A thermodynamic study of liquid Cu-Cr alloys and metastable liquid immiscibility

he thermodynamic acitivity of chromium in liquid Cu-Cr alloys is measured in the temperature range from 1473 to 1873 K using the solid state cell: Pt, W, Cr + Cr2O3 |(Y2O3) ThO2|Cu - Cr + Cr2O3, Pt The activity of copper and the Gibbs energy of mixing of the liquid alloy are derived. Activities exhibit large positive deviations from Raoult's law. The mixing properties can be represented by a pseudo-subregular solution model in which the excess entropy has the same type of functional dependence on composition as the enthalpy of mixing: ΔGE = XCr(1 - XCr)[60880 - 18750 XCr)-- T(16.25 - 7.55 XCr)]J mol-1 Pure liquid Cu and Cr are taken as the reference states. The results predict a liquid-liquid metastable miscibility gap, with TC = 1787 (±3) K and XCr = 0.436 (±0.02), lying below the liquidus. The results obtained in this study are in general agreement with experimental information reported in the literature, but provide further refinement of the thermodynamic parameters.

Phase Equilibria in the System Al2O3-CaO-CoO and Gibbs Energy of Formation of Ca3CoAl4O10

An isothermal section of the system Al2O3-CaO-CoO at 1500 K has been established by equilibrating 22 samples of different compositions at high temperature and phase identification by optical and scanning electron microscopy, X-ray diffraction, and energy dispersive spectroscopy after quenching to room temperature. Only one quaternary oxide, Ca3CoAl4O10, was identified inside the ternary triangle. Based on the phase relations, a solid-state electrochemical cell was designed to measure the Gibbs energy of formation of Ca3CoAl4O10 in the temperature range from 1150 to 1500 K. Calcia-stabilized zirconia was used as the solid electrolyte and a mixture of Co + CoO as the reference electrode. The cell can be represented as: ( - )\textPt,\textCaAl 2 \textO 4 + \textCa 1 2 \textAl 1 4 \textO 3 3 + \textCa 3 \textCoAl 4 \textO 10 + \textCo//(CaO)ZrO 2 \text// \textCoO + \textCo,\text Pt ( + ). (−)PtCaAl2O4+Ca12Al14O33+Ca3CoAl4O10+Co//(CaO)ZrO2//CoO+Co Pt (+) From the emf of the cell, the standard Gibbs energy change for the Ca3CoAl4O10 formation reaction, CoO + 3/5CaAl2O4 + 1/5Ca12Al14O33 → Ca3CoAl4O10, is obtained as a function of temperature: \Updelta Gr\texto Unknown control sequence '\Updelta'/J mol−1 (±50) = −2673 + 0.289 (T/K). The standard Gibbs energy of formation of Ca3CoAl4O10 from its component binary oxides, Al2O3, CaO, and CoO is derived as a function of temperature. The standard entropy and enthalpy of formation of Ca3CoAl4O10 at 298.15 K are evaluated. Chemical potential diagrams for the system Al2O3-CaO-CoO at 1500 K are presented based on the results of this study and auxiliary information from the literature.

Thermodynamic properties of calcium titanates: CaTiO3, Ca4Ti3O10, and Ca3Ti2O7

The chemical potentials of CaO in two-phase fields (TiO2 + CaTiO3), (CaTiO3 + Ca4Ti3O10), and (Ca4Ti3O10 + Ca3Ti2O7) of the pseudo-binary system (CaO + TiO2) have been measured in the temperature range (900 to 1250) K, relative to pure CaO as the reference state, using solid-state galvanic cells incorporating single crystal CaF2 as the solid electrolyte. The cells were operated under pure oxygen at ambient pressure. The standard Gibbs free energies of formation of calcium titanates, CaTiO3, Ca4Ti3O10, and Ca3Ti2O7, from their component binary oxides were derived from the reversible e.m.f.s. The results can be summarised by the following equations: CaO(solid) + TiO2(solid) → CaTiO3(solid), ΔG° ± 85/(J · mol−1) = −80,140 − 6.302(T/K); 4CaO(solid) + 3TiO2(solid) → Ca4Ti3O10(solid), ΔG° ± 275/(J · mol−1) = −243,473 − 25.758(T/K); 3CaO(solid) + 2TiO2(solid) → Ca3Ti2O7(solid), ΔG° ± 185/(J · mol−1) = −164,217 − 16.838(T/K). The reference state for solid TiO2 is the rutile form. The results of this study are in good agreement with thermodynamic data for CaTiO3 reported in the literature. For Ca4Ti3O10 Gibbs free energy of formation obtained in this study differs significantly from that reported by Taylor and Schmalzried at T = 873 K. For Ca3Ti2O7 experimental measurements are not available in the literature for direct comparison with the results obtained in this study. Nevertheless, the standard entropy for Ca3Ti2O7 at T = 298.15 K estimated from the results of this study using the Neumann–Koop rule is in fair agreement with the value obtained from low-temperature heat capacity measurements.

