Polysulfone — sulfonated poly(ether ether) ketone blend membranes: systematic synthesis and characterisation

The effect of sulfonated poly(ether ether ketone) (SPEEK) in membrane formation and separation properties has been investigated in polysulfone(PSU)/SPEEK/N-methyl-2-pyrrolidinone (NMP) systems. Charged ultrafiltration/nanofiltration membranes were obtained reliably in the range of 0.5–5 wt.% SPEEK in the polymer blend. All PSU/SPEEK blend membranes had substantially higher water flux, salt rejection, porosity and greatly reduced particle adhesion compared to the PSU base membrane. Further, all of these properties varied systematically with variation of SPEEK content. Reproducibility and stability of the membrane properties was excellent. Pore sizes determined from dextran retention data and AFM measurements showed reasonable agreement. Membranes with 5 wt.% SPEEK demonstrated excellent overall properties. Such membranes had very high permeability, 22.6±1.6×10⁻¹¹ m³ s⁻¹ N⁻¹, 0.999 fractional rejection of 4000 Da dextran, 0.65 rejection of 0.001 M NaCl, and only 0.75 mN m⁻¹ adhesion of a 4 μm silica particle. Such membranes are very promising for scale-up of production and testing on real process streams.     

High performance direct methanol fuel cells based on acid–base blend membranes containing benzotriazole

Novel acid–base blend membranes consisting of acidic sulfophenylated poly(ether ether ketone ketone) (Ph-SPEEKK) and various amounts of basic polysulfone tethered with 5-amino-benzotriazole (PSf-BTraz) have been prepared and characterized. The blend membranes show higher proton conductivity and lower liquid uptake and dimensional swelling compared to plain Ph-SPEEKK and sulfonated poly(ether ether ketone) (SPEEK) membranes. The Ph-SPEEKK/PSf-BTraz blend membranes with optimized basic polymer contents exhibit lower methanol crossover and higher performance with improved stability in direct methanol fuel cells (DMFC) at various methanol concentrations (1–10 M) than plain Ph-SPEEK and Nafion-115 membranes.     

Post-irradiation time effects on the graft of poly(ethylene-alt-tetrafluoroethylene) (ETFE) films for ion exchange membrane application

Grafting of styrene followed by sulfonation onto poly(ethylene-alt-tetrafluoroethylene) (ETFE) was studied for synthesis of ion exchange membranes. Radiation-induced grafting of styrene onto ETFE films was investigated after simultaneous irradiation (in post-irradiation condition) using a ⁶⁰Co source. The ETFE films were irradiated at 20 kGy dose at room temperature and chemical changes were monitored after contact with styrene for grafting. The post-irradiation time was established at 14 days when the films were remained in styrene/toluene 1:1 v/v. After this period the grafting degree was evaluated in the samples. The grafted films were sulfonated using chlorosulfonic acid and 1, 2-dichloroethane 20:80 (v/v) at room temperature for 5 h. The membranes were analyzed by infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), thermogravimetric measurements (TG) and degree of grafting (DOG). The ion exchange capacity (IEC) of membranes was determined by acid–base titration and the values for ETFE membranes were achieved higher than Nafion^® films. Preliminary single cell performance was made using pure H₂ and O₂ as reactants at a cell temperature of 80 °C and atmospheric gas pressure. The fuel cell performance of ETFE films was satisfactory when compared to state-of-art Nafion^® membranes.     

Influence of acid–base properties of cobalt–molybdenum catalysts supported on magnesium orthophosphates in isomerization of 3,3-dimethylbut-1-ene

Synthesis and physico-chemical characterization of a pure magnesium phosphate (MgP) prepared by coprecipitation, and MgP modified by introduction of cobalt–molybdenum (4–12 wt.% of MoO₃ with the Co/Mo ratio fixed at 0.5) have been carried out. The structural properties of these catalysts were characterized by X-ray diffraction, their textural properties were determined by N₂ adsorption–desorption isotherms and the dispersion of cobalt–molybdenum was studied by XPS spectroscopy. Their acid properties have been investigated by in situ FT-IR spectroscopy of adsorbed molecules, often, 2,6-dimethylpyridine (pK_a = 6.7), pyridine (pK_a = 5.3). Co–Mo incorporation leads to a modification in the MgP acid–base properties, especially on the acid sites type and number. Thus, lower loading of cobalt–molybdenum species decreased the number of strong Lewis acid sites whereas higher loading increased it. It was found that Lewis acid sites on magnesium phosphates play an important role in the isomerization of 3,3-dimethylbut-1-ene.The 3,3-dimethylbut-1-ene (33DMB1) conversion increases with the reaction temperature from 493 to 653 K for MgP, but decreases after 573 K for MgP supported by Co–Mo. A linear relationship between both types of acid sites and conversion values was found. The deactivation of the catalysts appears at high reaction temperature (>573 K).     

