Effects of Zr and Ti doping on the dielectric response of CeO2: A comparative first-principles study

Zr doping in ceria (CeO2) results in enhanced static dielectric response compared to pure ceria. On the other hand, Ti doping in ceria keeps its dielectric constant unchanged. We use first-principles density functional theory calculations based on pseudopotentials and a plane wave basis to determine electronic properties and dielectric response of Zr/Ti-doped and oxygen-vacancy-introduced ceria. Softening of phonon modes is responsible for the enhancement in dielectric response of Zr-doped ceria compared to that of pure ceria. The ceria-zirconia mixed oxides should have potential use as high-k materials in the semiconductor industry. (c) 2010 Elsevier Ltd. All rights reserved.

Nucleation and growth of Al2O3/metal composites by oxidation of aluminum alloys

The nucleation and growth mechanisms during high temperature oxidation of liquid Al-3% Mg and Al-3% Mg-3% Si alloys were studied with the aim of enhancing our understanding of a new composite fabrication process. The typical oxidation sequence consists of an initial event of rapid but brief oxidation, followed by an incubation period of limited oxide growth after which bulk Al2O3/Al composite forms. A duplex oxide layer, MgO (upper) and MgAl2O4 (lower), forms on the alloy surface during initial oxidation and incubation. The spinel layer remains next to the liquid alloy during bulk oxide growth and is the eventual repository for most of the magnesium in the original alloy. Metal microchannels developed during incubation continuously supply alloy through the composite to the reaction interface. During the growth process, a layered structure exists at the upper extremity of the composite, consisting of MgO at the top surface, MgAl2O4 (probably discontinuous), Al alloy, and finally the bulk Al2O3 composite containing microchannels of the alloy. The bulk oxide growth mechanism appears to involve continuous formation and dissolution of the Mg-rich oxides at the surface, diffusion of oxygen through the underlying liquid metal, and epitaxial growth of Al2O3 on the existing composite body. The roles of Mg and Si in the composite growth process are discussed.

Relation between effective atomic charge and chemical shifts in X-ray absorption spectra of transition-metal compounds

Chemical shifts of K absorption discontinuities, Delta E, of several manganese, iron and cobalt oxides with the metal in the formal oxidation states between +2 and +4, have been measured. These data, together with data in the literature on other compounds of these metals, can be fitted into the expression Delta E=aq+bq2, where q is the effective atomic charge on the metal. Theoretical considerations also support this functional relationship between Delta E and q.

Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5 from component oxides have been measured using solid state galvanic cells incorporating CaF2 as the solid electrolyte under pure oxygen at a pressure of 1.01 x 10(5) Pa Because the superconducting compound YBa2Cu3O7-delta coexists with any two of the phases CuO, BaCuO2 and Y2BaCuO5, the data on BaCuO2 and Y2BaCuO5 obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.

The Blackett Memorial Lecture, 1991: Chemical Insights into High-Temperature Superconductors

The high-temperature superconductors are complex oxides, generally containing two-dimensional CuO2 sheets. Various families of the cuprate superconductors are described, paying special attention to aspects related to oxygen stoichiometry, phase stability, synthesis and chemical manipulation of charge carriers. Other aspects discussed are chemical applications of cuprates, possibly as gas sensors and copper-free oxide superconductors. All but the substituted Nd and Pr cuprates are hole-superconductors. Several families of cuprates show a nearly constant n(h) at maximum T(c). Besides this universality, the cuprates exhibit a number of striking common features. Based on Cu(2p) photoemission studies, it is found that the Cu-O charge-transfer energy, DELTA, and the Cu(3d)-O(2p) hybridization strength, t(pd), are key factors in the superconductivity of cuprates. The relative intensity of the satellite in the Cu(2p) core-level spectra, the polarizability of the CuO2 sheets as well as the hole concentration are related to DELTA/t(pd). These chemical bonding factors have to be explicitly taken into account in any model for superconductivity of the cuprates.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

A2MoTiO7−x (Atriple bond; length as m-dashrare earth or Y): a new series of oxide pyrochlores prepared by topochemical reduction of A2MoTiO8 scheelites

A series of anion-deficient pyrochlore oxides of the formula A2MoTiO7−x (xless-than-or-equals, slant0.5), where Atriple bond; length as m-dashSm, Gd, Tb, Dy, Ho, Er, Lu and Y, has been prepared by reduction of A2MoTiO8 scheelites. The scheelite-to-pyrochlore conversion is reversible, indicating that the reaction is likely to be topochemical. The oxidation states of molybdenum and titanium are most probably Mo(III) and Ti(IV) for the limiting composition of the pyrochlores A2MoTiO6.5. The new pyrochlores are non-metallic and paramagnetic as expected.