Distributed Function Computation over Fields and Rings via Linear Compression of Sources

The setting considered in this paper is one of distributed function computation. More specifically, there is a collection of N sources possessing correlated information and a destination that would like to acquire a specific linear combination of the N sources. We address both the case when the common alphabet of the sources is a finite field and the case when it is a finite, commutative principal ideal ring with identity. The goal is to minimize the total amount of information needed to be transmitted by the N sources while enabling reliable recovery at the destination of the linear combination sought. One means of achieving this goal is for each of the sources to compress all the information it possesses and transmit this to the receiver. The Slepian-Wolf theorem of information theory governs the minimum rate at which each source must transmit while enabling all data to be reliably recovered at the receiver. However, recovering all the data at the destination is often wasteful of resources since the destination is only interested in computing a specific linear combination. An alternative explored here is one in which each source is compressed using a common linear mapping and then transmitted to the destination which then proceeds to use linearity to directly recover the needed linear combination. The article is part review and presents in part, new results. The portion of the paper that deals with finite fields is previously known material, while that dealing with rings is mostly new.Attempting to find the best linear map that will enable function computation forces us to consider the linear compression of source. While in the finite field case, it is known that a source can be linearly compressed down to its entropy, it turns out that the same does not hold in the case of rings. An explanation for this curious interplay between algebra and information theory is also provided in this paper.

Enantiospecific synthesis of pacifigorgianes

Enantiospecific synthesis of the sesquiterpenes pacifigorgianes has been described. (R)-Carvone has been employed as the chiral starting material and an entropy assisted ring-closing metathesis reaction by Grubbs first generation catalyst was employed as the key strategy.

Implications of a viscosity bound on black hole accretion

Motivated by the viscosity bound in gauge/gravity duality, we consider the ratio of shear viscosity (eta) to entropy density (s) in black hole accretion flows. We use both an ideal gas equation of state and the QCD equation of state obtained from lattice for the fluid accreting onto a Kerr black hole. The QCD equation of state is considered since the temperature of accreting matter is expected to approach 10(12) K in certain hot flows. We find that in both the cases eta/s is small only for primordial black holes and several orders of magnitude larger than any known fluid for stellar and supermassive black holes. We show that a lower bound on the mass of primordial black holes leads to a lower bound on eta/s and vice versa. Finally we speculate that the Shakura-Sunyaev viscosity parameter should decrease with increasing density and/or temperatures. (C) 2012 Elsevier B.V. All rights reserved.

Thermal instability and the feedback regulation of hot haloes in clusters, groups and galaxies

We present global multidimensional numerical simulations of the plasma that pervades the dark matter haloes of clusters, groups and massive galaxies (the intracluster medium; ICM). Observations of clusters and groups imply that such haloes are roughly in global thermal equilibrium, with heating balancing cooling when averaged over sufficiently long time- and length-scales; the ICM is, however, very likely to be locally thermally unstable. Using simple observationally motivated heating prescriptions, we show that local thermal instability (TI) can produce a multiphase medium with similar to 104 K cold filaments condensing out of the hot ICM only when the ratio of the TI time-scale in the hot plasma (tTI) to the free-fall time-scale (tff) satisfies tTI/tff? 10. This criterion quantitatively explains why cold gas and star formation are preferentially observed in low-entropy clusters and groups. In addition, the interplay among heating, cooling and TI reduces the net cooling rate and the mass accretion rate at small radii by factors of similar to 100 relative to cooling-flow models. This dramatic reduction is in line with observations. The feedback efficiency required to prevent a cooling flow is similar to 10-3 for clusters and decreases for lower mass haloes; supernova heating may be energetically sufficient to balance cooling in galactic haloes. We further argue that the ICM self-adjusts so that tTI/tff? 10 at all radii. When this criterion is not satisfied, cold filaments condense out of the hot phase and reduce the density of the ICM. These cold filaments can power the black hole and/or stellar feedback required for global thermal balance, which drives tTI/tff? 10. In comparison to clusters, groups have central cores with lower densities and larger radii. This can account for the deviations from self-similarity in the X-ray luminositytemperature () relation. The high-velocity clouds observed in the Galactic halo can be due to local TI producing multiphase gas close to the virial radius if the density of the hot plasma in the Galactic halo is >rsim 10-5 cm-3 at large radii.

