Structure and electrical properties of sputtered lithium cobaltite thin films

LixCoOy films with x < 1 and y > 2 have been prepared by radio-frequency (rf) sputtering from high temperature (HT) LiCoO2 targets. Their structures have been examined with high resolution electron microscopy. Conductivities have been studied between 77 and 400 K. The electrochemical behaviour of film electrodes have been investigated with Li/LiClO4-PC/LixCoOy cells. The annealed films consist of nanocrystalline domains with amorphous boundaries. Electrical conductivities appear to arise from variable-range hopping (VRH) of holes. The films form good electrodes with operating potentials between 2.7 and 3.8 V. The observations have been discussed on the basis of a tentative and heuristic molecular orbital based energy band diagram. (C) 2002 Published by Elsevier Science Ltd.

Lanthanum cobaltite black pigments with perovskite structure

In this work La1-xCaxCoO3 (x = 0-0.4) pigments were synthesized by the polymeric precursor method with heat treatments at 700, 800 and 900 C for 4 h. The powders were characterized by colorimetry, UV-vis spectroscopy and powder X-ray diffraction (XRD). The X-ray diffraction patterns showed the presence of a single phase perovskite, changing its structure from rhombohedral to cubic, when calcium was added to the lattice. All of the pigments had a black colour with a strong absorption over the whole of the visible spectrum as a consequence of the different oxidation states of cobalt and the high short-range disorder. The substitution of Ca2+ for La3+ did not influence the pigment colour but decreased its final cost. © 2013 Elsevier Ltd. All rights reserved.

The biological application of cobalt

This review collects and summarises the biological applications of the element cobalt. Small amounts of the ferromagnetic metal can be found in rock, soil, plants and animals, but is mainly obtained as a by-product of nickel and copper mining, and is separated from the ores (mainly cobaltite, erythrite, glaucodot and skutterudite) using a variety of methods. Compounds of cobalt include several oxides, including: green cobalt(II) (CoO), blue cobalt(II,III) (Co3O4), and black cobalt(III) (Co2O3); four halides including pink cobalt(II) fluoride (CoF2), blue cobalt(II) chloride (CoCl2), green cobalt(II) bromide (CoBr2), and blue-black cobalt(II) iodide (CoI2). The main application of cobalt is in its metal form in cobalt-based super alloys, though other uses include lithium cobalt oxide batteries, chemical reaction catalyst, pigments and colouring, and radioisotopes in medicine. It is known to mimic hypoxia on the cellular level by stabilizing the α subunit of hypoxia inducing factor (HIF), when chemically applied as cobalt chloride (CoCl2). This is seen in many biological research applications, where it has shown to promote angiogenesis, erythropoiesis and anaerobic metabolism through the transcriptional activation of genes such as vascular endothelial growth factor (VEGF) and erythropoietin (EPO), contributing significantly to the pathophysiology of major categories of disease, such as myocardial, renal and cerebral ischaemia, high altitude related maladies and bone defects. As a necessary constituent for the formation of vitamin B12, it is essential to all animals, including humans, however excessive exposure can lead to tissue and cellular toxicity. Cobalt has been shown to provide promising potential in clinical applications, however further studies are necessary to clarify its role in hypoxia-responsive genes and the applications of cobalt-chloride treated tissues.

Thermal decomposition of rare-earth trioxalatocobaltates

The thermal decomposition of rare-earth trioxalatocobaltates LnCo(C2O4)3 · x H2O, where Ln = La, Pr, Nd, has been studied in flowing atmospheres of air/oxygen, argon/ nitrogen, carbon dioxide and a vacuum. The compounds decompose through three major steps, viz. dehydration, decomposition of the oxalate to an intermediate carbonate, which further decomposes to yield rare-earth cobaltite as the final product. The formation of the final product is influenced by the surrounding gas atmosphere. Studies on the thermal decomposition of photodecomposed lanthanum trioxalatocobaltate and a mechanical mixture of lanthanum oxalate and cobalt oxalate in 1 : 2 molar ratio reveal that the decomposition behaviour of the two samples is different. The drawbacks of the decomposition scheme proposed earlier have been pointed out, and logical schemes based on results obtained by TG, DTA, DTG, supplemented by various physico-chemical techniques such as gas and chemical analyses, IR and mass spectroscopy, surface area and magnetic susceptibility measurements and X-ray powder diffraction methods, have been proposed for the decomposition in air of rare-earth trioxalatocobaltates as well as for the photoreduced lanthanum salt and a mechanical mixture of lanthanum and cobalt oxalates.

