Composition-controlled metal-insulator transitions and minimum metallic conductivity in the oxide systems LaNi1-xMxO3 (M = Cr, Mn, Fe, or Co)

The composition-controlled metal-insulator transition in the perovskite systems LaNi1-xMxO3 (M = Cr, Mn, Fe, and Co) has been investigated by transport measurements over the temperature range 12-300 K. These systems, which have critical electron densities (nc) in the range (1-2) -1020 electrons cm-3, exhibit sharp metal-insulator transitions at the base temperature. The corresponding minimum metallic conductivity (Ï-min), separating the localized and itinerant electronic regimes, is of the order of 102 ohm-1 cm-1. Particular attention is paid to the idea of Ï-min scaling with nc, and our present results are compared with earlier studies of the metal-insulator transition in low (e.g., Ge:Sb) and high (e.g., metal-ammonia, supercritical Hg) electron-density systems. A link is established between the transport and magnetic properties of the title systems at the metal-insulator transition.

Preparation, structure, and magnetic properties of isostructural La3MAlS7 and La3MFeS7 (M = Mg, Mn, Fe, Co, Ni, or Zn)

A series of quaternary metal sulfides of the general formula La3MM′S7 (M = Mn, Fe, Co; M′ = Al and M = Mg, Mn, Fe, Co, Ni; M′ = Fe) consisting of linear chains of face shared MS6 octahedra and isolated M′S4 tetrahedra has been prepared and studied. The aluminium compounds La3MAlS7 (M = Mn, Fe, Co) exhibit linear chain antiferromagnetism. Magnetic behavior of other La3MFeS7 sulfides has been examined in detail. The magnetic susceptibility of La3MgFeS7 shows that tetrahedral site Fe3+ undergoes a transition from Image to S = 2 spin state around 150 K.

Ce CORE level X-ray photo electron spectroscopy of CeX2Si2 (X = Fe, Co, Ni and Cu)

Ce(3d) and (4d) core level XPS spectra of CeX = Fe, Co, Ni and Cu) suggest that the mean valence of Ce was as well as 4f hybridization strength decrease systematically from Fe to Cu. This observation is in agreement with the results of Bremstrahlung Isochromat Spectroscopy (BIS), but in disagreement with LIII-edge data reported earlier.

Mixed valency in the high-temperature phases of transition metal molybdates,AMoO4 (A=Fe, Co, Ni)

Transition metal molybdates of the formulaAMoO4 whereA=Fe, Co or Ni exhibit a first-order phase transition between 670K–970K. An investigation of the lowtemperature (lt) and high-temperature (ht) phases by x-ray photoelectron spectroscopy, x-ray absorption spectroscopy, magnetic susceptibility and other physical methods shows that the phase transition is associated with a valence change of the typeA 2++Mo6+αA 3++Mo5+ in the cases of iron and cobalt molybdates.

Magnetic interactions in the oxide systems LaNi1-xMxO3 (M = Cr, Fe, or Co)

Magnetic susceptibilities of several members of the series of oxides of the general formula LaNi1-xMxO3 (M = Cr, Fe, or Co) are reported. The oxides show evidence for interesting ferrimagnetic (Cr and Co) and antiferromagnetic (Fe) interactions.

Experimental and Computational Characterization of Alloy--Spinel--Corundum Equilibrium in the System Fe--Co--Al--O at 1873K

The three-phase equilibrium between alloy, spinel solid solution and alpha -Al sub 2 O sub 3 in the Fe--Co--Al--O system at 1873k was fully characterized as a function of alloy composition using both experimental and computational methods. The equilibrium oxygen content of the liquid alloy was measured by suction sampling and inert gas fusion analysis. The O potential corresponding to the three-phase equilibrium was determined by emf measurements on a solid state galvanic cell incorporating (Y sub 2 O sub 3 )ThO sub 2 as the solid electrolyte and Cr + Cr sub 2 O sub 3 as the reference electrode. The equilibrium composition of the spinel phase formed at the interface between the alloy and alumina crucible was measured by electron probe microanalysis (EPMA). The experimental results were compared with the values computed using a thermodynamic model. The model used values for standard Gibbs energies of formation of pure end-member spinels and Gibbs energies of solution of gaseous O in liquid Fe and cobalt available in the literature. The activity--composition relationship in the spinel solid solution was computed using a cation distribution model. The variation of the activity coefficient of O with alloy composition in the Fe--Co--O system was estimated using both the quasichemical model of Jacob and Alcock and Wagner's model along with the correlations of Chiang and Chang and Kuo and Chang. The computed results of spinel composition and O potential are in excellent agreement with the experimental data. Graphs. 29 ref.--AA

Preparation, characterization, spectral and thermal analyses of (N2H5)2MCl4·2H2O (M = Fe, Co, Ni and Cu); crystal structure of the iron complex

Hydrazinium metal chlorides, (N2H5)2MCl4·2H2O (where M = Fe, Co, Ni and Cu), have been prepared from the aqueous solutions of the respective metal chlorides and hydrazine hydrochloride (N2H4·HCl or N2H4·2HCl) and investigated by spectral and thermal analyses. The crystal structure of the iron complex has been determined by direct methods and refined by full-matrix least-squares to an R of 0.023 and Rw of 0.031 for 1495 independent reflections. The structure shows ferrous ion in an octahedral environment bonded by two hydrazinium cations, two chloride anions and two water molecules. In the complex cation [Fe(N2H5)2(H2O)2Cl2]2+, the coordinated groups are in trans positions.

