Preparation of zeolite-incorporated PDMS membranes for pervaporation separation of isopropanol-water mixtures

ZSM-5 zeolite-incorporated poly(dimethyl siloxane) membranes were prepared and molecular dispersion of zeolite in the membrane matrix was confirmed by scanning electron microscopy. After studying the behavior of membrane swelling at 30°C, the membranes were subjected to pervaporation separation of isopropanol-water mixtures at 30, 40 and 50°C. The effects of zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was discussed on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass%) exhibits the highest separation selectivity of 80.84 and flux of 6.78 × 10^?2kg/m²h at 30°C for 5 mass% of isopropanol in the feed. From the temperature dependency of diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane (M) exhibits higher E_p and E_D values compared to zeolite-incorporated membranes, signifying that permeation and diffusion require more energy for transport through a pure membrane, owing to its dense nature. Obviously, zeolite-incorporated membranes require less energy due to their molecular sieving action attributed to the presence of straight and sinusoidal channels in the framework of zeolite. All the zeolite-incorporated membranes exhibit positive ΔH_s values, suggesting that the heat of sorption is dominated by the Henry's mode of sorption.     

Effect of TiO2 nanoparticles on the surface morphology and performance of microporous PES membrane

PES-TiO₂ composite membranes were prepared via phase inversion by dispersing TiO₂ nanopaticles in PES casting solutions. The crystal structure, thermal stability, morphology, hydrophilicity, permeation performance, and mechanical properties of the composite membranes were characterized in detail. XRD, DSC and TGA results showed that the interaction existed between TiO₂ nanopaticles and PES and the thermal stability of the composite membrane had been improved by the addition of TiO₂ nanopaticles. As shown in the SEM images, the composite membrane had a top surface with high porosity at low loading amount of TiO₂, which was caused by the mass transfer acceleration in exposure time due to the addition of TiO₂ nanopaticles. At high loading amount of TiO₂, the skinlayer became much looser for a significant aggregation of TiO₂ nanopaticles, which could be observed in the composite membranes. EDX analysis also revealed that the nanoparticles distributed in membrane more uniformly at low loading amount. Dynamic contact angles indicated that the hydrophilicity of the composite membranes was enhanced by the addition of TiO₂ nanopaticles. The permeation properties of the composite membranes were significantly superior to the pure PES membrane and the mean pore size also increased with the addition amount of TiO₂ nanopaticles increased. When the TiO₂ content was 4%, the flux reached the maximum at 3711 L m⁻² h⁻¹, about 29.3% higher than that of the pure PES membrane. Mechanical test also revealed that the mechanical strength of composite membranes enhanced as the addition of TiO₂ nanopaticles.     

Synthesis and properties of side-chain-type ion exchange membrane PEEK-g-StSO3Na for bipolar membranes

Side-chain-type ion exchange membranes (PEEK-g-StSO₃Na) were prepared by grafting poly (ether ether ketone) (PEEK) containing propenyl groups with sodium sulfonic styrene (StSO₃Na) and KH570. PEEK was synthesized by the aromatic nucleophilic polycondensation reaction of 4,4′-difluorobenzophenone, bisphenol A and diallylbisphenol A. The synthesized copolymers with the -SO₃Na group on the side chain of polymers possessed high molecular weights. The cross-linking reaction was carried out through a sol-gel reaction of the trimethoxysilane group. The copolymer membranes exhibited excellent mechanical properties due to their aromatic structure extending through the backbone and flexible StSO₃Na aliphatic chains. The ion exchange capacities (IECs) of the membranes ranged from 2.27 to 2.50 mmol g⁻¹ and the water content ranged from 107.2 to 126.1%, with both parameters increasing with StSO₃Na grafting degree. The H⁺ permeability of copolymer membranes increased with increasing IEC, reaching value above 0.3056 mol/L at 2 h, which is higher than that of Nafion^® 117 at the same measurement condition. They displayed reasonably high H⁺ permeability due to the higher acidity of benzoyl sulfonic acid group, the larger interchain spacing, which is available for water occupation, and the lower AC impedance of the bipolar membrane.     

