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.

Implementation of conditional phase-shift gate for quantum information processing by NMR, using transition-selective pulses

Experimental realization of quantum information processing in the field of nuclear magnetic resonance (NMR) has been well established. Implementation of conditional phase-shift gate has been a significant step, which has lead to realization of important algorithms such as Grover's search algorithm and quantum Fourier transform. This gate has so far been implemented in NMR by using coupling evolution method. We demonstrate here the implementation of the conditional phase-shift gate using transition selective pulses. As an application of the gate, we demonstrate Grover's search algorithm and quantum Fourier transform by simulations and experiments using transition selective pulses. (C) 2002 Elsevier Science (USA). All rights reserved.

Phase diagram for the system Nd-Mn-O and thermodynamic properties of NdMnO3 and NdMn2O5

Studies on the phase relations in the system Nd-Mn-O at 1223 K showed two stable ternary compounds, NdMnO3 and NdMn2O5. An isothermal section of the ternary phase diagram for the system Nd-Mn-O was constructed based on phase analysis of samples quenched after equilibration using XRPD and EDS. An advanced version of the solid-state cell incorporating a buffer electrode was used to determine the Gibbs energies of decomposition of NdMnO3 and NdMn2O5 in the temperature range from 925 to 1400 K. Pure oxygen gas at 0.1 MPa was used as the reference electrode, and yttria-stabilized zirconia as the solid electrolyte. The buffer electrode was designed to prevent polarization of the three-phase electrode and ensure accurate data. The measured oxygen potential corresponding to the reaction,2 Nd2O3 + 4 MnO + O-2 --> 4 NdMnO3 can be represented by the equation,Amu(o2) / J.mol(-1) (+/-580) = -523 960 + 170.96 (T/K)Similarly, for the formation of NdMn2O5 according to the reaction,3 NdMnO3 + Mn3O4 + O-2 --> 3 NdMn2O5 Amu(o2) / J.mol(-1) (+/-660) = - 269 390 + 181.74 (T/K) (C) 2002 Elsevier Science Ltd. All rights reserved.

Phase diagram of a two-species lattice model with a linear instability

We discuss the properties of a one-dimensional lattice model of a driven system with two species of particles in which the mobility of one species depends on the density of the other. This model was introduced by Lahiri and Ramaswamy (Phys. Rev. Lett., 79, 1150 (1997)) in the context of sedimenting colloidal crystals, and its continuum version was shown to exhibit an instability arising from linear gradient couplings. In this paper we review recent progress in understanding the full phase diagram of the model. There are three phases. In the first, the steady state can be determined exactly along a representative locus using the condition of detailed balance. The system shows phase separation of an exceptionally robust sort, termed strong phase separation, which survives at all temperatures. The second phase arises in the threshold case where the first species evolves independently of the second, but the fluctuations of the first influence the evolution of the second, as in the passive scalar problem. The second species then shows phase separation of a delicate sort, in which long-range order coexists with fluctuations which do not damp down in the large-size limit. This fluctuation-dominated phase ordering is associated with power law decays in cluster size distributions and a breakdown of the Porod law. The third phase is one with a uniform overall density, and along a representative locus the steady state is shown to have product measure form. Density fluctuations are transported by two kinematic waves, each involving both species and coupled at the nonlinear level. Their dissipation properties are governed by the symmetries of these couplings, which depend on the overall densities. In the most interesting case,, the dissipation of the two modes is characterized by different critical exponents, despite the nonlinear coupling.

Phase transformation and semiconductor-metal transition in thin films of VO2 deposited by low-pressure metalorganic chemical vapor deposition

Thin films of the semiconducting, monoclinic vanadium dioxide, VO2(M) have been prepared on ordinary glass by two methods: directly by low-pressure metalorganic chemical vapor deposition (MOCVD), and by argon-annealing films of the VO2(B) phase deposited by MOCVD. The composition and microstructure of the films have been examined by x-ray diffraction, scanning electron microscopy, and transmission electron microscopy. Films made predominantly of either the B or the M phase, as deposited, can only be obtained over a narrow range of deposition temperatures. At the lower end of this temperature range, the as-deposited films are strongly oriented, although the substrate is glass. This can be understood from the drive to minimize surface energy. Films of the B phase have a platelet morphology, which leads to an unusual microstructure at the lower-deposition temperatures. Those grown at similar to370 degreesC convert to the metallic, rutile (R) phase when annealed at 550 degreesC, whereas those deposited at 420 degreesC transform to the R phase only at 580 degreesC. (When cooled to room temperature, the annealed films convert reversibly from the R phase to the M phase.) Electron microscopy shows that annealing leads to disintegration of the single crystalline VO2(B) platelets into small crystallites of VO2(R), although the platelet morphology is retained. When the annealing temperature is relatively low, these crystallites are nanometer sized. At a higher-annealing temperature, the transformation leads to well-connected and similarly oriented large grains of VO2(R), enveloped in the original platelet. The semiconductor-metal transition near 68 degreesC leads to a large jump in resistivity in all the VO2(M) films, nearly as large as in epitaxial films on single-crystal substrates. When the annealed films contain well-connected large grains, the transition is very sharp. Even when preferred orientation is present, the transition is not as sharp in as-deposited VO2(M), because the crystallites are not densely packed as in annealed VO2(B). However, the high degree of orientation in these films leads to a narrow temperature hysteresis. (C) 2002 American Institute of Physics.