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

Chemical Shift of the X-Ray K-Absorption Edge of Cu in Some of Its Compounds, Complexes and Superconductors

Chemical shifts, ΔE, of the X-ray K-absorption edge in several compounds, complexes of copper including its superconducting oxides possessing formal oxidation states +1 and +2 have been measured. It has been shown that the chemical shift is primarily governed by the effective ionic charge on the absorbing ion and the nature of the atoms in the first coordination shell around the absorbing ion. The relation between the chemical shift, ΔE , and the effective charge q on the absorbing ion is found to be ΔE=Aq+Bq2+Cq3+Dq4 (A, B, C and D are constants). The effects of electronegativity, atomic number, oxidation state, crystal structure, the valence d-orbital electrons, etc. on the X-ray absorption chemical shift have been discussed. ©1990 The Physical Society of Japan

Formation and preservation of pedogenic carbonates in South India, links with paleo-monsoon and pedological conditions: Clues from Sr isotopes, U-Th series and REEs

The influence of the pedogenic and climatic contexts on the formation and preservation of pedogenic carbonates in a climosequence in the Western Ghats (Karnataka Plateau, South West India) has been studied. Along the climosequence, the current mean annual rainfall (MAR) varies within a 80 km transect from 6000 mm at the edge of the Plateau to 500 mm inland. Pedogenic carbonates occur in the MAR range of 500-1200 mm. In the semi-arid zone (MAR: 500-900 mm), carbonates occur (i) as rhick hardpan calcretes on pediment slopes and (ii) as nodular horizons in polygenic black soils (i.e. vertisols). In the sub-humid zone (MAR: 900-1500 mm), pedogenic carbonates are disseminated in the black soil matrices either as loose, irregular and friable nodules of millimetric size or as indurated botryoidal nodules of centimetric to pluricentimetric size. They also occur at the top layers of the saprolite either as disseminated pluricentimetric indurated nodules or carbonate-cemented lumps of centimetric to decimetric size. Chemical and isotopic (Sr-87/Sr-86) compositions of the carbonate fraction were determined after leaching with 0.25 N HCl. The corresponding residual fractions containing both primary minerals and authigenic clays were digested separately and analyzed. The trend defined by the Sr-87/Sr-86 signatures of both labile carbonate fractions and corresponding residual fractions indicates that a part of the labile carbonate fraction is genetically linked to the local soil composition. Considering the residual fraction of each sample as the most likely lithogenic source of Ca in carbonates, it is estimated that from 24% to 82% (55% on average) of Ca is derived from local bedrock weathering, leading to a consumption of an equivalent proportion of atmospheric CO2. These values indicate that climatic conditions were humid enough to allow silicate weathering: MAR at the time of carbonate formation likely ranged from 400 to 700 mm, which is 2- to 3-fold less than the current MAR at these locations. The Sr, U and Mg contents and the (U-234/U-238) activity ratio in the labile carbonate fraction help to understand the conditions of carbonate formation. The relatively high concentrations of Sr, U and Mg in black soil carbonates may indicate fast growth and accumulation compared to carbonates in saprolite, possibly due to a better confinement of the pore waters which is supported by their high (U-234/U-238) signatures, and/or to higher content of dissolved carbonates in the pore waters. The occurrence of Ce, Mn and Fe oxides in the cracks of carbonate reflects the existence of relatively humid periods after carbonate formation. The carbonate ages determined by the U-Th method range from 1.33 +/- 0.84 kyr to 7.5 +/- 2.7 kyr and to a cluster of five ages around 20 kyr, i.e. the Last Glacial Maximum period. The young occurrences are only located in the black soils, which therefore constitute sensitive environments for trapping and retaining atmospheric CO2 even on short time scales. The maximum age of carbonates depends on their location in the climatic gradient: from about 20 kyr for centimetric nodules at Mule Hole (MAR = 1100 mm/yr) to 200 kyr for the calcrete at Gundlupet (MAR = 700 mm/yr, Durand et al., 2007). The intensity of rainfall during wet periods would indeed control the lifetime of pedogenic carbonates and thus the duration of inorganic carbon storage in soils. (C) 2010 Elsevier Ltd. All rights reserved.