Materials and ion transport property studies on hot-press casted solid polymer electrolyte membranes: [(1 − x) PEO: x KIO3]

Materials and ion transport property characterization in Solid Polymer Electrolyte (SPE) membranes: (1 − x) PEO: x KIO₃, where x = 0, 10, 20, 30, 40, 50 wt.%, have been studied. SPE films have been prepared following two casting techniques: a novel hot-press (extrusion) and the traditional solution cast. Hot-press technique is a completely dry/solvent free/rapid/inexpensive procedure as compared to solution cast method and has recently been receiving wider acceptability to cast membranes of ion conducting polymeric electrolytes.‘Log σ − x’ study revealed σ-maxima at salt concentration x = 30 wt.% for SPE film prepared by both the methods. However, hot-pressed SPE film: 70 PEO: 30 KIO₃ exhibited relatively higher room temperature conductivity (σ ∼ 4.40 × 10^− 7 S cm^− 1) than that of the solution casted film. This has been referred to as Optimum Conducting Composition (OCC) SPE film. Materials characterization in OCC SPE film has been done by XRD, FTIR and DSC techniques. These studies confirmed the complexation of salt in the polymeric host. Some basic ionic parameters viz. conductivity (σ), ionic mobility (μ), mobile ion concentration (n), ionic transference number (t_ion) have been determined using different experimental procedures to understand the ion transport behaviour in OCC SPE material. The temperature dependent conductivity measurement has also been carried out and the activation energy (E_a) has been computed from the linear least square fitting of ‘log σ − 1 / T’ Arrhenius plot.     

PVA–APTEOS/TEOS Hybrid Sol–Gel Pervaporation Membrane for Dehydration of Ethanol

Novel organic–inorganic hybrid membranes were prepared by co-hydrolysis and co-condensation reactions of aminopropyltriethoxysilane (APTEOS) and tetraethylorthosilicate (TEOS) in poly(vinyl alcohol) (PVA) aqueous solution. These sol–gel reactions make a silica nanoparticles network which cross-links the structure of membranes. As a result, swelling properties of the membranes change due to these cross-linking reactions. The relative molar content of APTEOS to (APTEOS + TEOS) was changed from 0.0 to 0.75. The effect of APTEOS to (APTEOS + TEOS) on morphology as well as pervaporation performance of the membranes for dehydration of ethanol was investigated. It was found out that the hybrid membranes with a certain mass ratio of 1:1 (APTEOS + TEOS to PVA) exhibit higher permselectivity and more permeation flux for dehydration of ethanol aqueous mixtures compared with the PVA–TEOS membranes. Because hydrolysis and condensation reactions of mixed silanes make smaller silica nanoparticles, the permeability properties of the membranes improve in comparison with those of the membranes prepared using a single silane.     

Preparation of poly(vinyl alcohol)–silicone based hybrid membranes for the pervaporation separation of water–acetic acid mixtures

Hybrid membranes were prepared using poly(vinyl alcohol) (PVA) and tetraethylorthosilicate (TEOS) via hydrolysis followed by condensation. The obtained membranes were characterized by Fourier transform infrared spectroscopy, wide-angle x-ray diffraction and differential scanning calorimetry. A remarkable decrease in degree of swelling was observed with increasing TEOS content in membranes and is attributed to the formation of hydrogen bonding and covalent bonds in the membrane matrix. The pervaporation performance of these membranes for the separation of water–acetic acid mixtures was investigated in terms of feed concentration and the content of TEOS used as cross-linking agent. The membrane containing 1 : 2 mass ratio of PVA and TEOS gave the highest separation selectivity of 1116 with a flux of 3.33 × 10^?2kg/m²h at 30°C for 10 mass% of water in the feed. Except for membrane M-1, the observed values of water flux are close to the values of total flux in the investigated composition range, signifying that the developed membranes are highly water selective. From the temperature dependence of diffusion and permeation values, the Arrhenius apparent activation parameters have been estimated. The resulting activation energy values obtained, showing that water permeation is lower than that of acetic acid, suggest that the membranes have higher separation efficiency. The activation energy values calculated for total permeation and water permeation are close to each other for all the membranes except membrane M-1, signifying that coupled-transport is minimal because of the higher selective nature of membranes. The negative heat of sorption values (ΔH _s) for water in all the membranes suggests a Langmuir mode of sorption.     

