MEASUREMENT OF CATALYTIC ACTIVITY VARIATION FOR H2O2 OXIDATION AT A COBALT PORPHYRIN COATED ELECTRODE

A rapid rotation-scan method was used for the electrocatalytic oxidation of H2O2 at a cobalt protoporphyrin modified pyrolytic graphite electrode (CoPP/PG). The rate constant of H2O2 oxidation at the CoPP/PG electrode at different potentials and in different pH solutions was measured. The variation of catalytic activity with reaction charges (Q) passed through the electrode was analyzed. This provided a convenient electrochemical method to study the passivation and poisoning of catalytic sites with time.

Study of the Adsorption of Fibrinogen on Gold-Coated Silicon Wafer by an Impedance Method

In 0.1 mol/l KH2PO4–Na2HPO4 (pH 7.80) buffer solution, the potential of zero charge (PZC) and the open circuit potential of gold-coated silicon were determined to be about −0.6 and +0.10 V (vs SCE), respectively. The open circuit potential was higher than the PZC, which indicated that the surface of the gold-coated electrode had a positive charge. The ellipsometry experiment showed that the adsorption of fibrinogen onto the gold-coated silicon wafer surface arrived at a saturated state when the adsorption time exceeded 50 min. The percentage of surface without adsorbed protein, θ, was about 63%. This means that the proportion of surface actually occupied by fibrinogen was only about 37% after the adsorption arrived at saturation. The solution/protein capacitance value was determined in an impulse state around −0.59 V (vs SCE) and was stable (4.2×10−5 F) at other potentials.

CATALYTIC REDUCTION OF HEMOGLOBIN AT THIONINE CHEMICALLY MODIFIED ELECTRODE AND FIA APPLICATIONS

Thionine-containing chemically modified electrode (cme) was constructed with glassy carbon substrate by potential sweep oxidation, electrodeposition and adsorption procedures, and electrocatalytic reduction of hemoglobin was carried out and characterized at the cme under batch and flow conditions. Comparison of the catalytic response toward hemoglobir obtained at the cme was made mainly in terms of the potential dependence, the detectability and long-term stability. When used in flow injection analysis (FIA) experiments with the detector monitored at a constant potential applied at -0.35 V vs sce, detection limit of 0.15-1.5 pmol level of hemoglobin injected was achieved at the cme, with linear response range over 2 orders of magnitude. All the cme s retained more than 70% of their initial hemoglobin response level over 8 h of continuous service in the flow-through system.

Polyaniline modified electrodes for detection of dyes

Polyaniline (PANI) is one of the most extensively used conjugated polymers in the design of electrochemical sensors. In this study, we report electrochemical dye detection based on PANI for the adsorption of both anionic and cationic dyes from solution. The inherent property of PANI to adsorb dyes has been explored for the development of electrochemical detection of dye in solution. The PANI film was grown on electrode via electrochemical polymerization. The as grown PANI film could easily adsorb the dye in the electrolyte solution and form an insulating layer on the PANI coated electrode. As a result, the current intensity of the PANI film was significantly altered. Furthermore, PANI coated stainless steel (SS) electrodes show a change in the current intensity of Fe2+/Fe3+ redox peaks due to the addition of dye in electrolyte solution. PANI films coated on both Pt electrodes and non-expensive SS electrodes showed the concentration of dye adsorbed is directly proportional to the current intensity or potential shift and thus can be used for the quantitative detection of textile dyes at very low concentrations. (C) 2011 Elsevier B.V. All rights reserved.

An alternative approach to ascertain the rate-determining steps of TiO2 photoelectrocatalytic reaction by electrochemical impedance spectroscopy

In an attempt to ascertain the rate-determining steps (RDS) of TiO2 photoelectrocatalytic (PEC) reaction, the PEC oxidation of sulfosalicylic acid (SSA) solution in a TiO2-coated electrode reactor system was monitored by applying the electrochemical impedance spectroscopy (EIS) method. In the meantime, an EIS mathematical model was first established to theoretically simulate the PEC reaction. Based on the EIS model, the theoretical simulation indicates three typical reactions in a PEC oxidation process, which include the charge-transfer-dominated reaction, both the charge-transfer- and adsorption-dominated reaction, and the adsorption-dominated reaction. The experimental results of EIS measurement showed that there was only one arc/semicircle on the EIS plane display when the external bias applied was below 200 mV (vs SCE) in the SSA PEC degradation whereas there were two arcs/semicircles when the externally applied bias exceeded 200 mV (vs SCE). The experimental results have a good agreement with the model simulation. The EIS method in this study provides an easier way to determine the RDS in a PEC oxidation process, which would be helpful to better control the reaction in practice.

