The effect of laser remelting on the corrosion susceptibility and mechanical properties of Ti-35Nb-4Sn (mass%) alloy is investigated across the remelted track profile. In comparison to the cold-rolled microstructure of base metal, recrystallization of heat affected zone (HAZ) improved plastic energy absorption and pitting corrosion resistance, by the reduction of active sites for pit nucleation. In fusion zone, however, passivation was compromised by the formation of dendritic microstructure with Sn enriched interdendritic region, where preferential pitting corrosion occurred. Fusion zone was the most anodic region and presented a corrosion potential difference of 35 mV, in comparison to the adjacent and most cathodic HAZ. Electrochemical impedance analysis showed that spontaneous passivation was most effective in base metal, that developed a thicker and more compact passive film. Local increase in elastic modulus and microhardness of fusion zone shows that laser remelting is a viable processing route for the manufacturing of biomaterials with functionally graded properties.

A crescente ocorrência de antibióticos e seus metabólitos estão cada vez maiores em águas superficiais e subterrâneas, causando impactos significativos no meio ambiente e necessitando de desenvolvimento de novos tratamentos para a remoção completa de tais contaminantes. Este trabalho apresenta o estudo da eletrogeração de peróxido de hidrogênio (H2O2) em meio ácido e a degradação do analgésico dipirona em um reator de fluxo eletroquímico usando um eletrodo de difusão gasosa (GDE) modificado com 5,0% ftalocianina de cobalto (II) (CoPc) e pressurizado com O2. A maior produção de H2O2 alcançada foi de 133 mg L-1 a um potencial aplicado de -2,1 V (vs. Pt//Ag/AgCl/KCl s) e os melhores resultados para a degradação da dipirona foram obtidos sob condições eletro-Fenton, em que o carbono orgânico total (TOC) foi reduzido 62,8% após 90 min de reação e 49,1 kW h de energia foi consumida por kg de dipirona degradada.

The increasing occurrence of antibiotics and their metabolites in surface and ground waters is causing a significant impact on the environment and needing of developing novel treatments for the complete removal of such contaminants. This paper presents the study of the electrogeneration of hydrogen peroxide (H2O2) in acidic medium and the degradation of the analgesic dipyrone in an electrochemical flow reactor using a gas diffusion electrode (GDE) modified with 5.0% cobalt (II) phthalocyanine (CoPc) and pressurized with O2. The highest yield of H2O2 (133 mg L-1) was achieved after 90 min of electrolysis at an applied potential of -2.1 V (vs. Pt//Ag/AgCl/KCl s) and the best results for degradation of dipyrone were obtained under electro-Fenton conditions, where the total organic carbon (TOC) was reduced 62.8% after 90 min of reaction and 49.1 kW h of energy was consumed per kg of dipyrone degraded.

This work reports the development of GDE for electrogeneration of H2O2 and their application in the degradation process of Reactive Blue 19 dye. GDE produced by carbon black with 20% polytetrafluoroethylene generated up to 500 mg L-1 of H2O2 through the electrolysis of acidic medium at -0.8 V vs Ag/AgCl. Reactive Blue 19 dye was degraded most efficiently with H2O2 electrogenerated in the presence of Fe(II) ions, leading to removal of 95% of the original color and 39% of TOC at -0.8 V vs Ag/AgCl.

Este artigo descreve a utilização da microscopia eletroquímica de varredura (SECM) no modo geração pelo substrato/coleta pela ponta (SG/TC), com o objetivo de elucidar aspectos mecanísticos da deposição eletrolítica e redissolução anódica de íons Pb2+ na presença de Cu2+, utilizando-se um eletrodo de carbono vítreo como substrato. Um pico anódico foi observado entre os principais picos correspondentes à redissolução dos metais puros. A posição, intensidade e forma deste pico foram investigadas e foi verificado que eram função da razão entre as concentrações de Pb2+ e Cu2+. Os resultados sugerem que o pico é devido à dissolução do chumbo depositado sobre cobre, resultante de uma deposição em regime de subtensão. A SECM forneceu informações adicionais para o entendimento dos mecanismos de redissolução que não seriam obtidas a partir da análise apenas da resposta voltamétrica.

