Surface termination of CePt5/Pt(111): the key to chemical inertness

The surface termination of CePt5/Pt(111) is determined experimentally by LEED-IV. In accordance with recent theoretical predictions, a dense Pt terminated surface is being found. Whereas the CePt5 volume lattice comprises Pt kagome layers, additional Pt atoms occupy the associated hole positions at the surface. This finding provides a natural explanation for the remarkable inertness of the CePt5 intermetallic. Implications of the structural relaxations determined by LEED-IV analysis are discussed with regard to observations by scanning tunneling microscopy and electron spectroscopies.

Ab initio calculation of the BCC Fe-Al-Mo (Iron-Aluminum-Molybdenum) phase diagram: Implications for the nature of the tau(2) phase

The metastable phase diagram of the BCC-based ordering equilibria in the Fe-Al-Mo system has been calculated via a truncated cluster expansion, through the combination of Full-Potential-Linear augmented Plane Wave (FP-LAPW) electronic structure calculations and of Cluster Variation Method (CVM) thermodynamic calculations in the irregular tetrahedron approximation. Four isothermal sections at 1750 K, 2000 K, 2250 K and 2500 K are calculated and correlated with recently published experimental data on the system. The results confirm that the critical temperature for the order-disorder equilibrium between Fe(3)Al-D0(3) and FeAl-B2 is increased by Mo additions, while the critical temperature for the FeAl-B2/A2 equilibrium is kept approximately invariant with increasing Mo contents. The stabilization of the Al-rich A2 phase in equilibrium with overstoichiometric B2-(Fe,Mo)Al is also consistent with the attribution of the A2 structure to the tau(2) phase, stable at high temperatures in overstoichiometric B2-FeAl. (C) 2009 Elsevier Ltd. All rights reserved.

Hyperfine interaction studies with (181)Ta and (111)Cd probes in the compound Ti(2)Ag

By using the time-differential perturbed angular correlation technique, the electric field gradients (EFG) at (181)Hf/(181)Ta and (111)In/(111)Cd probe sites in the MoSi(2)-type compound Ti(2)Ag have been measured as a function of temperature in the range from 24 to 1073 K. Ab initio EFG calculations have been performed within the framework of density functional theory using the full-potential augmented plane wave + local orbitals method as implemented in the WIEN2k package. These calculations allowed assignments of the probe lattice sites. For Ta, a single well-defined EFG with very weak temperature dependence was established and attributed to the [4(e)4mm] Ti site. For (111)Cd probes, two of the three measured EFGs are well defined and correlated with substitutional lattice sites, i.e. both the [4(e)4mm] Ti site and the [2(a)4/mmm] Ag site.

Non-Fermi-liquid behavior in UCu(4+x)Al(8-x) compounds

We report on experimental studies of the Kondo physics and the development of non-Fermi-liquid scaling in UCu(4+x)Al(8-x) family. We studied 7 different compounds with compositions between x = 0 and 2. We measured electrical transport (down to 65 mK) and thermoelectric power (down to 1.8 K) as a function of temperature, hydrostatic pressure, and/or magnetic field. Compounds with Cu content below x = 1.25 exhibit long-range antiferromagnetic order at low temperatures. Magnetic order is suppressed with increasing Cu content and our data indicate a possible quantum critical point at x(cr) approximate to 1.15. For compounds with higher Cu content, non-Fermi-liquid behavior is observed. Non-Fermi-liquid scaling is inferred from electrical resistivity results for the x = 1.25 and 1.5 compounds. For compounds with even higher Cu content, a sharp kink occurs in the resistivity data at low temperatures, and this may be indicative of another quantum critical point that occurs at higher Cu compositions. For the magnetically ordered compounds, hydrostatic pressure is found to increase the Neel temperature, which can be understood in terms of the Kondo physics. For the non-magnetic compounds, application of a magnetic field promotes a tendency toward Fermi-liquid behavior. Thermoelectric power was analyzed using a two-band Lorentzian model, and the results indicate one fairly narrow band (10 meV and below) and a second broad band (around hundred meV). The results imply that there are two relevant energy scales that need to be considered for the physics in this family of compounds. (C) 2011 Elsevier B.V. All rights reserved.

Synthesis and magnetic characterization of TmCo(2)B(2)C

A new quaternary intermetallic borocarbide TmCo(2)B(2)C has been synthesized via rapid-quench of an arc-melted ingot. Elemental and powder-diffraction analyses established its correct stoichiometry and single-phase character. The crystal structure is isomorphous with that of TmNi(2)B(2)C (I4/mmm) and is stable over the studied temperature range. Above 7 K, the paramagnetic state follows modified Curie-Weiss behavior (chi = C/(T - theta) + chi(0)) wherein chi(0) = 0.008(1) emu mol(-1) with the temperature-dependent term reflecting the paramagnetism of the Tm subsystem: mu(eff) = 7.6(2) mu(B) (in agreement with the expected value for a free Tm(3+) ion) and theta = -4.5(3) K. Long-range ferromagnetic order of the Tm sublattice is observed to develop around similar to 1 K. No superconductivity is detected in TmCo(2)B(2)C down to 20 mK, a feature which is consistent with the general trend in the RCo(2)B(2)C series. Finally, the influence of the rapid-quench process on the magnetism (and superconductivity) of TmNi(2)B(2)C will be discussed and compared to that of TmCo(2)B(2)C.

