Neutron diffraction study of the coupling between spin, lattice, and structural degrees of freedom in 0.8BiFeO(3)-0.2PbTiO(3)

A powder neutron diffraction study was carried out on 0.8BiFeO(3)-0.2PbTiO(3) in the temperature range 27-1000 degrees C. The system exhibits magnetic transition at similar to 300 degrees C and a rhombohedral (R3c)-cubic (Pm3m) ferroelectric phase transition at similar to 650 degrees C. Anomalous variation in the lattice parameters and the octahedral tilt angle is observed across the magnetic transition temperature. In the magnetic phase, the c parameter is contracted and the octahedral tilt angle is slightly increased. The results suggest coupling between the spin, lattice and structural degrees of freedom. (C) 2011 American Institute of Physics. doi:10.1063/1.3555093]

''Phase reversal'' of non-resonant microwave absorption in superconducting YBaCuO/CuO powder mixtures

Non-resonant microwave absorption is studied as a function of temperature and composition in superconducting YBa2Cu3O7/CuO ceramic composite samples. In pure YBa2Cu3O7 only normal field dependence of the absorption is observed, where as in composites an anomalous non-monotonic field dependence is seen. The results are explained using an extended resistively shunted junction model and invoking the occurrence of junctions with phase difference psi(0) such that pi/2 < psi(0) < 3 pi/2. Copyright (C) 1996 Elsevier Science Ltd

Milling maps and amorphization during mechanical alloying

The effect of various milling parameters such as, milling intensity, ball:powder weight ratio and number of balls on the glass forming ability of an elemental blend of composition Ti50Ni50 has been studied by mechanical alloying. In order to understand the results, all the milling parameters have been converted into two energy parameters, namely, impact energy of the ball and the total energy of milling. In a milling map of these two parameters, the conditions for amorphous phase formation have been isolated. A similar exercise has been carried out for Ti50Cu50 as a function of milling time at two milling intensities. The results indicate that a minimum impact energy of the ball and a minimum total energy are essential for amorphization by mechanical alloying.

Phase evolution and densification of spray pyrolysed ZrO2-Al2O3 powders

Devitrification of spray pyrolysed, amorphous ZrO2-Al2O3 solid solution produces nanocrystalline microstructures (grain sizes 10-20 nm). In this study, spray pyrolysed amorphous ZrO2-40 mol% Al2O3 powder displayed good sinterability during decomposition, after spraying, of the nitrate precursors up to 1023K. Hot pressing of fully pyrolysed, pre-sintered (more than 70% dense) pellets at 923K and 750 MPa produced an amorphous pellet with less than 2% porosity. The results indicate the possibility of producing dense, amorphous pellets that can be heat treated further to produce nanocrystalline microstructures conducive for superplasticity.

Magnetic properties of mechanically alloyed nanocrystalline Ni3Fe

Disordered nanocrystalline Ni3Fe alloy was prepared by mechanical alloying of elemental powders. X-ray diffractograms show the formation of Ni3Fe single phase. The chemical composition and morphology of the powder have been obtained by using EDAX and SEM analysis respectively. While the saturation magnetisation decreases with milling time, the coercivity increases. The width of the hyperfine field distributions obtained from Mossbauer studies shows that the alloy is highly disordered Atomic ordering is found to take place at a faster rate compared to that in the bulk alloy. (C) 1999 Acta Metallurgica Inc.

Crystal structure and thermal and electrical properties of the perovskite solid solution Nd1-xSrxFeO3-delta (0 <= x <= 0.4)

The crystal structure, thermal expansion and electrical conductivity of strontium-doped neodymium ferrite (Nd1-xSrxFeO3-delta where 0less than or equal toxless than or equal to0.4) were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction. The orthorhombic distortion decreases with increasing Sr substitution. The pseudocubic lattice parameter shows a minimum at x=0.3. The thermal expansion curves for x=0.2-0.4 displayed rapid increase in slope at higher temperatures. The electrical conductivity increased with Sr content and temperature. The calculated activation energies for electrical conduction decreased with increasing x. The electrical conductivity can be described by the small polaron hopping mechanism. The charge compensation for divalent ion on the A-site is provided by the formation of Fe4+ ions on the B site and vacancies on the oxygen sublattice. The results indicate two defect domains: for low values of x, the predominant defect is Fe4+ ions, whereas for higher values of x, oxygen vacancies dominate. (C) 2002 Elsevier Science B.V. All rights reserved.

