Electrochemical stability of anodic titanium oxide films grown at potentials higher than 3 V in a simulated physiological solution

The cathodic behaviour of oxides formed on titanium electrodes in physiological solutions at potentials between 3 and 5 V (vs. SCE) was studied by cyclic voltammetry. In case of anodic polarization at potentials higher than 3 V (vs. SCE), a cathodic peak at similar to 0.4 V (vs. SCE) appears in the cathodic scan, which could be due to the reduction of unstable peroxides. The results show that this peak depends on the anodic potential and the oxidation time. This behaviour supposedly is due to the formation of unstable titanium peroxides like TiO3 during anodization. Based on repetitive oxidation-reduction processes can be concluded that the created amount of TiO3 inside of the TiO2 surface layer seems to be constant. (c) 2006 Elsevier Ltd. All rights reserved.

Oxidative dissolution of research-grade minerals by Thiobacillus ferrooxidans and Thiobacillus thiooxidans

Solution- and solid-phase changes associated with galena (PbS) and sphalerite (ZnS) oxidation by T. ferrooxidans and T. thiooxidans, were determined. In experiments with galena, anglesite (PbSO4) was detected as a solid-phase product in biotic and abiotic experiments. In T. ferrooxidans cultures supplemented with FeSO4, jarosite [MFe3 (SO4)(2) (OH)(6)] was also detected as a new solid phase product, whereas SO was not detected in the residues. In sphalerite experiments, minor amounts of SO accumulated in FeSO4-amended sphalerite media with or without T. ferrooxidans or T. thiooxidans. Jarosite was only detected in T. ferrooxidans culture with FeSO4. By comparison with T. thiooxidans, T. ferrooxidans was more efficient in the oxidation of galena and sphalerite.

A dissolution and reaction modeling for hydrolysis of TEOS in heterogeneous TEOS-water-HCl mixtures under ultrasound stimulation

A simplified dissolution and reaction modeling was employed to study the hydrolysis of heterogeneous tetraethoxysilane (TEOS)-water-HCl mixtures under ultrasound stimulation. The nominal pH was changed from 0.8 to 2.0. The acid specific hydrolysis rate constant was determined as k = 6.1 mol(-1) 1 min(-1) [H+](-1) at 39 degreesC, in good agreement with the literature. Along the heterogeneous step of the reaction, the ultrasound maintains an additional quantity of water under a virtual state of dissolution besides the water dissolved due to the homogenizing effect of the alcohol produced in the reaction. The forced virtually dissolved water is probably represented by water at the TEOS-water interface during the heterogeneous step of the reaction. The mean radius of the heterogeneity represented by water dispersed in TEOS phase, while hydrolysis has not started yet, was evaluated as about 290 A. The HCl concentration accordingly increases the hydrolysis rate constant but its fundamental role on the immiscibility gap of the TEOS-water-ethanol system has not been unequivocally established. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Electrochemical studies with a Cu-5wt.%Ni alloy in 0.5 M H2SO4

The electrochemical behavior of the annealed Cu-5wt.%Ni alloy in 0.5 M H2SO4 was studied by means of open-circuit potential (E-OCP) measurements, cyclic voltammetry, electrochemical impedance spectroscopy (EIS), and quasi-stationary linear potential sweep. The hydrodynamics of the system was also studied. This material is constituted by a single a, phase. The anodic behavior of a Cu-Ni alloy in H2SO4 consists fundamentally on the electrodissolution of Cu, its main component, and the formation of a sulfur-containing passive layer. The presence of Ni decreases the rate of Cu oxidation, mostly at high positive potentials. The impedance spectra, obtained for the unrotating electrode, can be interpreted in terms of a simple charge-transfer reaction across a surface layer. When the electrode is rotated, the occurrence of an inductive loop evidenced the existence of an adsorbed layer. All the resistance estimated from the proposed equivalent circuits diminished with the electrode rotation rate, emphasizing the influence of ion transport in the overall electrode process. The system presented two anodic Tafel slopes: 40 mV dec(-1) for E < 255 mV and 67 mV dec(-1) for E > 275 mV. A Tafel slope of 40 mV dec(-1) evidences that copper dissolution can be interpreted in terms of the mechanism proposed by Mattsson and Bockris. The second Tafel suggests that at potentials more positive than 275 mV, copper dissolves according to a mechanism that considers the disproportionation of adsorbed Cu(1) species. (C) 2003 Elsevier Ltd. All rights reserved.

