Síntese e caracterização do carbeto de molibdênio nanoestruturado para fins catalíticos na reação de oxidação parcial do metano

The nanostructures materials are characterized to have particle size smaller than 100 nm and could reach 1 nm. Due to the extremely reduced dimensions of the grains, the properties of these materials are significantly modified relatively when compared with the conventional materials. In the present work was accomplished a study and characterization of the molybdenum carbide, seeking obtain it with particles size in the nanometers order and evaluate its potential as catalyst in the reaction of partial methane oxidation. The method used for obtaining the molybdenum carbide was starting from the precursor ammonium heptamolybdate of that was developed in split into two oven, in reactor of fixed bed, with at a heating rate of 5ºC/min, in a flow of methane and hydrogen whose flow was of 15L/h with 5% of methane for all of the samples. The studied temperatures were 350, 500, 600, 650, 660, 675 and 700ºC and were conducted for 0, 60, 120 and 180 minutes, and the percent amount and the crystallite size of the intermediate phases were determined by the Rietveld refinement method. The carbide obtained at 660ºC for 3 hours of reaction showed the best results, 24 nm. Certain the best synthesis condition, a passivating study was accomplished, in these conditions, to verify the stability of the carbide when exposed to the air. The molybdenum carbide was characterized by SEM, TEM, elemental analysis, ICP-AES, TG in atmosphere of hydrogen and TPR. Through the elemental analysis and ICP-AES the presence carbon load was verified. TG in atmosphere of hydrogen proved that is necessary the passivating of the molybdenum carbide, because occur oxidation in room temperature. The catalytic test was accomplished in the plant of Fischer-Tropsch of CTGAS, that is composed of a reactor of fixed bed. Already the catalytic test showed that the carbide presents activity for partial oxidation, but the operational conditions should be adjusted to improve the conversion

Avaliação cinética e potencial do Nb2O5 obtido a partir de um complexo de nióbio para formação do oleato de metila através da reação de esterificação do ácido oleico

Among the heterogeneous catalysts materials made from niobium show up as an alternative to meet the demand of catalysts for biodiesel production. This study aims to evaluate the potential of a heterogeneous catalyst derived from a complex of niobium in the reaction of methyl esterification of oleic acid. The catalyst was synthesized after calcination at different temperatures of a niobium complex ((NH4)3[NbO(C2O4)3].H2O) generating a niobium oxide nanostructure with a different commercial niobium oxide used to synthesize the complex. The commercial niobium oxide, the complex niobium and niobium catalyst were characterized by thermogravimetry (TG and DTA), surface area analysis (BET), scanning electron microscopy (SEM) and X-ray diffraction (XRD), showing the catalyst has researched morphological and crystallographic indicating a catalytic potential higher than that of commercial niobium oxide characteristics. Factorial with central composite design point, with three factors (calcination temperature, molar ratio of alcohol/oleic acid and mass percentage of catalyst) was performed. Noting that the optimal experimental point was given by the complex calcination temperature of 600°C, a molar ratio alcohol/oleic acid of 3.007/1 and the catalyst mass percentage of 7.998%, with a conversion of 22.44% oleic acid in methyl oleate to 60 min of reaction. We performed a composite linear and quadratic regression to determine an optimal statistical point of the reaction, the temperature of calcination of the complex at 450°C, the molar ratio of alcohol/oleic acid 3.3408/1 and mass percentage of catalyst of 7.6833% . Kinetic modeling to estimate parameters for heterogeneous catalysis it set well the experimental results with a final conversion of 85.01% with 42.38% of catalyst and without catalyst at 240 min reaction was performed. Allowing to evaluate the catalyst catalytic studied has the potential to be used in biodiesel production

Avaliação de catalisadores a base de carbeto e nitreto de molibdênio na obtenção de lactitol via hidrogenação da lactose

Seeking a greater appreciation of cheese whey was developed to process the hydrogenation of lactose for the production of lactitol, a polyol with high added value, using the catalyst Ni / activated carbon (15% and 20% nickel), the nitride Mo2N, the bimetallic carbide Ni-Mo/ activated carbon and carbide Mo2C. After synthesis, the prepared catalysts were analyzed by MEV, XRD, laser granulometry and B.E.T. The reactor used in catalytic hydrogenation of lactose was the type of bed mud with a pressure (68 atm), temperature (120 oC) and stirring speed (500 rpm) remained constant during the experiments. The system operated in batch mode for the solid and liquid and semi-continuous to gas. Besides the nature of the catalyst, we studied the influence of pH of reaction medium for Mo2C carbide as well as evaluating the character of the protein inhibitor and chloride ions on the activity of catalysts Ni (20%)/Activated Carbon and bimetallic carbide Ni-Mo/Activated Carbon. The decrease in protein levels was performed by coagulation with chitosan and adsorption of chloride ions was performed by ion exchange resins. In the process of protein adsorption and chloride ions, the maximum percentage extracted was about 74% and 79% respectively. The micrographs of the powders of Mo2C and Mo2N presented in the form of homogeneous clusters, whereas for the catalysts supported on activated carbon, microporous structure proved impregnated with small particles indicating the presence of metal. The results showed high conversion of lactose to lactitol 90% for the catalyst Ni (20%)/Activated Carbon at pH 6 and 46% for the carbide Mo2C pH 8 (after addition of NH4OH) using the commercial lactose. Monitoring the evolution of the constituents present in the reaction medium was made by liquid chromatography. A kinetic model of heterogeneous Langmuir Hinshelwood type was developed which showed that the estimated constants based catalysts promoted carbide and nitride with a certain speed the adsorption, desorption and production of lactitol