Defeitos pontuais nos compostos intermetálicos ZrNi e Zr/sub 2/Ni estudados por dinâmica molecular

Empregamos a técnica de Dinâmica Molecular para estudar propriedades de defeitos pontuais nos compostos intermetálicos ZrNi e Zr2Ni. Descrevemos as configurações estáveis de defeitos e mecanismos de migração, assim como as energias envolvidas. Os potenciais interatômicos foram derivados do Embedded Atom Model. No intuito de levar em conta a variação de estequiometria causada pela presença de alguns tipos de defeitos em intermetálicos, apresentamos um método numérico que fornece a energia efetiva de formação de defeitos e aplicamos o método ao ZrNi e Zr2Ni. Os resultados mostraram que vacâncias são mais estáveis na sub—rede do Ni, com energia de formação de 0,83 e-0,61 eV em ZrNi e Zr2Ni, respectivamente. Vacâncias de Zr são instáveis em ambos compostos; elas decaem espontaneamente em pares anti—sítio e vacância de Ni. Configurações e energias de formação de intersticiais também foram calculadas e mostraram comportamentos similares. Em ZrNi, a migração de vacâncias ocorre preferencialmente nas direções [025] e [100], com as respectivas energias de migração 0,67 e 0,73 eV, e é um processo essencialmente bidimensional no plano (001). Em Zr,Ni, a migração de vacâncias é unidimensional, ocorrendo na direção [001], com energia de migração de 0,67 eV. Em ambos compostos a presença de defeitos de anti—sítio de Ni diminui a energia de migração da vacância de Ni em até 3 vezes e facilita a movimentação em três dimensões. Mecanismos de anel não são energeticamente eficientes em comparação com saltos diretos. As configurações estáveis de intersticiais em ambos compostos consistem em um átomo de Ni sobre o plano (001) entre dois vizinhos de Zr fora do plano. Intersticiais de Zr são instáveis e tendem a deslocar um átomo de Ni, ocupando seu sítio. Energias de deslocamento foram estudadas através de simulações de irradiação de ambos compostos. Durante o processo de colisão binária, um potencial universal ZBL foi usado para colisões a curta distância. Para distâncias intermediárias usamos um potencial de união arbitrário. Zr mostrou—se mais difícil de ser arrancado de seu sítio do que Ni. Encontramos valores de energia de deslocamento no intervalo de aproximadamente 29 eV até 546 eV. Alguns resultados experimentais são mostrados e apresentam boa concordância com os cálculos.

Thermal and electrochemical study of solid-state reaction of mercury with Pt-20% Rh alloy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

On Ti-18Si-6B and Ti-7.5Si-22.5B powder alloys prepared by high-energy ball milling and sintering

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

Mechanochemical synthesis of ceramic powders with perovskite structure

The mechanical activation is one of the most effective method for obtaining highly disperse system due to mechanical action stress fields form in solids during milling procedure. This effect results in changes of free energy, leading to release of heat, formation of a new surface, formation of different crystal lattice defects and initiation of solid-state chemical reaction. The accumulated deformation energy determines irreversible changes of crystal structure and consequently microstructure resulting in the change of their properties. Mechanochemical processing route has been developed recently for the production of intermetallic and alloy compounds. The intrinsic advantage of this process is that the solid-state reaction is activated due to mechanical energy instead of the temperature. It was shown that the chemical reactivity of starting materials could be improved significantly after mechanochemical activation and, subsequently, the calcination temperature was reduced. Besides, it was apparent that the mechanochemical treatment could enhance the reactivity of constituent oxides; however, the sintering process could not be avoided to develop the desired ceramics. A novel mechanochemical technique for synthesis of fine-grained perovskite structured powders has shown that it is possible to form perovskite at room temperature. The effect of milling on the formation of perovskite structure of barium titanate (BT), lead titanate (PT), PZT, PZN, magnesium niobate (PMN) and LM ceramic materials was analyzed. The dielectric properties of sintered ceramics are comparable with those prepared by other methods in the literature. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Solid state reactions in the platinum-mercury system

Thermogravimetry, Differential Scanning Calorimetry and other analytical techniques (Energy Dispersive X-ray Analysis; Scanning Electron Microscopy; Mapping Surface; X-ray Diffraction; Inductively Coupled Plasma Atomic Emission Spectroscopy and Cold Vapor Generation Atomic Absorption Spectroscopy) have been used to study the reaction of mercury with platinum foils. The results suggest that, when heated, the electrodeposited Hg film reacts with Pt to form intermetallic compounds each having a different stability, indicated by at least three mass loss steps. Intermetallic compounds such as PtHg4, PtHg and PtHg2 were characterized by XRD. These intermetallic compounds were the main products formed on the surface of the samples after partial removal of bulk mercury via thermal desorption. The Pt(Hg) solid solution formation caused great surface instability, attributed to the atomic size factor between Hg and Pt, facilitating the acid solution's attack to the surface.