Determination of low-aliphatic aldehydes indoors by micellar electrokinetic chromatography using sample dissolution manipulation for signal enhancement

This work describes a novel approach for the analysis of selected aldehydes (formaldehyde, acetaldehyde, propionaldehyde, and acrolein) and acetone in environmental samples using micellar electrokinetic chromatography (MEKC). The method is based on the reaction of carbonyl compounds with 3-methyl-2-benzothiazoline hydrazone (MBTH) that gives an azine intermediate with maximum absorbance at 216 nm. A systematic evaluation of sample dissolution medium was conducted as a means to enhancing sensitivity. In the best condition, samples were dissolved in 0.030 mol.L-1 tetraborate solution. This condition presented enhancement factors in the range of 35-54 for the aldehydes under investigation, computed as the improvement of the concentration limits of detection (LODs) with reference to the sample dissolved in pure water. The running buffer was 0.020 mol.L-1 tetraborate, pH 9.3, containing 0.050 mol-L-1 sodium dodecyly sulfate (SIDS). The overall methodology presented several advantages over established methods for aldehydes. Worthy mentioning that MBTH is available in high purity degree, dispensing laborious reagent purification procedures. A few method validation parameters were determined revealing good migration time repeatability (< 2.5% coefficient of variation, CV) and area repeatability (< 4% CV), excellent linearity (20-120 mug/L, r > 0.995) and adequate sensitivity for environmental applications. The LODs with respect to each single aldehyde were in the range of 0.54-4.0 mug.L-1 and 11 mug.L-1 for acetone. The methodology was applied to the determination of aldehydes indoors. Samples were collected in an impinger flask containing 0.05% MBTH solution, at a flow rate of 0.80 L.min(-1), during 2.5 h, at different times during the day. The most abundant carbonyls in the samples were acetone, followed by formaldehyde and acetaldehyde, with estimate peak concentrations of 452, 5.2 and 2.2 ppbv, respectively.

Anodic oxidation of formaldehyde on Pt-modified SnO2 thin film electrodes prepared by a sol-gel method

Pt-modified SnO2 electrodes were prepared onto titanium substrates in the form of thin films of similar to2 mum at different temperatures in the range from 200 to 400degreesC. Surface morphology was examined by scanning electron microscopy (SEM). It was found that Pt-SnO2 sol-gel layers are significantly rough and have a low porosity. X-ray diffraction (XRD) studies showed that the films consist of Pt nanoparticles with average size varying from about 5 to 10 nm, depending on the preparation temperature, and amorphous tin oxide. X-ray photoelectron spectroscopy (XPS) was employed to determine the superficial composition of the electrodes and demonstrated the presence of Sn4+ in all the samples. XPS spectra of the Pt 4f electrons showed the presence of Pt in the zero-valence state as well as in ionic forms. The general electrochemical behavior was characterized by cyclic voltammetry in 1 mol l(-1) HClO4 and the electrocatalytic activity towards the oxidation of formaldehyde was investigated by potential sweeps and chronoamperometry. The results obtained show that the Pt-SnO2/Ti system exhibits a significant catalytic activity for the oxidation of formaldehyde, with an onset potential below 0.1 V. (C) 2004 Elsevier Ltd. All rights reserved.

Procedure optimization of silicate rocks dissolution in open vessels for ICP-AES analysis.

The main variables found on procedure of the dissolution silicate rocks using acid dissolution in teflon open vessel for analysis of micro elements by ICP-AES has been determined. The results obtained for some samples showed strong dependence of the rock mineralogical composition, then it was recommended an alkaline fusion step after acid dissolution. The decomposition procedure use 20 mi of an acid mixture of HF:HNO3 in the proportion 3:1 for a fraction of 250 mg pulverized sample. The recommended temperatures were 60 degrees C for attack and 90 degrees C for acid volatilization. The fusion step with 50 mg LiBO2 at 1000 degrees C may be used if non-attacked residue is observed in the solution. The whole time was 6 h per sample. Nine types os silicate rocks that show mineralogical and chemical different compositions were chosen for obtaining the optimization of the variables. The elements used were Ce, Y, Yb and Zr. In addition, ultrassonic nebulization has been used. The percentual standard deviations obtained for five determinations were 0.7 and 1.4 for triplicate samples. The mineralogical and textural information from the petrographical analysis of the samples indicated the need of increasing the fusion step on the optimized procedure.

