Theoretical analysis of x-ray-absorption near-edge fine structure at the O and metal K edges of LaFeO3 and LaCoO3

We present experimental x-ray-absorption spectra at the oxygen and 3d transition-metal K edges of LaFeO3 and LaCoO3. We interpret the experimental results in terms of detailed theoretical calculations based on multiple-scattering theory. Along with providing an understanding of the origin of various experimental features, we investigate the effects of structural distortions and the core-hole potential in determining the experimental spectral shape. The results indicate that the core-hole potential as well as many-body effects within the valence electrons do not have any strong effect on the spectra suggesting that the spectral features can be directly interpreted in terms of the electronic structure of such compounds.

Crystal structure of nonadentate tricompartmental ligand derived from pyridine-2,6-dicarboxylic acid: Spectroscopic, electrochemical and thermal investigations of its transition metal(II) complexes

The coordinating behavior of a new dihydrazone ligand, 2,6-bis(3-methoxysalicylidene) hydrazinocarbonyl]pyridine towards manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) has been described. The metal complexes were characterized by magnetic moments, conductivity measurements, spectral (IR, NMR, UV-Vis, FAB-Mass and EPR) and thermal studies. The ligand crystallizes in triclinic system, space group P-1, with alpha=98.491(10)degrees, beta=110.820(10)degrees and gamma=92.228(10)degrees. The cell dimensions are a=10.196(7)angstrom, b=10.814(7)angstrom, c=10.017(7)angstrom, Z=2 and V=1117.4(12). IR spectral studies reveal the nonadentate behavior of the ligand. All the complexes are neutral in nature and possess six-coordinate geometry around each metal center. The X-band EPR spectra of copper(II) complex at both room temperature and liquid nitrogen temperature showed unresolved broad signals with g(iso) = 2.106. Cyclic voltametric studies of copper(II) complex at different scan rates reveal that all the reaction occurring are irreversible. (C) 2011 Elsevier B.V. All rights reserved.

Regarding the effect of aging heat treatment on the failure behaviour of a SiC reinforced Al based metal matrix composite

In the present study, 6061 Al metallic matrix was reinforced by 12.2 wt% df SiC particulates using liquid metallurgy route. The composite material thus obtained was extruded and characterized in the as-solutionized and peak aged conditions in order to delineate the effect of aging associated precipitation of secondary phases on the tensile fracture behavior of the composite samples. The results' of microstructural characterization studies carried out using scanning electron microscope revealed the increased presence of precipitated secondary phases in the metallic matrix and a more pronounced interfacial segregation of alloying elements in case of peak aged samples when compared to the as-solutionized samples. The results of the fractographic studies conducted on the as-solutionized samples revealed that the failure was dominated by the SiC particulates cracking while for the peak aged samples the fracture surface revealed a comparatively more pronounced SiC/6061 Al debonding and reduced SiC particulates cracking. This change in the failure behavior was rationalized in terms of embrittlement of the interfacial region brought about by the aging heat treatment and is correlated, in addition, with the mechanical properties of the composite samples in as-solutionized and peak aged conditions.

Metal-insulator transition in a degenerate Hubbard model

We have studied the metal-insulator transition at integer fillings in a triply degenerate Hubbard model using the Lanczos method. The critical Coulomb interaction strength U-c, is found to depend strongly on the band filling, with U-c similar to root 3 W (W is the bandwidth) at half filling for this case with threefold degeneracy. We discuss the implications of our results on metal-insulator transitions in strongly correlated systems in general, and on the unusual electronic ground state of the alkali-metal-doped fullerenes, in particular. [S0163-1829(99)11003-8].

Microstructure and properties of squeeze cast Cu-carbon fibre metal matrix composite

There have been reported attempts of producing Cu based MMCs employing solid phase routes. In this work, copper was reinforced with short carbon fibres by pressure infiltration (squeeze casting) of molten metal through dry-separated carbon fibres. The resulting MMC's microstructure revealed uniform distribution of fibres with minimum amount of clustering. Hardness values are considerably higher than that for the unreinforced matrix. Addition of carbon fibres has brought in strain in the crystal lattice of the matrix, resulting in higher microhardness of MMCs and improved wear resistance. Tensile strength values of MMCs at elevated temperatures are considerably higher than that of the unreinforced matrix processed under identical conditions. (C) 1999 Kluwer Academic Publishers.

