Novel membranes based on poly(5‐(methacrylamido)tetrazole) and sulfonated polysulfone for proton exchange membrane fuel cells

Proton‐exchange membrane fuel cells (PEMFC)s are increasingly regarded as promising environmentally benign power sources. Heterocyclic molecules are commonly used in the proton conducting membranes as dopant or polymer side group due to their high proton transfer ability. In this study, 5‐(methacrylamido)tetrazole monomer, prepared by the reaction of methacryloyl chloride with 5‐aminotetrazole, was polymerized via conventional free radical mechanism to achieve poly(5‐(methacrylamido)tetrazole) homopolymer. Novel composite membranes, SPSU‐PMTetX, were successfully produced by incorporating sulfonated polysulfone (SPSU) into poly(5‐(methacrylamido)tetrazole) (PMTet). The sulfonation of polysulfone was performed with trimethylsilyl chlorosulfonate and high degree of sulfonation (140%) was obtained. The homopolymers and composite membranes have been characterized by NMR, FTIR, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). ¹H‐NMR and FTIR confirmed the sulfonation of PSU and the ionic interaction between sulfonic acid and poly(5‐(methacrylamido)tetrazole) units. TGA showed that the polymer electrolyte membranes are thermally stable up to ～190°C. Scanning electron microscopy analysis indicated the homogeneity of the membranes. This result was also supported by the appearance of a single T_g in the DSC curves of the blends. Water uptake and proton conductivity measurements were, as well, carried out. Methanol permeability measurements showed that the composite membranes have similar methanol permeability values with Nafion 112. The maximum proton conductivity of anhydrous SPSU‐PMTet0.5 at 150°C was determined as 2.2 × 10^?6 S cm^?1 while in humidified conditions at 20°C a value of 6 × 10^?3 S cm^?1 was found for SPSU‐PMTet2. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40107.     

Polypropylene membranes modified with interpenetrating polymer networks for the removal of chromium ions

Polypropylene (PP) membranes incorporating poly[(ar‐vinylbenzyl) trimethylammonium chloride] P(ClVBTA), and poly[sodium (styrene sulfonate)] P(SSNa) were modified via an “in situ” radical polymerization synthesis. Two methods were used for impregnation of the reactive solution: pressure injection and plasma superficial activation with argon gas. The following conditions were varied: the monomer concentrations, number of injections, and cross‐linked concentration. The modified polypropylene membranes were then characterized using scanning electron microscopy/energy dispersive X‐ray spectroscopy, Fourier transform‐infrared spectroscopy, electrokinetic potential, and Donnan dialysis for the chromium ions transport. The modified membranes exhibited a hydrophilic character with a water uptake capacity between 15% and 20% and a percent modification between 2.5% and 4.0%. This was compared with the results of an unmodified polypropylene membrane as the blank and the mentioned polypropylene membrane has not the capacity to uptake water because this kind of material is highly hydrophobic. Hexavalent chromium ions were efficiently transported by the modified membranes containing P(ClVBTA) via a plasma method and it achieved 59.2% extraction at pH 9.0 using a 1‐mol L^?1 NaCl extraction agent. Therefore, unmodified polypropylene membrane shows an extraction percentage close to 10% from the hexavalent chromium ions at pH 9.0. In the same way, the trivalent chromium transport using membranes modified with P(SSNa) achieved 49.0% extraction at pH 2.0 using 1 × 10^?1 mol L^?1 HNO₃ and 1 mol L^?1 NaCl as the extraction agents. Moreover, the unmodified polypropylene membrane reached a value close to 10% from the trivalent chromium ions using 1 × 10^?1 mol L^?1 HNO₃ and 1 mol L^?1 NaCl. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41953.     

Solubility parameter estimation and phase inversion modeling of bentonite-doped polymeric membrane systems

Effects of bentonite concentration on morphology and permeation characteristics of bentonite-doped polysulfone membranes were investigated. Solubility sphere for bentonite was constructed to estimate its solubility parameter. Thermodynamic modeling of phase inversion of this system was carried out using Flory–Huggins theory. The trade-off between thermodynamic and kinetic parameters was used to predict the membrane morphology for bentonite concentration varying from 0 to 5 wt %. The porosity of bentonite-doped membranes decreased up to 3 wt % that increased thereafter. Morphological analysis showed dense cross section with finger-like macrovoids at 3 wt % beyond which it changed to honeycomb structure with large circular voids. Permeability of 3 wt % membrane was the lowest (5.6 × 10⁻¹² m/Pa s) with 95% bovine serum albumin rejection. Contact angle of the membranes decreased from 83 to 66° with bentonite addition making the membrane more hydrophilic. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48450.     