Platinum surface modification with cerium species and the effect against the methanol anodic reaction

Spontaneous deposition and electrochemical deposition by potential perturbation programs were used to place cerium-containing species on platinum surfaces in acid solution. Cyclic voltammetric profiles of cerium-modified platinum surfaces obtained after potentiostatic or potentiodynamic procedures (applied in the true hydrogen evolution region) differ from those recorded after spontaneous methods. However, the catalytic effects are nearly the same on these cerium-modified platinum surfaces for methanol electrooxidation, i.e. lower onset potential values for the anodic reaction. Besides, a different electrocatalytic effect was observed at large positive potentials on methanol oxidation due to the cerium oxide capability of oxygen storage. This effect is observed on platinum modified by a drastic potentiostatic procedure (by applying -2.0 V) in cerium(IV) acid solution. (C) 2008 Elsevier B.V. All rights reserved.

Controlled growth of anodic aluminium oxide films with hexagonal array of nanometer-sized pores filled with textured copper nanowires

Anodic aluminium oxide (AAO) films exhibiting a homogeneous morphology of parallel pores perpendicular to the surface were prepared in a two-step anodization process and filled with copper by electrochemical deposition. The optimum growth conditions for the formation of freestanding AAO films with hexagonal compact array of cylindrical pores were studied by field emission scanning electron microscopy and small angle X-ray scattering. The results show well-defined periodic structures with uniform pores size distribution for films with pore diameters between 40 and 70 nm prepared using different voltages and temperatures during the second anodization step. X-ray photoelectron spectroscopy and X-ray diffraction analysis of AAO films filled with copper show the formation of nanowires with high structural order, exhibiting a preferential crystalline orientation along the (2 2 0) axis and only small fraction of copper oxides. The best results for textured Cu nanowires were obtained at a reduction potential of -300 mV. (C) 2009 Elsevier Ltd. All rights reserved.

Oxidative dissolution of covellite by Thiobacillus ferrooxidans

Oxidation of research-grade covellite was investigated in respirometric and growth experiments with Thiobacillus ferrooxidans. Covellite was directly oxidized by T. ferrooxidans in respirometric experiments, but the pH of mineral salts medium increased to prohibitively high values because of high sulfide concentrations. In glycine-H 2SO 4 buffered medium the pH remained steady and the oxygen uptake activity of T. ferrooxidans was not inhibited. In cultures growing with covellite as the sole source of energy, the pH increased to about 4. Redox potential increased to 500-600 mV during bacterial oxidation of covellite in the presence and absence of additional Fe 2+, whereas it remained mostly at about 350 mV in abiotic control. Jarosite was a major solid-phase product in T. ferrooxidans cultures. The solubilization of copper from covellite in inoculated flasks was higher than that obtained in control flasks and was not enhanced in the presence of additional Fe 2+.The sample also contained bornite (Cu 5FeS 4) which released iron in solution under all experimental conditions. Accumulation of S 0 was apparent only in inoculated covellite samples. © 1997 Elsevier B.V. All rights reserved.