Performance and scaling of a 1.2 V/1.5 Ah nickel/metal hydride cell to a 6 V/1.5 Ah battery

A 1.2 V/1.5 Ah positive-limited nickel/metal hydride cell has been studied to determine its charge-discharge characteristics at different rates in conjunction with its AC impedance data. The faradaic efficiency of the cell is found to be maximum at similar to 70% charge input. The cell has been scaled to a 6 V/1.5 Ah battery. The cycle-life data on the battery suggest that it can sustain a prolonged charge-discharge schedule with little deterioration in its performance.

Tensile flow behaviour of 2.25Cr-1Mo ferritic steel base metal and simulated heat affected zone structures of 2.25Cr-1Mo weld joint

Tensile tests in the temperature range 298 to 873 K have been performed on 2.25Cr-1Mo base metal and simulated heat affected zone (HAZ) structures of its weld joint, namely coarse grain bainite, fine grain bainite and intercritical structure. Tensile flow behaviour of all the microstructural conditions could be adequately described by the Hollomon equation (sigma = K-1 epsilon(n1)) at higher (> 623 K) temperatures. Deviation from the Hollomon equation was observed at low strains and lower (< 623 K) temperatures. The Ludwigson modification of Hollomon's equation, sigma = K-1 epsilon(n1) + exp (K-2 + n(2) epsilon), was found to describe the flow curve. In general, the flow parameters n(1), K-1, n(2) and K-2 were found to decrease with increase in temperature except in the intermediate temperature range (423 to 623 K). Peaks/plateaus were observed in their variation with temperature in the intermediate temperature range coinciding with the occurrence of serrated flow in the load-elongation curve. The n(1) Value increased and the K-1 value decreased with the type of microstructure in the order: coarse grain bainite, fine grain bainite, base metal and intercritical structure. The variation of nl with microstructure has been rationalized on the basis of mean free path (MFP) of dislocations which is directly related to the inter-particle spacing. Larger MFP of dislocations lead to higher strain hardening exponents n(1).

An ab-initio study of the role of lone pairs in the structure and insulator-metal transition in SnO and PbO

We have performed density functional calculations on tetragonal SnO and PbO (litharge) in the space group P4/nmm with the specific intention of examining the role played by Sn 5s and Pb 6s lone pairs in stabilizing the structure, and in giving rise to semi-metallic behavior (of SnO at ambient pressure and of PbO in the gamma phase). Use of the electron localization function has permitted real-space visualization of the lone pair in these structures. We also discuss the electronic structure of the orthorhombic PbO (massicot, space group Pbma) which again has localized lone pairs, contrary to some earlier expectation. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Dendritic encapsulation of amino acid-metal complexes. Synthesis and studies of dendron-functionalized L-tyrosine-metal (Zn-II, Co-II) complexes

This paper describes the synthesis, characterization and studies of dendrimers possessing an amino acid-metal complex as the core. Using Frechet-type polyaryl ether dendrons, L-tyrosine-metal (Zn-II and Co-II) complex cored dendrimers of 0-4 generations were synthesized. The metal complexation of the tyrosine unit at the focal point of these dendrons took place smoothly, in excellent yields, even though the sizes of the dendrons increase as the generations advance. Spectrophotometric titrations with CoII metal ion confirmed the formation of a 2 : 1 dendritic ligand to metal complex and the existence of a pseudotetrahedral geometry at the metal centre is also inferred. Cyclic voltammetric studies of dendrimer-Co-II complexes showed that while the electron transfer of Co-II to Co-I was facile for generations 0-2, such a process was difficult with generations 3 and 4, indicating a rigid encapsulation of the metal ion centre by proximal dendron groups. Further reduction of Co-I to Co-0 and the corresponding oxidation processes appear to be limited by adsorption at the surfaces of the electrodes.

Insulator-metal transition and magnetoresistance of La0.5Ca0.5MnOy induced by tuning the oxygen content

The oxygen content of La0.5Ca0.5MnOy was tuned by annealing the samples at high temperatures in flowing nitrogen with graphite powder nearby. The reduction of oxygen content has dramatic effect on the electrical transport and magnetic properties. The samples with y=2.983, 2.83, and 2.803 show an insulator-metal transition, and an unusual temperature and magnetic-field dependence of the magnetoresistance. The paramagnetic-ferromagnetic transition also shifts to lower temperatures and the antiferromagnetic transition at lower temperature is suppressed. The results are discussed in terms of the effect of oxygen vacancies on the various properties of La0.5Ca0.5MnOy. (C) 2002 American Institute of Physics.

