Composition,structure and mechanical properties of metal oxide coatings produced on titanium using plasma spraying and modified by micro-arc oxidation

Metal oxide coatings on VT6 titanium alloy were formed by plasma spraying of aluminum oxide powder and subsequent microarc oxidation at a current density from 1 to 3?kA/m². As a result of combined treatment, metal oxide coatings consisting of a mixture of aluminum and titanium oxides were obtained on the surface of titanium samples. The most pronounced changes in the morphology of the plasma-sprayed coating were observed at the highest current density of 3?kA/m². The open porosity decreased from 56% to 38% due to the modification by micro-arc discharges, whereas the microhardness increased from 1013?±?150 HV to 1639?±?31 HV.     

An experimental study of a fixed bed chlor-alkali reactor

A 100 A continuous ‘flow-by’ chlor-alkali membrane reactor was constructed with both anode and cathode consisting of fixed beds of 0.6 to 1 mm diameter graphite particles. The reactor was operated over a range of conditions with and without co-current flow of air or oxygen to the cathode. With an anolyte of 5 M NaCl and catholyte 1.4–3 M NaOH the reactor produced sodium hydroxide and chlorine with ≥80% efficiency at temperatures 28–100°C, absolute pressure 270–970 kPa and superficial current density up to 3.3 kA m^?2. For operation at 100°C and an average pressure of 870 kPa with no gas delivered to the cathode, the cell voltage increased linearly from 2.5V at 0.3 kA m^?2 (10 A) to 4.0 V at 3.3 kA m^?2 (100 A). When oxygen was delivered to the cathode at 1 litre min^?1 under 870 kPa average pressure, the corresonding cell voltages were 1.6 V at 0.3 kA m^?2 to 3.4 V at 3.3 kA m^?2. In operation with air under the same conditions the cell voltage rose from 1.6 V at 0.3 kA m^?2 to 3.1 V at 1.6 kA m^?2. The performance of the oxygen cathode deteriorated with lower pressure and temperature due to mass transfer constraints on the oxygen reaction in the fixed bed electrode.     

Electrochemical regeneration of ceric sulphate in an undivided cell

Ceric sulphate (0–0.5 m) was generated electrochemically from cerous sulphate slurries (0.5–0.8 m total cerium) in 1.61 m sulphuric acid, at 50 °C, using a bench scale differential area undivided electrochemical cell with an anode to cathode ratio of eleven. A cell current efficiency for Ce(IV) of 90% was obtained at an anode current density of 0.25 A cm^–2. An empirical model illustrates an increase in overall current efficiency for Ce(IV) with an increase in electrolyte velocity, an increase in total cerium concentration, and a decrease in the cell current. From separate kinetic studies on rotating electrodes, both, anode and cathode kinetics were found to be affected by cerium sulphate adsorption processes. Anode adsorption of cerous sulphate species leads to inhibited mass transfer and negatively affected current efficiencies for Ce(IV). Cathode adsorption of cerium sulphate is thought to be responsible for high cathode current efficiencies for hydrogen (93–100%). The dissolved cerous sulphate concentration increased with increasing ceric sulphate and total cerium sulphate concentrations resulting in slurries with a stable dissolved cerous sulphate concentration of as high as 0.851 m in 1.6 m H₂SO₄ at room temperature.     

Synthesis and evaluation of a ruthenium–copper oxide/silica catalyst derived from microemulsion processing

Bimetallic Ru–Cu catalysts supported on SiO₂ have been synthesized in microemulsions using sodium metasilicate (Na₂SiO₃), copper nitrate (Cu(NO₃)_2·3H₂O) and ruthenium chloride (RuCl₃) at 28 °C. The microemulsion system consists of sodium 1,4‐bis(2‐ethylhexyl) sulfosuccinate (AOT) and sodium dodecyl sulphate (SDS), cyclohexane, and an aqueous solution of sodium metasilicate or metal salts. The catalysts have been characterized by XPS, EDX/SEM with line scanning and they possess a very narrow pore size distribution (around 38 Å) and relatively high specific surface areas (around 400 m²/g). The catalytic results of the N₂O decomposition reveal that higher conversions of N₂O can be achieved by the catalysts synthesized from the microemulsion process at lower temperatures (around 400 °C).     

