Solid state electrochemical sensor for monitoring Mg in Al refining process

Novel solid-state electrochemical sensors have been designed using the Mg2+ cation conductors incorporating novel solid-state reference electrodes for in-line monitoring of Mg in molten Al during the refining process and also for in-line monitoring of Mg content in molten Al in the alloying process. In this paper we report the preparation of Mg2+ ion conductors, MgAl2O4 and MgZr4(PO4)6, by the solid state ceramic synthesis route, measurement of their electrical properties using ac-impedance spectroscopy and application of the above cation conductors for designing novel electrochemical sensors for monitoring Mg dissolved in molten Al. The activation energy for Mg2+ ion conduction in MgAl2O4 is 2.08 eV and in MgZr4(PO4)6 is 1.7 eV, respectively. The sensors have been found to respond rapidly to change in Mg content in molten aluminium around 1000 K.

Gibbs energy of formation of CaCu3Ti4O12 and phase relations in the system CaO-CUO/CU2O-TiO2

he standard Gibbs energy of formation of CaCu3Ti4O12 (CCTO) from CaTiO3, CuO and TiO2 has been determined as a function of temperature from 925 to 1350 K using a solid-state electrochemical cell with yttria-stabilized zirconia as the solid electrolyte. Combining this result with information in the literature on CaTiO3, the standard Gibbs energy of formation of CCTO from its component binary oxides, CaO, CuO and TiO2, has been obtained: View the MathML source (CaCu3Ti4O12)/J mol−1 (±600) = −125231 + 6.57 (T/K). The oxygen chemical potential corresponding to the reduction of CCTO to CaTiO3, TiO2 and Cu2O has been calculated from the electrochemical measurements as a function of temperature and compared on an Ellingham diagram with those for the reduction of CuO to Cu2O and Cu2O to Cu. The oxygen partial pressures corresponding to the reduction reactions at any chosen temperature can be read using the nomograms provided on either side of the diagram. The effect of the oxygen partial pressure on phase relations in the pseudo-ternary system CaO–CuO/Cu2O–TiO2 at 1273 K has been evaluated. The phase diagrams allow identification of secondary phases that may form during the synthesis of the CCTO under equilibrium conditions. The secondary phases may have a significant effect on the extrinsic component of the colossal dielectric response of CCTO.

Large reduction of leakage current by graded-layer La doping in (Ba0.5, Sr0.5)TiO3 thin films

A large reduction in the leakage current behavior in (Ba, Sr)TiO3 (BST) thin films was observed by graded-layer donor doping. The graded doping was achieved by introducing La-doped BST layers in the grown BST films. The films showed a large decrease (about six orders of magnitude) in the leakage current in comparison to undoped films at an electric field of 100 kV/cm. The large decrease in leakage current was attributed to the formation of highly resistive layers, originating from compensating defect chemistry involved for La-doped films grown in oxidizing environment. Temperature-dependent leakage-current behavior was studied to investigate the conduction mechanism and explanations of the results were sought from Poole–Frenkel conduction mechanism.

Supercapacitor studies on globular polypyrrole microstructures developed by a facile electrochemical route

Micrometre-scale polypyrrole (PPy) structures are synthesised for electrochemical supercapacitor applications by a facile electrochemical route. Globular polypyrrole microstructures of size < 5 μm are grown on stainless steel (SS-304) substrate by electro-polymerisation of pyrrole on oxygen microbubble templates electrochemically generated and stabilised in the presence of surfactant/supporting electrolyte/ dopant b-naphthalene sulfonic acid (b-NSA). Microstructures obtained with scan range of 0??1.6 V (against Ag/AgCl) are uniformly distributed over the surface with high coverage density of 5 x 105 to 8 x 10 cm-2. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the formed microstructures are of Β-NSA doped PPy. Scanning electron microscopy showed the uniform spread and good coverage of microstructures over the substrate. Supercapacitor properties of PPy films are investigated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge methods with 1.0 M KCl as electrolyte in a three-electrode electrochemical cell. Specific capacitance of 583 Fg-1 is obtained, which is greater than the values (350-400 Fg-1 highest) usually reported for this material. Electrochemical impedance spectroscopy proves the superc

Electrochemical detection and removal of lead in water using poly(propylene imine) modified re-compressed exfoliated graphite electrodes

Modification of exfoliated graphite (EG) electrode with generation 2 poly(propylene imine) dendrimer by electrodeposition resulted in an electrochemical sensor which was used to detect lead ions in water to a limit of 1 ppb and a linear response between 2.5 and 40 ppb using square wave anodic stripping voltammetry (SW-ASV). Pb(II) was also removed from spiked water sample using a 40-mm diameter unmodified EG electrode with an applied potential of -1,000 mV for 180 min. A removal efficiency of 99% was calculated from a 150 mL sample. The results obtained in both cases using SW-ASV, correlated with atomic absorption spectroscopy.