Sulfonated polyethersulfone Cardo membranes for direct methanol fuel cell

Novel proton conducting membranes, sulfonated polyethersulfone Cardo (SPES-C), were prepared with concentrated sulfonic acid at room temperature. The degree of sulfonation was controlled by reaction time. Their proton conductivity and methanol permeability as a function of temperature were investigated. The SPES-C membranes with 70% DS were still not water soluble and had low degree of swelling. With the level of 70% sulfonation, proton conductivity was 0.011 S/cm at 80 °C, 0.0338 S/cm at 110 °C, which approached that of Nafion^® 115 membrane at the same conditions. Methanol permeability of SPES-C membranes was considerably smaller than that of Nafion^® 115 membrane over the temperature 25–80 °C.     

Membrane characterization by solute transport and atomic force microscopy

Various ultrafiltration and nanofiltration membranes were characterized by solute transport and also by atomic force microscope (AFM). The molecular weight cut-off (MWCO) of the membranes studied were found to be between 3500 and 98,000 Daltons. The mean pore size (μ_p) and the geometric standard deviation (σ_p) around mean ranged from 0.7 to 11.12 nm and 1.68 to 3.31, respectively, when calculated from the solute transport data. Mean pore sizes measured by AFM were about 3.5 times larger than calculated from the solute transport. Pore sizes measured by AFM were remarkably fitted to the log-normal probability distribution curve. Pore sizes of the membranes with low MWCO (20,000 Daltons and lower) could not be measured by AFM because of indistinct pores. In most cases, the pore density ranged from 38 to 1291 pores/μm². In general, the pore density was higher for the membrane having lower MWCO. Surface porosity was around 0.5–1.0% as measured from the solute transport and was 9.5–12.9% as obtained from AFM images. When membranes were coated with a thin layer of sulfonated polyphenylene oxide, mean pore sizes were reduced for all the membranes. Surface roughness was also reduced on coating.     

Characterization of non-uniformly charged ion-exchange membranes prepared by plasma-induced graft polymerization

Cation-exchange membranes were prepared by plasma-induced grafting of sulfonated glycidyl methacrylate (GMA) and porous polypropylene (PP) membranes. The chemical and physical structures of the prepared membranes were investigated using Fourier transform infrared spectroscopy (FTIR), field emission-scanning electron microscopy (FESEM) and electron-probe micro-analyzing (EPMA). The membranes were also characterized in terms of their electrochemical properties. A non-uniform distribution of fixed charges across the membrane matrix was detected by EPMA analysis. This non-uniform distribution of the fixed charges is the result of using water as solvent for the monomer which led to a fast reaction on the membrane surface and a slow diffusion of the monomer into the pores of the membrane. The prepared membranes exhibited moderate ion-exchange capacities (2.53–3.30 mmol/g dry membrane) and electrical resistances (0.349–0.589 Ω cm²) and an ion permselectivity comparable to that of the commercial membrane CM-1 (Tokuyama Corp.), while the water content of the membranes was significantly higher than that of the commercial membrane. The higher water content of the membranes is the result of water occupying the pores in the bulk of the support membrane after the dense layers with fixed charges are formed on the membrane surfaces by the grafting reaction. The relatively high ion permselectivity in spite of the high water sorption of the membranes is the result of the high fixed charge density in the layers on the membrane surfaces. Current versus voltage curves and the chronopotentiometric measurements revealed that the sulfonated GMA-g-PP membranes can be operated effectively at high current density.     

The oxidation of ascorbate at copolymeric sulfonated poly(aniline) coated on glassy carbon electrodes

Self-doped poly(aniline)s as electrode coatings to catalyze ascorbate oxidation are revisited in this article. Sulfonated poly(aniline) (SPAN) was deposited on glassy carbon electrodes as a copolymer of aniline and its sulfonated derivative, 2-aminobenzenesulfonic acid (2-ABSA). The resulting deposits are reproducible and show good stability and electroactivity at pH > 7, enabling studies at typical physiological pH values. Calibration curves were obtained using a rotating disc electrode at a sampling potential of 0.2 V, displaying linear dependence in the region 0–20 mM ascorbate. A kinetic model based on the Michaelis–Menten reaction mechanism, previously validated for poly(aniline) composites, was used to analyse the form of the calibration curve leading to values of the effective reaction constants K_ME and k′_ME. New calibration curves constructed for different sampling potentials were used to elucidate the rate limiting step at saturated kinetics. Rotating disc voltammetry performed at increasing pH (from pH 2 to 9) showed a dramatic decrease in the limiting current, without any evidence for a change in the reaction mechanism.     

