Estudo do mecanismo de corrosão por pites em água do mar de aços inoxidáveis supermartensíticos microligados com Nb e Ti

Os aços inoxidáveis supermartensíticos (SMSS) são usados em ambientes agressivos devido à sua boa soldabilidade, boas propriedades mecânicas em temperaturas elevadas e superior resistência à corrosão sob tensão. Aplicações na exploração de petróleo demandam superior combinação de propriedades e os aços inoxidáveis duplex e superduplex têm sido aplicados nessa área, a despeito de seus custos elevados. Os SMSS consistem numa alternativa técnica e econômica ao uso daqueles aços. Nesse trabalho, adições de Nb e Ti foram realizadas com o intuito de minimizar o efeito de sensitização, promover o refino de grãos e foram estudados os aspectos microestruturais e a resistência à corrosão por pites em água do mar. A formação e a evolução dos pites foram acompanhadas por ensaios de corrosão, microscopia óptica e eletrônica, focalizando suas morfologias. O aço com Ti apresentou o melhor desempenho quanto à corrosão, com o maior potencial de corrosão e menor potencial de pite entre os aços em estudo. O aço com Nb, apesar de apresentar potencial de corrosão superior ao do aço sem adição, teve um potencial de pite inferior ao do mesmo.

A biosensor based on immobilization of lactate oxidase in a PB-CTAB film for FIA determination of lactate in beer samples

An amperometric lactate biosensor with lactate oxidase immobilized into a Prussian Blue (PB) modified electrode was fabricated. The advantage of using cetyltrimethylammonium bromide (CTAB) in the electrodeposition step of PB films onto glassy carbon surfaces was confirmed taking into account both the stability and sensitivity of the measurements. The biosensor was used in the development of a FIA amperometric method for the determination of lactate. Under optimal operating conditions (pH = 6.9, E = -0.1 V), the linear response of the method was extended up to 0.28 µmol L-1 lactate with a limit of detection of 0.84 mmol L-1. The repeatability of the method for injections of a 0.28 mmol L-1 lactate solution was 2.2 % (n = 18). The usefulness of the method was demonstrated by determining lactate in beer samples and the results were in good agreement with those obtained by using a reference spectrophotometric enzyme method.

Universal resistance capacitance crossover in current-voltage characteristics for unshunted array of overdamped Nb-AlOx-Nb Josephson junctions

We report on some unusual behavior of the measured current-voltage characteristics (CVC) in artificially prepared two-dimensional unshunted array of overdamped Nb-AlO(x)-Nb Josephson junctions. The obtained nonlinear CVC are found to exhibit a pronounced (and practically temperature independent) crossover at some current I(cr) = (1/2 beta(C)-1)I(C) from a resistance R dominated state with V(R)=R root I(2)-I(C)(2) below I(cr) to a capacitance C dominated state with V(C) = root(h) over bar /4eC root I-I(C) above I(cr). The origin of the observed behavior is discussed within a single-plaquette approximation assuming the conventional resistively shunted junction model with a finite capacitance and the Ambegaokar-Baratoff relation for the critical current of the single junction. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3407566]

Influence of film thickness on the crystallization of Ni-doped amorphous silicon samples

This work reports on the crystallization of amorphous silicon (a-Si) films doped with 1 at. % of nickel. The films, with thicknesses ranging from 10 to 3000 nm, were deposited using the cosputtering method onto crystalline quartz substrates. In order to investigate the crystallization mechanism in detail, a series of undoped a-Si films prepared under the same deposition conditions were also studied. After deposition, all a-Si films were submitted to isochronal thermal annealing treatments up to 1000 degrees C and analyzed by Raman scattering spectroscopy. Based on the present experimental results, it is possible to state that (a) when compared to the undoped a-Si films, those containing 1 at. % of Ni crystallize at temperatures similar to 100 degrees C lower, and that (b) the film thickness influences the temperature of crystallization that, in principle, tends to be lower in films thinner than 1000 nm. The possible reasons associated to these experimental observations are presented and discussed in view of some experimental and thermodynamic aspects involved in the formation of ordered Si-Si bonds and in the development of Ni-silicide phases. (c) 2008 American Institute of Physics.

