Synthesis of Cuprates of Perovskite Structure in the Ba-Pb-Cu-O, Ba-Bi-Cu-O, and Ba-Pb-Tl-Cu-O Systems: Possible High Tc Superconductivity in a Perovskite-like Phase in the Ba-Pb-Tl-Cu-O System

Cubic cuprates (a not, vert, similar 18.6 Å) with a BaCuO2-type structure were obtained in the Ba-Pb-Cu-O and Ba-Bi-Cu-O systems by the reaction of the component oxides at a high temperature (1370-1420 K), followed by quenching. By annealing these phases in oxygen at 1070-1120 K, perovskite-like phase (a not, vert, similar 4.3 Å) of the formulae BaPb1-xCuxO3-y and BaBi1-xCuxO3-y (0 < x ? 0.5) were obtained. A perovskite of nominal composition BaPb0.25Tl0.25 Cu0.5O3-y, prepared by a similar procedure, was found to be superconducting with a Tc of not, vert, similar 70 K.

Thickness-dependent fcc-hcp phase transformation in polycrystalline titanium thin films

Polycrystalline Ti thin films are shown to gradually transform from face-centered cubic (fcc) to hexagonal close-packed structure (hcp) with increasing film thickness. Diffraction stress analysis revealed that the fcc phase is formed in a highly compressive hcp matrix (>= 2 GPa), the magnitude of which decreases with increasing film thickness. A correlation between stress and crystallographic texture vis-a-vis the fcc-hcp phase transformation has been established. The total free energy change of the system upon phase transformation calculated using the experimental results shows that the fcc-hcp transformation is theoretically possible in the investigated film thickness regime (144-720 nm) and the hcp structure is stable for films thicker than 720 nm, whereas the fcc structure can be stabilized in Ti films much thinner than 144 nm. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Metastable phase formation during mechanical alloying of Al-Ge and Al-Si alloys

In this paper we report the mechanical alloying behaviour of elemental aluminium with diamond cubic elements Ge and Si. A metastable crystalline phase with rhombohedral crystal structure forms in Al-70 Ge-30 and Al-60 Ge-40 alloy compositions. The phase always coexists with elemental constituents and decomposes over a broad temperature range. No such metastable phase could be observed in the Al-Si system. We also report X-ray diffractometry and differential scanning calorimetry results suggestive of amorphization. Finally a comparison was made of the present result with that obtained in rapid solidification.

Role of B2O3 on the phase stability and long phosphorescence of SrAl2O4 : Eu, Dy

The role of B2O3 addition on the long phosphorescence of SrAl2O4:Eu2+, Dy3+ has been investigated. B2O3 is just not an inert high temperature solvent (flux) to accelerate grain growth, according to SEM results. B2O3 has a substitutional effect, even at low concentrations. by way of incorporation of BO4 in the corner-shared AlO4 framework of the distorted 'stuffed' tridymite structure of SrAl2O4. which is discernible from the IR and solid-state MAS NMR spectral data. With increasing concentrations, B2O3 reacts with SrAl2O4 to form Sr4Al4O25 together with Sr-borate (SrB2O4) as the glassy phase, as evidenced by XRD and SEM studies. At high B2O3 contents, Sr4Al14O25 converts to SrAl2B2O7 (cubic and hexagonal), SrAl12O19 and Sr-borate (SrB4O7) glass. Sr4Al14O25:Eu2+, Dy3+ has also been independently synthesized to realize the blue emitting (lambda(em)approximate to490 nm) phosphor. The afterglow decay as well as thermoluminescence studies reveal that Sr4Al14O25:Eu, Dy exhibits equally long phosphorescence as that of SrAl2O4:Eu2+, Dy3+. In both cases, long phosphorescence is noticed only when BO4 is present along with Dy3+ and Eu2+. Here Dy3+ because of its higher charge density than Eu2+ prefers to occupy the Sr sites in the neighbourhood of BO4, as the effective charge on borate is more negative than that of AlO4. Thus. Dy3+ forms a substitutional defect complex with borate and acts as an acceptor-type defect center. These defects Eu2+ ions and the subsequent thermal release of hole at room temperature followed by the trap the hole generated by the excitation of recombination with electron resulting in the long persistent phosphorescence. (C) 2003 Elsevier Science B.V. All rights reserved.

Size and temperature dependent stability and phase transformation in single-crystal zirconium nanowire

A novel size dependent FCC (face-centered-cubic) -> HCP (hexagonally-closed-pack) phase transformation and stability of an initial FCC zirconium nanowire are studied. FCC zirconium nanowires with cross-sectional dimensions < 20 are found unstable in nature, and they undergo a FCC -> HCP phase transformation, which is driven by tensile surface stress induced high internal compressive stresses. FCC nanowire with cross-sectional dimensions > 20 , in which surface stresses are not enough to drive the phase transformation, show meta-stability. In such a case, an external kinetic energy in the form of thermal heating is required to overcome the energy barrier and achieve FCC -> HCP phase transformation. The FCC-HCP transition pathway is also studied using Nudged Elastic Band (NEB) method, to further confirm the size dependent stability/metastability of Zr nanowires. We also show size dependent critical temperature, which is required for complete phase transformation of a metastable-FCC nanowire.