Development of a high-performance polysulfone hybrid ultrafiltration membrane using hydrophilic polymer-functionalized mesoporous SBA − 15 as filler

A novel polysulfone hybrid ultrafiltration membrane was developed by blending hydrophilic poly[poly(ethylene glycol) methyl ether methacrylate] [P(PEGMA)] grafted mesoporous SBA-15 [SBA-g-P(PEGMA)] as filler. The hydrophilic SBA-g-P(PEGMA) fillers were synthesized via surface-initiated atom transfer radical polymerization. The effects of the SBA-g-P(PEGMA) fillers on the prepared hybrid membranes were systematically investigated. Compared with pristine SBA-15 fillers, SBA-g-P(PEGMA) fillers contributed to higher hydrophilicity and a more developed pore structure in the hybrid membranes. Specifically, SBA-15 grafted with a moderate P(PEGMA) molecular weight could better preserve the valid open-ended filler pore structure in the membrane matrix, thus facilitating membrane permeability. The pure water flux of the as-prepared polysulfone (PSF)/SBA-g-P(PEGMA) membrane was three times that of the PSF/SBA-15 membrane (271.7 L m⁻² h⁻¹ vs. 88.2 L m⁻² h⁻¹) with similar membrane selectivity. Moreover, the PSF/SBA-g-P(PEGMA) membranes showed improved antifouling property. This work paves the way for developing high-performance hybrid membranes by blending of hydrophilic polymer-functionalized mesoporous fillers in the future. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47353.     

Novel fixed‐carrier membranes for CO2 separation

A new membrane material having two kinds of CO₂ carriers was obtained. Composite membranes were prepared with the material and support membranes. The facilitated transport of CO₂ through these membranes was performed with pure CH₄ and CO₂ as well as CH₄/CO₂ mixtures containing 50 vol % CO₂. The results show that the membranes possess better CO₂ permeance than that of other fixed carrier membranes reported in the literature. In the measurements with pure gases, at 26°C, 0.013 atm of CO₂ pressure, the membrane with polysulfone support displays a CO₂ permeance of 7.93 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ ideal selectivity of 212.1. In the measurements with mixed gases, at 26°C, 0.016 atm of CO₂ partial pressure, the membrane displays a CO₂ permeance of 1.69 × 10^?4 cm³ /cm² s cmHg and CO₂/CH₄ selectivity of 48.1. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2222–2226, 2002     

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     

Evaluation of a hollow fiber oxygenator for use in bubble—free mammalian cell bioreactors

The oxygen transfer capabilities of a hollow fiber oxygenator for intended use in bubble-free aerated bioreactors have been evaluated experimentally. The oxygenator (480 mL), which is the main component of an artificial heart/lung unit used routinely in cardiopulmonary bypass procedures, was assessed for use in a recycle stream to determine if the oxygen requirements in bubble-free hybridoma cell bioreactors could be supported on a large scale. Oxygen transfer to simulated medium in a 15 L bioreactor was found to depend primarily on the liquid recirculation rate (1 to 5 L/min) and was not seriously affected by the air flowrate in the oxygenator (0.5 to 15 L/min). Based on the experimentally determined mass transfer coefficient across the membrane, it was found that the oxygenator could support a 100 L fermentor at an average cell density of 2xl0⁶ cells/mL with a specific uptake rate of 4.8 mgO₂/(10⁹ cells - h).Furthermore, if oxygen enriched air were to be used in the oxygenator, a single unit could support cell densities beyond 8xl0⁶cells/mL in a 100 L working volume fermentor.     

Preparation and gas separation performance of silicone-coated polysulfone membranes

Composite membranes (CM) were prepared by coating the dense surface of different asymmetric polysulfone flat membranes (AM) with a solution of silicone rubber polymer. The surface porosity (ε) of the dense skin AM samples varied between 4 × 10^?5 and 1·5 × 10^?8, with an average mean pore size between 0·10 and 0·07 μm. Scanning electron microscopy (SEM), gas permeation experiments (H₂, N₂, CH₄, CO₂) and a simple resistance model were used for the determination of structure-permeability relationships. This study indicates that the CM prepared with polysulfone AM having ε < 3 × 10^?7, coated with a concentration of 6% silicone solution and a contact time of 1 min, has the best gas separation performance, with selectivities very close to the intrinsic polysulfone selectivities.     

