Investigation of the CO tolerance mechanism at several Pt-based bimetallic anode electrocatalysts in a PEM fuel cell

The electrocatalysis of CO tolerance of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C at a PEM fuel cell anode has been investigated using single cell polarization and online electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), in situ X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO(2) start at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particulary for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H(2)/CO, the formation of CO(2) is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. (C) 2008 Elsevier Ltd. All rights reserved.

Thermodynamics and Lithium Intercalation in CeO(2)-TiO(2) Thin Film

The kinetics and the thermodynamics of electrochemical intercalation of lithium into CeO(2)-TiO(2) films prepared by the sol-gel process were studied by galvanostatic intermittent titration technique (GITT) as function of the depth of lithium intercalation. The open-circuit-potential versus x in Li(x)(CeO(2)-TiO(2)) curve consists of two straight lines with different slopes, one in the range of 0.03 <= x <= 0.09 and the other of 0.09 < x <= 0.15. The standard Gibbs energy for lithium intercalation Delta G(1)(0) was 6kJ/mol for x = 0.09 in Li(x)(CeO(2)-TiO(2)) at room temperature. The chemical diffusion coefficient value, D(Li+), of lithium intercalation into thin film oxide was 2.14.10(-11) cm(2)/s at x = 0.15, and the value of the component diffusion coefficient D(Li+),(k) was about one order of magnitude lower than the coefficient of chemical diffusion.

The impact of water concentration on the catalytic oxidation of ethanol on platinum electrode in concentrated phosphoric acid

The electro-oxidation of ethanol on platinum in phosphoric acid opens the door to promote the oxidation reaction at higher temperatures. However, the effect of the presence of water is not well understood. In this work, the electro-oxidation of ethanol on platinum was studied in concentrated phosphoric acid containing different concentrations of water at room temperature. The results show that effect of bulk water on the rate electro-oxidation is highest at 0.60 V and decreases for increasing potentials. This was suggested as due to the increasing formation of oxygenated species on the electrode surface with potential, which in turn is more efficient than the increase of water content in the electrolyte. Altogether, these results were interpreted as an evidence of a Langmuir-Hinshelwood step involving oxygenated species as one of the adsorbed partners. (C) 2009 Elsevier B.V. All rights reserved.

Estudos de Durabilidade Frente ao Ataque Ácido de Compósitos Portland-Polímero para Cimentação de Poços de Petróleo

Portland-polymers composites are promising candidates to be used as cementing material in Northeastern oil wells of Brazil containing heavy oils submitted to steam injection. In this way, it is necessary to evaluate its degradation in the commonly acidizind agents. In addition, to identify how aggressive are the different hostile environments it is an important contribution on the decision of the acidic systems to be used in. It was investigated the performance of the Portland-polymer composites using powdered polyurethane, aqueous polyurethane, rubber tire residues and a biopolymer, those were reinforced with polished carbon steel SAE 1045 to make the electrochemical measurements. HCl 15,0 %, HCl 6,0 % + HF 1,5 % (soft mud acid), HCl 12,0 % + HF 3,0 % (regular mud acid) and HAc 10 % + HF 1,5 % were used as degrading environment and electrolytes. The more aggressive acid solution to the plain Portland hardened cement paste was the regular mud acid, that showed loss of weight around 23.0 %, followed by the soft mud acid, the showed 11.0 %, 15.0 % HCl with 7,0 % and, at last the 10.0 % HAc plus HF 1.5 % with just 1.0 %. The powdered polyurethane-composite and the aqueous polyurethane one showed larger durability, with reduction around 87.0 % on the loss of weight in regular mud acid. The acid attack is superficial and it occurs as an action layer, where the degraded layer is responsible for the decrease on the kinetic of the degrading process. This behavior can be seen mainly on the Portland- aqueous polyurethane composite, because the degraded layer is impregnated with chemically modified polymer. The fact of the acid attack does not have influence on the compressive strength or fratography of the samples, in a general way, confirms that theory. The mechanism of the efficiency of the Portland-polymers composites subjected to acid attack is due to decreased porosity and permeability related with the plain Portland paste, minor quantity of Ca+2, element preferentially leached to the acidic solution, wave effect and to substitute part of the degrading bulk for the polymeric one. The electrolyte HAc 10 % + HF 1,5 % was the least aggressive one to the external corrosion of the casing, showing open circuit potentials around +250 mV compared to -130 mV to the simulated pore solution to the first 24 hours immersion. This behavior has been performed for two months at least. Similar corrosion rates were showed between both of the electrolytes, around 0.01 μA.cm-2. Total impedance values, insipient arcs and big polarization resistance capacitive arcs on the Nyquist plots, indicating passivity process, confirm its efficiency. In this way, Portlandpolymers composites are possible solutions to be succeed applied to oilwell cementing concomitant submitted to steam injection and acidizing operation and the HAc 10,0 % + HF 1,5 % is the less aggressive solution to the external corrosion of the casing