This paper describes the application of scanning electrochemical microscopy (SECM) in the substrate-generation/tip-collection (SG/TC) mode to elucidate mechanistic aspects of the deposition and stripping of Pb2+ ions in the presence of Cu2+ into a glassy carbon substrate electrode. A stripping peak was observed between the main peaks corresponding to the pure metals. Its position, height and shape were investigated, and the peak intensity was found to depend on the Pb2+/Cu2+ concentration ratio. The results suggested that this peak was due to the dissolution of lead deposited in copper, as a result of an underpotential deposition. The scanning electrochemical microscope provided additional information towards the understanding of the stripping mechanisms in analytical studies. In particular, the SECM-tip response yielded direct evidence about the speciation of some of the compounds evolved during stripping. This information was not available from the voltammetric response of the substrate electrode alone.

The gravimetric and electrochemical tests are the most common techniques used in determining the corrosion rate. However, the use of electrochemical polarization is limited to electrolytes with sufficient conductivity for which Tafel curves are linear. In this study, we investigated a technique in which working microelectrodes of AISI 1020 steel were used to obtain the Tafel curves in diesel oil. The strategy was to reduce the electrode area and hence the ohmic drop. The diameter of the microelectrode was reduced to a value where the compensation of the Tafel curves became unnecessary. The results showed that for electrodes with diameters below 50 μm, the ohmic drop tends to a minimum and independent of the microelectrode diameter.

A remoção de CuII (10 mg L-1) complexado por ácido húmico comercial (100 mg L-1) foi estudada a diferentes densidades de corrente (30-80 mA cm-2) usando uma célula filtro-prensa, ânodo de Ti/Ru0.3Ti0.7O2 e cátodo de aço inoxidável. As eletrólises foram feitas com e sem membrana separando os compartimentos da célula [aniônica homogênea (Nafion R117), catiônica heterogênea (Ionac MC-3470) e aniônica heterogênea (Ionac MA-3475)]. A influência da membrana na velocidade de remoção de CuII foi maior com as catiônicas. Foi obtida eficiência de corrente de ca. 55% (Ionac MC-3470) para remoção de CuII a 30 mA cm-2. Combinando oxidação e redução, foi obtida remoção de 100% de CuII com eficiência de corrente de 75%. A etapa principal para a remoção é interação eletrostática com o ânodo, seguida pela difusão através da membrana e deposição sobre o cátodo. Adicionalmente, a degradação oxidativa de ácido húmico contribui com a velocidade de remoção de CuII.

The removal of CuII (10 mg L-1) complexed by commercial humic acid (100 mg L-1) was studied at different current densities (30-80 mA cm-2) using a filter-press cell, Ti/Ru0.3Ti0.7O2 anode and stainless steel cathode. The electrolyses were performed with and without membrane separating the cell compartments [(homogeneous anionic (Nafion R117), heterogeneous cationic (Ionac MC-3470) and heterogeneous anionic (Ionac MA-3475)]. The influence of the membrane on the rate of CuII removal was bigger for cationic membranes. Current efficiencies up to ca. 55% (Ionac MC-3470) for CuII removal at 30 mA cm-2 were obtained. By combining oxidation and reduction, 100% CuII removal was achieved at current efficiencies of 75%. The main path for the removal is the electrostatic interaction with the anode followed by diffusion through the membrane and deposition at the cathode. Additionally, the oxidative degradation of humic acid contributes to the rate of CuII removal.

Este trabalho apresenta um estudo comparativo da eficiência eletroquímica na eletrogeração de peróxido de hidrogênio in situ usando eletrodos da difusão gasosa modificados com os catalisadores orgânicos redox: 2-etilantraquinona, 2-terc-butilantraquinona e azobenzeno em meio de 0,1 mol L-1 H2SO4 + 0,1 mol L-1 K2SO4, pH = 1. A produção de peróxido de hidrogênio está diretamente relacionada ao potencial aplicado e a concentração dos catalisadores adicionados. A modificação dos eletrodos resultou em um aumento significativo no rendimento de H2O2 (30%) alcançando 850 mg L-1 e o sobrepotencial da reação de redução do oxigênio foi deslocado para valores menos negativos (400 mV vs Ag/AgCl para os eletrodos modificados com quinonas e 300 mV vs. Ag/AgCl para os eletrodos modificados com azobenzeno) comparado ao eletrodo de difusão gasosa não modificado, reduzindo o consumo de energia de 596,5 para 232,4 kWh kg-1. Os resultados indicaram que o melhor eletrodo para a eletrogeração do H2O2 é o eletrodo de difusão gasosa modificado com 10% de 2-etilantraquinona, o qual apresentou a melhor relação custo/benefício.