Oxidative dissolution of chalcopyrite by Thiobacillus ferrooxidans

The oxidative dissolution of research-grade chalcopyrite was characterized in respirometric and growth experiments with Thiobacillus ferrooxidans. In respirometric experiments with chalcopyrite, the pH of mineral salts medium increased to values that inhibited the oxygen uptake activity of T. ferrooxidans. In glycine-H 2SO 4 buffered medium the pH remained stable and oxygen uptake was not inhibited. In cultures growing with chalcopyrite as the sole source of energy, pH changes were only minor during the incubation. The redox potential values increased to about 600 mV during the bacterial oxidation of chalcopyrite in the presence and absence of additional Fe 2+, while they remained at about 350 mV in abiotic control flasks. Iron in chalcopyrite was solubilized and oxidized to Fe 3+ by T. ferrooxidans. In the abiotic controls, by comparison, less iron was solubilized and it remained as Fe 2+. Jarosite was a major solid- phase product in T. ferrooxidans cultures. The solub'flization of copper from chalcopyrite in inoculated flasks was enhanced in the presence of additional Fe 2+.Accumulation of S 0, reflecting partial oxidation of the S-entity of chalcopyrite, was apparent from the x-ray diffraction analysis of solid residues from the inoculated flasks as well the abiotic controls. © 1997 Elsevier B.V. All rights reserved.

The effect of chloride ions and A. ferrooxidans on the oxidative dissolution of the chalcopyrite evaluated by electrochemical noise analysis (ENA)

It is believed that the dissolution of chalcopyrite (CuFeS2) in acid medium can be accelerated by the addition of Cl- ions, which modify the electrochemical reactions in the leaching system. Electrochemical noise analysis (ENA) was utilized to evaluate the effect of the Cl- ions and Acidithiobacillus ferrooxidans on the oxidative dissolution of a CPE-chalcopyrite (carbon paste electrode modified with chalcopyrite) in acid medium. The emphasis was on the analysis of the admittance plots (Ac) calculated by ENA. In general, a stable passive behavior was observed, mainly during the initial stages of CPE-chalcopyrite immersion, characterized by a low passive current and a low dispersion of the Ac plots, mainly after bacteria addition. This can be explained by the adhesion of bacterial cells on the CPE-chalcopyrite surface acting as a physical barrier. The greater dispersions in the Ac plots occurred immediately after the Cl- ions addition, in the absence of bacteria characterizing an active-state. In the presence of bacteria the addition of Clions only produced some effect after some time due to the barrier effect caused by bacteria adhesion. © (2009) Trans Tech Publications.

Pulp tissue dissolution when the use of sodium hypochlorite and EDTA alone or associated

Purpose: The aim of the present study was to evaluate the tissue dissolving capacity of various concentrations of sodium hypochlorite either alone or in combination with 17% EDTA. Methods: Eighty bovine pulp fragments were prepared, and their weight was determined using a precision balance. Each pulp fragment was immersed for 2 hours in a solution/mixture that was based on the following groups: G1-saline solution; G2-0.5% NaOCl; G3-1.0% NaOCl; G4-2.5% NaOCl; G5-17% EDTA; G6-0.5% NaOCl+17% EDTA; G7-1.0% NaOCl+ 17% EDTA; and G8-2.5% NaOCl+17% EDTA. The final weight was measured, and the weight loss was calculated. A statistical analysis was performed using either the Student's t-test for paired samples or an ANOVA and Tukey tests (P<0.05 was considered to be significant). Results: We measured a significant difference between the sample weight before and after treatment for each of the tested groups (P<0.05). The 2.5% sodium hypochlorite solution (G4) completely dissolved the pulp tissue within the test period. NaOCl+EDTA was less effective than sodium hypochlorite alone at dissolving the pulp tissue (P<0.05), and EDTA alone (G5) did not markedly dissolve the pulp tissue. Conclusion: Using EDTA together with NaOCl reduced the tissue dissolving properties compared with NaOCl alone, regardless of the concentration of NaOCl that was used. © 2011 Só et al.; licensee EDIPUCRS.

Direct simultaneous determination of Pb(II) and Cu(II) in biodiesel by anodic stripping voltammetry at a mercury-film electrode using microemulsions

A mercury film electrode was used to determine direct and simultaneously Pb(II) (at -410 mV) and Cu(II) (at -100 mV) in biodiesel by anodic stripping voltammetry. A linear response was obtained for Pb(II) and Cu(II) in the 2.00 × 10-8-1.00 × 10-7 mol L-1 concentration range and detection limits were 2.91 × 10-9 mol L-1 and 4.69 × 10-9 mol L-1 for Pb(II) and Cu(II), respectively, with recovery around of 100.0%. © 2012 Elsevier Ltd. All rights reserved.