980 resultados para IRREVERSIBLE ELECTROCHEMICAL PROCESS
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The influence of heat-treatments on the electrochemical behavior of thermal spray Cr3C2-NiCr coatings prepared by high velocity oxygen fuel (HVOF) was studied in NaCl solution, at 25 degrees C, using open-circuit potential (E-OC) and electrochemical impedance spectroscopy (EIS) measurements. Coating characterization were performed before and after the heat-treatments and electrochemical tests by scanning electron microscopy, X-ray diffraction, and Auger electron spectroscopy. In addition to the changes in the original powder composition occurring during HVOF process, heat-treatment performed at 450 degrees C caused no significant changes in electrochemical response compared with untreated sample, and at 760 degrees C the main difference was the formation of a thin and defective layer of Cr2O3 at the coating surface, which increased the total impedance at the first day of immersion. Higher influence on the electrochemical was noted for samples treated at 880 degrees C, which also showed higher E-OC and total impedance, and lower corrosion current. This behavior was interpreted considering the formation of a chromium oxide layer on the coating surface, dissolution and decomposition of smaller carbide particles and their surface enrichment with Cr due to C diffusion and dissolution into the matrix, and possible Ni, Cr, and Fe diffusion to coating/substrate interface. (c) 2006 the Electrochemical Society.
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Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The presumably soluble KFe(+3)[Fe(2+)(CN)(6)] structure of electrochemically synthesized hexacyanoferrate materials (Prussian Blue) containing K(+) ions was determined for the first time in this study. Prior to drawing conclusions from a structural analysis, the main goal was to make a precise analysis of the inferred soluble structure, that is, KFe(+3) [Fe(2+)(CN)(6)], which is frequently referred to in the literature as the final stable electrochemically synthesized structure. Indeed, a successful X-ray powder diffraction experiment using X-ray synchrotron radiation was made of a powder placed in a 0.5 mm diameter borosilicate glass capillary, which was obtained by removing sixty 90 nm thin films from the substrates on which they were prepared. However, the conclusions were highly unexpected, because the structure showed that the [Fe(CN)61 group was absent from similar to 25% of the structure, invalidating the previously presumed soluble KFe(+3)[Fe(2+)(CN)(6)] structure. This information led to the conclusion that the real structure of Prussian Blue electrochemically synthesized after the stabilization process is Fe(4)[Fe(CN)(6)](3)center dot mH(2)O containing a certain fraction of inserted K(+) ions. In fact, based on an electrogravimetric analysis (Gimenez-Romero et al., J. Phys. Chem. B 2006, 110, 2715 and 19352) complemented by the Fourier maps. it is possible to affirm that the K(+) was part of the water crystalline substructure. Therefore, the interplay mechanism was reexamined considering more precisely the role played by the water crystalline substructure and the K+ alkali metal ion. As a final conclusion, it is proposed that the most precise way to represent the structure of electrochemically synthesized and stabilized hexacyanoferrate materials is Fe(4)(3+) Fe(2+)(CN)(6)](3)center dot[K(h)(+)center dot OH(h)(-)center dot mH(2)O]. The importance of this result is that the widespread use of the terms soluble and insoluble in the electrochemical literature could be reconsidered. Indeed, only one type of structure is insoluble, and that is Fe(4)[Fe(CN)(6)](3)center dot mH(2)O hence, the use of the terms soluble and insoluble is inappropriate from a structural point of view. The result of the presence of the [Fe(CN)61 vacancy a, roup is that the water Substructure cannot be ignored in the ionic interplay mechanism which controls the intercalation and redox process, as was previously confirmed by electrogravimetric analyses (Gimenez-Romero et al., J. Phys. Chem. B 2006, 110, 2715 Garcia-Jareno et al., Electrochim. Acta 1998, 44, 395: Kulesza, Inorg. Chem. 1990, 29, 2395).