Scale-up of the perforated bipole trickle-bed electrochemical reactor for the generation of alkaline peroxide

This paper reports work on the scale-up of a perforated bipole trickle-bed electrochemical reactor for the electro-synthesis of alkaline peroxide. The reactor uses a relatively simple cell configuration in which a single electrolyte flows with oxygen gas in a flow-by graphite felt cathode, sandwiched between a microporous polyolefin diaphragm and a nickel mesh/perforated Grafoil anode/bipole. Both one and two-cell reactors are scaled-up from cathode dimensions 120 mm high by 25 mm wide and 3.2 mm thick (reactor-A) to 630 mm high by 40 mm wide and 3.2 mm thick (reactor-B). The scale-up is achieved by the use of constrictions that prevent segregation of the 2-phase flow in the larger cell, combined with switching from a polypropylene to a polyethylene diaphragm with improved transport properties and raising the electrolyte feed concentration from 1 to 2 M NaOH.For the one-cell reactor-B with a polypropylene diaphragm, operating on a feed of 1 M NaOH and oxygen at 900 kPa(abs)/20 °C, the peroxide current efficiency at a superficial current density of 5 kA m⁻² increases from 27% (un-constricted cathode) to 57% with a constricted cathode. The corresponding current efficiencies at 3–5 kAm⁻² for reactor-A and the constricted reactor-B are respectively 69–64% and 66–57%. Under similar conditions at 3–5 kA m⁻² the one-cell constricted reactor-B with a polyethylene diaphragm gives current efficiencies of 88–64%, and changing to an electrolyte of 2 M NaOH raises this range to 90–80%. At 3–5 kA m⁻² the equivalent two-cell (bipolar) constricted reactor-B shows current efficiencies of 82–74% and at 5 kA m⁻² obtains 0.6 M peroxide in 2 M NaOH with specific energy 6.5 kWh per kg H₂O₂.     

New concepts in the scale-up of chlorine-caustic mercury cells

Mercury cells of conventional design embody an elongated cathode, with a length which is a multiple of the width. For commercial cells installed to date this multiple is never less than 5 and for most models it is greater than 7. This elongated configuration has also been retained for cell sizes of highest current rating (up to 500 kA) and highest current density (up to 15 kA m^–2) as allowed by activated titanium anodes. While being in conformity with tradition, such geometry, when applied to the largest cells, neglects some fundamental rules based on hydrodynamics. New requirements must in fact be fulfilled to obtain optimum mercury flow at the highest current capacities and the highest current densities that characterize the ultimate trend. When the length-to-width ratio is kept below the present typical range, the cell performance also improves because of a decrease of the harmful effects due to accumulation of mercury butter on the cathode surface.List of symbols I current capacity (kA) - i cathode current density (kA m^–2) - C amalgam concentration (% Na) - L cathode length (m) - W cathode width (m) - S cathode area (m²) - Q mercury flow-rate (1 min^–1) - Re thickness Reynolds number ([3]) - t mercury cathode thickness (mm) - J cathode slope (mm m^–1) - k,m,n constants - amalgam density (13.6 g cm^–3) - amalgam dynamic viscosity (0.015 P)     

NaB5C–B5/C Composite Ceramics Prepared by Reaction Sintering in Na Vapor

Reaction sintering of sodium carbaboride (NaB₅C) was performed by heating compacts of mixtures of amorphous boron (B) and carbon black (C) powders (B/C molar ratio, 5/1) at 1173 K in Na vapor. The ceramics obtained from the compacts of B₅/C powder mixed with a ball mill (compact density, 1.67 Mg/m³) were the composites of NaB₅C (74 mass%) and unreacted B₅/C (26 mass%). The bulk density and bending strength of the composite ceramics were 2.04 ± 0.03 Mg/m³ and 320.9 ± 10.4 MPa, respectively. Transmission electron microscope observation revealed that nanometer‐size amorphous grains of B or C were included in the matrix of NaB₅C.     

Electrochemical removal of sodium ion from fermented food composts

Fermented food composts, to be recycled into fertilizer and animal feed, require sodium chloride concentrations to be less than 1 wt% due to several toxicities. Electrochemical methods are used to remove sodium ions from fermented food composts. By washing the compost with tap water (with no electric current applied), 48% of the initial sodium ion is removed. With an electric current density of 3 mA/cm² (the distance between the electrodes is 16 cm), the removal efficiency increases to 96% for a 36 h operation. Major factors influencing the efficiency are the treatment time and the electric current density. Removal efficiency increases with energy demand to yield 96% removal at 60 Kwh/m². Due to the difference in relative ionic mobility, less than 9% of calcium is removed, during the same operation time, which supports the feasibility of this method.     