Infrared spectroscopic study of LiCoO2 thin films

Site disorder of Co3+ ions in sputtered films of lithium cobaltite has been examined using infrared spectroscopy. Both transmission and reflectance modes have been used to characterize the nature of IR absorption. It is found that Co3+ in the sputtered films occupy two types of octahedral sites that differ in the nature of second-neighbor environment. Li+ ions exhibit two bands, which may arise from tetrahedral and octahedral site occupancies or from the presence of disordered regions in the films. (C) 2002 Elsevier Science (USA).

Synthesis and thermoelectric properties of Ca2.6Nd0.4Co4O9 compound

The layered cobaltite Ca2.6Nd0.4Co4O9 was synthesized by the solid-state reaction. Their crystal structure was determined by the X-ray powder diffraction and CELL program. The prepared Ca2.6Nd0.4Co4O9 compound has the monoclinic symmetry. The electrical conductivity and Seebeck coefficient were measured from room temperature to 700 degreesC in air. Both the properties increase while rising temperature. The thermoelectric power of Ca2.6Nd0.4Co4O9 is about 242.4 muV (.) K-1. The results imply a promising way to enhance the thermoelectric properties of the layered cobaltite oxides by optimizing their composition and microstructure.

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

The Ni-Cu-PGE sulfide ores of the komatiite-hosted Fortaleza de Minas deposit, Brazil: Evidence of hydrothermal remobilization

The Fortaleza de Minas Ni-Cu-PGE sulfide deposit is hosted by Archean komatiitic rocks of the Morro do Ferro greenstone belt, near the southwestern margin of the Sa (aFrancisco) over tildeo Francisco craton, Minas Gerais state, Brazil. The deposit contains 6 million tonnes of ore with an average grade of 2.2 wt% Ni, 0.4% Cu, 0.05% Co and 1.2 ppm PGE+Au, and comprises (i) a main orebody, which is metamorphosed, deformed and transposed along a regional shear zone, consisting mainly of disseminated, brecciated and stringer sulfide ores that are interpreted to be of early magmatic origin, and (ii) PGE-rich discordant veins that are hosted in N-S- and NE-SW-trending late faults that cross-cut the main orebody. The discordant PGE-rich ore (up to 4 ppm total PGE) is characterized by thin, discontinuous and irregular veins and lenses of massive sulfides hosted by serpentinite and talc schist, and is relatively undeformed if compared with the early types of ore. It is composed mainly of pyrrhotite, pentlandite, chalcopyrite, magnetite, carbonates, and amphiboles, with minor cobaltite-gersdorffite, sphalerite, ilmenite, and quartz, and rarely maucherite (Ni11Asg), tellurides and platinum-group minerals (PGM). Omeeite, irarsite, sperrylite, and Ni-bearing merenskyite are the main PGM, followed by minor amounts of testibiopalladite and an unknown phase containing Ru, Te, and As. The PGM occur either included in, or at the margins of, sulfides, sulfarsenides, silicates and oxides, or filling fractures in pyrrhotite, pentlandite, and chalcopyrite, suggesting that they started to precipitate with these minerals and continued to precipitate after the sulfides were formed. The mantle-normalized metal distribution of the two samples of discordant veins shows distinct patterns: one richer in Ni-Pd-Ir-Rh-Ru-Os and another with higher amounts of Cu-Pt-Bi. Both are strongly depleted in Cr if compared with the metamorphosed magmatic ore of this deposit, which follows the general Kambalda-type magmatic trend. on the basis of structural, mineralogical and geochemical evidence, we propose that the PGE-rich discordant ore may have formed by remobilization of metals from the deformed, metamorphosed magmatic orebody (which shows a depleted pattern in these elements) by reduced (pyrrhotite - pentlandite - pyrite are stable), neutral to alkaline and carbonic fluids (carbonate-stable). The PGE may have been transported as bisulfide complexes, and precipitated as tellurides (mainly Pd) and arsenides (Pt, Rh, Ru, Os, Ir) in the late N-S and NE-SW-trending faults owing to a decrease in the activity of S caused by the precipitation of sulfides in the veins.

