Nonstoichiometry, defects and thermodynamic properties of YFeO3, YFe2O4 and Y3Fe5O12

Oxygen nonstoichiometry of three ternary oxides. YFeO3-delta, YFe2O4-alpha and Y3Fe5O12-theta. in the system Y-Fe-O was investigated as a function of oxygen partial pressure by thermogravimetry at high temperature. The defects responsible for nonstoichiometry were identified as oxygen vacancies for YFeO3-delta and YFe2O4-alpha although the manner of variation of nonstoichiometric parameter with oxygen partial pressure for these two oxides is quite different. Cation interstitials are the predominant defects in Y3Fe5O12-theta. Gibbs energies of formation of the three nonstoichiometric oxides were determined using solid-state electrochemical cells in the temperature range from 975 to 1475 K. YFe2O4-alpha was found to be stable only above 1391 K. Gibbs energies of formation of the three stoichiometric compounds from their component binary oxides were obtained by combining information from solid state cells with results of thermogravimetric analysis using the Gibbs-Duhem relation. The results can be summarized as: (1/2)Y2O3 + (1/2)Fe2O3 -> YFeO3;Delta G(f(ox))(O)(+/- 250)(J/mol) = 17, 126-8.263T (1/2)Y2O3 + FeO + (1/2)Fe2O3 -> YFe2O4;Delta G(f(ox))(O)(+/- 260)(J/mol) = -10,352-13.24T (3/2)Y2O3 + (5/2)Fe2O3 -> Y3Fe5O12;Delta G(f(ox))(O)(+/- 780)(J/mol) = -56, 647-31.091T. (C) 2012 Elsevier B.V. All rights reserved.

(Ba3MTiMO9)-Ti-III-O-V (M-III = Fe, Ga, Y, Lu, M-V = Nb, Ta, Sb) perovskite oxides Synthesis, structure and dielectric properties

We describe the synthesis structures and dielectric properties of new perovskite oxides of the formula (Ba3MTiMO9)-Ti-III-O-V for M-III = Fe Ga Y Lu and M-V = Nb Ta Sb While M-V = Nb and Ta oxides adopt disordered/partially ordered 3C perovskite structures where M-III/Ti/M-V metal-oxygen octahedra are corner connected the M-V = Sb oxides show a distinct preference for the 6H structure where Sb-V/Ti-IV metal-oxygen octahedra share a common face forming (Sb Ti)O-9 dimers that are corner-connected to the (MO6)-O-III octahedra The preference of antimony oxides (Sb-V 4d(10)) for the 6H structure which arises from a special Sb-V-O chemical bonding that tends to avoid linear Sb-O-Sb linkages unlike Nb-V/Ta-V d(0) atoms which prefer similar to 180 degrees Nb/Ta-O-Nb/Ta linkages - is consistent with the crystal chemistry of M-V-O oxides in general The dielectric properties reveal a significant difference among Mill members All the oxides with the 3C structure excepting those with Mill = Fe show a normal low loss dielectric behaviour with epsilon = 20-60 in the temperature range 50-400 degrees C the M-III = Fe members with this structure (M-V = Nb Ta) display a relaxor-like ferroelectric behaviour with large E values at frequencies <= 1 MHz (50-500 degrees C) (C) 2010 Elsevier Masson SAS All rights reserved

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

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 single-walled carbon nanotubes using binary (Fe, Co, Ni) alloy nanoparticles prepared in situ by the reduction of oxide solid solutions

Passing a H-2-CH4 mixture over oxide spinels containing two transition elements as in Mg0.8MyMz'Al2O4 (M, M' = Fe, Co or Ni, y + z = 0.2) at 1070 degrees C produces small alloy nanoparticles which enable the formation of carbon nanotubes. Surface area measurements are found to be useful for assessing the yield and quality of the nanotubes. Good-quality single-walled nanotubes (SWNTs) have been obtained in high yields with the FeCo alloy nanoparticles, as evidenced by transmission electron microscope images and surface area measurements. The diameter of the SWNTs is in the 0.8-5 nm range, and the multiwalled nanotubes, found occasionally, possess very few graphite layers. (C) 1999 Elsevier Science B.V. All rights reserved.

Mossbauer study of La1-xCaxMn1-y (57)FeyO(3) with x = 0, 0.25; y=0.01

Temperature dependent Mossbauer measurements are done on the samples of La1- xCaxMn1-y (FeyO3)-Fe-57 with x=0 and 0.25, and y=0.01. With decreasing temperature, the specimen with x=0.25 shows a paramagnetic to ferromagnetic transition around 175 K. In the specimen x=0.0, the temperature dependence of both the center shift (delta) and the recoilless fraction (f) can be fitted very well with the Debye theory with a theta(D)=320+/-50 K. But for the specimens with x=0.25, f and delta show distinct deviations from the Debye behavior in the temperature range in which the resistivity shows a sharp decrease. Dips observed in both the f and delta around the transition temperature suggest that the Jahn-Teller distortion observed in these systems is dynamic in nature.

First-order structural transition in the magnetically ordered phase of Fe(1.13)Te

Specific heat, resistivity, magnetic susceptibility, linear thermal expansion (LTE), and high-resolution synchrotron x-ray powder diffraction investigations of single crystals Fe(1+y) Te (0.06 <= y <= 0.15) reveal a splitting of a single, first-order transition for y <= 0.11 into two transitions for y >= 0.13. Most strikingly, all measurements on identical samples Fe(1.13)Te consistently indicate that, upon cooling, the magnetic transition at T(N) precedes the first-order structural transition at a lower temperature T(s). The structural transition in turn coincides with a change in the character of the magnetic structure. The LTE measurements along the crystallographic c axis display a small distortion close to T(N) due to a lattice striction as a consequence of magnetic ordering, and a much larger change at T(s). The lattice symmetry changes, however, only below T(s) as indicated by powder x-ray diffraction. This behavior is in stark contrast to the sequence in which the phase transitions occur in Fe pnictides.

Antiferromagnetism in Fe1+y Te and Superconductivity in K (x) Fe2Se2

Iron-based layered chalcogenides are interesting because of their structural magnetic and superconducting properties. Single crystals of the parent binary chalcogenides, Fe1+y Te, and intercalated ternary chalcogenides, K0.8Fe2Se2, are grown and investigated in detail. Single crystals are grown by modified horizontal Bridgman method. Fe1+y Te demonstrates an antiferromagnetic (AFM) transition at T (N) =67 K which is identified as a magnetostructural transition. By varying the concentration of excess Fe, we have tuned T (N) over a range of temperature from 67 to 57 K. The superconducting properties of K0.8Fe2Se2 crystals are explored by magnetization measurements. A superconducting transition is observed at T (C) =31 K. The lower critical field of K0.8Fe2Se2 is estimated from field variation of magnetization measurements.