Supercapacitor studies on globular polypyrrole microstructures developed by a facile electrochemical route

Micrometre-scale polypyrrole (PPy) structures are synthesised for electrochemical supercapacitor applications by a facile electrochemical route. Globular polypyrrole microstructures of size <5 mu m are grown on stainless steel (SS-304) substrate by electro-polymerisation of pyrrole on oxygen microbubble templates electrochemically generated and stabilised in the presence of surfactant/supporting electrolyte/dopant beta-naphthalene sulfonic acid (beta-NSA). Microstructures obtained with scan range of 0-1.6 V (against Ag/AgCl) are uniformly distributed over the surface with high coverage density of 5 x 10(5) to 8 x 10 cm(-2). Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy revealed that the formed microstructures are of beta-NSA doped PPy. Scanning electron microscopy showed the uniform spread and good coverage of microstructures over the substrate. Supercapacitor properties of PPy films are investigated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge/discharge methods with 1.0 M KCl as electrolyte in a three-electrode electrochemical cell. Specific capacitance of 583 Fg(-1) is obtained, which is greater than the values (350-400 Fg(-1) highest) usually reported for this material. Electrochemical impedance spectroscopy proves the supercapacitance behaviour and explains the special inductive component of impedance observed in the high-frequency regime because of the globular structures of PPy deposited

Electrochemical oxidation of boron containing compounds on titanium carbide and its implications to direct fuel cells

Electrochemical oxidation of sodium borohydride (NaBH(4)) and ammonia borane (NH(3)BH(3)) (AB) have been studied on titanium carbide electrode. The oxidation is followed by using cyclic voltammetry, chronoamperometry and polarization measurements. A fuel cell with TiC as anode and 40 wt% Pt/C as cathode is constructed and the polarization behaviour is studied with NaBH(4) as anodic fuel and hydrogen peroxide as catholyte. A maximum power density of 65 mW cm(-2) at a load current density of 83 mA cm(-2) is obtained at 343 K in the case of borhydride-based fuel cell and a value of 85 mW cm(-2) at 105 mA cm(-2) is obtained in the case of AB-based fuel cell at 353 K. (C) 2011 Elsevier Ltd. All rights reserved.

Some adsorption-nucleation-based models for electrochemical phase formation

A new class of models which are based on adsorption, nucleation growth and their coupling is discussed. In particular, the potentiostatic response of a model that involves nucleative phase growth via direct incorporation and adsorptive discharge of metal ions on the free area is analysed for both instantaneous and progressive nucleation. This model is able to predict certain experimental features in the potentiostatic transient, like the initial fall, shoulder or maximum (as well as minimum) which have not been predicted by models analysed hitherto.Limiting behaviour for short and long times as well as a description of the above-mentioned features in terms of model parameters are given.A special case of the above model, viz. a reversible adsorption–nucleation model, wherein the adsorption is very fast, is shown to give rise to transients which can be distinguished from the pure nucleation-growth transients only by its parametric dependence, but not by the form.

Dioxomolybdenum reagents in organic synthesis: utility of redox capability to design reduction and oxidation

The usefulness of dioxomolybdenum reagents in oxo-transfer reactions have been reviewed. The redox ability of dioxomolybdenum reagent has been utilized in designing several synthetic methods, which are useful in organic synthesis. Several reactions such as oxidation of alcohols, sulfides, amines, azides olefins etc are accomplished by using dioxomolybdenum reagents. Similarly, it is also demonstrated that dioxomolybdenum complex is useful in performing reduction of aldehydes, ketones, esters, azides etc. A fine tuning of reaction conditions provides suitable conditions to perform either oxidation or reduction by using catalytic amount of reagents. The oxidation reactions are further simplified by employing the polymer supported molybdenum reagents.