Morphology, structure and magnetic properties of cobalt–nickel films obtained from acidic electrolytes containing glycine

This paper focuses on the development and optimization of electroplated cobalt–nickel (CoNi) alloys for use in biomedical microdevices. CoNi films were electrodeposited from glycine-containing electrolyte solutions at acidic pH. The influence of pH (2.5–5), temperature (55 and 80 °C), current density (from −5 to −40 mA cm⁻²), glycine concentration (0.5 and 1 mol dm⁻³) and the nature of the metal salts (chlorides or sulphates) on the composition and the magnetic properties of the films were systematically analyzed. The cobalt content varied between 50 and 83 wt% depending on the applied conditions. As a result, deposits showed variable morphologies, different structures (either hexagonal close-packed (hcp) or mixed hcp and face-centered cubic phases) and tunable magnetic properties, ranging from semi-hard (18.51 kA m⁻¹, i.e. 233 Oe) to very soft (1.43 kA m⁻¹, i.e. 18 Oe). To understand the role of glycine in this system, a comparison of the electrochemical processes, and the structural and magnetic properties is made for samples produced in glycine-containing and glycine-free baths.     

Preparation and optimization of ZrO2 modified P2-type Na2/3Ni1/6Co1/6Mn2/3O2 with enhanced electrochemical performance as cathode for sodium ion batteries

Surface stabilization is necessary for cathode materials to gain a long-term cycling stability because of unfavorable side reactions and exfoliation caused by corrosive environment. To improve the cyclic stability of P2-type ternary cathode Na_2/3Ni_1/6Co_1/6Mn_2/3O₂ for sodium ion batteries, we prepare a ZrO₂-coated Na_2/3Ni_1/6Co_1/6Mn_2/3O₂ through a simple wet chemical method. The coating layer is distributed homogeneously on the surface, and the fraction of ZrO₂ (1 wt-%, 2 wt-%, 3 wt-%, 4 wt-%, 5 wt-%) helps control the thickness of the coating layer. It turns out that all the materials exhibit pure P2 structure without any impurities. The material with a 2 wt-% ZrO₂ coating exhibits the best electrochemical performance in rate capability and long-term cyclic stability. It delivers a superior initial discharge capacity of 140 mA h·g⁻¹ between 2 and 4.5 V at 20 mA g⁻¹. Even cycles at high current density (100 mA g⁻¹), it shows 106 mA h·g⁻¹ reversible discharge capacity with 88% capacity retention after 300 cycles. The improvement in electrochemical performance is attributed to the segregation of cathode materials from the corrosive electrolyte by the nano-sized ZrO₂ layer. The EIS results confirm that a thin ZrO₂ coating layer can effectively protect the electrode from dissolution and stabilize the SEI film. This study can be used to develop the electrochemical performance of cathode materials for sodium ion batteries by surface modification via ZrO₂.     

Removal of arsenic from drinking water by the electrocoagulation using Fe and Al electrodes

A novel technique of electrocoagulation (EC) was attempted in the present investigation to remove arsenic from drinking waters. Experiments were carried out in a batch electrochemical reactor using Al and Fe electrodes with monopolar parallel electrode connection mode to assess their efficiency. The effects of several operating parameters on arsenic removal such as pH (4–9), current density (2.5–7.5 A m⁻²), initial concentration (75–500 μg L⁻¹) and operating time (0–15 min) were examined. Optimum operating conditions were determined as an operating time of 12.5 min and pH 6.5 for Fe electrode (93.5%) and 15 min and pH 7 for Al electrode (95.7%) at 2.5 A m⁻², respectively. Arsenic removal obtained was highest with Al electrodes. Operating costs at the optimum conditions were calculated as 0.020 € m⁻³ for Fe and 0.017 € m⁻³ for Al electrodes. EC was able to bring down aqueous phase arsenic concentration to less than 10 μg L⁻¹ with Fe and Al electrodes. The adsorption of arsenic over electrochemically produced hydroxides and metal oxide complexes was found to follow pseudo second-order adsorption model. Scanning electron microscopy was also used to analyze surface topography of the solid particles at Fe/Al electrodes during the EC process.     

