Electrochemical behavior of cobalt oxide coatings on cold-rolled steel in alkaline sodium sulfate

The electrochemical behavior of a coating of cobalt oxide on cold-rolled steel in alkaline sodium sulfate was Studied using the electrochemical techniques of open-circuit potential measurements and electrochemical impedance spectroscopy. The coating was prepared at different annealing temperatures ranging from 350 to 750 degreesC and characterized by SEM, EDX and XRD. Below 550 degreesC the composition of the coating was basically of Co3O4. At 750 degreesC CoO was formed and big cracks appeared on the film exposing an inner layer of iron oxides. Analysis of the EIS data is very difficult because of the complexity of the interface structure. It can be inferred that the charge transfer resistance of the coatings prepared at 350 and 450 C were higher than those for the coatings prepared at temperatures above 550 degreesC. (C) 2002 Published by Elsevier B.V. Ltd.

Completeness of beta-phase decomposition reaction in Cu-Al-Ag alloys

The completeness of beta-phase decomposition reaction in the Cu-11wt%Al-xwt%Ag alloys (x = 0, 1, 2, and 3) was studied using differential scanning calorimetry (DSC), X-ray diffractometry (XRD), and optical microscopy (OM). The results indicated that beta-phase transformations are highly dependent on cooling rate and on the presence of Ag. on slow cooling, the silver presence prevents the beta- and beta(1)-phase decomposition; thus, inducing the martensitic phase formation. After rapid cooling, a new thermal event is observed and the reverse martensitic transformation is shifted to lower temperatures.

Determination of cobalt marker in cow ruminal fluid by EDXRF and SRTXRF

This article describes a comparison of conventional energy-dispersive X-ray fluorescence (EDXRF) and synchrotron radiation total-reflection X-ray fluorescence (SRTXRF) for Co determination in ruminal fluid from Holstein cow. This element is used as marker for animal nutrition studies. For EDXRF, 200 mu l of the sample were dried on 6.35 mu m Mylar filmat 60 degrees C. The excitation was carried out using an X-ray tube with Mo target and Zr filter operated at 30 kV/ 20 mA. For SRTXRF, 10 mu l of the samplewere pipetted on a Lucite carrier and dried at 60 degrees C. In both the techniques, Ga was used as internal standard and the acquisition time was 200 s. The trueness of both techniques was evaluated through the standard addition method, the recoveries obtained by SRTXRF and EDXRF were 76 and 99%, and the limits of detection, 13 and 240 mu g l(-1), respectively. Copyright (C) 2011 John Wiley & Sons, Ltd.

Thermogravimetric and UV-vis spectroscopic studies of chromium redox reactions in rutile pigments

In this study undoped and Cr, Sb or Mo doped TiO(2) were synthesized by polymeric precursor method and characterized by X-ray diffraction, UV-VIS spectroscopy, infrared spectroscopy and thermogravimetry (TG). The TG curves showed a continuous mass loss assigned to the hydroxyl elimination and Cr(6+) reduction. Doped TiO(2) samples showed a higher mass loss assigned to water and gas elimination at lower temperatures. In these doped materials a decrease in the anatase-rutile phase transition temperature was observed. After calcination at 1,000 A degrees C, rutile was obtained as a single phase material without the presence of Cr(6+).

Influence of doping on the preferential growth of alpha-MoO3

MoO3 is a lamellar material with applications in different areas, as solid lubricants, catalysis, solar cells, etc. In the present work, MoO3 powders, synthesized by the polymeric precursor method, were doped with nickel or cobalt. The powder precursors were characterized by TG/DTA. After calcination between 500 and 700 degrees C, the samples were characterized by X-ray diffraction, infrared and Raman spectroscopy and scanning electron microscopy. beta-MoO3 was obtained after calcination at low temperatures. With the temperature increase, alpha-MoO3 is observed, with a preferential growth of the (0 2k 0) planes, when the material is doped and calcined at 700 degrees C. Doping with nickel increases five times the preferential growth. As a consequence, plate-like particles are observed. (c) 2007 Elsevier B.V. All rights reserved.

Electrooxidation and determination of dopamine using a Nafion (R)-cobalt hexacyanoferrate film modified electrode

The electrocatalysis of dopamine has been studied using a cobalt hexacyanoferrate film (CoHCFe)-modified glassy carbon electrode. Using a rotating disk CoHCFe-modified electrode, the reaction rate constant for dopamine was found to be 3.5 x 105 cm(3) mol(-1) s(-1) at a concentration of 5.0 x 10(-5) mol L-1. When a Nafion (R) film is applied to the CoHCFe-modified electrode surface a high selectivity for the determination of dopamine over ascorbic acid was obtained. The analytical curve for dopamine presented linear dependence over the concentration range from 1.2 x 10(-5) to 5.0 x 10(-4) mol L-1 with a slope of 23.5 mA mol(-1) L and a linear correlation coefficient of 0.999. The detection limit of this method was 8.9 x 10(-6) mol L-1 and the relative standard deviation for five measurements of 2.5 x 10(-4) mol L-1 dopamine was 0.58%.

