost equal to that of Pebax (26). The experimental data were further subjected to a theoretical analysis using the resistance model. It was found that the porosity and the thickness of the dense section of PES substrate were an order of magnitude higher than those of PEI substitute. The porosity/thickness ratio of PEI substrate was, however, higher than PES, explaining the higher permeance of PEI/Pebax composite membrane. Substrates with porosities much higher than the Henis-Tripodi gas separation membrane were used in this work, aiming to achieve the selectivity of Pebax, rather than those of the substrate membrane materials.     

Preparation and properties of poly(acrylic acid) composite membranes

A new type of membrane has been prepared for hyperfiltration (reverse osmosis) desalination that is essentially a very thin polyelectrolyte membrane. It is prepared by casting an aqueous solution of a polyelectrolyte, specifically poly(acrylic acid) (PAA), directly on one surface of a finely porous support membrane. In hyperfiltration tests, these composite membranes exhibit desalination performance comparable in dilute solutions to that observed with cellulose acetate membranes of the Loeb-Sourirajan type. The water flux through these membranes is linear in the pressure up to 100 atm. Salt rejection is a function of pressure; it is also a function of the concentration of the feed solution and the charge of the counterion, in qualitative agreement with the Donnan ion-exclusion mechanism. Typical long-term results range from water fluxes of 2 × 10^?3 g/cm²-sec (50 gal/ft²-day) and 80% salt rejection to 0.2 × 10^?3 g/cm²-sec (5 gal/ft²-day) and >99.5% salt rejection at 1500 psi with 0.3 wt-% NaCl. These membranes appear to be useful for brackish water desalination.     

Synthesis, characterization and thermal properties of soluble aromatic poly(amide imide)s

Novel diamines such as N,N′-bis(aminoaryl)terephthalamido-2-carboxylic acids (BATCA), which contain primary amine, amide and carboxylic acid groups and are soluble in dilute aqueous NaOH solution, were synthesized by reacting aromatic diamines with trimellitic anhydride chloride in dimethylformamide. Poly(amide imide)s containing 3:1 ratio of amide:imide groups in the polymer chain were prepared by low temperature solution polymerization of BATCAs with isophthaloyl chloride or terephthaloyl chloride in dimethylformamide at 5-10 °C to form poly(amide amic acid)s, and followed by treating with a mixture of triethylamine and acetic anhydride. The PAIs were soluble in polar aprotic solvents like dimethylformamide, dimethylacetamide, dimethylsulphoxide and N-methylpyrrolidone, and have inherent viscosities in the range of 0.30-0.66 dL/g. The PAIs were characterized by IR, ¹H NMR and ¹³C NMR techniques. Thermogravimetric analysis (TGA) has shown that the initial decomposition temperatures of the polymers are in the range of 250-440 °C, depending upon the structures of diamine and diacid chloride. The glass transition temperatures of the PAIs are in the range of 128-320 °C. The IDT and T_g values of the polymers containing terephthaloyl unit are higher by about 20-40 °C than those of the polymers with isophthaloyl unit. BATCA could be utilized for the preparation of thin film composite membranes having PAA/PAI barrier layer on PES by in situ interfacial polymerization with IPC/TPC/TMC.     

Synthesis and characterization of PVA/PES thin film composite nanofiltration membrane modified with TiO2 nanoparticles for better performance and surface properties

Novel polyethersulfone (PES)/poly (vinyl alcohol) (PVA)/titanium dioxide (TiO₂) composite nanofiltration membranes were prepared by dip-coating of PES membrane in PVA and TiO₂ nanoparticles aqueous solution. Glutaraldehyde (GA) was used as a cross-linker for the composite polymer membrane in order to enhance the chemical, thermal as well as mechanical stabilities. TiO₂ nanoparticles with different concentrations (0, 0.05, 0.1, 0.5 wt.%) were coated on the surface of PVA/PES composite membrane. The morphological study was investigated by atomic force microscopy (AFM), scanning surface microscopy (SEM) and along with X-ray diffraction (XRD). In addition, the membranes performances, in terms of permeate flux, ion rejection and swelling factor were also investigated. It was found that the increase in TiO₂ solution concentration can highly affect the surface morphology and filtration performance of coated membranes. The contact angle measurement and XRD studies indicated that the TiO₂ nanoparticles successfully were coated on the surface of PVA/PES composite membranes. However, rougher surface was obtained for membranes by TiO₂ coating. The filtration performance data showed that the 0.1 wt.% TiO₂-modified membrane presents higher performance in terms of flux and NaCl salt rejection. Finally, TiO₂ modified membranes demonstrated the lower degree of swelling.     

The influence of membrane formation parameters on structural morphology and performance of PES/PDMS composite membrane for gas separation

In this study, influence of membrane preparation parameters on structural morphology and performance of polyethersulfone/polydimethylsiloxane (PES/PDMS) composite membrane was investigated for gas separation. Asymmetric PES flat sheet membranes were composed by phase inversion method and used as supports. PES composite membranes were fabricated by coating silicone rubber as selective layer on the top surface of support. Effects of different concentrations of PES and PDMS, solvent type, and support thickness on membrane performance were investigated for separation of oxygen from nitrogen. The optimized superior membrane was further modified using polyvinylidenfluoride, methanol and ethanol as additives in PES solutions and/or in water coagulation bath to promote the membrane capability. The results showed that addition of ethanol and methanol in cast solution and coagulation bath can greatly affect the morphology and hence the performance of the prepared membranes. The permeance changes have the contrary trend with solubility parameter difference between solvent and nonsolvent mixture, for instance when this parameter difference was lowest, higher permeance was obtained. Support and coating polymer concentration can control the permeance. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Swelling behavior and pervaporation properties of new composite membrane systems: Porous polyethylene film‐poly(acrylic acid) hydrogel

A new type of composite membrane for pervaporation has been developed. These membranes were prepared by free‐radical copolymerization of acrylic acid with a macromolecular polyfunctional crosslinker (allylhydroxyethylcellulose) inside the porous polyethylene (PE) film. It was shown that the porous structure of the PE matrix is filled with poly(acrylic acid) (PAA), and a layer of acid is formed on the film surface. To investigate the effect of the porous matrix on the composite membrane properties, a hydrogel membrane of crosslinked PAA was also prepared without the matrix using the same procedure. PAA in both membranes was in the neutralized form (K⁺). Swelling behavior of the membranes and their separation characteristics for pervaporation were investigated in water–ethanol solutions depending on the ethanol concentration. All membranes exhibited a high degree of equilibrium swelling (Q = 20–50 g/g) in dilute ethanol solutions (0–30 vol %), and Q sharply dropped to 1.5–2 g/g at a EtOH concentration of 30–40 vol % due to collapse of the gel. All membranes under study were highly permeable and selective to water over a wide range of ethanol concentrations in the feed (50–96 vol %), but composite membranes had a higher separation factor due to the restriction effect of the matrix porous structure on swelling of PAA(K⁺) inside the pores. However, composite membranes were characterized by a lower permeation rate, compared to the crosslinked PAA membranes without a matrix, because of their lower effective surface for diffusion. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1461–1465, 2004