Synthesis and characterization of self-assembled nanofiber-bundles of V(2)O(5): their electrochemical and field emission properties

High-quality self-assembled V(2)O(5) nanofiber-bundles (NBs) are synthesized by a simple and direct hydrothermal method using a vanadium(V) hydroxylamido complex as a vanadium source in the presence of HNO(3). The possible reaction pathway for the formation of V(2)O(5) NBs is discussed and demonstrated that HNO(3) functions both as an oxidizing and as an acidification agent. V(2)O(5) NBs are single-crystals of an orthorhombic phase that have grown along the [010] direction. A bundle is made of indefinite numbers of homogeneous V(2)O(5) nanofibers where nanofibers have lengths up to several micrometres and widths ranging between 20 and 50 nm. As-prepared V(2)O(5) NBs display a high electrochemical performance in a non-aqueous electrolyte as a cathode material for lithium ion batteries. Field emission properties are also investigated which shows that a low turn-on field of similar to 1.84 V mu m(-1) is required to draw the emission current density of 10 mu Lambda cm(-2).

Electrochemical Integration of Graphene with Light-Absorbing Copper-Based Thin Films

We present an electrochemical route for the integration of graphene with light-sensitive copper-based alloys used in optoelectronic applications. Graphene grown using chemical vapor deposition (CVD) transferred to glass is found to be a robust substrate on which photoconductive CuxS films of 1-2 mu m thickness can be deposited. The effect of growth parameters on the morphology and photoconductivity of CuxS films is presented. Current-voltage (I-V) characterization and photoconductivity decay experiments are performed with graphene as one contact and silver epoxy as the other.

Hypersonic wave drag reduction in re-entry capsules using concentrated energy deposition

Experiments are carried out in a shock tunnel at a nominal Mach number of 5.75 in order to study the effect of concentrated energy deposition on the drag force experienced by a 120° blunt cone. Electrical energy was deposited along the stagnation streamline of the model using a high voltage DC discharge circuit (1.5 – 3.5KW) and the drag force was measured by a single component accelerometer balance. Numerical simulations were also carried complimenting the experiments. These simulations showed a substantial drag reduction (20% ~ 65%) whereas the experiments show no appreciable reduction in drag

Pulsed plasma treatment for NOx reduction from filtered/unfiltered stationary diesel engine exhaust

A detailed study on the removal of oxides of nitrogen (NOx) from the filtered/unfiltered exhaust of a stationary diesel engine was carried out using non-thermal plasma (pulsed electrical discharge plasma) process and cascaded processes namely plasma- adsorbent and plasma-catalyst processes. The superior performance of discharge plasma with regard to NOx removal, energy consumption and formation of by-products in unfiltered exhaust environment is identified. In the cascaded plasma-adsorbent process, the plasma was cascaded with adsorbents (MS13X/Activated alumina/Activated charcoal). The cascaded process treating unfiltered exhaust exhibits a very high NOx removal compared to the individual processes and further, the cascaded process gives almost the same NOx removal efficiency irrespective of type of adsorbent used. In the cascaded plasma- catalyst process, the plasma was cascaded with activated alumina catalyst at high temperature. The synergy effect and improved performance of the cascaded process are explained. Further, experiments were conducted at room temperature as well as at higher temperatures.

Corona treatment for NOx reduction from stationary diesel engine exhaust: Impact of nature of energization and exhaust composition

A detailed study on the removal of oxides of nitrogen (NOx) from the exhaust of a stationary diesel engine was carried out using non-thermal plasma (dielectric barrier discharge) process. The objective of the study was to explore the effect of different voltage energizations and exhaust composition on the NOx removal process. Three types of voltage energizations, namely AC, DC and Pulse were examined. Due to the ease of generation of high voltage AC/DC electrical discharges from automobile/Vehicular battery supply for possible retrofitting in exhaust cleaning circuit, it was found relevant to investigate individual energisation cases in detail for NOx removal. AC and Pulse energisations exhibit a superior NOx removal efficiency compared to DC energisation. However,Pulse energisation is found to be more energy efficient. Experiments were further carried out with filtered/ unfiltered (raw) exhaust under pulse energisations. The results were discussed with regard to NOx removal, energy consumption and formation of by-products.