Laser synthesis of palladium-alumina composite membranes for production of high purity hydrogen from gasification

This paper describes a special method of laser-based deposition to synthesize palladium-ceramic composite membranes. Thin film Pd was deposited on a ceramic substrate by Nd-YAG laser irradiation of coating precursor PdCl₂ on γ-alumina substrate. The parameters of the laser processing technique were optimized to synthesize metal-ceramic composite membranes. The physical and chemical characteristics of Pd coated γ-alumina membranes were studied and compared with various other alumina membranes referenced in the literature. Hydrogen permeation experiments were performed in a CO + CO₂ + CH₄ + H₂ environment under typical catalytic steam gasifier exit conditions. The Pd-ceramic composite showed good mechanical and thermal stability and resulted in a hydrogen permeability flux of about 0.061 mol/m² s. The activation energy of the Pd membrane was found to be 5.39 kJ/mol in a temperature range of 900-1300 °F.     

Preparation of highly ordered mesoporous AlSBA-15-SO3H hybrid material for the catalytic synthesis of chalcone under solvent-free condition

Single-step preparation of SBA-15 materials functionalized with both propylsulfonic acid groups and aluminum species (AlSBA-15-SO₃H) was carried out by hydrothermal treatment of a mixture of aluminum isopropoxide, 3-mercaptopropyltriethoxysilane, tetraethoxysilane, and triblock copolymer surfactant. At Si/Al molar ratio of 11-96, the materials exhibited well-ordered hexagonally arranged mesopores with pore diameter of ca. 9 nm, BET surface area of 546.9-666.0 m² g⁻¹, and pore volume of 0.82-1.03 cm³ g⁻¹. As-prepared AlSBA-15-SO₃H was successfully used in the Claisen-Schmidt condensation reaction of benzaldehyde with acetophenone to produce chalcone under solvent-free condition, and the influence of the reaction parameters including temperatures, molar ratios of BZD to APN, and aluminum loadings were considered during the chalcone synthesis procedure. It showed that AlSBA-15-SO₃H exhibited significantly high catalytic activity and selectivity, outperforming the reference catalysts such as sulfuric acid, ZSM-5, and acidic MCM-49. In addition, the catalytic stability and regeneration of AlSBA-15-SO₃H was studied.     

Effect of copper ions implantation on corrosion behavior of zircaloy-4 in 1 M H2SO4

In order to study the effect of copper ion implantation on the aqueous corrosion behavior, samples of zircaloy-4 were implanted with copper ions with fluences ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc source (MEVVA) operated at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. Glancing angle X-ray diffraction (GAXRD) was employed to examine the phase transformation due to the copper ion implantation. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zircaloy-4 in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zircaloy-4 implanted with copper ions when the fluence is smaller than 5 × 10¹⁶ ions/cm². The corrosion resistance of implanted samples declined with increasing the fluence. Finally, the mechanism of the corrosion behavior of copper-implanted zircaloy-4 was discussed.     

Invalidating mechanism of bis (3-sulfopropyl) disulfide (SPS) during copper via-filling process

The invalidating process and related mechanism of bis (3-sulfopropyl) disulfide (SPS) during copper via-filling process were investigated by means of electrochemical polarization measurement, and the mass spectrometry (MS) testing was employed to confirm the molecular weight (MW) and the structure of SPS invalidating products. Meanwhile, quantum chemistry calculation was used to verify the rationality of the proposed invalidating course. These results suggest that the solution containing SPS has invalidated after the passed charges (PC) reached 15 Ah L⁻¹ under electrifying condition. The adsorption ability of SPS decrease gradually with the increase of PC during the invalidating process. The invalidation of SPS is an oxidation process related to the dissolved oxygen in the solution, during which the active functional group -S-S- is oxidized to -SO_x-SO_y-. As a result, the accelerating effect of SPS on copper reduction will gradually diminish.     