Spin, charge, and orbital correlations in the one-dimensional t(2g)-orbital Hubbard model

We present the zero-temperature phase diagram of the one-dimensional t(2g)-orbital Hubbard model, obtained using the density-matrix renormalization group and Lanczos techniques. Emphasis is given to the case of the electron density n=5 corresponding to five electrons per site, while several other cases for electron densities between n=3 and 6 are also studied. At n=5, our results indicate a first-order transition between a paramagnetic (PM) insulator phase, with power-law slowly decaying correlations, and a fully polarized ferromagnetic (FM) state by tuning the Hund's coupling. The results also suggest a transition from the n=5 PM insulator phase to a metallic regime by changing the electron density, either via hole or electron doping. The behavior of the spin, charge, and orbital correlation functions in the FM and PM states are also described in the text and discussed. The robustness of these two states against varying parameters suggests that they may be of relevance in quasi-one-dimensional Co-oxide materials, or even in higher dimensional cobaltite systems as well.

Gênese dos corpos de sulfeto maciço hidrotermal e platinóides associados no depósito de Fortaleza de Minas (MG)

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

Gold mineralisation in the Caledonides of the British Isles with special reference to the Dolgellau Gold-belt, North Wales and the Southern Uplands, Scotland. Available in 2 volumes.

Two aspects of gold mineralisation in the Caledonides of the British Isles have been investigated: gold-telluride mineralisation at Clogau Mine, North Wales; and placer gold mineralisation in the Southern Uplands, Scotland. The primary ore assemblage at Clogau Mine is pyrite, arsenopyrite, cobaltite, pyrrhotine, chalcopyrite, galena, tellurbismuth, tetradymite, altaite, hessite, native gold, wehrlite, hedleyite, native bismuth, bismuthunite and various sulphosalts. The generalised paragenesis is early Fe, Co, Cu, As and S species, and later minerals of Pb, Bi, Ag, Au, Te, Sb. Electron probe micro-analysis (EPMA) of complex telluride-sulphide intergrowths suggests that these intergrowths formed by co-crystallisation/replacement processes and not exsolution. Minor element chemical variation, in the sulphides and tellurides, indicates that antimony and cadmium are preferentially partitioned into telluride minerals. Mineral stability diagrams suggest that during gold deposition log bf aTe2 was between -7.9 and -9.7 and log bf aS2 between -12.4 and -13.8. Co-existing mineral assemblages indicate that the final stages of telluride mineralisation were between c. 250 - 275oC. It is suggested that the high-grade telluride ore shoot was the result of remobilisation of Au, Bi, Ag and Te from low grade mineralisation elsewhere within the vein system, and that gold deposition was brought about by destabilisation of gold chloride complexes by interaction with graphite, sulphides and tellurbismuth. Scanning electron microscopy of planer gold grains from the Southern Uplands, Scotland, indicates that detailed studies on the morphology of placer gold can be used to elucidate the history of gold in the placer environment. In total 18 different morphological characteristics were identified. These were divided on an empirical basis, using the relative degree of mechanical attrition, into proximal and distal characteristics. One morphological characteristic (a porous/spongy surface at high magnification) is considered to be chemical in origin and represent the growth of `new' gold in the placer environment. The geographical distribution of morphological characteristics has been examined and suggests that proximal placer gold is spatially associated with the Loch Doon, Cairsphairn and Fleet granitoids. Quantitative EPMA of the placer gold reveals two compositional populations of placer gold. Examination of the geographical distribution of fineness suggests a loose spatial association between granitoids and low fineness placer gold. Also identified was chemically heterogeneous placer gold. EPMA studies of these heterogeneities allowed estimation of annealing history limits, which suggest that the heterogeneities formed between 150 and 235oC. It is concluded, on the basis of relationships between morphology and composition, that there are two types of placer gold in the Southern Uplands: (i) placer gold which is directly inherited from a hypogene source probably spatially associated with granitoids; and (ii) placer gold that has formed during supergene processes.