Effect of hydrophilic poly(ethylene glycol) methyl ether additive on the structure,morphology, and performance of polysulfone flat sheet ultrafiltration membrane

In this work, effects of hydrophilic poly(ethylene glycol) methyl ether (PEGME) 5000 additive on the structure, morphology, and performance of polysulfone (PSF) membrane have been investigated. The membranes are prepared with direct blending of PEGME5000 (0–9 wt %) with two compositions of PSF (12 and 15 wt %) into N-methyl-2-pyrrolidone and further characterized in terms of morphology, structure, fouling, and ultrafiltration performance. The ternary phase diagram is plotted to investigate the thermodynamic stability of the system. Moreover, protein adsorption tests are conducted using bovine serum albumin (BSA) to see the effect of PEGME5000 on surface hydrophilicity. The ultrafiltration experiments are performed using humic acid (HA) solution and oil-in-water (o/w) emulsion. The result showed that, the contact angle decreased from 64° to 46° and from 67.6° to 49° for 12M and 15M membranes, respectively, indicating an improved hydrophilicity. The 12M and 15M membranes with 9 wt % of PEGME5000 have the lowest BSA adsorption due to highest antifouling property. The maximum permeability was obtained 0.72 and 0.51 L/m² h kPa for 12M5 and 15M3, respectively, due to maximum porosity which is also supported by the morphological result. In HA permeation, 12M5 and 15M3 achieved a maximum Flux _RR around 0.95 and 0.91, respectively, which was remarkably higher compared to 0.61 and 0.62 Flux _RR of 12M0 and 15M0. Also, PEGME5000 significantly affected the structure and morphology of the membranes. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47163.     

CO2‐facilitated transport through poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate)/polysulfone composite membranes

Poly(N‐vinyl‐γ‐sodium aminobutyrate‐co‐sodium acrylate) (VSA–SA)/polysulfone (PS) composite membranes were prepared for the separation of CO₂. VSA–SA contained secondary amines and carboxylate ions that could act as carriers for CO₂. At 20°C and 1.06 atm of feed pressure, a VSA–SA/PS composite membrane displayed a pure CO₂ permeation rate of 6.12 × 10^?6 cm³(STP)/cm² s cmHg and a CO₂/CH₄ ideal selectivity of 524.5. In experiments with a mixed gas of 50 vol % CO₂ and 50 vol % CH₄, at 20°C and 1.04 atm of feed pressure, the CO₂ permeation rate was 9.2 × 10^?6 cm³ (STP)/cm² s cmHg, and the selectivity of CO₂/CH₄ was 46.8. Crosslinkages with metal ions were effective for increasing the selectivity. Both the selectivity of CO₂ over CH₄ and the CO₂ permeation rate had a maximum against the carrier concentration. The high CO₂ permeation rate originated from the facilitated transport mechanism, which was confirmed by Fourier transform infrared with attenuated total reflectance techniques. The performance of the membranes prepared in this work had good stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 275–282, 2006     

Preparation of composite anion exchange membranes based on in-situ copolymerization of N-vinyl formamide and divinylbenzene in porous PTFE

A series of composite anion exchange membranes was synthesized via in-situ copolymerization of various ratios N-vinyl formamide (NVF) and divinylbenzene (DVB), supported by porous polytetrafluoroethylene (PTFE) polymer matrix, and followed by alkaline hydrolysis, and quaternization of the composite membranes with epoxypropyltrimethylammonium chloride (EPTMAC). FTIR and SEM analyses revealed that the composite membranes were successfully prepared. Moreover, the hydrophilic property of the composite membrane improved by introduction of the quaternized poly(NVF-co-DVB) copolymer. Water uptake, swelling ratio, and conductivity showed upward trends by increase of NVF amount. The copolymer with 95% of NVF showed the highest elongation at break (102%, room temperature) and conductivity (5.15 × 10⁻² S/cm, 80°C). After immersion of the PNDB_95%-N membrane in 5 mol/L NaOH solution for 96 h at room temperature, the conductivity (60°C) of the membrane decreased to 3.99 × 10⁻² S/cm. Moreover, the membrane registered weight loss under 4.5%, caused by degradation of the quaternary ammonium groups in NaOH solution. All in all, in 3 mol/L methanol solutions, the composite membranes showed permeability ranging from 7.6% to 19.7%, if compared to the Nafion®-115 membrane, showing good alcohol resistance.     