Estudo do comportamento dos aços ferramentas soldados em fadiga

Sabendo-se que a fadiga é uma redução gradual da capacidade de carga do componente pela ruptura lenta e gradual do material. E que este defeito decorre do avanço infinitesimal de microtrincas, que se formam no interior do material, imperceptível a olho nu, como também é notório que a presença dos elementos de liga nos aços, propicia alterações nas propriedades metalurgias e mecânicas no material, aplicado à obra. Por outro lado, ao ser submetido a processamentos dos mais diversos, os mesmos, deformam nas zonas elásticas, plásticas e ao fim rompem-se. Ressaltando-se o objetivo deste estudo, destina se abordar as uniões soldadas, nos estágios em que ficam sujeitas a altas temperaturas e resfriam sem controle, até a temperatura ambiente. Ao fim, são solicitados por carregamentos cíclicos constantes ou alternados. Nesta particularidade, espera-se detectar mudanças estruturais profundas na Zona Termicamente Afetada – ZTA, em razão do superaquecimento sofrido, tanto na proximidade do ponto central da poça de fusão como na região localizada na vizinhança. Como não dispomos de parâmetros suficientes e necessários ao controle destas alterações, propomos analisar a ZTA da junta soldada, com a finalidade de avaliar o comportamento metalúrgico e suas implicações causadas pelas interações gás-metal. Analisar os efeitos resultantes do triangulo formado pelo material base aço AISI/SAE 4340, SAE 1020 chanfrados em V e o eletrodo revestido E-6013. A análise da estrutura será realizada pelas técnicas de ensaio metalográfico usando o método da microscopia óptica – MO o qual é de ampla difusão nas comunicações técnicas e cientificas, através das quais, distinguirão as transformações multifásicas. Transformações estas, distintas pelas transformações das austenitas diretas em martensitas sem passar pelas ferritas e perlitas. Com estas identidades, o metalógrafo pode caracterizar e predizer as reações futuras das estruturas mediante a análise das solicitações, a que possam estar submetidas. Para analisar o comportamento em fadiga dos materiais em questão, adota-se como parâmetro auxiliar, o ensaio do pêndulo de Charpy. Portanto, pelos resultados obtidos, conclui-se que as estruturas são comprometidas por tensões internas em conseqüência fragilizam, mas o procedimento de soldagem pode ser adotado, seguido de recozimento para alivio de tensões, se não fizer trincas.

Comparação de junta soldada aço carbono/ aço inox utilizando como metal de adição aço carbono e aço inox

In contemporary industrial, welding processes are widely used, this is the most important process of joining metals used industrially. The welding can be used to build simple structures, like doors and gates for instance, in the same way can be used in situations of high responsibility, such as the nuclear industry and oil industry. Dissimilar welding is a case of welded joints, is characterized by the junction between different materials, for this case, stainless steel and carbon steel that are widely used in steam lines, power plants, nuclear reactors, petrochemical plants. Because their different mechanical and corrosive properties, the join, stainless steel with carbon steel, not only meets environmental requirements and also reduces cost. By using penetrating liquid tests, macrograph, hardness and tensile test was compared the possibility of replacing the current use of 309 rods as filler metal in dissimilar welding between carbon steel and stainless steel by add-on material carbon steel essentially, in this case E7018 coated electrode was used, but without the coating. After analysis of the results and for comparison, was proposed with some certainty that it is possible to replace the addition of materials, thus leading economy in this process widely used in the modern industry

Construção de um equipamento de ensaio de desgaste micro abrasivo por esfera rotativa fixa para análise do desgaste em revestimento duro aplicado por soldagem