Synthesis, infrared spectra and thermoanalytical properties of transition metal sulfite hydrazine hydrates

Transition metal sulfite hydrazine hydrates, MSO3·xN2H4·yH2O whereM=Mn, Fe, Co, Ni and Zn have been prepared and characterized by chemical analysis, infrared spectra, thermoanalytical and combustion studies. The colours,x andy parameters of the complexes varied depending upon the preparation conditions. Thermal decomposition characteristics differ from metal to metal yielding metal oxides at relatively low temperatures.Mittels chemischer Analyse, IR-Spektren, thermoanalytischen und Verbrennungsstudien wurden die Hydrazinhydrate der hergestellten Übergangsmetallsulfite MSO3·xN2H4·yH2O mitM=Mn, Fe, Co, Ni und Zn beschrieben. Farbe sowie die Parameterx undy der Komplexe hängen von den Herstellungsbedingungen ab. Die thermische Zersetzung, bei der bei relativ niedrigen Temperaturen Metalloxide entstehen, ist von Metall zu Metall verschieden.

Phase Relations in the System CaO-Fe2O3-Y2O3 at 1273 K and Compatibility Between Y1-xCaxFeO3-0.5x and Stabilized Zirconia

Phase relations in the system CaO-Fe2O3-Y2O3 in air (P-O2/P-o = 0.21) were explored by equilibrating samples representing eleven compositions in the ternary at 1273 K, followed by quenching to room temperature and phase identification using XRD. Limited mutual solubility was observed between YFeO3 and Ca2Fe2O5. No quaternary oxide was identified. An isothermal section of the phase diagram at 1273 K was constructed from the results. Five three-phase regions and four extended two-phase regions were observed. The extended two-phase regions arise from the limited solid solutions based on the ternary oxides YFeO3 and Ca2Fe2O5. Activities of CaO, Fe2O3 and Y2O3 in the three-phase fields were computed using recently measured thermodynamic data on the ternary oxides. The experimental phase diagram is consistent with thermodynamic data. The computed activities of CaO indicate that compositions of CaO-doped YFeO3 exhibiting good electrical conductivity are not compatible with zirconia-based electrolytes; CaO will react with ZrO2 to form CaZrO3.

Four decades of research in solid state chemistry

Solid state chemistry was in its infancy when the author got interested in the subject. In this article, the author outlines the manner in which the subject has grown over the last four decades, citing representative examples from his own contributions to the different facets of the subject. The various aspects covered include synthesis, structure, defects, phase transitions, transition metal oxides, catalysts, superconductors, metal clusters and fullerenes. In an effort to demonstrate the breadth and vitality of the subject, the author shares his own experiences and aspirations and gives expression to the agony and ecstacy in carrying out experimental research in such a frontier area in India.

Combustion synthesis and properties of fine-particle rare-earth-metal zirconates, Ln2Zr2O7

Fine-particle rare-earth-metal zirconates, Ln2Zr2O7, where Ln = La, Ce, Pr, Nd, Sm, Gd and Dy having the pyrochlore structure have been prepared using a novel combustion process. The process employs aqueous solutions of the corresponding rare-earth-metal nitrate, zirconium nitrate and carbohydrazide/urea in the required molar ratio. When the solution is rapidly heated to 350–500 °C it boils, foams and burns autocatalytically to yield voluminous oxides. The formation of single-phase Ln2Zr2O7 has been confirmed by powder X-ray diffraction, infrared and fluorescence spectroscopy. The solid combustion products are fine, having surface areas in the range 6–20 m2 g–1. The cold-pressed Pr2Zr2O7 compact when sintered at 1500 °C, 4 h in air, achieved 99% theoretical density.

Influence of cast versus wrought microstructure on the processing map for hot working of stainless steel type AISI 304

Processing maps for hot working of as-cast and wrought stainless steels of type AISI 304 have been developed in the temperature range 600 to 1250°C and strain rate range 0.001 to 100 s−1. The domain of dynamic recrystallization (DRX) in as-cast material occurs at higher temperatures (1250°C) and lower strain rates (0.001 s−1) than in the wrought steel (1100°C and 0.01 s−1). The effect is explained in terms of enhanced nucleation rate of DRX due to the carbide, ferrite particles, stable oxides/nitrides and second-phase intermetallics in the as-cast microstructure. The DRX domain is wider in the wrought material although the peak efficiency is less (32%) than in the as-cast case (40%). The flow instability regime is not significantly affected by the initial microstructure