Methane conversion reactions on Ni catalysts promoted with Rh: Influence of support

Ni catalysts supported on gamma-Al(2)O(3) and Mg(Al)O were prepared with and without Rh as a promoter and tested in the reforming of methane in the presence of excess methane, simulating a model biogas. The effects of adding synthetic air on the methane conversion and the formation of carbon were assessed. The catalysts were characterized by X-ray spectroscopy (EDS), surface area (BET), X-ray diffraction (XRD), Temperature-programmed reduction (TPR), X-ray absorption near-edge structure (XANES) and XPD. The results showed that in catalysts without Rh, the Ni interacts strongly with the supports, showing high reduction temperatures in TPR tests. The addition of Rh increased the amount of reducible Ni and facilitated the reduction of the species interacting strongly with the support. In the catalytic tests, the samples promoted with Rh suffered higher carbon deposition. The in situ XPD suggested that on the support gamma-Al(2)O(3), the presence of Rh probably led to a segregation of Ni species with time on stream, leading to carbon deposition. On the support MgAlO, the presence of Rh improved the dispersion of Ni, by reducing the Ni(0) crystallite size, suggesting that in this case the carbon deposition was due to a favoring of CH(4) decomposition by Rh. (C) 2011 Elsevier B.V. All rights reserved.

Modeling precipitation and its effect on recrystallization during hot strip rolling of niobium steels

Using a physically based model, the microstructural evolution of Nb microalloyed steels during rolling in SSAB Tunnplåt’s hot strip mill was modeled. The model describes the evolution of dislocation density, the creation and diffusion of vacancies, dynamic and static recovery through climb and glide, subgrain formation and growth, dynamic and static recrystallization and grain growth. Also, the model describes the dissolution and precipitation of particles. The impeding effect on grain growth and recrystallization due to solute drag and particles is accounted for. During hot strip rolling of Nb steels, Nb in solid solution retards recrystallization due to solute drag and at lower temperatures strain-induced precipitation of Nb(C,N) may occur which effectively retard recrystallization. The flow stress behavior during hot rolling was calculated where the mean flow stress values were calculated using both the model and measured mill data. The model showed that solute drag has an essential effect on recrystallization during hot rolling of Nb steels.

Estudo da moagem de alta energia e sinterização de pós compósitos W-Cu

The Tungsten/copper composites are commonly used for electrical and thermal objectives like heat sinks and lectrical conductors, propitiating an excellent thermal and electrical conductivity. These properties are dependents of the composition, crystallite size and production process. The high energy milling of the powder of W-Cu produces an dispersion high and homogenization levels with crystallite size of W very small in the ductile Cu phase. This work discusses the effect of the HEM in preparation of the W-25Cu composite powders. Three techniques of powder preparation were utilized: milling the dry with powder of thick Cu, milling the dry with powder of fine Cu and milling the wet with powder of thick Cu. The form, size and composition of the particles of the powders milled were observed by scanning electron microscopy (SEM). The X-ray diffraction (XRD) was used to analyse the phases, lattice parameters, size and microstrain of the crystallite. The analyse of the crystalline structure of the W-25Cu powders milled made by Rietveld Method suggests the partial solid solubility of the constituent elements of the Cu in lattice of the W. This analyse shows too that the HEM produces the reduction high on the crystallite size and the increase in the lattice strain of both phases, this is more intense in the phase W

Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Sinterização de Ce1-XEuXO2-(X/2) para aplicação como eletrólito sólido em células a combustível de temperaturas intermediárias

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size

Comportamento da adição do carbeto de nióbio (nBC) na matriz metálica do aço ferrítico 15kH2mfa

The 15Kh2MFA steel is a kind of Cr-Mo-V family steels and can be used in turbines for energy generation, pressure vessels, nuclear reactors or applications where the range of temperature that the material works is between 250 to 450°C. To improve the properties of these steels increasing the service temperature and the thermal stability is add a second particle phase. These particles can be oxides, carbides, nitrites or even solid solution of some chemical elements. On this way, this work aim to study the effect of addition of 3wt% of niobium carbide in the metallic matrix of 15Kh2MFA steel. Powder metallurgy was the route employed to produce this metallic matrix composite. Two different milling conditions were performed. Condition 1: milling of pure 15Kh2MFA steel and condition 2: milling of 15Kh2MFA steel with addition of niobium carbide. A high energy milling was carried out during 5 hours. Then, these two powders were sintered in a vacuum furnace (10-4torr) at 1150 and 1250°C during 60 minutes. After sintering the samples were normalized at 950°C per 3 minutes followed by air cooling to obtain a desired microstructure. Results show that the addition of niobium carbide helps to mill faster the particles during the milling when compared with that steel without carbide. At the sintering, the niobium carbide helps to sinter increasing the density of the samples reaching a maximum density of 7.86g/cm³, better than the melted steel as received that was 7,81g/cm³. In spite this good densification, after normalizing, the niobium carbide don t contributed to increase the microhardness. The best microhardness obtained to the steel with niobium carbide was 156HV and to pure 15Kh2MFA steel was 212HV. It happened due when the niobium carbide is added to the steel a pearlitic structure was formed, and the steel without niobium carbide submitted to the same conditions reached a bainitic structure