Rational synthesis of α-MnO2 and γ-Mn2O3 nanowires with the electrochemical characterization of α-MnO2 nanowires for supercapacitor

An acidification-hydrothermal method was developed to synthesize α-MnO₂ nanowires, which was subsequently treated with ethanol, resulting in γ-Mn₂O₃ nanowire bundles on a large scale. The electrochemical characterization was carried out by cyclic voltammetry, which indicated that the α-MnO₂ nanowires in 0.5 mol L⁻¹ Na₂SO₄ aqueous electrolyte was of an excellent electrode material for supercapacitor at the scan rate of 10 mV S⁻¹ in the range of 0.0-0.85 V.     

Influence of titanium ions implantation on corrosion behavior of zirconium in 1 M H2SO4

In order to study the effect of titanium ion implantation on the aqueous corrosion behavior of zirconium, specimens were implanted with titanium ions with fluence ranging from 1 × 10¹⁶ to 1 × 10¹⁷ ions/cm², using a metal vapor vacuum arc (MEVVA) source at an extraction voltage of 40 kV. The valence states and depth distributions of elements in the surface layer of the samples were analyzed by X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES), respectively. The potentiodynamic polarization technique was employed to evaluate the aqueous corrosion resistance of implanted zirconium in a 1 M H₂SO₄ solution. It was found that a significant improvement was achieved in the aqueous corrosion resistance of zirconium implanted with titanium ions. The larger the fluence, the better is the corrosion resistance of implanted sample. Finally, the mechanism of the corrosion behavior of titanium-implanted zirconium was discussed.     

A novel method for the assembly of nano-zeolite crystals on porous stainless steel microchannel and then zeolite film growth

A new method that is simple, efficient, and clean was developed for seeding surfaces with a monolayer of covalently bonded zeolite seeds. This method was used to seed the microchannels fabricated on porous stainless steel with NaA nano-zeolites enabling the deposition and growth of defect-free zeolite film. The NaA nano-zeolites were attached to the surface of the stainless steel via alkoxysilane linkers (e.g., 3-chloropropyltrimethoxysilane and 3-aminopropyltrimethoxysilane) grafted on the stainless steel. The NaA zeolite grown on the microchannel by hydrothermal synthesis consists of intergrown, (1 1 1)-oriented pyramidal NaA crystals that completely clad the stainless steel grains. The zeolite cladding the grains grew uniformly until the zeolite layers of neighboring grain impinges, then intergrew to fully bridge the gaps between the grains forming a defect-free film layer. A separation factor of 10,000 and a flux of 0.04 kg m⁻² h⁻¹ were obtained for water pervaporation from a 3 wt% water-benzaldehyde solution at room temperature.     

Preparation and performance of polysulfone-sulfonated poly(ether ether ketone) blend ultrafiltration membranes. Part I

Ultrafiltration membranes were prepared from blends with polysulfone (PSf) and sulfonated poly(ether ether ketone) (SPEEK) by phase inversion technique. The blend membranes were prepared with polymer composition from 0 to15 wt%. Sulfonated poly(ether ether ketone) was used to improve the performance and permeability of blended membranes. The effects of polymer composition on compaction, pure water flux, water content, and membrane hydraulic resistance were studied. The membranes were also subjected to the determination of pore statistics and molecular weight cut-off (MWCO) determination studies by using different molecular weight of proteins. The porosity, pore size of the membranes increased with increasing concentrations of SPEEK in the casting solution. Similarly, the MWCOs of the blend membranes ranged from 20 to 45 kDa, depending on the various polymer blend compositions. The pure water flux of the PSf/SPEEK blend membranes increases from 16.7 to 61.5 l m⁻² h, when the concentration of SPEEK increased from 0 to 15 wt%. Scanning electron microscope (SEM) results qualitative evidence for the trends observed for the pore statistics and MWCO studies.     