Electro-electrodialysis of hydriodic acid using the cation exchange membrane cross-linked by accelerated electron radiation

Electro-electrodialysis (EED) of hydriodic acid with HI molality of ca. 9.5 mol/kg was examined in the presence of iodine using a commercial cation exchange membrane (CMB) as a separator. For the increase of the selectivity of proton permeation, the membrane was cross-linked by accelerated electron radiation. The membrane properties (area resistance, ion exchange capacity (IEC), water content) of the cross-linked membranes were measured. The area resistance in 2 mol/dm³ KCl solution of the cross-linked membranes decreased as compared with that of the non-cross-linked membrane (original of CMB membrane). The IEC and water content of cross-linked membranes at each dose rate had almost the same value as that of non-cross-linked membrane. Electro-electrodialysis of hydriodic acid with HI molality of ca. 9.5 mol/kg was examined at 75 °C with 9.6 A/dm². The cross-linked cation exchange membrane by accelerated electron radiation had higher selectivity of the proton permeation by cross-linking structure of polymer than that of the non-cross-linked membrane.     

Water-swollen cation-exchange membranes prepared using poly(vinyl alcohol) (PVA)/poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA)

A water-swollen type of poly(vinyl alcohol) (PVA)/poly(styrene sulfonic acid-co-maleic acid) (PSSA-MA) cation-exchange membrane was prepared and characterized in terms of its electrochemical properties including ion-exchange capacity (IEC), electrical resistance, and transport number, etc. PVA/PSSA-MA membranes exhibited low electrical resistance and highly swelling property. In spite of 2–4 times higher water swelling ratio (WSR) than that of CMX (Tokuyama Corp., Japan), the transport number of the prepared membrane was comparable to that of the commercial membrane (t_n>0.93). Moreover, the electric resistance of PVA/PSSA-MA membrane was measured as low as 1.0–1.5 Ω cm². Further, in this study, interrelation between the membrane characteristics and crosslinking was investigated, and the result exhibited that the crosslinking degree is one of major factors affecting the ion transport through a water-swollen ion-exchange membrane (IEM).     

Papain incorporated chitin dressings for wound debridement sterilized by gamma radiation

Wound debridement is essential for the removal of necrotic or nonviable tissue from the wound surface to create an environment conducive to healing. Nonsurgical enzymatic debridement is an attractive method due to its effectiveness and ease of use. Papain is a proteolytic enzyme derived from the fruit of Carica papaya and is capable of breaking down a variety of necrotic tissue substrates. The present study was focused on the use of gamma radiation for sterilization of papain dressing with wound debriding activity. Membranes with papain were prepared using 0.5% chitin in lithium chloride/dimethylacetamide solvent and sterilized by gamma radiation. Fluid absorption capacity of chitin–papain membranes without glycerol was 14.30±6.57% in 6 h. Incorporation of glycerol resulted in significant (p<0.001) increase in the absorption capacity. Moisture vapour transmission rate of the membranes was 4285.77±455.61 g/m²/24 h at 24 h. Gamma irradiation at 25 kGy was found suitable for sterilization of the dressings. Infrared (IR) spectral scanning has shown that papain was stable on gamma irradiation at 25–35 kGy. The irradiated chitin–papain membranes were impermeable to different bacterial strains and also exhibited strong bactericidal action against both Gram-positive and Gram-negative bacteria. The fluid handling characteristics and the antimicrobial properties of chitin–papain membranes sterilized by gamma radiation were found suitable for use as wound dressing with debriding activity.     

Protonation thermodynamics of some aminophenol derivatives in NaCl(aq) (0 ⩽ I ⩽3 mol · kg−1) at T = 298.15 K

The acid–base properties of four aminophenol derivatives, namely m-aminophenol (L1), 4-amino-2-hydroxytoluene (L2), 2-amino-5-ethylphenol (L3) and 5-amino-4-chloro-o-cresol (L4), are studied by potentiometric and titration calorimetric measurements in NaCl_(aq) (0 ? I ? 3 mol · kg^?1) at T = 298.15 K. The dependence of the protonation constants on ionic strength is modelled by the Debye–Hückel, SIT (Specific ion Interaction Theory) and Pitzer equations. Therefore, the values of protonation constants at infinite dilution and the relative interaction coefficients are calculated. The dependence of protonation enthalpies on ionic strength is also determined. Distribution (2-methyl-1-propanol/aqueous solution) measurements allowed us to determine the Setschenow coefficients and the activity coefficients of neutral species. Experimental results show that these compounds behave in a very similar way, and common class parameters are reported, in particular for the dependence on ionic strength of both protonation constants and protonation enthalpies.     