Study of a high power density sodium polysulfide/bromine energy storage cell

Nickel catalyst supported on carbon was made by reduction of nickelous nitrate with hydrogen at high temperature. Ni/C catalyst characterization was carried out by XRD. It was found that the crystal phase of NiS and NiS₂ appeared in the impregnated catalyst. Ni/C and Pt/C catalysts gave high performance as the positive and negative electrodes of a sodium polysulfide/bromine energy storage cell, respectively. The overpotentials of the positive and negative electrodes were investigated. The effect of the electrocatalyst loading and operating temperature on the charge and discharge performance of the cell was investigated. A power density of up to 0.64 W cm^–2 (V = 1.07 V) was obtained in this energy storage cell. A cell potential efficiency of up to 88.2% was obtained when both charge and discharge current densities were 0.1 A cm^–2.     

Formic acid oxidation by carbon-supported palladium catalysts in direct formic acid fuel cell

The oxidation of formic acid by the palladium catalysts supported on carbon with high surface area was investigated. Pd/C catalysts were prepared by using the impregnation method. 30 wt% and 50 wt% Pd/C catalysts had a high BET surface area of 123.7 m²/g and 89.9 m²/g, respectively. The fuel cell performance was investigated by changing various parameters such as anode catalyst types, oxidation gases and operating temperature. Pd/C anode catalysts had a significant effect on the direct formic acid fuel cell (DFAFC) performance. DFAFC with Pd/C anode catalyst showed high open circuit potential (OCP) of about 0.84 V and high power density at room temperature. The fuel cell with 50 wt% Pd/C anode catalyst using air as an oxidant showed the maximum power density of 99 mW/cm². On the other hand, a fuel cell with 50 wt% Pd/C anode catalyst using oxygen as an oxidant showed a maximum power density of 163 mW/cm² and the maximum current density of 590 mA/cm² at 60 °C.     

Nitrogen doped graphene/cobalt-based catalyst layers of a PEM fuel cell: Performance evaluation and multi-objective optimization

The proton exchange membrane fuel cell could be made more commercially viable by substituting the expensive platinic catalyst without loss of performance. This should be done simultaneously through optimization and use of a non-precious metal catalyst. In this study, multi-objective optimization of the catalyst layer was done on nonprecious metal catalysts. Nitrogen-doped graphene (NG)-based cobalt was synthesized as a non-precious metal catalyst. Differential equations were solved at the modeling stage by the shooting method, and objective functions were solved at the optimization stage using sequential quadratic programming. NG-based cobalt was evaluated in a cell and then compared with the platinum catalyst. Results present the synthesized non-precious catalyst as an appropriate replacement for existing precious metal catalyst. Also, the polarization curve demonstrates that the current modeling is in good agreement with NG-based cobalt catalyst. Finally, the Pareto curve at the voltage of 0.6 V (and 300 A/m² current density in the base case) indicated that the best tradeoff between cost and performance of the catalyst layer was achieved when the current density was increased in the range of 5% to 15%.     

Bifunctional electrodes for an integrated water-electrolysis and hydrogen-oxygen fuel cell with a solid polymer electrolyte

An alternative concept of an integrated water electrolysis/hydrogen-hydrogen fuel cell using metal electrocatalysts and a solid polymer electrolyte is described. Instead of operating both electrodes as hydrogen and oxygen electrodes respectively the electrodes are used as oxidation and reduction electrodes in both modes of operation. A more suitable selection of electrocatalysts and an improved cell design are possible; both can increase the efficiency of the cell considerably. New results on the electrocatalytic activity of various noble-metal containing catalysts with respect to both oxygen evolution and hydrogen oxidation in a proton exchange membrane-cell at 80°C are reported. Kinetic data derived from Tafel plots of the oxygen evolution polarization curves agree closely with those of experiments with aqueous sulphuric acid electrodes. This agreement allows the determination of kinetic parameters for electrocatalysts difficult to prepare in solid smooth electrodes but easy to be made into porous deposits. Polarization curves of the hydrogen oxidation reaction clearly indicate a relative activity rating of the studied catalysts. In cycling tests the lifetime stability of the new bifunctional oxidation electrode was determined. Polarization data obtained under these conditions agree with those obtained in earlier experiments where electrodes were exposed to only one type of oxidation reaction. During a test of 10 cycles (30 min of electrolyser and 30 min of fuel cell mode each) no changes in the electrode potential were observed. With the conventional cell design employing a hydrogen and an oxygen electrode both catalyzed with platinum and a current density of 100 mA cm^–2 a storage efficiency of 50% was calculated; with the alternative concept of oxidation and reduction electrodes and selected oxidation catalysts this was improved to 57%. With further improvements these efficiencies seem possible even at current densities of 500 mA cm^–2.     