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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A post-PCR nucleic acid work by comparing experimental data, from electrochemical genosensors, and bioinformatics data, derived from the simulation of the secondary structure folding and prediction of hybridisation reaction, was carried out in order to rationalize the selection of ssDNA probes for the detection of two Bonamia species, B. exitiosa and B. ostreae, parasites of Ostrea edulis.Six ssDNA probes (from 11 to 25 bases in length, 2 thiolated and 4 biotinylated) were selected within different regions of B. ostreae and B. exitiosa PCR amplicons (300 and 304 bases, respectively) with the aim to discriminate between these parasite species. ssDNA amplicons and probes were analyzed separately using the "Mfold Web Server" simulating the secondary structure folding behaviour. The hybridisation of amplicon-probe was predicted by means of "Dinamelt Web Server". The results were evaluated considering the number of hydrogen bonds broken and formed in the simulated folding and hybridisation process, variance in gaps for each sequence and number of available bases. In the experimental part, thermally denatured PCR products were captured at the sensor interface via sandwich hybridisation with surface-tethered probes (thiolated probes) and biotinylated signalling probes. A convergence between analytical signals and simulated results was observed, indicating the possibility to use bioinformatic data for ssDNA probes selection to be incorporated in genosensors. (C) 2011 Elsevier B.V. All rights reserved.
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The electrochemical behavior of metallic chromium in aqueous solutions containing chloride ions at different pH was studied by means of open-circuit potential vs. time measurements, cyclic voltammetry and electrochemical impedance spectroscopy. The composition of the surface oxides was analyzed by XPS. For solutions with pH<3 the formation of a passive layer occurs via a dissolution/precipitation process while for pH>3 the mechanism changes. XPS analysis revealed that Cr2O3 basically constitutes the passive layer.
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The electrochemical response of chalcopyrite was studied using electrochemical noise analysis (ENA). The assay was carried out under constant aeration using 30 mL in two electrochemical cells containing iron-free mineral salts solution. These cells were initially monitored for 56 hours, After 72 hours, 7.25x 10(10) cells mL(-1) of A, ferrooxidans strain LR were added in both cells and monitored until 128 h. Subsequent to this period, 0.927 mmol L-1 of silver ions and 400 mmol L-1 of chloride ions were added each one separately. Both conditions were monitored until 168 hours. According to results obtained, it was observed that Cl- ions addition induced an accelerated corrosion process. However, there is a tendency of the system to reach the stationary state due to repassivation of the electrodic surface. In the other side, the Ag+ addition contributed for the maintenance of the oxidant atmosphere, in spite of controversial effect caused by considerable variations in the R-n values, resulting in a instability in the chalcopyrite reactivity.
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The electrochemical oxidation of (benzylideneacetone)dicarbonyl(phosphine)iron(0) and benzylideneacetone)dicarbonyl(phosphite)iron(0) complexes was studied by cyclic voltammetry and controlled potential electrolysis in 0.5 M NaClO4 (dimethyl formamide). The results suggest that the electrode process involves a complicated mechanism, the species formed in the first oxidation step being highly unstable and its decomposition producing free benzylideneacetone, free phosphine or phosphite, solvated iron(II) species and carbon monoxide which adsorbs on the platinum electrode. A linear relationship between E(p/2)ox and the ligand parameter P(L) was obtained with E(s) = 0.41 V and beta = 0.964, where E(s) and beta-denote electron-richness and polarizability of the metal centre, respectively.
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The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.
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The microbiological leaching of chalcopyrite (CuFeS2) is of great interest because of its potential application to many CuFeS2-rich ore materials. However, the efficiency of the microbiological process is very limited because this mineral is one of the most refractory to bacterial attack. Knowledge of bacterial role during chalcopyrite oxidation is very important in order to improve the efficiency of bioleaching operation. The oxidative dissolution of a massive chalcopyrite electrode by Acidithiobacillus ferrooxidans was evaluated by electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). A massive chalcopyrite electrode was utilized in a Tait-type electrochemical cell in acid medium for different immersion times in the presence or absence of bacterium. The differences observed in the impedance diagrams were correlated with the adhesion process of bacteria on the mineral surface. (C) 2004 Elsevier B.V. All rights reserved.
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The electrochemical reduction of benzenesulfinic, p-toluenesulfinic, and p-nitrobenzenesulfinic acids was studied in dimethylsulfoxide solutions. From cyclic voltammetry experiments, a chemical reaction following the first electron transfer was detected during the reduction process. A cyclic voltammetry technique using ultramicroelectrodes has provided kinetic parameters for the electron-transfer steps, from which it was possible to observe the influence of the ring substituent on the electrochemical reduction. The mechanism of the electroreduction of aromatic sulfinic acids in dimethylsulfoxide depends upon the nucleophilic attack of the radical anion produced on the starting compound during the reduction processes.