A capillary water retention effect to improve medium-temperature fuel cell performance

We demonstrate that small and narrow hydrophilic conducting domain morphology in sulfonated aromatic membranes leads to much better fuel cell performance at medium temperature and low humidity conditions than those with larger hydrophilic domains. A comparison of three types of sulfonated poly(arylene ether sulfone)s (SPAES) with random, block, and graft architecture indicates that small hydrophilic domain sizes (< 5 nm) appear to be important in supporting water retention under low relative humidity (RH) conditions intended for medium temperature (> 100 °C) fuel cell applications. The graft copolymer outperformed both a random copolymer and multiblock copolymer at 120 °C and 35% RH fuel cell operating conditions due to capillary condensation of water within the 3–5 nm hydrophilic domains.     

Macroporous chitin affinity membranes for wheat germ agglutinin purification from wheat germ

Macroporous chitin membranes of controlled porosity and pore sizes have been prepared. They have good mechanical properties and allow high flow rates of protein solutions at low pressure drops. Because of the numerous N-acetyl-D-glucosamine (GlcNAc) moieties they contain, the chitin membranes can be used for the separation of some valuable proteins both as affinity ligands and support matrix, without further modification. Due to their high porosity and high adsorption surface area, the chitin membranes provide a larger number of accessible binding sites for the wheat germ agglutinin than the chitin beads do. The adsorption capacity for wheat germ agglutinin (180 mg/g chitin membrane) is about 20 times larger than that of chitin beads. Because of the numerous binding sites, multiple-point bindings are involved in the protein adsorption. For this reason, a strong eluant, namely a 1 M acetic acid aqueous solution, had to be used to efficiently recover the wheat germ agglutinin from the membrane. The wheat germ agglutinin was extracted from wheat germ with 0.05 M HCl, precipitated with ammonium sulfate, dialyzed against 0.01 M Tris–HCl buffer (pH 8.5), and purified on the chitin membrane. A high purity (>99%) wheat germ agglutinin with high yield (∼50 mg/100 g wheat germ) was obtained.     

Polyimide-derived carbon nanofiber membranes as anodes for high-performance flexible lithium ion batteries

Heteroatoms-doped carbon nanofiber membranes with flexible features were prepared by electrospinning with heterocyclic polyimide (PI) structures containing biphenyl and pyrimidine rings. The products with optimized treatment could achieve 695 mAh/g at 0.1 A/g and retain 245 mAh/g at 1.5 A/g after 300 cycles when used as anode for Li-ion batteries.     

Pervaporation separation of aromatic/aliphatic hydrocarbons by crosslinked poly(methyl acrylate-co-acrylic acid) membranes

Copolymers of methyl acrylate and acrylic acid were synthesized to fabricate membranes ionically crosslinked using aluminum acetylacetonate for the separation of toluene/i-octane mixtures by pervaporation at high temperatures. The formation of the ionic crosslinking via bare aluminum cations was characterized by UV–VIS spectroscopy and solubility tests. Reproducibility and the reliability of the methodology for membrane formation and crosslinking were confirmed. The effects of acrylic acid content, crosslinking conditions, pervaporation temperature, and feed composition on the normalized flux and the selectivity for toluene/i-octane mixtures were determined. A typical crosslinked membrane showed a normalized flux of 26 kg μm m⁻² h⁻¹ and a selectivity of 13 for a 50/50 wt.% feed mixture at 100°C. The pervaporation properties including solubility selectivity and diffusivity selectivity are discussed in terms of swelling behavior. The performance of the current membranes were benchmarked against other membrane materials reported in the literature.     

Multiwavelength spectrophotometric determination of acidity constants of 1-（2-thiazolylazo）-2-naphthol in methanol-water mixtures

The acid-base properties of 1-(2-thiazolylazo)-2-naphthol (TAN) in mixtures of methanol-water at 25℃and an ionic strength of 0.1 mol/L are studied by a multi-wavelength spectrophotometric method.The acidity constants of all related equilibria are estimated using the whole spectral fitting of the collected data to an established factor analysis model DATAN program was used for determination of acidity constants.The corresponding pK_a values in methanol-water mixtures were determined.There is a linear relationship between acidity constants and the mole fraction of methanol in the solvent mixtures.     