This paper reports a comparative study of the electrochemical performance of in situ hydrogen peroxide electrogeneration on gas diffusion electrodes modified by organic redox catalysts 2-ethylanthraquinone, 2-terc-butylanthraquinone and azobenzene in medium of 0.1 mol L-1 H2SO4 plus 0.1 mol L-1 K2SO4, pH = 1. Hydrogen peroxide generation proved strongly dependent on the applied potential and on the concentration of added catalysts. Electrode modifications led to a significant increase in H2O2 yield (30%) reaching 850 mg L-1, and the overpotential for oxygen reduction shifted to less negative values (400 mV vs Ag/AgCl for electrodes modified by quinones and 300 mV vs Ag/AgCl for electrodes modified by azobenzene) compared to noncatalyzed gas diffusion electrodes, resulting in reduced energy consumption of 596.5 to 232.4 kWh kg-1. The results indicated that the best electrode for H2O2 electrogeneration is the gas diffusion electrode modified with 10% of 2-ethylanthraquinone, offering the best cost to benefit ratio.

Este trabalho apresenta um estudo do desempenho de dois anodos comerciais de óxidos de metais nobres (DSA®) no processo eletroquímico para a oxidação de cianetos. Os revestimentos estudados foram 70TiO2/30RuO2 e 55Ta2O5/45IrO2, em um substrato de Ti. A eficiência dos dois materiais no processo de eletrooxidação de cianeto livre foi comparada usando a voltametria linear e a eletrólise a potencial constante. O eletrodo 70TiO2/30RuO2 apresentou a melhor eficiência na eletrooxidação de cianetos livres.

This paper presents a study of the performance of two commercial dimensionally stable anode (DSA®) oxide coatings in the electrochemical process for cyanide oxidation. The coatings studied were 70TiO2/30RuO2 and 55Ta2O5/45IrO2, on Ti substrate. The efficiency of both materials in the electro-oxidation of free cyanide was compared using linear voltammetry and electrolysis at constant potential. The 70TiO2/30RuO2 electrode shows a better performance in the electro-oxidation of free cyanide.

Organic compounds responsible for the color of wastewaters are usually refractory to biological digestion. In this paper the photo-assisted electrolysis process is used for color removal from three of the most colored wastewaters, which are daily generated in large amounts: the E1 bleach Kraft mill effluent, a textile reactive dye effluent and a landfill leachate. Electrolysis was carried out at 26,5 mA cm-2 in a flow reactor in which the anode surface was illuminated by a 400 W high pressure Hg bulb. In all experiments 70-75% of color reduction was observed which was also followed by a net organic load oxidation.

Neste trabalho foi realizado um estudo visando a potencial aplicação de dois eletrodos comerciais tipo DSA<FONT FACE=Symbol>â</FONT> no tratamento eletroquímico de efluentes aquosos. Anodos com composição superficial 70TiO2/30RuO2 e 45IrO2/55Ta2O5 foram usados num reator de fluxo com densidades de corrente de 15 a 150 mA.cm-2 e velocidade da solução de 0,24 m.s-1. Os resultados mostram que fenol e as quinonas são degradados até concentrações muito baixas, embora apenas uma pequena fração seja mineralizada. A partir de uma solução com 100 mg.L-1 de fenol, a 100 mA.cm-2, após cinco horas de eletrólise foram encontrados 0,4 mg.L-1 de fenol, 1 mg.L-1 de hidroquinona e 7 mg.L-1 de benzoquinona. TOC foi reduzido em 35%.

In this paper the potentiality of two types of DSA<FONT FACE=Symbol>â</FONT> commercial electrodes, for electrochemical treatment of effluents, is investigated. Oxide anodes, with nominal composition of 70TiO2/30RuO2 and 45IrO2/55Ta2O5, were used in a flow-cell reactor for the electrooxidation of phenol. Comparative results were presented as phenol concentration decay as a function of electrolysis time, as well as COD and TOC concentration reduction. The cell reactor was operated at current densities, ranging from 15 to 150 mA cm-2 and solution linear velocity was 0.24 m s-1. Results reported in this paper showed that phenol and quinones were degraded to a very low concentration, besides only a small portion of the organic carbon is reduced. Starting from 100 mg L-1, after five hours of electrolysis at 100 mA cm-2, concentrations reached 0.4 mg L-1 of phenol, 1 mg L-1 of hydroquinone, 7 mg L-1 of benzoquinone and TOC was reduced by 35%.