Adsorption and electrochemistry of hemoglobin on Chi-carbon nanotubes composite film

This study describes the noncovalently functionalization of carbon nanotubes (CNTs) with natural biopolymer chitosan (Chi) as substrate for hemoglobin (Hb) immobilization. The noncovalently Chi-functionalized CNTs possessed an improved solubility in aqueous solution and was beneficial to form three-dimensional configuration of the CNTs film electrode. The adsorbed Hb in Chi-CNTs interface showed a pair of quasi-reversible redox peak with a formal potential of −0.34 V (vs. SCE) in 0.10 M pH 7.0 phosphate buffer solution and possessed good bioelectrochemical catalytic activities toward the reductions of H₂O₂.     

Stability, oxygen permeability and chemical expansion of Sr(Fe,Al)O3 − δ- and Sr(Co,Fe)O3 − δ-based membranes

Perovskite-type SrFe_0.7Al_0.3O_3 − δ and SrCo_0.8Fe_0.2O_3 − δ, and two related dual-phase composites with nominal compositions (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 and (SrCo_0.8Fe_0.2O_3 − δ)_0.7(SrAl₂O₄)_0.3, were comparatively studied employing controlled-atmosphere dilatometry, thermogravimetry, Mössbauer spectroscopy, and measurements of steady-state oxygen permeation fluxes through dense ceramic membranes. The composite materials display lower thermal and chemical expansion compared to the parent single-phase perovskites. The thermal expansion coefficients at 1023-1223 K are however still high, (20-23) × 10^− 6 K^− 1 at atmospheric oxygen pressure and (17-18) × 10^− 6 K^− 1 at p(O₂) = 10 Pa, thus limiting the range of possible membrane reactor configurations. Sr(Co,Fe)O_3 − δ-based materials exhibit extensive vacancy-ordering processes in inert atmospheres, resulting in a slow relaxation of the oxygen nonstoichiometry, chemical expansion and oxygen permeation fluxes. In comparison to Sr(Fe,Al)O_3 − δ, the stability of cobalt-containing ceramics in CO₂ is also poor, which leads to a partial blocking of the membrane surface by decomposition products and degradation of the oxygen transport. Thermogravimetric analysis showed that the interaction with carbon dioxide occurs even at elevated temperatures, up to 1223 K. Under high oxygen chemical potential gradients such as air/(H₂-H₂O), the composite membranes showed kinetically stable operation without bulk decomposition at 1073 K. The kinetic stabilization associated with surface-limited oxygen permeation was confirmed by the conversion-electron Mössbauer spectroscopy analysis of one (SrFeO_3 − δ)_0.7(SrAl₂O₄)_0.3 membrane exposed to dry CH₄ at 1173 K, where no traces of Fe²⁺ and metallic iron were detected in the reduced surface layer.     

Synthesis of modified vermiculite by interaction with aromatic heterocyclic amines

Vermiculite of general formula [Si_6.85Al_1.15][Mg_4.68Al_0.51Fe_0.63]O₂₀(OH)₄Ca_0.128Na_0.032K_0.094 reacted with heteroaromatic amines α-, β-, and γ-picolines from aqueous solution. The products were characterized by elemental analysis, infrared spectroscopy, and X-ray diffraction. The intercalated nanocompounds maintained the crystallinity and changed the original interlayer distance of 1422 pm to 1474, 1456, and 1474 pm, for the sequence of the guest picoline molecules. Natural and intercalated vermiculite can remove copper at the solid/liquid interface; removal 0.40 mmol g⁻¹ was obtained for the original matrix, and 1.10, 0.92, and 1.33 mmol g⁻¹ for the intercalated forms. These values are near the capacity of cation exchange (CEC) of this clay mineral, which can be possibly used as source of copper removal from aqueous solution.     