Electrochemistry of organometallic compounds. Part II. Oxidations of alkyl and aryl derivatives of bis(salicylaldehyde)ethylenediimine cobalt(III) in dimethylformamide

The influence of the axial organic ligand R on the electrochemical oxidation of the compounds [RCoIII(salen)DMF)], where salen is bis(salicylaldehyde)ethylenediimine, and R CH3, C2H5, n-C3H7, n-C4H9, s-C4H9, i-C4H9, CH2Cl, CF3CH2, c-C6H11CH2, c-C6H11, C6H5, C6H5CH2, p-CH3C6H4CH2, and p-NO2C6H4CH2, was studied by means of cyclic voltametry in dimethylformamide (DMF), 0.2 M in tetraethylammonium perchlorate (TEAP), at 25 and -20°C, with a platinum disc working electrode. The above-mentioned compounds can be classified according to their electrochemical behavior. (a) The complexes with R CH3, C2H5, n-C3H7, n-C4H9, c-C6H11CH2, and C6H5 undergo a reversible one-electron oxidation in the 10-50 V s-1 potential scan range. At slower scan rates, the oxidized product decomposes chemically. At -20°C, this chemical step is slow, and a reversible one-electron electrochemical oxidation is observed. (b) The compounds with R CH2Cl, C6H5CH2, p-CH3C6H4CH2 and p-NO2C6H4CH2 undergo a quasi-reversible one-electron oxidation at room temperaure. At -20°C, the electrochemical process becomes more complex. A following chemical reactions is coupled to the quasi-reversible one-electron transfer. Two reduction peaks are observed. (c) The compounds with R i-C4H9, s-C4H9, and c-C6H11 undergo a reversible one-electron oxidation at -20°C. At room temperature, the irreversible chemical reaction following the electron transfer step is too fast to allow the isolation of the electrochemical step. (d) At -20°C, the derivatives with R C2H5, c-C6H11 CH2 and c-C6H11 are adsorbed at the electrode surface. Evidence indicates that the reagent in these reactions is the pentacoordinated species [RCoIII(salen)]. A linear free-energy relationship between E1/2 (for reversible processes) and the Taft polar parameters o* was obtained with a slope of ρ* = 0.25 ± 0.03. As expected, the benzyl derivatives which present mesomeric effects do not fit this polar correlation. The rated of the electrochemical oxidation is also affected by the nature of the ligand R. For the ligands which are strong electron-withdrawing groups and for the benzyl derivatives, the rate of the electrochemical oxidation of the metal ion decreases at room temperature. At lower temperatures, it is suggested that the oxidation to the CoIV-R species is followed by a chemical reaction in which this complex is partly transformed into a CoIII(R*) species, which is reduced at a much more cathodic potential than the Co(IV) species. © 1979.

Electrochemistry of organometallic compounds. Part IV. Oxidations of benzylic derivatives and p-substituted benzylic derivatives of bis(dimethylglyoximato) and bis(salicylaldehyde)o-phenylenediimine cobalt(III) in dimethylformamide

The electrochemical oxidation of some p-substituted benzylic derivatives of Co(III) dimethylglyoximato and Co(III)bis(salicylaldehydc)o-phenylenediimine in dimethylformamide. 0.2 M in tetraethyammonium perchlorate, on a platinum electrode, at several temperatures, is described as an ECE type, the first electrochemical step being a quasi-reversible one-electron charge transfer at room temperature. At temperatures around -20°C, or lower, the influence of the irreversible chemical decomposition of the oxidized species, via a solvent or other nucleophilic-assisted reaction, is negligible. It is suggested that at low temperatures the oxidation to the formally CoIV-R species is followed by an isomerization reaction in which this complex is partially transformed in a CoIII-(R) species or a s π-complex which undergoes an electroreduction at less positive potentials than those corresponding to the reduction of the CoIV-R species. © 1982.

Sequential spectrophotometric determination of chromium(III) and chromium(VI) using flow injection analysis

A flow injection analysis (FIA) procedure for the speciation of Cr(III) and Cr(VI) using the 1,5-diphenylcarbazide (DPC) method is presented. As Cr(III) does not interfere in the Cr(VI) - DPC reaction, both Cr(VI) and total chromium [after the on-line oxidation of Cr(III) by Ce(IV)] are sequentially determined. Cr(III) is obtained by difference. Under the experimental conditions described, the calibration graphs are linear up to 2 μg mh1 of Cr(VI) and 4 μg ml-1 of Cr(III). The detection limits found were 18 ng ml -1 for Cr(VI) and 55 ng ml-1 for Cr(III), at a signal to noise ratio of 3. The common interfering elements in the Cr(VI) - DPC reaction were investigated under dynamic FIA conditions. The FIA method was also compared with the conventional spectrophotometric procedure.