Studies on the Electrocatalytic Reduction of Hydrogen Peroxide on a Glassy Carbon Electrode Modified With a Ruthenium Oxide Hexacyanoferrate Film

The electrocatalytic reduction of hydrogen peroxide on a glassy carbon (GC) electrode modified with a ruthenium oxide hexacyanoferrate (RuOHCF) was investigated using rotating disc electrode (RDE) voltammetry aiming to improve the performance of the sensor for hydrogen peroxide detection. The influence of parameters such as rotation speed, film thickness and hydrogen peroxide concentration indicated that the rate of the cross-chemical reaction between Ru(II) centres immobilized into the film and hydrogen peroxide controls the overall process. The kinetic regime could be classified as LSk mechanism, according to the diagnostic table proposed by Albery and Hillman, and the kinetic constant of the mediated process was found to be 706 mol(-1) cm(3) s(-1). In the LSk case the reaction layer is located at a finite layer close to the modifier layer/solution interface

Polymer matrix sensitizing effect on photoluminescence properties of Eu(3+)-beta-diketonate complex doped into poly-beta-hydroxybutyrate (PHB) in film form

In this work is reported the sensitization effect by polymer matrices on the photoluminescence properties of diaquatris(thenoyltrifluoroacetonate)europium(III), [Eu(tta)(3)(H(2)O)(2)], doped into poly-beta-hydroxybutyrate (PHB) with doping percentage at 1, 3, 5, 7 and 10% (mass) in film form. TGA results indicated that the Eu(3+) complex precursor was immobilized in the polymer matrix by the interaction between the Eu(3+) complex and the oxygen atoms of the PHB polymer when the rare earth complex was incorporated in the polymeric host. The thermal behaviour of these luminescent systems is similar to that of the undoped polymer, however, the T(onset) temperature of decomposition decreases with increase of the complex doping concentration. The emission spectra of the Eu(3+) complex doped PHB films recorded at 298 K exhibited the five characteristic bands arising from the (5)D(0) -> (7)F(J) intraconfigurational transitions (J = 0-4). The fact that the quantum efficiencies eta of the doped film increased significantly revealed that the polymer matrix acts as an efficient co-sensitizer for Eu(3+) luminescent centres and therefore enhances the quantum efficiency of the emitter (5)D(0) level. The luminescence intensity decreases, however, with increasing precursor concentration in the doped polymer to greater than 5% where a saturation effect is observed at this specific doping percentage, indicating that changes in the polymeric matrix improve the absorption property of the film, consequently quenching the luminescent effect.

Optimization of Heat Treatment Profiles Applied to Nanometric-Scale Nb(3)Sn Wires With Cu-Sn Artificial Pinning Centers

Nb(3)Sn is one of the most used superconducting materials for applications in high magnetic fields. The improvement of the critical current densities (J(c)) is important, and must be analyzed together with the optimization of the flux pinning acting in the material. For Nb(3)Sn, it is known that the grain boundaries are the most effective pinning centers. However, the introduction of artificial pinning centers (APCs) with different superconducting properties has been proved to be beneficial for J(c). As these APCs are normally in the nanometric-scale, the conventional heat treatment profiles used for Nb(3)Sn wires cannot be directly applied, leading to excessive grain growth and/or increase of the APCs cross sections. In this work, the heat treatment profiles for Nb(3)Sn superconductor wires with Cu(Sn) artificial pinning centers in nanometric-scale were analyzed in an attempt to improve J(c) . It is described a methodology to optimize the heat treatment profiles in respect to diffusion, reaction and formation of the superconducting phases. Microstructural, transport and magnetic characterization were performed in an attempt to find the pinning mechanisms acting in the samples. It was concluded that the maximum current densities were found when normal phases (due to the introduction of the APCs) are acting as main pinning centers in the global behavior of the Nb(3)Sn superconducting wire.