Current‐limiting action of mixed‐phase BaTiO3 ceramic semiconductors

Stable and highly reproducible current‐limiting characteristics are observed for polycrystalline ceramics prepared by sintering mixtures of coarse‐grained, donor‐doped BaTiO3 (tetragonal) as the major phase and ultrafine, undoped cubic perovskite such as BaSnO3, BaZrO 3, SrTiO3, or BaTiO3 (cubic). The linear current‐voltage (I‐V) relation changes over to current limiting as the field strength increases, when thermal equilibrium is attained. The grain‐boundary layers with low donor and high Sn, Zr, or Sr have depleted charge carrier density as compared to that in the grain bulk. The voltage drop at the grain‐boundary layers diminishes the temperature gradient between the interior and surface regions.

The study of pressure induced structural phase transition in spin-frustrated Yb2Ti2O7 pyrochlore

Our in situ x-ray diffraction and Raman measurements of Yb2Ti2O7 pyrochlore show that it undergoes a reversible structural phase transition from cubic pyrochlore to a monoclinic phase at similar to 28.6 GPa. Analysis of the x-ray data shows the transition to be thermodynamically first order and the high pressure phase to be substitutionally disordered. These experimental results are supported by our first principles calculations. (C) 2012 American Institute of Physics. [doi:10.1063/1.3681300]

Temperature gradient induced phase transitions and morphological changes in diamond thin film

The diamond films were deposited onto a wurtzite gallium nitride (GaN) thin film substrate using hot-filament chemical vapor deposition (HFCVD). During the film deposition a lateral temperature gradient was imposed across the substrate by inclining the substrate. As grown films predominantly showed the hexagonal phase, when no inclination was applied to the substrate. Tilting the substrate with respect to the heating filament by 6 degrees imposed a lateral temperature gradient across the substrate, which induced the formation of a cubic diamond phase. Diamond grains were predominantly oriented in the (100) direction. However, a further increase in the substrate tilt angle to 12 degrees, resulted in grains oriented in the (111) direction. The growth rate and hence the morphology of diamond grains varied along the inclined substrate. The present study focuses on the measurements of dominant phase formation and crystal orientation with varying substrate inclination using orientation-imaging microscopy (OIM). This technique enables direct examination of individual diamond grains and their crystallographic orientation. (C) 2012 Elsevier B.V. All rights reserved.

Structural and phase dependent thermo and photoluminescent properties of Dy(OH)(3) and Dy2O3 nanorods

Hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods were prepared by hydrothermal method. Dy(OH)(3) nanorods was directly obtained at 180 degrees C for 20 h after hydrothermal treatment whereas subsequently heat treatment at 750 degrees C for 2 h gives pure cubic Dy2O3. SEM micrographs reveal that needle shaped rods with different sizes were observed in both the phases. TEM results also confirm this. The TL response of hexagonal Dy(OH)(3) and cubic Dy2O3 nanorods have been analyzed for gamma-irradiation over a wide range of exposures (1-5 kGy). TL glow peak intensity increases with gamma dose in both the phases. The activation energy (E), order of kinetics (6), and frequency factor (s) for both the phases have been determined using Chen's peak shape method. The simple glow curve shape, structure and linear response to gamma-irradiation over a large span of exposures makes the cubic Dy2O3 as a useful dosimetric material to estimate high exposures of gamma-rays. (c) 2012 Elsevier Ltd. All rights reserved.

Nucleation-Growth Mode of Cubic-Tetragonal Transition with Coexistence of Phases over a Wide Temperature Interval in the High Temperature Ferroelectric Systems PbTiO3-BiMeO3:Me = Sc , and Zn1/2Ti1/2

Temperature dependent X-ray powder diffraction and dielectric studies have been carried out on tetragonal compositions of (1-x) PbTiO 3(x) BiMeO 3; Me similar to Sc and Zn 1/2 Ti 1/2. The cubic and the tetragonal phases coexist over more than 100 degrees C for 0.70 PbTiO 30.3 Bi ( Zn 1/2 Ti 1/2) O 3 and 0.66 PbTiO 30.34 BiScO 3. The wide temperature range of phase coexistence is shown to be an intrinsic feature of the system, and is attributed to the increase in the degree of the covalent character of the ( Pb +Bi ) O bond with increasing concentration of Bi at the Pb -site. The d-values of the {111} planes of the coexisting phases are nearly identical, suggesting this plane to be the invariant plane for the martensitic type cubic-tetragonal transformation occurring in these systems.