Influence of the heat treatment in the electrochemical corrosion of Al-Zn-Mg alloys

The localized corrosion of Al-(5.03%)Zn-(1.67%)Mg-(0.23%)Cu alloys and high purity Al has been studied using electrochemical techniques, optical microscopy, SEM and EDX. The samples were previously submitted to different heat treatments in which coherent and incoherent MgZn 2 precipitates with different distribution and aggregation degree were produced. The influence of NaCl and Na 2SO 4, dissolved oxygen, immersion time and convection were studied. In NaCl solutions, pitting potentials for the alloys were more negative than for aluminium, indicating an increase in their susceptibility to localized corrosion. Moreover, annealed and cold-rolled alloys presented more negative pitting and repassivation potentials than those submitted to age hardening with direct or interrupted quenching. In annealed and cold-rolled samples, pit nucleation and propagation takes place in the zones where MgZn 2 is accumulated. In the case of the age-hardened alloys, a double pitting behaviour is observed, the first one in the magnesium and zinc enriched regions and the second in the matrix. While the cold water quenched alloy is susceptible to stress corrosion craking, the alloy submitted to the interrupted quenching process is less susceptible to intergranular attack. The sulphate ion shifts the pitting potential of aluminium and the alloys by chloride towards more positive values because it impedes local accumulations of the latter. © 1992 Chapman & Hall.

Anelastic relaxation due to OH pairs in NbZr alloys

In the last 30 years several studies have been made to understand the relaxation mechanisms of the hydrogen atoms present in transition metals and their alloys. In this work, we observed the stress-induced ordering of hydrogen atoms around the interstitial oxygen atoms near the niobium matrix atoms. We studied this relaxation process by measuring the attenuation of longitudinal ultrasonic waves. These measurements were made in Nb1.0%Zr polycrystalline alloys at 10 and 30 MHz, pure and doped with 0.7 and 4.2 at.% hydrogen. The results revealed a thermally activated relaxation structure around 202 K and 235 K for 10 MHz and 30 MHz respectively. This relaxation structure increases with increasing hydrogen concentration. © 1994.

Effect of cobalt(II) oxide and manganese(IV) oxide on sintering of tin(IV) oxide

Additions of 0.5 to 2.0 mol% of CoO or MnO2 onto SnO, promote densification of this oxide up to 99% of theoretical density. The temperature of the maximum shrinkage rate (TM) and the relative density in the maximum densification rate (p*) during constant sintering heating rate depend on the dopant concentration. Thus, dopant concentration controls the densifying and nondensifying mechanisms during sintering. The densification of SnO2 witih addition of CoO or MnO, is explained in terms of the creation of oxygen vacancies.

Phonons in binary BCC lithium-sodium alloys

The dispersion relations along the principal symmetry directions in BCC lithium-sodium alloys are calculated using second-order perturbation theory. The local modified Hoshino-Youngmodel potential was used for the lithium and the local Harrison model potential for sodium. The phonon density of states, the root mean square displacements and (Θ-T) curves are also calculated. In the absence of experimental data, just the theoretical predictions are presented here.

Optical properties of chromium-doped fluoroindate glasses

This work reports on the optical properties of Cr3+ ions in the pseudoternary system InF3-GdF3-GaF3. Linear properties, investigated through absorption and emission spectra, provide information on the crystal field, the frequency, and number of phonons emitted during the absorption to the 4T2 band and the emission to the 4A2 ground state, and the Fano antiresonance line shape in the vicinity of the 4A2→2E transition. A study of the nonlinear refractive index as a function of the wavelength, carried out with the Z-scan technique, provides spectroscopic data about electronic transitions starting from the excited state.

Structure of cobalt (II) perchlorate adsorbed on silica gel surface chemically modified with benzimidazole molecule

Covalently attached benzimidazole molecules on silica gel surface, ≡SiL (where L = N-propyl-benzimidazole), adsorbs Co(ClO4)2 from non-aqueous solvent by forming a surface complex according to the reaction: m ≡SiL + Co(ClO4)2 → (≡SiL)mCo(ClO4)2. The equilibrium constant and the adsorption capacity, determined by applying the Langmuir equation were b = 3.0 × 103 L mol-1 and Ns= 0.098 × 10-3 mol g-1, respectively. The metal is bonded through the nitrogen atom and the perchlorate ion is not coordinated. The ESR study indicated that the complex has essentially an octahedral geometry with tetragonal distortion, with the electrons of the four nitrogen atoms interacting with the cobalt central metal ion in the equatorial plane. Only one complex species was detected on the surface.