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.

PL due to Discrete Gap Levels in Some Chalcogenide Glasses- A Configurational Coordinate Diagram Illustration

Photoluminescence (PL) studies were carried out on a-Se and a few Ge20Se80−xBix and Ge20Se70−xBixTe10 bulk glassy semiconductors at 4.2 K with Ar+ laser as excitation source. While a-Se and samples with lesser at% of Bi show fine structured PL with a large Stokes shift, samples with higher at% of Bi did not show any detectable PL. The investigations show at least three radiative recombination transitions. Features extracted by deconvoluting the experimental spectra show that the discrete gap levels associated with the inherent coordination defects are involved in the PL transitions. Absence of PL in samples with higher Bi at% are explained on the basis of nonradiative transition mechanisms. Overall PL mechanism involving gap levels in chalcogenide glasses is illustrated with the help of a configurational coordinate diagram.

Identifying Robust Plans through Plan Diagram Reduction

Estimates of predicate selectivities by database query optimizers often differ significantly from those actually encountered during query execution, leading to poor plan choices and inflated response times. In this paper, we investigate mitigating this problem by replacing selectivity error-sensitive plan choices with alternative plans that provide robust performance. Our approach is based on the recent observation that even the complex and dense "plan diagrams" associated with industrial-strength optimizers can be efficiently reduced to "anorexic" equivalents featuring only a few plans, without materially impacting query processing quality. Extensive experimentation with a rich set of TPC-H and TPC-DS-based query templates in a variety of database environments indicate that plan diagram reduction typically retains plans that are substantially resistant to selectivity errors on the base relations. However, it can sometimes also be severely counter-productive, with the replacements performing much worse. We address this problem through a generalized mathematical characterization of plan cost behavior over the parameter space, which lends itself to efficient criteria of when it is safe to reduce. Our strategies are fully non-invasive and have been implemented in the Picasso optimizer visualization tool.

Multi-agent Search using Voronoi partitions

This paper addresses the problem of multiagent search in an unknown environment. The agents are autonomous in nature and are equipped with necessary sensors to carry out the search operation. The uncertainty, or lack of information about the search area is known a priori as a probability density function. The agents are deployed in an optimal way so as to maximize the one step uncertainty reduction. The agents continue to deploy themselves and reduce uncertainty till the uncertainty density is reduced over the search space below a minimum acceptable level. It has been shown, using LaSalle’s invariance principle, that a distributed control law which moves each of the agents towards the centroid of its Voronoi partition, modified by the sensor range leads to single step optimal deployment. This principle is now used to devise search trajectories for the agents. The simulations were carried out in 2D space with saturation on speeds of the agents. The results show that the control strategy per step indeed moves the agents to the respective centroid and the algorithm reduces the uncertainty distribution to the required level within a few steps.

The Co Cr S ternary diagram at 1223 K and applications to corrosion

Ternary phase relations in the Co-Cr-S system at 1223 K were determined using microprobe analysis of quenched samples. The results are consistent with the data available on the binary systems. A complete solid solution exists between cobalt monosulfide and chromium monosulfide. The CoCr2S4 thiospinel is the only ternary compound formed. A sulfur potential diagram was constructed for the region involving equilibrium between alloy and monosulfide based on thermodynamic data on the Co-Cr, Co-S, and Cr-S binary systems and the ternary information obtained in this study. The sulfidation behavior of Co-Cr alloys reported in the literature is discussed in light of the sulfur potential diagram.

A new matched thermochemical diagram for vacuum refining of nickel and cupronickel alloys

Sulfur and oxygen dissolved in nickel and cupronickel melts can be remwed as gaseous oxides of sulfur by a vacuum treatment. Presented in this paper is a new matched thermcxhemical disgran~ that permit.. direct evaluation of the equilibrium partial pressure of SO, as a function of temperature wer an alloy of specified compition. The matched thermochemical diagram consists of a central plot which shows the integral Gibbs' energy of mixing for the binary system SO, at different temperatures. The central plot is flanked on either side by terminal plots of the chemical potentials of oxygen and sulfur, as functions of temperature, for different alloy compositions. By projecting the chemical wtentials of oxygen and sulfur from the terminal lots on to the central diagram, ihe equilibrium partial pressure of S0,can be directly ;cad on the nomograms on the central plot at different temperatures. The matched therrnochemical diagrams are useful in assuring the efficiency of vacuum refining.

System Nd-Pd-O: Phase diagram and thermodynamic properties of oxides using a solid-state cell with advanced features