Stability and performance of porous silica–zirconia composite membranes for pervaporation of aqueous organic solutions

Porous silica–zirconia membranes were fabricated by the sol–gel techniques to study their stability against water and the pervaporation performance of aqueous solutions of organic solvents. Zirconia (10–70 mol%) was added to silica to obtain silica–zirconia composite membranes by firing at 400–500 °C for pervaporation tests with organic solvent/water mixtures, such as iso-propyl alcohol (IPA)/water and tetrahydrofuran (THF)/water mixtures at their normal boiling points.The membrane coatings have been done effectively by the hot-coating methods proposed previously. Boiling water treatments introduced in the coating processes have made the membranes quite stable even in the high water concentration region of aqueous organic solutions at their normal boiling points. Zirconia contents larger than about 40 mol% have made the silica–zirconia membranes quite stable. The membranes of zirconia contents less than about 30 mol% were found not stable in a dilute aqueous solution of IPA. The membranes fabricated by the conventional dip-coating methods with slow drying were not stable against water because of the probable segregation of silica and/or silica-rich phases during drying.The membranes fired at lower temperature (400 °C) gave a higher water flux of around 500 mol m⁻² h⁻¹ (9 kg m⁻² h⁻¹) with a separation factor larger than 1500 at 10 wt.% of water in the boiling feed of IPA/water mixture, for example.     

Stability of NF membranes under extreme acidic conditions

Two commercial nanofiltration (NF) membranes (FilmTec NF-45 and Desal-5 DK) and two new NF-1 membranes made by BPT (Bio Pure Technology) for the purpose of a European Union funded research project (RENOMEM) were tested under extreme acidic conditions. The polyethersulphone (PES) ultrafiltration (UF) supports used for casting the BPT-NF-1 membranes were also tested under similar conditions. The 006 and 015 UF supports were found to be stable in 5% nitric acid at 20 and 80 °C for 4 and 3 months, respectively. Both supports (006 and 015) showed a significant reduction in flux after immersion in sulphuric acid at both temperatures. The BPT-NF-1 membranes showed excellent resistance to 20% sulphuric acid for up to 4 months at 20 °C but were attacked by the nitric acid solution. The resistance of the two commercial membranes in 20% sulphuric acid at 20 °C was generally lower than that of the BPT-NF-1 membranes. The NF-45 membrane was slightly more stable in 5% nitric acid at 20 °C. Degradation of the membrane occurred only after 2 months while both the Desal-5 DK and BPT-NF-1 membranes degraded during the first month. At the higher temperature of 80 °C in 5% nitric acid all membranes degraded in the first month.The cause of membrane degradation was attributed to oxidation of the thin NF selective skin layer in nitric acid and to acid-catalysed hydrolysis of this layer in sulphuric acid. Knowing the cause of membrane degradation is a step forward in developing a better and more stable nanofiltration membrane.     

TEMPO addition into pre-irradiated fluoropolymers and living-radical graft polymerization of styrene for preparation of polymer electrolyte membranes

We prepared proton exchange membranes (PEMs) by 2,2,6,6-tetramethylpiperidinyl-1-oxy (TEMPO)-mediated living-radical graft polymerization (LRGP) of styrene into fluoropolymer films and subsequent sulfonation. Poly(vinylidene fluoride) (PVDF) and poly(ethylene-co-tetrafluoroethylene) (ETFE) films were first irradiated and then treated with TEMPO solutions in various solvents. TEMPO addition was confirmed by the test of styrene grafting into TEMPO-treated films at 60 °C, at which the LRGP never proceeds. This test enabled us to differentiate the LRGP from the conventional graft polymerization. In order to gain a deep insight about TEMPO-addition reaction, the TEMPO-penetration behavior into the base polymer films was examined by a permeation experiment and computer simulation. Xylene and dioxane were appropriate solvents for the complete introduction of TEMPO into PVDF and ETFE films, respectively. Then, the LRGP of styrene was performed based on the fully TEMPO-capped films at 125 °C with various solvents. By using an alcoholic solvent, the degree of grafting was enhanced and it reached a maximum of 38%. This grafted film was sulfonated to prepare a PEM showing an ion exchange capacity of 2.2 meq/g and proton conductivity of 1.6×10^?1 S/cm.