Cause and Effect of Feedback: Multiphase Gas in Cluster Cores Heated by AGN Jets

Multiwavelength data indicate that the X-ray-emitting plasma in the cores of galaxy clusters is not cooling catastrophically. To a large extent, cooling is offset by heating due to active galactic nuclei (AGNs) via jets. The cool-core clusters, with cooler/denser plasmas, show multiphase gas and signs of some cooling in their cores. These observations suggest that the cool core is locally thermally unstable while maintaining global thermal equilibrium. Using high-resolution, three-dimensional simulations we study the formation of multiphase gas in cluster cores heated by collimated bipolar AGN jets. Our key conclusion is that spatially extended multiphase filaments form only when the instantaneous ratio of the thermal instability and free-fall timescales (t(TI)/t(ff)) falls below a critical threshold of approximate to 10. When this happens, dense cold gas decouples from the hot intracluster medium (ICM) phase and generates inhomogeneous and spatially extended Ha filaments. These cold gas clumps and filaments ``rain'' down onto the central regions of the core, forming a cold rotating torus and in part feeding the supermassive black hole. Consequently, the self-regulated feedback enhances AGN heating and the core returns to a higher entropy level with t(TI)/t(ff) > 10. Eventually, the core reaches quasi-stable global thermal equilibrium, and cold filaments condense out of the hot ICM whenever t(TI)/t(ff) less than or similar to 10. This occurs despite the fact that the energy from AGN jets is supplied to the core in a highly anisotropic fashion. The effective spatial redistribution of heat is enabled in part by the turbulent motions in the wake of freely falling cold filaments. Increased AGN activity can locally reverse the cold gas flow, launching cold filamentary gas away from the cluster center. Our criterion for the condensation of spatially extended cold gas is in agreement with observations and previous idealized simulations.

On maximum entropy and minimum KL-divergence optimization by Grobner basis methods

In this paper we study constrained maximum entropy and minimum divergence optimization problems, in the cases where integer valued sufficient statistics exists, using tools from computational commutative algebra. We show that the estimation of parametric statistical models in this case can be transformed to solving a system of polynomial equations. We give an implicit description of maximum entropy models by embedding them in algebraic varieties for which we give a Grobner basis method to compute it. In the cases of minimum KL-divergence models we show that implicitization preserves specialization of prior distribution. This result leads us to a Grobner basis method to embed minimum KL-divergence models in algebraic varieties. (C) 2012 Elsevier Inc. All rights reserved.

Stabilized SPH-based simulations of impact dynamics using acceleration-corrected artificial viscosity

Artificial viscosity in SPH-based computations of impact dynamics is a numerical artifice that helps stabilize spurious oscillations near the shock fronts and requires certain user-defined parameters. Improper choice of these parameters may lead to spurious entropy generation within the discretized system and make it over-dissipative. This is of particular concern in impact mechanics problems wherein the transient structural response may depend sensitively on the transfer of momentum and kinetic energy due to impact. In order to address this difficulty, an acceleration correction algorithm was proposed in Shaw and Reid (''Heuristic acceleration correction algorithm for use in SPH computations in impact mechanics'', Comput. Methods Appl. Mech. Engrg., 198, 3962-3974) and further rationalized in Shaw et al. (An Optimally Corrected Form of Acceleration Correction Algorithm within SPH-based Simulations of Solid Mechanics, submitted to Comput. Methods Appl. Mech. Engrg). It was shown that the acceleration correction algorithm removes spurious high frequency oscillations in the computed response whilst retaining the stabilizing characteristics of the artificial viscosity in the presence of shocks and layers with sharp gradients. In this paper, we aim at gathering further insights into the acceleration correction algorithm by further exploring its application to problems related to impact dynamics. The numerical evidence in this work thus establishes that, together with the acceleration correction algorithm, SPH can be used as an accurate and efficient tool in dynamic, inelastic structural mechanics. (C) 2011 Elsevier Ltd. All rights reserved.