Pressure-induced phase transitions in alpha-ZrMo2O8

We report high-pressure Raman, infrared (IR), and optical-absorption spectra of alpha-ZrMo2O8 (trigonal) up to 38 GPa at room temperature. The spectroscopic studies are consistent with diffraction results that show that alpha-ZrMo2O8 transforms into delta-ZrMo2O8 (monoclinic) at about 1 GPa and the delta phase converts to the epsilon phase (trielinic) at about 2.0 GPa. Optical-absorption measurements give an estimate of the band gap of about 0.6 eV at the lowest pressure. Band-gap changes with pressure are confirmed with visual observations. ZrMo2O8 changes from transparent at 5 GPa to yellow at 10 GPa, red at 18 GPa, and at about 30 GPa it becomes opaque.

Real-time kinetic analysis of hCG-monoclonal antibody interaction using radiolabeled hCG probe: presence of two forms of Ag-mAb complex as revealed by solid phase dissociation studies

Real-time kinetics of ligand-ligate interaction has predominantly been studied by either fluorescence or surface plasmon resonance based methods. Almost all such studies are based on association between the ligand and the ligate. This paper reports our analysis of dissociation data of monoclonal antibody-antigen (hCG) system using radio-iodinated hCG as a probe and nitrocellulose as a solid support to immobilize mAb. The data was analyzed quantitatively for a one-step and a two-step model. The data fits well into the two-step model. We also found that a fraction of what is bound is non-dissociable (tight-binding portion (TBP)). The TBP was neither an artifact of immobilization nor does it interfere with analysis. It was present when the reaction was carried out in homogeneous solution in liquid phase. The rate constants obtained from the two methods were comparable. The work reported here shows that real-time kinetics of other ligand-ligate interaction can be studied using nitrocellulose as a solid support. (C) 2002 Elsevier Science B.V. All rights reserved.

Spin-orbital ordering and mesoscopic phase separation in the double perovskite Ca2FeReO6

Neutron powder diffraction measurements on Ca2FeReO6 reveal that this double perovskite orders ferrimagnetically and shows anomalous lattice parameter behavior below T-C=521 K. Below similar to300 K and similar to160 K we observe that the high-T monoclinic crystal structure separates into two and three monoclinic phases, respectively. A magnetic field suppresses the additional phases at low T in favor of the highest-T phase. These manifestations of the orbital degree of freedom of Re 5d electrons indicate that these electrons are strongly correlated and the title compound is a Mott insulator, with competing spin-orbitally ordered states.

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.

Direct measurement of phase of foreward-scattered light using polarization heterodyne interferometer

We describe direct measurement of phase of ballistic photons transmitted through objects hidden in a turbid medium using a polarization interferometer employing a rotating analyzer. The unwrapped phase difference measurements from interferometry was possible for medium levels of turbidity and accurate phase measurement from the sinusoidal intensity was not detectable when l/l* is increased beyond 4.3. The measured phase on reconstruction using standard tomographic algorithms resulted in the recovery of the refractive index profile of the object hidden in the turbid medium.

Influence of martensite content and morphology on the toughness and fatigue behavior of high-martensite dual-phase steels

A series of high-martensite dual-phase (HMDP) steels exhibiting a 0.3 to 0.8 volume fraction of martensite (V m ), produced by intermediate quenching (IQ) of a vanadium and boron-containing microalloyed steel, have been studied for toughness and fatigue behavior to supplement the contents of a recent report by the present authors on the unusual tensile behavior of these steels. The studies included assessment of the quasi-static and dynamic fracture toughness and fatigue-crack growth (FCG) behavior of the developed steels. The experimental results show that the quasi-static fracturetoughness (K ICV ) increases with increasing V m in the range between V m =0.3 and 0.6 and then decreases, whereas the dynamic fracture-toughness parameters (K ID , K D , and J ID ) exhibit a significant increase in their magnitudes for steels containing 0.45 to 0.60 V m before achieving a saturation plateau. Both the quasi-static and dynamic fracture-toughness values exhibit the best range of toughnesses for specimens containing approximately equal amounts of precipitate-free ferrite and martensite in a refined microstructural state. The magnitudes of the fatigue threshold in HMDP steels, for V m between 0.55 and 0.60, appear to be superior to those of structural steels of a similar strength level. The Paris-law exponents (m) for the developed HMDP steels increase with increasing V m , with an attendant decrease in the pre-exponential factor (C).

Influence of synthesis route on structural phase transition in YBa2−xLaxCu3Oy (0

The compounds YBa2−xLaxCu3Oy, with compositions (0phase occurred at (0.15phase formation temperature is influenced by the starting materials used and ionic size considerations. These factors are shown to determine the composition at which the changeover from orthorhombic (superconducting) to tetragonal (non-superconducting) phase transition (O–T transition) occurs.

Novel phase-transition behavior near liquid/liquid critical points of aqueous solutions: Formation of a third phase at the interface

We report a novel phase behavior in aqueous solutions of simple organic solutes near their liquid/liquid critical points, where a solid-like third phase appears at the liquid/liquid interface. The phenomenon has been found in three different laboratories. It appears in many aqueous systems of organic solutes and becomes enhanced upon the addition of salt to these solutions.