Electrochemical characterization of the paste carbon modified electrode with KSr2Ni0.75Nb4.25O15-delta solid in catalytic oxidation of the dipyrone

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Structural characterization and Curie temperature determination of a sodium strontium niobate ferroelectric nanostructured powder

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tungsten permanent chemical modifier for fast estimation of Se contents in soil by graphite furnace atomic absorption spectrometry

A tungsten carbide coating on the integrated platform of a transversely heated graphite atomizer was used as a modifier for the direct determination of Se in soil extracts by graphite furnace atomic absorption spectrometry. Diethylenetriaminepentaacetic acid (0.0050 mol L-1) plus ammonium hydrogencarbonate (1.0 mol L-1) extracted predominantly available inorganic selenate from soil. The formation of a large amount of carbonaceous residue inside the atomizer was avoided with a first pyrolysis step at 600 degreesC assisted by air during 30 s. For 20 muL of soil extracts delivered to the atomizer and calibration by matrix matching, an analytical curve (10.0-100 mug of L-1) with good linear correlation (r = 0.999) between integrated absorbance and analyte concentration was established. The characteristic mass was similar to63 pg of Se, and the lifetime of the tube was similar to750 firings. The limit of detection was 1.6 mug L-1, and the relative standard deviations (n = 12) were typically <4% for a soil extract containing 50 mug of L-1. The accuracy of the determination of Se was checked for soil samples by means of addition/recovery tests. Recovery data of Se added to four enriched soil samples varied from 80 to 90% and indicated an accurate method.

Influence of the Substitutional Solute on the Mechanical Properties of Ti-Nb Binary Alloys for Biomedical Use

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Solid-liquid transition in Nb powder determined by third harmonic susceptibility

Measurements of the third harmonic of the AC-susceptibility were employed to determine the boundaries of the linear regime of the magnetic response of Nb powder. Non-linear contributions to the magnetic response reveal the occurrence of a structured phase, disappearing as the vortex lattice melts to the liquid state. A systematic study of the third harmonic was conducted to determine how its onset temperature depends on experimental parameters, such as the frequency and amplitude of the excitation field. The melting line (ML) has been extracted from the onset temperature measured at low-frequencies and low-excitation fields in the presence of DC magnetic fields. The study indicates that the ML can be described by a 3D vortex-glass model, except at lower fields, where the system experiences a depinning crossover, and the best description of the experimental data is provided by a 3D Bose-glass model. (c) 2008 Elsevier B. V. All rights reserved.

Nitrogen diffusion in the Nb-1.0wt%Zr measured by mechanical spectroscopy

The scientific and technological development in the area of new materials contributed to several applications of niobium and its alloys in nuclear power plants as well as in aerospace, aeronautics, automobile and naval industries. This paper presents the interstitial diffusion coefficients of nitrogen in solid solution in the Nb-1.0wt%Zr alloy using internal friction measurements obtained by mechanical spectroscopy, which uses a torsion pendulum operating at an oscillation frequency between 1.0 Hz and 10.0 Hz. The temperature range varies from 300K to 700K, at a heating rate of 1 K/min and vacuum better than 2 x 10(-6) Torr. The results showed an increase of the interstitial diffusion coefficient of nitrogen that was correlated with configurational considerations for the octahedral interstitials.

Oxygen Diffusion in an Nb-Ta Alloy Measured by Mechanical Spectroscopy

When metals that present bcc crystalline structure receive the addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, they undergo significant changes in their physical properties because they are able to dissolve great amounts of those interstitial elements, and thus form solid solutions. Niobium and most of its alloys possess a bcc crystalline structure and, because Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this study, mechanical spectroscopy (internal friction) measurements were performed on Nb-8.9wt%Ta alloys containing oxygen in solid solution. The experimental results presented complex internal friction spectra. With the addition of substitutional solute, interactions between the two types of solutes (substitutional and interstitial) were observed, considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for oxygen in this alloy.

Effect of heavy interstitials on anelastic properties of Nb-1.0 wt% Zr alloys

The mechanical properties of metals with bcc structure, such as niobium and its alloys, have changed significantly with the introduction of heavy interstitial elements. These interstitial elements (nitrogen, for example), present in the alloy, occupy octahedral sites and constitute an elastic dipole of tetragonal symmetry and might produce anelastic relaxation. This article presents the effect of nitrogen on the anelastic properties of Nb-1.0 wt% Zr alloys, measured by means of mechanical spectroscopy using a torsion pendulum. The results showed complex anelastic relaxation structures, which were resolved into their constituent peaks, representing each relaxation process. These processes are due to stress-induced ordering of the interstitial elements around the niobium and zirconium of the alloy.