Preparation and characterization of asymmetric polyethersulfone and thin-film composite polyamide nanofiltration membranes for water softening

In this research, two types of nanofiltration membranes were prepared and evaluated for water softening. Their nanofiltration performance was evaluated by cross-flow filtration using NaCl (1 g/l) and MgSO₄ (1 g/l) solution at 5 and 10 bar, 25 °C and 10 l/min. The morphological studies were performed with SEM and AFM instruments. In addition, the hydrophilicity of membranes was examined by contact angle measurements. In the first type, asymmetric polyethersulfone (PES) nanofiltration membranes were prepared using phase inversion induced by immersion precipitation technique. Different components such as polyvinylpyrrolidone (PVP), polyethyleneglycole (PEG), acrylic acid and Triton X-100 were used as additive in the PES casting solution, which lead to the formation of new asymmetric nanofiltration membranes. Two concentrations of PES (20 and 25 wt%) and two different non-solvents (pure water and mixture of water (80 vol.%) and IPA (20 vol.%)) were used for preparing asymmetric nanofiltration membranes. The morphological studies showed that the membranes prepared with non-solvent containing 20 vol.% IPA have smoother surface and smaller pores in surface and sub-layer compared to membranes prepared with pure water as non-solvent. The flux was decreased when higher polymer concentration and mixture of water and IPA were employed for membrane formation. However, NaCl and MgSO₄ rejections were improved. In the second type, thin-film composite polyamide nanofiltration membrane was fabricated using interfacial polymerization of 1,3-phenylenediamine (PDA) with trimesoyl chloride (TMC). A rough and dense film was formed on the PES support membrane by interfacial polymerization. The water permeability of composite membrane was 7 and 21 kg m⁻² h⁻¹ at 5 and 10 bar, respectively. Moreover, the rejection to the MgSO₄ as divalent salt (85 and 90%) was high compared to the NaCl as monovalent salt (64 and 67%).     

Synthesis and utilization of Mg/Al hydrotalcite for removing dissolved humic acid

It has been synthesized Mg/Al layered double hydroxide anionic clay (Mg/Al hydrotalcite) through direct precipitation by adding 0.5 M NaOH solution into a mixed solution containing Mg(NO₃)₂ and Al(NO₃)₃ with molar ratio of 0.1:0.05 until the medium acidity reached pH 10.1. The synthesized Mg/Al hydrotalcite was then utilized to remove dissolved humic acid in aqueous medium. The humic acid was isolated from peat soil taken in Gambut District, South Kalimantan, Indonesia using the recommended procedure of IHSS (International Humic Substances Society). The removal of humic acid was mostly occurred through simple sorption process without accompanied by significant intercalation. The sorption was optimum at pH 9.0, with the first order rate constant, capacity and energy of sorption were 5.50 × 10⁻³ min⁻¹, 0.12 mmol g⁻¹ (69 mg g⁻¹), and 28.32 kJ mol⁻¹, respectively.     

Fabrication of metal nano-structures using anodic alumina membranes grown in phosphoric acid solution: Tailoring template morphology

The influence of experimental parameters on the morphology of the porous structure and on the formation kinetics has been investigated for anodic alumina membranes (AAM) grown in aqueous H₃PO₄ at 160 V. It was found that pore aspect ratio and membrane porosity on the solution-side surface are influenced by tensiostatic charge, bath temperature and the presence of Al³⁺ ions in solution. Morphological and kinetic data, recorded in different conditions, give useful information on the growth mechanism of pore channels in phosphoric acid solution.Nickel nano-structures have been fabricated using AAM as template. Electroless deposition, performed by adding the reducing agent to a suitable bath in several steps, resulted in the formation of short metal nanotubes (about 5 μm long) in the upper part of the channels. Long Ni nanowires (up to 25 μm) with aspect ratio higher than 100 were obtained by pulsed unipolar electrodeposition from a Watt bath. In this case, both the influence of some experimental parameters on the nanowires growth and the fast current transients during the electrodeposition steps were analyzed.