Modeling a perforated bipole trickle bed electrochemical reactor for the generation of alkaline peroxide

This paper describes the modeling of a novel perforated bipole electrochemical reactor with trickle-bed cathodes employed in the electrosynthesis of alkaline peroxide solutions. The model engages an electronic analogue of the 3D electrode/bipoles to solve the coupled material, energy and voltage (charge) balances that estimate the potential, current density, composition, pressure and temperature profiles through the reactor. The predictions of this model are compared to the performance of a bench scale experimental reactor operating at superficial current densities up to 5 kA m⁻². With eddy diffusion through the diaphragm as the single adjustable parameter the model shows good agreement with peroxide current efficiency but underestimates the electrochemical specific energy consumption by about 2 kWh/kg H₂O₂ at 5 kAm⁻².     

Electrochemical oxidation of sulphite ions at graphite electrodes

The electrochemical oxidation of sodium sulphite has been studied in aqueous sodium sulphate solution at two different graphite electrodes, one being of natural graphite (EC) and the other impregnated with phenol (ECK). The objective of the present work was to obtain some insight into the direct oxidation as well as the indirect oxidation, via produced oxygen radical species, of sulphite on non-metal electrodes. For this reason a study of the oxidation of sulphite in the concentration range between 0–0.10m in aqueous sodium sulphate using a batch electrochemical reactor, operating potentiostatically, was undertaken. The potential range was chosen between 1.0 to 2.5 V/SCE, and the concentration of the supporting electrolyte, sodium sulphate, was kept constant at 0.5m. A kinetic Tafel type law, considering irreversible behaviour for the direct sulphite oxidation and the mass transfer performance in regards to the experimental conditions were applied to predict the time variations of the sulphite conversion.     

High-rate electrochemical copper deposition on bars

The industrial electrodeposition of copper from cupric acid sulphate baths is typically carried out at approximately 3 kA m^?2. A much higher rate of copper deposition is necessary to improve this electroplating process significantly. To achieve this higher rate for the deposition of copper on a round bar, the solution flow is directed normal to the axis of a round bar. The current efficiencyη _Cu for copper deposition on a round bar, 9 mm in diameter, has been determined from 1 M H₂SO₄+1 M CuSO₄ bath as a function of current density, solution flow rate and temperature. A set of relations has been proposed for calculating the current efficiencyη _Cu for a broad range of parameters.     

A hybrid method through Faradaic rectification and a.c. impedance measurements for the corrosion rate determination of metal/oxide/electrolyte systems. II. Experimental results for anodized aluminium

An experimental verification of a method for the determination of the corrosion rate of metal/oxide/ electrolyte systems, using both faradaic rectification and a.c. impedance measurements, is reported using zone refined aluminium electrodes in 1 mol dm^–3 aqueous sodium sulphate at pH 1.9. The impedance and the rectification parameters due to the anodic oxide on the electrode have also been computed and used to determine instantaneous corrosion rate of the same system at different values of the pH. The direction and magnitude of rectification by this system are found to be sensitive to pH as well as dissolved oxygen in the electrolyte. They are explained by a decrease in equilibrium exchange current for the hydrogen evolution reaction with increase in pH and an inhibitive effect of oxygen on the former reaction.     

Preparation of ultra-light ceramic foams from waste glass and fly ash

Ultra-light ceramic foams were successfully prepared by a green spheres technique, which used waste glass powder and fly ash as the main material. Besides, borax and SiC were introduced as fluxing agent and foaming agent, respectively. The effects of fly ash content, borax content and sintering temperature on the microstructures and properties of ceramic foams were systematically investigated. The optimum composition is 30?wt-% fly ash, 70?wt-% waste glass, 15?wt-% borax and 0.5?wt-% SiC. Ultra-light ceramic foams sintered at 680–780°C possess bulk density of 0.14–0.41?g?cm^?3, porosity of 82.9–94.1%, compressive strength of 0.91–6.37?MPa and thermal conductivity of 0.070–0.121?W?m^?1?K^?1, respectively. This method is convenient, low-cost and environment friendly, which makes it a promising way for recycling solid wastes.