The correlation of structure and electronic properties near the surface of transition metal oxides

The strong couplings between different degrees of freedom are believed to be responsible for novel and complex phenomena discovered in transition metal oxides (TMOs). The physical complexity is directly responsible for their tunability. Creating surfaces/interfaces add an additional ' man-made' twist, approaching the quantum phenomena of correlated materials. ^ The dissertation focused on the structural and electronic properties in proximity of surface of three prototype TMO compounds by using three complementary techniques: scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and low energy electron diffraction, particularly emphasized the effects of broken symmetry and imperfections like defects on the coupling between charge and lattice degrees of freedom. ^ Ca1.5Sr0.5RuO4 is a layered ruthenate with square lattice and at the boundary of magnetic/orbital instability in Ca2-xSrxRuO4. That the substitution of Sr 2+ with Ca2+ causing RuO6 rotation narrows the dxy band width and changes the Fermi surface topology. Particularly, the γ(dxy) Fermi surface sheet exhibited hole-like in Ca1.5Sr0.5RuO4 in contrast to electron-like in Sr2RuO4, showing a strong charge-lattice coupling. ^ Na0.75CoO2 is a layered cobaltite with triangular lattice exhibiting extraordinary thermoelectric properties. The well-ordered CoO2-terminated surface with random Na distribution was observed. However, lattice constants of the surface are smaller than that in bulk. The surface density of states (DOS) showed strong temperature dependence. Especially, an unusual shift of the minimum DOS occurs below 230 K, clearly indicating a local charging effect on the surface. ^ Cd2Re2O7 is the first known pyrochlore oxide superconductor (Tc ∼ 1K). It exhibited an unusual second-order phase transition occurring at TS1 = 200 K and a controversial first-order transition at TS2 = 120 K. While bulk properties display large anomalies at TS1 but rather subtle and sample-dependent changes at TS2, the surface DOS near the EF show no change at T s1 but a substantial increase below TS2---a complete reversal as the signature for the transitions. We argued that crystal imperfections, mainly defects, which were considerably enhanced at the surface, resulted in the transition at TS2. ^

Preparação e caracterização de fibras e nanotubos de BiFeO3 e FeNbO4

Esta dissertação teve como objetivo a produção e caracterização física de fibras e nanotubos de BiFeO3 e FeNbO4. Para o desenvolvimento destes materiais utilizou-se a técnica de fusão com laser (LFZ), o método sol-gel (Pechini) e o método de poros absorventes. As amostras obtidas foram sujeitas a uma caracterização estrutural por difração de raios-X e espetroscopia de Raman, morfológica por microscopia electrónica de varrimento e elétrica por medidas de constante dielétrica. Os resultados obtidos com a técnica de difração de raios-X mostraram que o gel com tratamento a 750 ºC é polifásico. Para conseguir produzir nanotubos escolheu-se o LaCoO3 como material alternativo. Usando a técnica de fusão de zona com laser (LFZ) obtiveram-se fibras de BiFeO3, FeNbO4 e compósitos de BiFeO3+FeNbO4. Com esta técnica foram crescidas fibras a várias velocidades (5, 10, 25, 50, 100 e 200 mm/h), tendo os resultados obtidos com a difração de raios-X evidenciado que todas as amostras obtidas são polifásicas, sendo a amostra de 10 mm/h para o BiFeO3 e a de 5 mm/h para o FeNbO4 as que apresentam melhores propriedades. As amostras de 5 mm/h de todos os compósitos são aquelas que possuem menor quantidade de segundas fases e portanto foram alvo de estudo mais aprofundado. A caracterização dielétrica permitiu verificar que todas as amostras apresentam fenómenos de relaxação dielétrica. Verifica-se também que para o BiFeO3 a constante dielétrica é superior na amostra crescida à velocidade de 10 mm/h, para o FeNbO4 é superior na amostra crescida a 5 mm/h e nos compósitos a amostra com 75% de BiFeO3 e 25% de FeNbO4 apresenta um comportamento diferente das restantes, eventualmente devido à sua microestrutura singular.

Geologia, petrologia, geocronologia e mineralizações sulfetadas do complexo ézio, província mineral de carajás, Brasil

Dissertação (mestrado)—Universidade de Brasília, Instituto de Geociências, Pós-Graduação em Geologia, 2015.