An isothermal section of the phase diagram for the system Nd-Pd-O at 1350 K has been established by equilibration of samples representing 13 different compositions and phase identification after quenching by optical and scanning electron microscopy, x-ray diffraction, and energy dispersive analysis of x-rays. The binary oxides PdO and NdO were not stable at 1350 K. Two ternary oxides Nd4PdO7 and Nd2Pd2O5 were identified. Solid and liquid alloys, as well as the intermetallics NdPd3 and NdPd5, were found to be in equilibrium with Nd2O3. Based on the phase relations, three solidstate cells were designed to measure the Gibbs energies of formation of PdO and the two ternary oxides. An advanced version of the solid-state cell incorporating a buffer electrode was used for high-temperature thermodynamic measurements. The function of the buffer electrode, placed between reference and working electrodes, was to absorb the electrochemical flux of the mobile species through the solid electrolyte caused by trace electronic conductivity. The buffer electrode prevented polarization of the measuring electrode and ensured accurate data. Yttria-stabilized zirconia was used as the solid electrolyte and pure oxygen gas at a pressure of 0.1 MP a as the reference electrode. Electromotive force measurements, conducted from 950 to 1425 K, indicated the presence of a third ternary oxide Nd2PdO4, stable below 1135 (±10) K. Additional cells were designed to study this compound. The standard Gibbs energy of formation of PdO (†f G 0) was measured from 775 to 1125 Kusing two separate cell designs against the primary reference standard for oxygen chemical potential. Based on the thermodynamic information, chemical potential diagrams for the system Nd-Pd-O were also developed.

System Cu-Rh-O: Phase diagram and thermodynamic properties of ternary oxides CuRhO2 and CuRh204

An isothermal section of the phase diagram for the system Cu-Rh-O at 1273 K has been established by equilibration of samples representing eighteen different compositions, and phase identification after quenching by optical and scanning electron microscopy (SEM), X-ray diffraction (XRD), and energy dispersive analysis of X-rays (EDX). In addition to the binary oxides Cu2O, CuO, and Rh2O3, two ternary oxides CuRhO2 and CuRh2O4 were identified. Both the ternary oxides were in equilibrium with metallic Rh. There was no evidence of the oxide Cu2Rh2O5 reported in the literature. Solid alloys were found to be in equilibrium with Cu2O. Based on the phase relations, two solid-state cells were designed to measure the Gibbs energies of formation of the two ternary oxides. Yttria-stabilized zirconia was used as the solid electrolyte, and an equimolar mixture of Rh+Rh2O3 as the reference electrode. The reference electrode was selected to generate a small electromotive force (emf), and thus minimize polarization of the three-phase electrode. When the driving force for oxygen transport through the solid electrolyte is small, electrochemical flux of oxygen from the high oxygen potential electrode to the low potential electrode is negligible. The measurements were conducted in the temperature range from 900 to 1300 K. The thermodynamic data can be represented by the following equations: {fx741-1} where Δf(ox) G o is the standard Gibbs energy of formation of the interoxide compounds from their component binary oxides. Based on the thermodynamic information, chemical potential diagrams for the system Cu-Rh-O were developed.

Performance of a class of multi-robot deploy and search strategies based on centroidal voronoi configurations

This article considers a class of deploy and search strategies for multi-robot systems and evaluates their performance. The application framework used is deployment of a system of autonomous mobile robots equipped with required sensors in a search space to gather information. The lack of information about the search space is modelled as an uncertainty density distribution. The agents are deployed to maximise single-step search effectiveness. The centroidal Voronoi configuration, which achieves a locally optimal deployment, forms the basis for sequential deploy and search (SDS) and combined deploy and search (CDS) strategies. Completeness results are provided for both search strategies. The deployment strategy is analysed in the presence of constraints on robot speed and limit on sensor range for the convergence of trajectories with corresponding control laws responsible for the motion of robots. SDS and CDS strategies are compared with standard greedy and random search strategies on the basis of time taken to achieve reduction in the uncertainty density below a desired level. The simulation experiments reveal several important issues related to the dependence of the relative performances of the search strategies on parameters such as the number of robots, speed of robots and their sensor range limits.

Heterogeneous locational optimisation using a generalised Voronoi partition

In this paper a generalisation of the Voronoi partition is used for locational optimisation of facilities having different service capabilities and limited range or reach. The facilities can be stationary, such as base stations in a cellular network, hospitals, schools, etc., or mobile units, such as multiple unmanned aerial vehicles, automated guided vehicles, etc., carrying sensors, or mobile units carrying relief personnel and materials. An objective function for optimal deployment of the facilities is formulated, and its critical points are determined. The locally optimal deployment is shown to be a generalised centroidal Voronoi configuration in which the facilities are located at the centroids of the corresponding generalised Voronoi cells. The problem is formulated for more general mobile facilities, and formal results on the stability, convergence and spatial distribution of the proposed control laws responsible for the motion of the agents carrying facilities, under some constraints on the agents' speed and limit on the sensor range, are provided. The theoretical results are supported with illustrative simulation results.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.

Quantum Phase Diagram of One-Dimensional Spin and Hubbard Models with Transitions to Bond Order Wave Phases

Similar quantum phase diagrams and transitions are found for three classes of one-dimensional models with equally spaced sites, singlet ground states (GS), inversion symmetry at sites and a bond order wave (BOW) phase in some sectors. The models are frustrated spin-1/2 chains with variable range exchange, half-filled Hubbard models with spin-independent interactions and modified Hubbard models with site energies for describing organic charge transfer salts. In some range of parameters, the models have a first order quantum transition at which the GS expectation value of the sublattice spin < S-A(2)> of odd or even-numbered sites is discontinuous. There is an intermediate BOW phase for other model parameters that lead to two continuous quantum transitions with continuous < S-A(2)>. Exact diagonalization of finite systems and symmetry arguments provide a unified picture of familiar 1D models that have appeared separately in widely different contexts.