Análise aerodinâmica de perfis de asa para aeronaves experimentais tipo jn-1

The great importance in selecting the profile of an aircraft wing concerns the fact that its relevance in the performance thereof; influencing this displacement costs (fuel consumption, flight level, for example), the conditions of flight safety (response in critical condition) of the plane. The aim of this study was to examine the aerodynamic parameters that affect some types of wing profile, based on wind tunnel testing, to determine the aerodynamic efficiency of each one of them. We compared three types of planforms, chosen from considerations about the characteristics of the aircraft model. One of them has a common setup, and very common in laboratory classes to be a sort of standard aerodynamic, it is a symmetrical profile. The second profile shows a conFiguration of the concave-convex type, the third is also a concave-convex profile, but with different implementation of the second, and finally, the fourth airfoil profile has a plano-convex. Thus, three different categories are covered in profile, showing the main points of relevance to their employment. To perform the experiment used a wind tunnel-type open circuit, where we analyzed the pressure distribution across the surface of each profile. Possession of the drag polar of each wing profile can be, from the theoretical basis of this work, the aerodynamic characteristics relate to the expected performance of the experimental aircraft, thus creating a selection model with guaranteed performance aerodynamics. It is believed that the philosophy used in this dissertation research validates the results, resulting in an experimental alternative for reliable implementation of aerodynamic testing in models of planforms

Photoinduced hole-transfer in semiconducting polymer/low-bandgap cyanine dye blends: evidence for unit charge separation quantum yield

Power-conversion efficiencies of organic heterojunction solar cells can be increased by using semiconducting donor-acceptor materials with complementary absorption spectra extending to the near-infrared region. Here, we used continuous wave fluorescence and absorption, as well as nanosecond transient absorption spectroscopy to study the initial charge transfer step for blends of a donor poly(p-phenylenevinylene) derivative and low-band gap cyanine dyes serving as electron acceptors. Electron transfer is the dominant relaxation process after photoexcitation of the donor. Hole transfer after cyanine photoexcitation occurs with an efficiency close to unity up to dye concentrations of similar to 30 wt%. Cyanines present an efficient self-quenching mechanism of their fluorescence, and for higher dye loadings in the blend, or pure cyanine films, this process effectively reduces the hole transfer. Comparison between dye emission in an inert polystyrene matrix and the donor matrix allowed us to separate the influence of self-quenching and charge transfer mechanisms. Favorable photovoltaic bilayer performance, including high open-circuit voltages of similar to 1 V confirmed the results from optical experiments. The characteristics of solar cells using different dyes also highlighted the need for balanced adjustment of the energy levels and their offsets at the heterojunction when using low-bandgap materials, and accentuated important effects of interface interactions and solid-state packing on charge generation and transport.