Metal-organic chemical vapour deposition of thin films of cobalt on different substrates: study of microstructure

We have investigated the microstructure of thin films grown by metal-organic chemical vapour deposition using a beta-diketonate complex of cobalt, namely cobalt (11) acetylacetonate. Films were deposited on three different substrates: Si(100), thermally oxidised silicon [SiO2/Si(100)] and glass at the same time. As-grown films were characterised by X-ray diffraction, scanning electron microscopy, scanning tunnelling microscopy, atomic force microscopy and secondary ion mass spectrometry. Electrical resistivity was measured for all the films as a function of temperature. We found that films have very fine grains, resulting in high electrical resistivity Further, film microstructure has a strong dependence on the nature of the substrate and there is diffusion of silicon and oxygen into cobalt from the substrate. (C) 2002 Elsevier Science B.V. All rights reserved.

Phase transformation and semiconductor-metal transition in thin films of VO2 deposited by low-pressure metalorganic chemical vapor deposition

Thin films of the semiconducting, monoclinic vanadium dioxide, VO2(M) have been prepared on ordinary glass by two methods: directly by low-pressure metalorganic chemical vapor deposition (MOCVD), and by argon-annealing films of the VO2(B) phase deposited by MOCVD. The composition and microstructure of the films have been examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Films made predominantly of either the B or the M phase, as deposited, can only be obtained over a narrow range of deposition temperatures. At the lower end of this temperature range, the as-deposited films are strongly oriented, although the substrate is glass. This can be understood from the drive to minimize surface energy. Films of the B phase have a platelet morphology, which leads to an unusual microstructure at the lower-deposition temperatures. Those grown at similar to370 degreesC convert to the metallic, rutile (R) phase when annealed at 550 degreesC, whereas those deposited at 420 degreesC transform to the R phase only at 580 degreesC. (When cooled to room temperature, the annealed films convert reversibly from the R phase to the M phase.) Electron microscopy shows that annealing leads to disintegration of the single crystalline VO2(B) platelets into small crystallites of VO2(R), although the platelet morphology is retained. When the annealing temperature is relatively low, these crystallites are nanometer sized. At a higher-annealing temperature, the transformation leads to well-connected and similarly oriented large grains of VO2(R), enveloped in the original platelet. The semiconductor-metal transition near 68 degreesC leads to a large jump in resistivity in all the VO2(M) films, nearly as large as in epitaxial films on single-crystal substrates. When the annealed films contain well-connected large grains, the transition is very sharp. Even when preferred orientation is present, the transition is not as sharp in as-deposited VO2(M), because the crystallites are not densely packed as in annealed VO2(B). However, the high degree of orientation in these films leads to a narrow temperature hysteresis. (C) 2002 American Institute of Physics.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Self-assembled molecular films of tetraamino metal (Co, Cu, Fe) phthalocyanines on gold and silver. Electrochemical and spectroscopic characterization

The formation of molecular films of 2,9,16,23-tetraamino metal phthalocyanines [TAM(II)Pc; M (II) = Co, Cu, and TAM(III)Pc; M = Fe] by spontaneous adsorption on gold and silver surfaces is described. The properties of these films have been investigated by cyclic voltammetry, impedance, and FT-Raman spectroscopy. The charge associated with Co(II) and Co(I) redox couple in voltammetric data leads to a coverage of (0.35+/-0.05) x 10(-10) mol cm(-2), suggesting that the tetraamino cobalt phthalocyanine is adsorbed as a monolayer with an almost complete coverage. The blocking behavior of the films toward oxygen and Fe(CN)(6)(3-/4-) redox couple have been followed by cyclic voltammetry and impedance measurements. This leads to an estimate of the coverage of about 85 % in the case of copper and the iron analogs. FT-Raman studies show characteristic bands around 236 cm(-1) revealing the interaction between the metal substrate and the nitrogen of the -NH2 group on the phthalocyanine molecules.