Nitrogen diffusion in the Nb-2.0wt%Ti measured by mechanical spectroscopy

Metals that present bcc crystalline structure, when receiving addition of interstitial atoms as oxygen, nitrogen, hydrogen and carbon, undergo significant changes in their physical properties, being able to dissolve great amounts of those interstitial elements, thus forming solid solutions. Niobium and most of its alloys possess bcc crystalline structure and, as Brazil is the largest world exporter of this metal, it is fundamental to understand the interaction mechanisms between interstitial elements and niobium or its alloys. In this paper, mechanical spectroscopy (internal friction) measurements were performed in Nb-2.0wt%Ti alloys containing nitrogen in solid solution. The experimental results presented complex internal friction spectra and with the addition of substitutional solute, it was observed interactions between the two types of solutes (substitutional and interstitial), considering that the random distribution of the interstitial atoms was affected by the presence of substitutional atoms. Interstitial diffusion coefficients, pre-exponential factors and activation energies were calculated for nitrogen in the Nb-2.0wt%Ti alloys.

A theoretical study on the gas phase reactions of the anions NbO3-, NbO5-, and NbO2(0H)(2)(-) with H2O and O-2

The potential energy surfaces at the singlet (s) and the triplet (t) electronic states associated with the gas-phase ion/molecule reactions of NbO3-, NbO5-, and NbO2(OH)(2)(-) with H2O and O-2 have been investigated by means of DFT calculations at the B3LYP level. An analysis of the results points out that the most favorable reactive channel comprises s-NbO3- reacting with H2O to give an ion-molecule complex s-NbO3(H2O)without a barrier. From this minima, an intramolecular hydrogen transfer takes place between the incoming water molecule and an oxygen atom of the NbO3- fragment to render the most stable minimum, s-NbO2(OH)(2)(-). This oxyhydroxide system reacts with O-2 along a barrierless process to obtain the triplet t-NbO4(OH)(2)(-)-A intermediate, and the crossing point, CP1, between s and t electronic states has been characterized. The next step is the hydrogen-transfer process between the oxygen atom of a hydroxyl group and the one adjacent oxygen atom to render a minimum with the two OH groups near each other, t-NbO4(OH)(2)(-)-B. From this point, the last hydrogen migration takes place, to obtain the product complex, t-NbO5(H2O)(-), that can be connected with the singlet separated products, s-NbO5- and H2O. Therefore, a second crossing point, CP2, has been localized. The nature of the chemical bonding of the key minima (NbO3-, NbO2(OH)(2)(-), NbO4(OH)(2)(-)-B, and NbO5-) in both electronic states of the reaction and an interaction with O-2 has been studied by topological analysis of Becke-Edgecombe electron-localization function (ELF) and atoms-in-molecules (AIM) methodology. The niobium-oxygen interactions are characterized as unshared-electron (ionic) interactions and some oxygen-oxygen interactions as protocovalent bonds.

Theoretical study of the structure and stability of NbxOy, and NbxOy+ (x = 1-3; y = 2-5, 7, 8) clusters

Geometric, thermodynamic and electronic properties of cluster neutrals NbxOy and cations NbxOy+ (x = 1-3; y = 2-5, 7, 8) have been characterized theoretically. A DFT calculation using a hybrid combination of B3LYP with contracted Huzinaga basis sets. Numerical results of the relative stabilities, ionization potentials and band gaps of different clusters are in agreement with experiment. Analysis of dissociation channels supports the more stable building blocks as formed by NbO2, NbO2+ NbO3 and NbO3+ stoichiometries. The net atomic charges suggest that oxygen donor molecules can interact more favorably on central niobium atoms of cluster cations, while the interaction with oxygen acceptor molecules is more favorable on the terminal oxygen atoms of neutral clusters. A topological analysis of the electron localization function gradient field indicates that the clusters may be described as having a strong ionic interaction between Nb and O atoms. Published by Elsevier B.V. B.V.

Investigation on Surface Finishing of Components Ground with Lapping Kinematics: Lapgrinding Process

Over the last three decades, researchers have responded to the demands of industry to manufacture mechanical components with geometrical tolerance, dimensional tolerance, and surface finishing in nanometer levels. The new lapgrinding process developed in Brazil utilizes lapping kinematics and a flat grinding wheel dressed with a single-point diamond dresser in agreement with overlap factor (U(d)) theory. In the present work, the influences of different U(d) values on dressing (U(d) = 1, 3 e 5) and grain size of the grinding wheel made of silicon carbide (SiC = 800, 600 e 300 mesh) are analyzed on surface finishing of stainless steel AISI 420 flat workpieces submitted to the lapgrinding process. The best results, obtained after 10 minutes of machining, were: average surface roughness (Ra) 1.92 nm; 1.19 mu m flatness deviation of 25.4 mm diameter workpieces and mirrored surface finishing. Given the surface quality achieved, the lapgrinding process can be included among the ultra-precision finishing processes and, depending on the application, the steps of lapping followed by polishing can be replaced by the proposed abrasive process.