Effects of the high temperature plasma immersion ion implantation (PIII) of nitrogen in AISI H13 steel

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Estudo das ligas titânio-zircônio resultantes do processo de fundição plasma-skull para aplicações como biomateriais

The aim of this work was to study a series of 11 different compositions of Ti-Zr binary alloys resistance to aggressive environment, i. e., their ability to keep their surface properties and mass when exposed to them as a way to evaluate their performance as biomaterials. The first stage was devoted to the fabrication of tablets from these alloys by Plasma-Skull casting method using a Discovery Plasma machine from EDG Equipamentos, Brazil. In a second stage, the chemical composition of each produced tablet was verified. In a third stage, the specimen were submitted to: as-cast microstructure analysis via optical and scanning electron microscopy (OM and SEM), x-ray dispersive system (EDS) chemical analysis via SEM, Vickers hardness tests for mechanical evaluation and corrosion resistence tests in a 0.9% NaCl solution to simulate exposition to human saliva monitored by open circuit potential and polarization curves. From the obtained results, it was possible to infer that specimens A1 (94,07 wt% Ti and 5,93% wt% Zr), A4 (77,81 wt % Ti and 22,19 wt % Zr) and A8 (27,83 wt% Ti and 72,17 wt% Zr), presented best performance regarding to corrosion resistance, homogeneity and hardness which are necessary issues for biomaterials to be applied as orthopedic and odontological prosthesis

Estudo da eficácia do tensoativo sorbitano tween 80 veiculado em nanoemulsão contendo óleo de soja, como inibidor de corrosão

Nowadays, the use of chemicals that satisfactorily meet the needs of different sectors of the chemical industry is linked to the consumption of biodegradable materials. In this context, this work contemplated biotechnological aspects with the objective of developing a more environmentally-friendly corrosion inhibitor. In order to achieve this goal, nanoemulsion-type systems (NE) were obtained by varying the amount of Tween 80 (9 to 85 ppm) a sortitan surfactant named polyoxyethylene (20) monooleate. This NE-system was analyzed using phase diagrams in which the percentage of the oil phase (commercial soybean oil, codenamed as OS) was kept constant. By changing the amount of Tween 80, several polar NE-OS derived systems (O/W-type nanoemulsion) were obtained and characterized through light scattering, conductivity and pH, and further subjected to electrochemical studies. The interfacial behavior of these NE-OS derived systems (codenamed NE-OS1, S2, S3, S4 and S5) as corrosion inhibitors on carbon steel AISI 1020 in saline media (NaCl 3.5%) were evaluated by measurement of Open Circuit Potential (OCP), Polarization Curves (Tafel extrapolation method) and Electrochemical Impedance Spectroscopy (EIS). The analyzed NE-OS1 and NE-OS2 systems were found to be mixed inhibitors with quantitative efficacy (98.6% - 99.7%) for concentrations of Tween 80 ranging between 9 and 85 ppm. According to the EIS technique, maximum corrosion efficiency was observed for some tested NE-OS samples. Additionaly to the electrochemical studies, Analysis of Variance (ANOVA) and Principal Component Analysis (PCA) were used, characterization of the nanoemulsion tested systems and adsorption studies, respectively, which confirmed the results observed in the experimental analyses using diluted NE-OS samples in lower concentrations of Tween 80 (0.5 1.75 ppm)

Stability of cp-Ti and Ti-6Al-4V alloy for dental implants as a function of saliva pH - an electrochemical study

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The Role of Lipopolysaccharide on the Electrochemical Behavior of Titanium

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica for differential pulse adsorptive stripping analysis of nickel in ethanol fuel

A solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica (SiAt-SPCPE) was applied to Ni2+ determination in commercial ethanol fuel samples. The proposed method comprised four steps: (1) Ni2+ preconcentration at open circuit potential directly in the ethanol fuel sample, (2) transference of the electrode to an electrochemical cell containing DMG, (3) differential pulse voltammogram registering and (4) surface regeneration by polishing the electrode. The proposed method combines the high Ni2+ adsorption capacity presented by 2-aminothiazole organofunctionalized silica with the electrochemical properties of the Ni(DMG)2 complex, whose electrochemical reduction provides the analytical signal.All experimental parameters involved in the proposed method were optimized. Using a preconcentration time of 20 min, it was obtained a linear range from 7.5 x 10(-9) to 1.0 x 10(-6) mol L-1 with detection limit of 2.0 x 10(-9) mol L-1. Recovery values between 96.5 and 102.4% were obtained for commercial samples spiked with 1.0 mu mol L-1 Ni2+ and the developed electrode was totally stable in ethanolic solutions. The contents of Ni2+ found in the commercial samples using the proposed method were compared to those obtained by graphite furnace atomic absorption spectroscopy by using the F- and t-test. Neither the F- nor t-values exceeded the critical values at 95% confidence level, confirming that there are not statistical differences between the results obtained by both methods. These results indicate that the developed electrode can be successfully employed to reliable Ni2+ determination in commercial ethanol fuel samples without any sample pretreatment or dilution step. (c) 2006 Elsevier B.V. All rights reserved.