This paper presents some results that may be used as previous considerations to a hydrogen peroxide electrogeneration process design. A kinetic study of oxygen dissolution in aqueous solution is carried out and rate constants for oxygen dissolution are calculated. Voltammetric experiments on vitreous carbon cathode shown that the low saturation concentration drives the oxygen reduction process to a mass transfer controlled process which exhibits low values of limiting currents. Results have shown that the hydrogen peroxide formation and its decomposition to water are separated by 400 mV on the vitreous carbon surface. Diffusion coefficients for oxygen and hydrogen peroxide are calculated using data taken from Levich and Tafel plots. In a series of bulk electrolysis experiments hydrogen peroxide was electrogenerated at several potential values, and concentration profiles as a function of the electrical charged passed were obtained. Data shown that, since limiting current plateaus are poorly defined onto reticulated vitreous carbon, cathodic efficiency may be a good criterion for choosing the potential value in which hydrogen peroxide electrogeneration should be carried out.

Electrochemical methods applied to organic species transformation has been used as excellent synthesis tools. C-C bonds can be established, making possible polymer synthesis by both anodic and cathodic reactions of suitable monomer species at the working electrode surface. In this study, anodic procedure was used to electropolymerization of 2-mercaptobenzimidazole at reticulated glassy carbon (RGC) surface. 2-mercaptobenzimidazole presents ligand sites towards Hg2+, Ag+ and Cu2+ ions. The obtained material has been able to adsorb the above mentioned ions in aqueous solution.

Neste trabalho foram feitos experimentos usando técnicas de voltametria cíclica e pulso de potencial para o estudo do mecanismo de deposição do cobalto em meio de sulfato. A voltametria cíclica mostrou dois picos de dissolução, o que foi atribuído a dissolução de uma fase rica em hidrogênio e outra do metal quase puro. A análise cinética das curvas I-E na varredura reversa mostraram que, para uma solução com 0,37 M Co(II) e pH 6, o potencial de equilíbrio do par Co/Co(II) é -0,58 V vs. SCE e a corrente de troca, Io = 4,8 x 10-6 A cm-2. Os experimentos de pulso de potencial mostraram que o depósito de cobalto sobre o eletrodo de carbono vítreo apresenta nucleação progressiva seguido de crescimento tridimensional. Ambas as técnicas confinnaram que a deposição do cobalto acontece em duas etapas, com a transferência de um elétron cada.

Experiments of cobalt deposition on a vitreous carbon electrode were carried out using cyclic voltammetry and potential steps techniques, in a sulfate medium. Cyclic voltammetry showed two stripping peaks that were attnbuted to the dissolution of two phases: a hydrogen nch cobalt phase and a bulk cobalt phase. Kinetic analysis of I-E response on the reverse scan for a 0.37 M of Co(II), pH 6, presented a value of -0.58 V vs. SCE for the equilibrium potential of the Co/Co(II) couple. The exchange current density was estimated as Io = 4.8 x 10-6 A cm-2 in this solution. Potential step experiments showed that the cobalt deposit on vitreous carbon is formed by a mechanism of progressive nucleation followed by 3-D growth. Both techniques confirmed that cobalt deposition takes place in two single electron steps.

O objetivo do presente trabalho foi estabelecer um processo eletrolítico para remover metais de efluentes aquosos usando um catodo tridimensional de carbono vítreo reticulado. Durante o desenvolvimento do trabalho foi estudado a influência do fluxo do eletrólito e da porosidade do eletrodo. A célula eletrolítica utilizou potenciais tais que a reação de redução ocorreu sob controle de transporte de massa. A célula demonstrou eficiência na remoção de chumbo, zinco e cobre, reduzindo a concentração desses metais de 50 mg.L-1 a 0,1 mg.L-1 em 20 min de recirculação da solução.

The aim of the present study was to establish an electrolytic method for the removal of metals from wastewater using a three dimensional, reticulated vitreous carbon cathode. During the development of the experimental set up, particular attention was paid to the electrolyte flow rate and to the cathode porosity. The electrolytic cell employed potential values in such a way that the metals reduction reaction occurred under mass transport control. These potentials were determined by hydrodynamic voltammetry on a vitreous carbon rotating disc electrode. The cell proved to be efficient in removing copper, zinc and lead and it was able to reduce the levels of these metals from 50 mg/L to 0.1 mg/L.