Enhancement of fatigue life of Ni-Ti-Fe shape memory alloys by thermal cycling

The effect of thermal cycling on the load-controlled tension-tension fatigue behavior of a Ni-Ti-Fe shape memory alloy (SMA) at room temperature was studied. Considerable strain accumulation was observed to occur in this alloy under both quasi-static and cyclic loading conditions. Though, in all cases, steady-state is reached within the first 50-100 cycles, the accumulated steady-state strain, epsilon(p.ss), is much smaller in thermally cycled alloy. As a result, the fatigue performance of them was found to be significantly enhanced vis-a-vis the as-solutionized alloy. Furthermore, under load-controlled conditions, the fatigue life of Ni-Ti-Fe alloys was found to be exclusively dependent on epsilon(p.ss). Observations made by profilometry and differential scanning calorimetry (DSC) indicate that the 200-500% enhancement in fatigue life of thermally cycled alloy is due to the homogeneous distribution of the accumulated fatigue strain. (C) 2010 Elsevier B.V. All rights reserved.

Electron energy loss spectroscopic study of Cr(CO)6, Mo(CO)6 and W(CO)6 in the vapour phase

Electron energy loss spectra (EELS) of Cr, Mo and W hexacarbonyls in the vapour phase are reported. Most of the bands observed are similar to those in optical spectra, but the two high energy transitions in the 9·8–11·2 eV region are reported here for the first time. Based on the orbital energies from the ultraviolet photoelectron spectra and the electronic transition energies from EELS and earlier optical studies, the molecular energy level schemes of these molecules are constructed.

Interdiffusion study on Co(W) solid solution and topological close-packed mu phase in Co-W system

An interdiffusion study is conducted on the Co-W system by a diffusion couple technique. The interdiffusion coefficient of the Co(W) solid solution and the Co7W6 mu phase is determined. The activation energy is found to increase with the W content of the Co(W) solid solution. (C) 2010 Elsevier Ltd. All rights reserved.

An electron diffraction study of quasicrystals in Ti-37 at% Mn and Ti-24 at% Mn-13 at% Fe alloys

Electron diffraction studies were carried out to establish the icosahedral phase formation in rapidly quenched Ti-37 at% Mn and Ti-24 at% Mn-13 at% Fe alloys. Distortions in the diffraction spots and diffuse intensities in the diffraction patterns were investigated. The existence of a rational approximant structure and a decagonal like phase are also reported.

A study of cubic bismuth oxides of the type bi(26-X)m(X)O(40-delta) (m=ti, mn, fe, co, ni or pb) related to gamma-bi2O3

A structural investigation of cubic oxides (space group I23) of the formula Bi(26-x)M(x)O(40-delta) (M = Ti, Mn, Fe, Co, Ni and Pb) related to the Y-Bi2O3 phase has been carried out by the Rietveld profile analysis of high-resolution X-ray powder diffraction data in order to establish the cation distributions. Compositional dependence of the cation distribution has been examined in the case of Bi26-xCoxO40-delta (1 < x < 16). The study reveals that in Bi(26-X)M(X)O(40-delta) with M = Ti, Mn, Fe, Co or Pb, the M cations tend to occupy tetrahedral (2a) sites when x < 2 while the octahedral (24f) sites are shared by the excess Co or Ni cations with Bi atoms when x > 2. Also experimental magnetic moments of Mn, Co and Ni derivatives have been used to establish the valence state and distribution of these cations.

Synthesis of new transition metal nitrides, MWN2 (Mtriple bond; length as m-dashMn, Co, Ni)

We report the synthesis of ternary transition metal nitrides of the formula MWN(2) for M=Mn, Co, Ni by reaction of the corresponding MWO(4) with NH3 gas at 600-700 degrees C. MnWN2 is isostructural with the already-known FeWN2, crystallizing in a hexagonal structure (a=2.901(2), b=16.48(5) Angstrom) related to LiMoN2. CoWN2 and NiWN2 (which are isostructural amongst themselves) adopt a different hexagonal structure with a smaller c parameter. While the Mn and Fe nitrides are semiconducting, the Co and Ni nitrides are semimetallic.