Pós-graduação em Engenharia Mecânica - FEIS

Electrooxidation of formic acid at platinum nanoclusters electrodeposited on PEDOT coated carbon paper electrode

Nanoclusters of Pt were electrochemically deposited on a conducting polymer, namely, poly(3,4-ethylenedioxythiophene) (PEDOT), which was also electrochemically deposited on carbon paper current collector. PEDOT facilitated uniform distribution of Pt nanoclusters, when compared with Pt electrodeposition on bare carbon paper substrate. Spectroscopy data indicated absence of any interaction between PEDOT and Pt. The electrochemically active surface area as measured from carbon monoxide adsorption followed by its oxidation was several times greater for Pt-PEDOT/C electrode in comparison with Pt/C electrode. The catalytic activity of Pt-PEDOT/C electrode for electrooxidation of formic acid was significantly greater than that of Pt/C electrode. Amperometry data suggested that the electrodes were stable for continuous oxidation of HCOOH.

Polyaniline-coated carbon particles and their electrode behavior in organic carbonate electrolyte

In an attempt to increase the interface stability of carbon used in Li-ion batteries, a thin conducting polyaniline (PANI) film was fabricated on the surface of carbon by in situ chemical polymerization. The chemical and electrochemical properties of the composite material were characterized using X-ray diffraction, Raman spectroscopy, scanning electron microscope, cyclic voltammetry, and electrochemical impedance spectroscopy. It was confirmed that the PANI film has an obvious effect on the morphology and the electrochemical performance of carbon. The results could be attributed to the electronic and electrochemical activity of the conducting PANI films.

Toluidine blue modified self-assembled silica gel coated gold electrode as biosensor for NADH

A toluidine blue modified gold electrode was constructed using self-assembled silica gel technique. Firstly, toluidine blue was encapsulated within 3D network of silica self-assembly monolayer on the surface of gold electrode. Secondly, another layer of silica sol was further assembled to protect from leaching of mediator or possible contamination. The electrochemical characteristics of toluidine blue immobilized within self-assembled silica gel were studied in detail. The modified electrode was applied for electrochemical oxidation of NADH with satisfactory results.

In-situ FTIR spectroelectrochemical investigation of cobalt(II)-cyanoferrate polymeric film coated on a glassy carbon electrode

Cobalt(II)-cyanoferrate polymeric film has been electrochemically deposited on a glassy carbon electrode and investigated by cyclic voltammetry and in-situ reflection FTIR spectroscopy. A reorientation of the terminal C=N groups upon redox reactions was proposed. The stretching vibration mode of the terminal C=N groups associated with Fe(III) was observed at 2122 cm(-1), however, the stretching vibration mode for terminal groups associated with Fe(II) did not appear. This process could result in a switch between lattice-closed and lattice-opened surface structure. (C) 1997 Elsevier Science B.V.

In situ external reflection FTIR spectroelectrochemical investigation of poly(o-phenylenediamine) film coated on a platinum electrode

The electrochemically deposited poly(o-phenylenediamine) film on a Pt electrode has been investigated utilizing in situ external reflection FTIR spectroelectrochemistry technique. The prepared ladder polymer film is found to be partially ring-opened. The dopant ClO4- is evidenced to orient in such a way that more than one oxygen atom attach to the charge sites of the polymer. This suggests that positive charges of oxidized polymer are partially delocalized over the whole chains. The proton movement observed during the oxidation reaction is associated with the solvated MeCN molecule. It is proposed that the proton diffusion, dissolvation and protonation of the film may be essential to the electrochemical reduction reaction of the film. Copyright (C) 1996 Elsevier Science Ltd.

DETERMINATION OF CATECHOL DERIVATIVES ON PRETREATMENT AND COPOLYMER COATED GLASSY-CARBON ELECTRODE

A glassy carbon electrode was pretreated electrochemically and was coated with a copolymer of maleic acid anhydride attached with Eastman-AQ55D (MA/AQ). The voltammetric behavior of a series of biologically important compounds, such as dopamine, L-DOPA, D