Aplicação de microemulsões na solubilização de frações pesadas de petróleo

This work presents studies related to the use of microemulsions in the solubilization of heavy crude oil fractions responsible by the formation of deposits. The first stage of the work was addressed to the construction of phases diagrams, with the intention of determining the area within which the microemulsion is formed. The following systems were studied: UNITOL L 90 n-Butanol - Water - Kerosene (system 1); UNITOL L 90 - n-Butanol - Water - Xylene (system 2); UNITOL L 90 n-Butanol - Water - Kerosene/Xylene 10% (system 3); UNITOL L 90 - Sec-Butanol - Water - Xylene (system 4). In parallel experiments of physical adsorption were carried out by the static method, with the intention of simulating natural conditions of reservoirs. Crude oil of the Fazenda Belém field (Rio Grande do Norte), was used as solute, xylene as solvent and the Assu sandstone (Rio Grande do Norte, Brazil) and Botucatu sandstone (Paraná, Brazil) as rock reservoirs. The curves of adsorption presented the S format type, in agreement with the classification proposed by Giles, Smith and Huitson (1974). The solubilization process was accomplished in the batch method, by varying the time of agitation, the microemulsions and the solid/solution ratio. The experiments showed that the microemulsions presented high efficiency in the solubilization of the crude oil adsorbed on the sandstones. System 2 presented an efficiency of 99% for the Assu sandstone and 97% for the Botucatu sandstone

Análise cristalográfica da solução sólida com estrutura tipo Tungstênio Bronze de niobato de potássio e estrôncio dopado com ferro

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

Determination of the oxygen and nitrogen interstitial diffusion coeficient in niobium by mechanical spectroscopy

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

Effect of the Oxygen on the Mechanical Properties of Ti-Mo Systems Alloys

Titanium alloys normally contain oxygen, nitrogen, or carbon as impurities, and although this concentration is low, these impurities cause changes in the mechanical properties of Ti alloys. Oxygen is a strong alpha-phase stabilizer and its addition causes solid-solution strengthening, shape memory effect, and superelasticity. The most promising alloys are those with Nb, Zr, Ta, and Mo as alloying elements. In this paper, the preparation, processing, and characterization of Ti-Mo alloys (5 and 10 wt%) used as biomaterials are presented, along with the influence of oxygen on their mechanical properties. The addition of oxygen causes an increase in the elasticity modulus of the Ti-5Mo alloy due to an increase in the alpha' phase volume fraction, which possesses a higher modulus than the alpha '' phase. Ti-10Mo possesses a mixture between alpha '' and beta phases, oxygen enters these two structures and causes a dominating effect.

Anelastic spectroscopy in a Ti alloy used as biomaterial

Ti and its alloys have been used thoroughly in the production of prostheses and dental implants due to their properties, such as high corrosion resistance, low elasticity modulus and high mechanical strength/density relation. Among the Ti-based alloys, the Ti-35Nb-7Zr-5Ta (TNZT) is one that presents the smallest elasticity modulus, making it an excellent alternative to be used as a biomaterial. In this paper, mechanical spectroscopy measurements were made in TNZT alloys containing several quantities of oxygen and nitrogen in solid solution. Mechanical spectroscopy measurements were made by using a torsion pendulum, operating at an oscillation frequency in the interval 4-30 Hz, temperature in the range 100-700 K, heating rate of about 1 K/min and vacuum lower than 10(-5) Torr. Complex relaxation structures and a reduction in the elasticity modulus were observed for the heat-treated and doped samples. The observed peaks were associated with the interactions of interstitial atoms and the alloy elements. (C) 2009 Elsevier B.V. All rights reserved.

Anelastic relaxation due to hydrogen in Ti-35Nb-7Zr-5Ta alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Structural Characterization of Nanocrystalline Sb-Doped SnO2 Xerogels by Multiedge X-ray Absorption Spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Diffusion of Nitrogen in Ti-13V-11Cr-3Al Alloys

Metals with a bcc crystalline structure such as Ti-13V-11Cr-3Al alloys have their physical properties significantly changed through the addition of interstitial elements such as oxygen and nitrogen. These metals can dissolve substantial amounts of interstitial elements forming solid solutions. Mechanical spectroscopy measurements constitute a powerful tool for studying interactions of these interstitial elements with other elements that make up the alloy. From these measurements, it is possible to obtain information regarding diffusion, interstitial concentration, interaction between interstitials, and other imperfections of the crystalline lattice, In this paper, Ti-13V-11Cr-3Al alloys with several amount of nitrogen, in a solid solution, were studied using mechanical spectroscopy (internal friction) measurements. The results presented complex internal friction spectra which were resolved in a series of constituent Debye peaks corresponding to different interactions and interstitial diffusion coefficients. Pre-exponential factors and activation energies were calculated for nitrogen in theses alloys.

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.