Composition and orientation effects on the final recrystallization texture of coarse-grained Nb-containing AISI 430 ferritic stainless steels

Composition and orientation effects on the final recrystallization texture of three coarse-grained Nb-containing AISI 430 ferritic stainless steels (FSSs) were investigated. Hot-bands of steels containing distinct amounts of niobium, carbon and nitrogen were annealed at 1250 degrees C for 2h to promote grain growth. In particular, the amounts of Nb in solid solution vary from one grade to another. For purposes of comparison, the texture evolution of a hot-band sheet annealed at 1030 degrees C for 1 min (finer grain structure) was also investigated. Subsequently, the four sheets were cold rolled up to 80% reduction and then annealed at 800 degrees C for 15 min. Texture was determined using X-ray diffraction and electron backscatter diffraction (EBSD). Noticeable differences regarding the final recrystallization texture and microstructure were observed in the four investigated grades. Results suggest that distinct nucleation mechanisms take place within these large grains leading to the development of different final recrystallization textures. (c) 2011 Elsevier B.V. All rights reserved.

Electrodeposition and characterization of Cu-Nb composite coatings

Copper coatings containing well-distributed Nb particles were obtained by co-electrodeposition in an acidic sulfate bath. Nb particle concentration in the bath was the most significant factor for the incorporation of Nb particles in copper, followed by stirring rate, whereas current density presented low significance. High Nb particle concentration and low stirring rate led to a higher incorporated Nb particle content. The microhardness of the composite layers was higher than that of pure copper deposits obtained under the same conditions due to copper matrix grain refinement and increased with the increase of both current density and incorporated Nb particle volume fraction. The corrosion resistance of Cu-Nb composites in 0.5 wt.% H(2)SO(4) solution at room temperature was higher than that of pure copper and increased with the increase of the Nb content. (C) 2010 Elsevier B.V. All rights reserved.

High Solids Content, Soap-Free, Film-Forming Latexes Stabilized by Laponite Clay Platelets

High solids content film-forming poly[styrene-co-(n-butyl acrylate)] [poly(Sty-co-BuA)] latexes armored with Laponite clay platelets have been synthesized by soap-free emulsion copolymerization of styrene and n-butyl acrylate. The polymerizations were performed in batch in the presence of Laponite and a methyl ether acrylateterminated poly(ethylene glycol) macromonomer in order to promote polymer/clay association. The overall polymerization kinetics showed a pronounced effect of clay on nucleation and stabilization of the latex particles. Cryo-transmission electron microscopy observation confirmed the armored morphology and indicated that the majority of Laponite platelets were located at the particle surface. The resulting nanostructured films displayed enhanced mechanical properties.

Heat treatment influence on the superconducting properties of nanometric-scale Nb(3)Sn wires with Cu-Sn artificial pinning centers

Since the discovery of Nb(3)Sn superconductors many efforts have been expended to improve the transport properties in these materials. In this work, the heat treatment profiles for Nb(3)Sn superconductor wires with Cu(Sn) artificial pinning centers (APCs) with nanometric-scale sizes were analyzed in an attempt to improve the critical current densities and upper critical magnetic field. The methodology to optimize the heat treatment profiles in respect to the diffusion, reaction and formation of the superconducting phases is described. Microstructural characterization, transport and magnetic measurements were performed in an attempt to relate the microstructure to the pinning mechanisms acting in the samples. It was concluded that the maximum current densities occur due to normal phases (APCs) that act as the main pinning centers in the global behavior of the Nb(3)Sn superconducting wire. The APC technique was shown to be very powerful because it permitted mixing of the pinning mechanism. This achievement was not possible in other studies in Nb(3)Sn wires reported up to now.