Crystal structure, thermal expansion and electrical conductivity of Nd0.7Sr0.3Fe1-xCoxO3 (0 <= x <= 0.8)

The crystal structure, thermal expansion and electrical conductivity of the solid solution Nd0.7Sr0.3Fe1-xCoxO3 for 0 less than or equal to x less than or equal to 0.8 were investigated. All compositions had the GdFeO3-type orthorhombic perovskite structure. The lattice parameters were determined at room temperature by X-ray powder diffraction (XRPD). The pseudo-cubic lattice constant decreased continuously with x. The average linear thermal expansion coefficient (TEC) in the temperature range from 573 to 973 K was found to increase with x. The thermal expansion curves for all values of x displayed rapid increase in slope at high temperatures. The electrical conductivity increased with x for the entire temperature range of measurement. The calculated activation energy values indicate that electrical conduction takes place primarily by the small polaron hopping mechanism. The charge compensation for the divalent ion on the A-site is provided by the formation of Fe4+ ions on the B-site (in preference to Co4+ ions) and vacancies on the oxygen sublattice for low values of x. The large increase in the conductivity with x in the range from 0.6 to 0.8 is attributed to the substitution of Fe4+ ions by Co4+ ions. The Fe site has a lower small polaron site energy than Co and hence behaves like a carrier trap, thereby drastically reducing the conductivity. The non-linear behaviour in the dependence of log sigmaT with reciprocal temperature can be attributed to the generation of additional charge carriers with increasing temperature by the charge disproportionation of Co3+ ions. (C) 2002 Elsevier Science B.V. All rights reserved.

High temperature phase chemistry of system Eu-Pd-O

An isothermal section of the phase diagram for the system Eu - Pd - O at 1223 K has been established by equilibration of samples representing 20 different compositions, and phase identification after quenching by optical and scanning electron microscopy, X-ray powder diffraction, and energy dispersive spectroscopy. Three ternary oxides, Eu4PdO7, Eu2PdO4, and Eu2Pd2O5, were identified. Liquid alloys and the intermetallic compounds EuPd2 and EuPd3 were found to be in equilibrium with EuO. The compound EuPd3 was also found to coexist separately with Eu3O4 and Eu2O3. The oxide phase in equilibrium with EuPd5 and Pd rich solid solution was Eu2O3. Based on the phase relations, four solid state cells were designed to measure the Gibbs energies of formation of the three ternary oxides in the temperature range from 925 to 1350 K. Although three cells are sufficient to obtain the properties of the three compounds, the fourth cell was deployed to crosscheck the data. An advanced version of the solid state cell incorporating a buffer electrode with yttria stabilised zirconia solid electrolyte and pure oxygen gas at a pressure of 0.1 MPa as the reference electrode was used for high temperature thermodynamic measurements. Equations for the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides Eu2O3 with C type structure and PdO have been established. Based on the thermodynamic information, isothermal chemical potential diagrams and isobaric phase diagrams for the system Eu - Pd - O have been developed.

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

The thermodynamics and phase behaviour of Tb2Pd2O5 and Er2Pd2O5

Isothermal sections of the phase diagrams for the systems Ln-Pd-O (with Ln = Tb or Er) have been established by equilibration of samples at T = 1223 K, and phase identification after quenching by optical and scanning electron microscopy (OM, SEM), energy dispersive spectroscopy (EDS), and X-ray powder diffraction (XRPD). Two oxide phases were stable along the binary Tb-O: Tb2O3+x, a phase of variable composition, and Tb7O12 at T = 1223K. The oxide PdO was not stable at this temperature. Only one ternary oxide Tb2Pd2O5 was identified in the Tb-Pd-O system. No ternary compound was found in the system Er-Pd-O at T = 1223K. However, the compound Er2Pd2O5 could be synthesized at T = 1075 K by the hydrothermal route. In both systems, the alloys and inter-metallic compounds were all found to be in equilibrium with the lanthanide sesquioxide Ln(2)O(3) (where Ln is either Tb or Er). Two solid-state cells, each incorporating a buffer electrode, were designed to measure the Gibbs energy of formation of the ternary oxides, using yttria-stabilized zirconia as the solid electrolyte and pure oxygen gas as the reference electrode. Electromotive force measurements were conducted in the temperature range (900-1275) K for Th-Pd-O system, and at temperatures from (900-1075) K for the system Er-Pd-O. The standard Gibbs energy of formation Delta(f)G(m)degrees,, of the inter-oxide compounds from their component binary oxides Ln(2)O(3) and PdO are represented by equations linear in temperature. Isothermal chemical potential diagrams for the systems Ln-Pd-O (with Ln = Tb or Er) are developed based on the thermodynamic information. (C) 2002 Elsevier Science Ltd. All rights reserved.