Thermodynamics of TmRhO3, Phase Equilibria, and Chemical Potentials in the System Tm-Rh-O

Phase equilibria in the system Tm-Rh-O at 1200 K is established by isothermal equilibration of selected compositions and phase identification after quenching to room temperature. Six intermetallic phases (Tm3Rh, Tm7Rh3, Tm5Rh3, Tm3Rh2, TmRh, TmRh2 +/-delta) and a ternary oxide TmRhO3 are identified. Based on experimentally determined phase relations, a solid-state electrochemical cell is devised to measure the standard free energy of formation of orthorhombic perovskite TmRhO3 from cubic Tm2O3 and beta-Rh2O3 in the temperature range from (900 to 1300) K. The results can be summarized as: Delta G(f,ox)(o) +/- 104/J.mol(-1) = -46474 + 3.925(T/K). Invoking the Neumann-Kopp rule, the standard enthalpy of formation of TmRhO3 from its constituent elements at 298.15 K is estimated as -1193.89 (+/- 2.86) kJ.mol(-1). The standard entropy of TmRhO3 at 298.15 K is evaluated as 103.8 (+/- 1.6) J.mol(-1).K-1. The oxygen potential-composition diagram and three-dimensional chemical potential diagram at 1200 K and temperature-composition diagrams at constant partial pressures of oxygen are computed from thermodynamic data. The compound TmRhO3 decomposes at 1688 (+/- 2) K in pure oxygen and at 1583 (+/- 2) K in air at standard pressure.

Temperature dependent structural and dielectric investigations of PbZr0.5Ti0.5O3 solid solution at the morphotropic phase boundary

PbZr1-xTixO3 ceramics synthesised by low temperature calcination followed by sintering at 1280 degrees C show a Morphotropic Phase Boundary (MPB) for compositions of x=0.44-0.51. The morphotropic phase boundary is wider for samples with smaller grain sizes due to the synthesis route. A Rietveld analysis is performed on a composition of x=0.5 composition to quantify the phase fractions of the tetragonal and monoclinic phases present in the PZT system. Temperature dependent X-ray diffraction and dielectric studies of PbZr0.5Ti0.5O3 composition demonstrated a phase transformation from monoclinic to tetragonal at 270 degrees C followed by a ferroelectric tetragonal to a paraelectric cubic transition at 370 degrees C. Thus, the poling of these ceramics should be performed below 270 degrees C to benefit from the presence of a monoclinic phase. (C) 2012 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

Effect of Manganese (II) Oxide on microstructure and ionic transport properties of nanostructured cubic zirconia

Effect of MnO addition on microstructure and ionic transport properties of nanocrystalline cubic(c)-ZrO2 is reported. Monoclinic (m) ZrO2 powders with 10-30 mol% MnO powder are mechanically alloyed in a planetary ball mill at room temperature for 10 h and annealed at 550 degrees C for 6 h. In all compositions m-ZrO2 transforms completely to nanocrystalline c-ZrO2 phase and MnO is fully incorporated into c-ZrO2 lattice. Rietveld's refinement technique is employed for detailed microstructure analysis by analyzing XRD patterns. High resolution transmission electron microscopy (HRTEM) analysis confirms the complete formation of c-ZrO2 phase. Presence of stoichiometric Mn in c-ZrO2 powder is confirmed by Electron Probe Microscopy analysis. XPS analysis reveals that Mn is mostly in Mn2+ oxidation state. A correlation between lattice parameter and oxygen vacancy is established. A detailed ionic conductivity measurement in the 250 degrees-575 degrees C temperature range describes the effect of MnO on conductivity of c-ZrO2. The ionic conductivity (s) of 30 mol% MnO alloyed ZrO2 at 550 degrees C is 0.04 s cm(-1). Electrical relaxation studies are carried out by impedance and modulus spectroscopy. Relaxation frequency is found to increase with temperature and MnO mol fraction. Electrical characterization predicts that these compounds have potentials for use as solid oxide fuel cell electrolyte material. (C) 2015 Elsevier Ltd. All rights reserved.

Effect of processing route on phase stability in equiatomic multicomponent Ti20Fe20Ni20Co20Cu20 high entropy alloy

The evolution of microstructure and phase formation in equiatomic Ti20Fe20Ni20Co20Cu20 high entropy alloy synthesised by conventional arc melting followed with suction casting and ball milling with spark plasma sintering route is distinctly different. The cast microstructure exhibits one body centre cubic and two face centre cubic high entropy phases based on titanium, cobalt and copper respectively along with a eutectic containing Ti2Ni type Laves phase. On the contrary, spinodal decomposed microstructure consisting of cobalt and copper solid solution is obtained in the sintered sample. However, long term annealing of cast sample at 950 degrees C reveals a eutectoid transformation with different phases than the cast sample. The aforementioned observations are discussed using CALPHAD thermodynamical approach and available literature.