Membranes for extracorporeal membrane oxygenator (ECMO): History,preparation, modification and mass transfer

Extracorporeal membrane oxygenator (ECMO) has been in development for nearly 70 years, and the oxygenator has gone through several generations of optimizations, with advances from bubble oxygenators to membrane oxygenators leading to more and more widespread use of ECMO. Membrane is the core of a ECMO system and the working mechanism of membrane oxygenator depends on the membrane material, from PDMS flat membrane to PMP hollow fiber membrane, which have experienced three generations. Blood compatibility on the surface of the membrane material is very vital, which directly determines the use duration of the oxygenator and can reduce the occurrence of complications. The mechanism of mass transfer is the basis of oxygenator operation and optimization. This review summarizes the membrane development history and preparation technology, modification approaches and mass transfer theory in the process of oxygen and blood exchange. We hoped that this review will provide more ideas for the study of gas blood exchange membrane.     

Preparation of an anion‐exchange membrane by the amination of chlorinated polypropylene and polyethyleneimine at a low temperature and its ion‐exchange property

An anion‐exchange membrane was prepared by the amination of chlorinated polypropylene and polyethyleneimine at a low temperature and was investigated with respect to not only its physical properties but also its electrochemical properties. The degrees of amination were 50.16, 53.76, 57.11, and 65.29% at 30, 40, 50, and 55°C, respectively. The base polymer membrane had no water uptake, whereas that of the aminated polymer membrane was 0.254, 0.296, 0.298, and 0.319 g of H₂O/g of dry membrane, respectively, with increasing amination. The prepared membranes possessed an ion‐exchange capacity in the range of 1.257–2.000 mequiv/g of dry membrane and a fixed ion concentration in the range of 4.492–6.261 mequiv/g of H₂O. The ionic conductivity of the aminated polymer membrane was highest when the water uptake was highest. Those of the prepared membrane were in the range of 0.89 × 10^?2 to 1.36 × 10^?2 S/cm. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation of anion exchange membrane by amination of chlorinated polypropylene and ethylenediamine and its properties

An anion exchange membrane was prepared by amination of chlorinated polypropylene (CPP) and ethylenediamine (EDA) at a low temperature and was investigated with respect to not only its physical properties but also its electrochemical properties. The degrees of amination were 46.05, 47.07, 50.56, and 56.58% at 30, 40, 50, and 55°, respectively. The CPP membrane had no water uptake, whereas, that of the CPP‐EDA membrane was 0.153, 0.243, 0.309, and 0.410 g of H₂O/g of dry membrane, respectively, with increasing amination. The CPP‐EDA membranes possessed an ion exchange capacity in the range 0.557–1.498 mequiv/g of dry membrane and a fixed ion concentration in the range 4.198–5.114 mequiv/g of H₂O. The ionic conductivity of the CPP‐EDA membrane was highest when the water uptake was highest. Those of the CPP‐EDA membrane were in the range 0.475 × 10^?2–0.999 × 10^?2 S/cm. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Separation of Humic Substances by Porous Ion-Exchange Membranes from Sulfonated Polysulfone

Abstract

Ultrafiltration involving sulfonated polysulfone membranes provides high efficiency for humic matter removal from water. The increase in ion-exchange capacity of the polymer matrix from 0.24 to 0.96 mmol SO₃H groups per 1 g of dry membrane increases the membrane pore diameter and its hydrophilicity, and thus the permeate flux from 0.05 to 3.69 m³/m²·d. In order to decrease the manufacturing cost, membranes from polysulfone and sulfonated polysulfone blends were investigated. It was shown that a one-to-one blend resulted in a membrane having similar antifouling properties to pure sulfonated polysulfone. Both membranes reject humic matter in the 91–98% range and show a flux decline of 5–30% as a result of surface fouling.     