Influence of temperature and strain rate on the flow stress of an FeAl alloy

The deformation behavior of an FeAl alloy processed by hot extrusion of water atomized powder has been investigated. Compression tests are performed in the temperature range 1073–1423 K and in the strain rate range 0.001–100 s−1 up to a true plastic strain of 0.5. The flow stress has been found to be strongly dependent on temperature as well as strain rate. The stress exponent in the power law rate equation is estimated to be in the range 7.0–4.0, decreasing with temperature. The activation energy for plastic flow in the range 1073–1373 K varies from 430 kJ mol−1 at low stresses to 340 kJ mol−1 at high stresses. However, it is fairly independent of strain rate and strain. The activation area has similarly shown a stress dependence and lies in the range 160–45b2. At 1423 K and at strain rates lower than 0.1 s−1 a strain rate sensitivity of 0.3 is observed with an associated activation energy of 375 kJ mol−1. The plastic flow in the entire range of temperature and strain rate investigated appears to be controlled by a diffusion mechanism. The results have revealed that it is possible to process the alloy by superplastic forming in the range 1373–1423 K at strain rates lower than 0.1 s−1.

Gas Sensing Properties of Tin Oxide Powder Synthesized in the Presence of Surfactants

Nanocrystalline tin oxide powder was prepared using a solution precipitation technique after adding the surfactant sodium bis (2-ethylhexyl) sulfosuccinate (AOT). Powders were characterized using X-ray diffraction (XRD), surface area (BET) and transmission electron microscopy (TEM). The gas sensitivity for surfactant added powders increased for liquid petroleum gas (LPG) as well as compressed natural gas (CNG), due to the decreased particle size and the increased surface area. The LPG gas sensitivity increased several times using phosphorus treated surfactant AOT.

Mixed ionic and electronic conduction in zirconia and its applications in metallurgy

Mixed ionic and electronic conduction in Zr02-based solid electrolytes was studied.The effect of impurities and second-phase particles on the mixed conduction parameter, P,, was measured for different types of ZrOZ electrolytes. The performance of solid-state sensors incorporating ZrOZ electrolytes is sometimes limited by electronic conduction in ZrOZ, especially at temperatures >I800 K. Methods for eliminating or minimizing errors in measured emf due to electronically driven transport of oxygen anions are discussed. Examples include probes for monitoring oxygen content in liquid steel as well as the newly developed sulfur sensor based on a ZrOz(Ca0) + CaS electrolyte. The use of mixed conducting ZrOZ as a semipermeable membrane or chemically selective sieve for oxygen at high temperatures is discussed. Oxygen transport from liquid iron to CO + C& gas mixtures through a ZrOZ membrane driven by a chemical potential gradient, in the absence of electrical leads or imposed potentials, was experimentally observed.

Crystal Structure, Thermal Expansion and ElectricaH Conductivity of Yo.sCao.2Fel-x Mnx03+o (0 < x < 1.0)

The crystal structure, thennal expansion and electrical conductivity of the solid solutions YOgCao.2Fel-x MnxOJ+c5 (0 ~ x ~ 1.0) were investigated. All compositions had the GdFeOrtype orthorhombic perovskite structure with trace amounts of a second phase present in case of x = 0.8 and 1.0. The lattice parameters were detennined at room tempe'rature by using X-ray powder diffraction (XRPD). The pseudocubic lattice constant decreased with increasing x. The average I inear thermal expansion coefficient (anv) in the temperature range from 673 to 973 K showed negligible change with x up to x = 0.4. The thennal expansion curve for x = I had a slope approaching zero in the temperature range from 648 to 948 K. The calculated activation energy values for electrical conduction indicate that conduction occurs primarily by the small polaron hopping mechanism. The drastic drop in electrical conductivity for a small addition of Mn (0 ~ x ~ 0.2) is caused by the preferential fonnation of Mn4t ion~ (rather than Fe4 +) which act as carrier traps. This continues till the charge compensation for the divalent ions on the A-site is complete. The results indicate that with further increase in manganese content (beyond x =0.4) in the solid solutions, there is an increase in exc :::ss oxygen and consequently, a small increase in Mn'll il>I1~, which are charge compensated by the formation of cation vancancies.