EBSD characterization of an ECAP deformed Nb single crystal

A niobium single crystal was subjected to equal channel angular pressing (ECAP) at room temperature after orienting the crystal such that [1 -1 -1] ayen ND, [0 1 -1] ayen ED, and [-2 -1 -1] ayen TD. Electron backscatter diffraction (EBSD) was used to characterize the microstructures both on the transverse and the longitudinal sections of the deformed sample. After one pass of ECAP the single crystal exhibits a group of homogeneously distributed large misorientation sheets and a well formed cell structure in the matrix. The traces of the large misorientation sheets match very well with the most favorably oriented slip plane and one of the slip directions is macroscopically aligned with the simple shear plane. The lattice rotation during deformation was quantitatively estimated through comparison of the orientations parallel to three macroscopic axes before and after deformation. An effort has been made to link the microstructure with the initial crystal orientation. Collinear slip systems are believed to be activated during deformation. The full constraints Taylor model was used to simulate the orientation evolution during ECAP. The result matched only partially with the experimental observation.

Obtaining and stability verification of superconducting phases of the Nb-Al and Nb-Sn systems by mechanical alloying and low-temperature heat treatments

The development of Nb(3)Al and Nb(3)Sn superconductors is of great interest for the applied superconductivity area. These intermetallics composites are obtained normally by heat treatment reactions at high temperature. Processes that allow formation of the superconducting phases at lower temperatures (<1000 degrees C), particularly for Nb(3)Al, are of great interest. The present work studies phase formation and stability of Nb(3)Al and Nb(3)Sn superconducting phases using mechanical alloying (high energy ball milling). Our main objective was to form composites near stoichiometry, which could be transformed into the superconducting phases using low-temperature heat treatments. High purity Nb-Sn and Nb-Al powders were mixed to generate the required superconducting phases (Nb-25at.%Sn and Nb-25at.%Al) in an argon atmosphere glove-box. After milling in a Fritsch mill, the samples were compressed in a hydraulic uniaxial press and encapsulated in evacuated quartz tubes for heat treatment. The compressed and heat treated samples were characterized using X-ray diffractometry. Microstructure and chemical analysis were accomplished using scanning electron microscopy and energy dispersive spectrometry. Nb(3)Al XRD peaks were observed after the sintering at 800 degrees C for the sample milled for 30 h. Nb(3)Sn XRD peaks could be observed even before the heat treatment. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis of Nb(2)O(5)center dot nH(2)O nanoparticles by water-in-oil microemulsion

Hydrous niobium oxide (Nb(2)O(5)center dot nH(2)O) nanoparticles had been Successfully prepared by water-in-oil microemulsion. They were characterized by X-ray diffraction (XRD), thermal analysis (TG/DTG), Fourier transform infrared spectroscopy (FTIR), BET surface area measurement, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The results showed that the nanoparticle was exactly Nb(2)O(5)center dot nH(2)O with spherical shape. Their BET surface area was 60 m(2) g(-1). XRD results showed that Nb(2)O(5)center dot nH(2)O nanoparticles with crystallite size in nanometer scale were formed. The crystallinity and crystallity size increased with increasing annealing temperature. TT-phase of Nb(2)O(5) was obtained when the sample is annealed at 550 degrees C. (C) 2009 Elsevier B.V. All rights reserved.

EIS study of Ti-23Ta alloy in artificial saliva

Although titanium and Ti-6Al-4V alloy have been widely used as dental materials, possible undesirable effects such as cytotoxic reactions and neurological disorder due to metal release led to the development of more corrosion resistant and V and Al free titanium alloys, containing Nb, Zr, Mo and Ta atoxic elements. Fluoride containing products used in the prevention of plaque formation and dental caries can affect the stability of the passive oxide films formed on the Ti alloys. In this work, the corrosion behaviour of the new Ti-23Ta alloy has been evaluated in artificial saliva of different pH and fluoride concentration using electrochemical impedance spectroscopy. Electrochemical impedance spectroscopy study showed that the oxide film formed on the alloy in artificial saliva consists of an inner compact film and an outer porous layer. The corrosion resistance of Ti-23Ta alloy which is reduced by increasing F concentration or decreasing pH is related to the resistance of the inner compact layer. The presence of fluoride and low pH of the saliva enhance the porosity of the oxide film and its dissolution.