Quaternized polysulfone‐based nanocomposite membranes and improved properties by intercalated layered double hydroxide

Two anions (dodecylbenzenesulfonate anion and stearate anion) are employed to synthesize intercalated layered double hydroxides (LDH) by co‐precipitation method. Then the intercalated LDHs are incorporated in the casting solutions of chloromethylated polysulfone (CMPSF) for fabricating quaternized polysulfone/LDH nanocomposite membranes. Fourier transform infrared, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy, and mastersizer laser particle size analysis are used to characterize the structure and morphology of LDHs and membranes. The properties of the composite membranes including water uptake, mechanical property, thermal stability, and ionic conductivity are investigated. Compared with other anion exchange membranes, both nanocomposite membranes containing 5% LDH sheets displayed better balanced performance. They exhibit the ionic conductivity of 3.58 × 10^?2 S cm^?1 and 3.86 × 10^?2 S cm^?1 at 60°C, respectively. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers     

Polysulfone‐based composite membranes with functionalized carbon nanotubes show controlled porosity and enhanced electrical conductivity

Composite membranes of functionalized (–COOH, –CONH₂, –N₃) carbon nanotubes/polysulfone (CNT/PS) synthesized by the phase‐inversion method show unique properties with respect to surface characteristics and the selective separation of metal ions from aqueous solution. Apart from the reduction in the pore size depending on the type of functionalities on the nanotubes, the pure water permeation could reach up to as high as ～600 L m^?2 h^?1 (LMH) at reduced pressures and could be due to the functionalized tips of the nanotubes on the membrane surface resulting from the phase inversion process used for the membrane fabrication. The membranes were characterized by small angle neutron scattering (SANS) to confirm the uniform distribution of the nanopores and the surface morphology of the membranes. Results show that rejection of Cu(II) was better than Pb(II) depending on the surface functionality. Interestingly, these membranes also showed enhanced conductivities in the range of 1.0 × 10^?2 S cm^?1, the conductivity depending on the type of functionality on the nanotubes, thus confirming the presence of functionalized nanotubes tips on the membrane surface. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43778.     

Molecule transfer mechanism in two-dimensional heterostructured lamellar membranes: The effects of dissolution and diffusion

Two-dimensional lamellar membranes are promising for efficient molecule transfer, while the underlying transfer mechanism is rarely elucidated. Herein, heterostructured nanosheets are prepared by self-assembling small-sized hydrophilic cyanuric acid melamine and hydrophobic g-C₃N₄ nanosheets. Resultant lamellar membranes show comparable affinity to polar and nonpolar solvents, allowing them to dissolve on membrane surface and diffuse through membrane channels. Results demonstrate that for lamellar membranes with distinct wettability, the permeance difference for polar solvents is originated from dissolution and diffusion processes, while that for nonpolar solvents is stemmed from dissolution process. Accordingly, corresponding equations which are suitable for heterostructured lamellar membranes are established. Importantly, polar solvents are induced to form ordered arrangement in hydrophilic nanodomains and then maintain the ordered state in hydrophobic nanodomains, affording a low-resistance transfer and high acetonitrile permeance of 1025 L m⁻² h⁻¹ bar⁻¹. In contrast, nonpolar solvents with disordered arrangement exhibit lower permeance than that of polar ones.     

New high permeable polysulfone/ionic liquid membrane for gas separation

In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO₂/CH₄ separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO₂/CH₄ separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO₂ permeation and CO₂/CH₄ selectivity due to high affinity of the ionic liquid to carbon dioxide. CO₂ permeation significantly increases from 4.3 Barrer (1 Barrer=10^-10 cm³(STP)·cm·cm^-2·s^-1·cmHg^-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH₄ molecules for CO₂ permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO₂/CH₄ separation membranes.     

Influence of Sulfonated Graphene Oxide on Sulfonated Polysulfone Membrane for Direct Methanol Fuel Cell

Novel proton exchange membranes consisting of an inorganic filler, namely sulfonated graphene oxide, embedded in sulfonated polysulfone were fabricated. The membrane performance depended on the sulfonated graphene oxide content possessed the functional groups to provide the interfacial interaction with sulfonated polysulfone through ionic channels and blocking effect. The membrane with 3% v/v sulfonated graphene oxide content embedded in the matrix was shown to be suitable for direct methanol fuel cell applications. The membrane exhibited the highest proton conductivity of 4.27?×?10^?3 S cm^?1 which was higher than that of Nafion117. Moreover, the membrane provided the lowest methanol permeability of 3.48?×?10^?7?cm²/s which was lower than that of Nafion117.