Thermal analysis and electrochemical study of Hg reactions on Pt-30% Ir alloy electrode

Thermogravimetry (TG), cyclic voltammetry (CV) and other analytical techniques were used to study the reactions of mercury with Pt-30% Ir alloy. The results allowed to suggest that an electrodeposited mercury film interacts with the substrate and when subjected to heat or electrochemical removal at least four mass loss steps or five peaks appeared during the mercury desorption process. The first two steps were attributed to Hg(0) removal probably from the bulk and from the adsorbed monolayer which wets the electrode surface. These two processes are responsible for peaks D and F in the cyclic voltammograms. The last two peaks (G, H) in CV were ascribed to the intermetallic compound decomposition. In TG curves, the last two steps were attributed to the PtHg4 (third step), and PtHg2 decomposition followed by Hg removal from the subsurface. The PtHg2 was formed by an eutectoide reaction: PtHg -> PtHg2+Hg(Pt-Ir). The Hg diffused to the subsurface was not detectable by cyclic voltammetry.

Thermogravimetry (TG) applied to the study of the reaction of mercury with platinum-rhodium alloy

Thermogravimetry (TG) energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), mapping surface, X-ray diffraction (XRD), inductively coupled plasma emission spectroscopy and atomic spectroscopy with cold vapor generation have been used to study the reaction of mercury with platinum-rhodium (Pt-Rh) alloy. The results suggest that, the electrodeposited Hg film reacts with Pt-Rh to form intermetallic compounds of different stability, when heated indicated by at least four weight loss steps. Intermetallic compounds as PtHg4 and PtHg2 was characterized by XRD. These intermetallic compound are the main product presents on the surface of the samples after remotion of the bulk mercury via thermal desorption techniques. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Metallurgical evaluation of a copper-based alloy for dental castings.

The present study was designed to evaluate the metallurgical properties of an experimental, low-cost copper-zinc-aluminum-nickel alloy for dental castings. Some specimens were subjected to heat treatment after induction casting. The extent of corrosion was determined by measuring weight loss of specimens stored in a sodium sulfite solution. In the as-cast specimens, tests demonstrated the presence of three phases: the first consisted of copper-zinc-aluminum, the second was similar but lower in copper and aluminum, and the third consisted of an intermetallic compound of manganese-nickel-phosphorus. After heat treatment, the first phase remained relatively constant, the second was converted to Cu3Al, and the third increased in volume. The weight loss from the as-cast specimens was eight times that of the heat-treated specimens. It was concluded that the heat treatment substantially changed the microstructure and improved the corrosion resistance of the experimental alloy.

Contribution to the study of the solid-state reaction of mercury with pure rhodium

Thermogravimetry (TG) and other analysis techniques (EDX, SEM, Mapping surface, X-ray diffraction, inductively coupled argon plasma emission spectroscopy and atomic spectrometry with cold vapor generation) were used to study the reaction of Hg with Rh. The results permitted the suggestion that, when subjected to heat, an electrodeposited Hg film reacts with Rh to form intermetallic products with different stabilities, as indicated by at least three mass loss steps. In the first step, between room temperature and 160°C, only the bulk Hg is removed. From this temperature up to about 175°C, the mass loss can be attributed to the desorption of a film of metallic Hg. The last step, from 175 to 240°C, can be ascribed to the removal of Hg from a thin dark film of RhHg2.

The role of coarse intermetallics in the localized corrosion behaviour of AA 2024-T3 in low concentrated chloride media

Aluminium alloy (AA) 2024-T3 is an important engineering material due to its widespread use in the aerospace industry. However, it is very prone to localized corrosion attack in chloride containing media, which has been mainly associated to the presence of coarse intermetallics (IMs). In this work the corrosion behaviour of aluminium alloy 2024-T3 in low concentrated chloride media was investigated using microscopy and electrochemical methods. SEM observations have shown that intermetallics with the same nominal composition present heterogeneous reaction rates, and that both types of coarse IMs normally found in the AA 2024-T3 microstructure corrode. Moreover, EDS analyses have shown important compositional changes in the corroded IMs, evidencing the selective corrosion of their more active constituents and the onset of an intense oxygen peak, irrespective to the IM nature. TEM/EDS observations on non-corroded samples have evidenced the heterogeneous composition within the IMs. On the other hand, the results of the electrochemical investigations, in accordance with the SEM/EDS observations, have evidenced that IMs corrosion dominates the electrochemical response of the alloy during the first hours of immersion in the test electrolyte. © 2009 by NACE International.