Copper determination in ethanol fuel by differential pulse anodic stripping voltammetry at a solid paraffin-based carbon paste electrode modified with 2-aminothiazole organofunctionalized silica

Solid paraffin-based carbon paste electrodes modified with 2-aminothiazole organofunctionalized silica have been applied to the anodic stripping determination of copper ions in ethanol fuel samples without any sample treatment. The proposed method comprised four steps: (1) copper ions preconcentration at open circuit potential directly in the ethanol fuel sample; (2) exchange of the solution and immediate cathodic reduction of the absorbate at controlled potential; (3) differential pulse anodic stripping voltammetry; (4) electrochemical surface regeneration by applying a positive potential in acid media. Factors affecting the preconcentration, reduction and stripping steps were investigated and the optimum conditions were employed to develop the analytical procedure. Using a preconcentration time of 20 min and reduction time of 120 s at -0.3 V versus Ag/AgCl(sat) a linear range from 7.5 x 10(-8) to 2.5 x 10(-6) mol L(-1) with detection limit of 3.1 x 10(-8) mol L(-1) was obtained. Interference studies have shown a decrease in the interference effect according to the sequence: Ni > Zn > Cd > Pb > Fe. However, the interference effects of these ions have not forbidden the application of the proposed method. Recovery values between 98.8 and 102.3% were obtained for synthetic samples spiked with known amounts of Cu(2+) and interfering metallic ions. The developed electrode was successfully applied to the determination of Cu(2+) in commercial ethanol fuel samples. The results were compared to those obtained by flame atomic absorption spectroscopy by using the F-test and t-test. Neither F-value nor t-value have exceeded the critical values at 95% confidence level, confirming that there are no significant differences between the results obtained by both methods. (c) 2006 Elsevier B.V. All rights reserved.

Influence of iron addition on the microstructure and the electrochemical corrosion of Al-Zn-Mg alloys

The effect of Fe addition on the microstructural properties and the corrosion resistance of Al-Zn-Mg alloys submitted to different heat treatments (cast, annealed and aged), has been studied in chloride solutions using optical microscopy (OM), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray (EDX), cyclic polarization (CP) and open circuit potential (o.c.p.) measurements. The presence of 0.3% Fe in the alloy limited the growth of the MgZn2 precipitates, both in the annealed and in the quenched specimens. No effect of Cr on the grain size in the presence of Fe was found because of the accumulation of Cr in the Fe-rich particles. Fe in the Al-Zn-Mg alloys also made them more susceptible to pitting. Pitting occurred mainly near the Fe-rich particles both, under o.c.p. conditions in O-2-saturated solutions and during the CP.

High-velocity oxyfuel Cr3C2-NiCr replacing hard chromium coatings

Comparative wear and corrosion properties of Cr3C2-NiCr (CC-TS) (a high-velocity oxyfuel [HVOF]) and hard chromium (HC) coating's obtained on a steel substrate have been studied. The structural characterization was done before and after measurements by optical microscopy, scanning electron microscopy, and scanning white light interferometry. Wear and corrosion properties were evaluated by ball on disk (ASTM G99-90), rubber wheel (ASTM G65-91), and electrochemical measurements of open circuit and polarization curves. The best corrosion and wear resistance was for the CC-TS obtained by HVOF. The open-circuit potential values measured for both samples after 18 h of immersion we're: -0.240 and -0.550 V, respectively, for CC-TS and HC, versus Ag/AgCl,KClsat. Three orders of magnitude lower volume loss were found for CC-TS (HVOF) after friction tests compared with HC.