Magnetocaloric effect and nature of magnetic transition in nanoscale Pr0.5Ca0.5MnO3

Systematic measurements pertinent to the magnetocaloric effect and nature of magnetic transition around the transition temperature are performed in the 10 nm Pr0.5Ca0.5MnO3 nanoparticles (PCMO10). Maxwell's relation is employed to estimate the change in magnetic entropy. At Curie temperature (T-C) similar to 83.5 K, the change in magnetic entropy (-Delta S-M) discloses a typical variation with a value 0.57 J/kg K, and is found to be magnetic field dependent. From the area under the curve (Delta S vs T), the refrigeration capacity is calculated at T-C similar to 83.5K and it is found to be 7.01 J/kg. Arrott plots infer that due to the competition between the ferromagnetic and anti-ferromagnetic interactions, the magnetic phase transition in PCMO10 is broadly spread over both in temperature as well as magnetic field coordinates. Upon tuning the particle size, size distribution, morphology, and relative fraction of magnetic phases, it may be possible to enhance the magnetocalorific effect further in PCMO10. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4759372]

Simulation of Influence of Bilayer Melting on Dynamics and Thermodynamics of Interfacial Water

We investigate the effect of bilayer melting transition on thermodynamics and dynamics of interfacial water using molecular dynamics simulation with the two-phase thermodynamic model. We show that the diffusivity of interface water depicts a dynamic crossover at the chain melting transition following an Arrhenius behavior until the transition temperature. The corresponding change in the diffusion coefficient from the bulk to the interface water is comparable with experimental observations found recently for water near 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) vesicles Phys. Chem. Chem. Phys. 13, 7732 (2011)]. The entropy and potential energy of interfacial water show distinct changes at the bilayer melting transition, indicating a strong correlation in the thermodynamic state of water and the accompanying first-order phase transition of the bilayer membrane. DOI: 10.1103/PhysRevLett.110.018303

Further results on geometric properties of a family of relative entropies

This paper extends some geometric properties of a one-parameter family of relative entropies. These arise as redundancies when cumulants of compressed lengths are considered instead of expected compressed lengths. These parametric relative entropies are a generalization of the Kullback-Leibler divergence. They satisfy the Pythagorean property and behave like squared distances. This property, which was known for finite alphabet spaces, is now extended for general measure spaces. Existence of projections onto convex and certain closed sets is also established. Our results may have applications in the Rényi entropy maximization rule of statistical physics.

QUAD: quality assessment of documents

We propose a set of metrics that evaluate the uniformity, sharpness, continuity, noise, stroke width variance,pulse width ratio, transient pixels density, entropy and variance of components to quantify the quality of a document image. The measures are intended to be used in any optical character recognition (OCR) engine to a priori estimate the expected performance of the OCR. The suggested measures have been evaluated on many document images, which have different scripts. The quality of a document image is manually annotated by users to create a ground truth. The idea is to correlate the values of the measures with the user annotated data. If the measure calculated matches the annotated description,then the metric is accepted; else it is rejected. In the set of metrics proposed, some of them are accepted and the rest are rejected. We have defined metrics that are easily estimatable. The metrics proposed in this paper are based on the feedback of homely grown OCR engines for Indic (Tamil and Kannada) languages. The metrics are independent of the scripts, and depend only on the quality and age of the paper and the printing. Experiments and results for each proposed metric are discussed. Actual recognition of the printed text is not performed to evaluate the proposed metrics. Sometimes, a document image containing broken characters results in good document image as per the evaluated metrics, which is part of the unsolved challenges. The proposed measures work on gray scale document images and fail to provide reliable information on binarized document image.

Evaluation of isopentane, R-245fa and their mixtures as working fluids for organic Rankine cycles

Low grade thermal energy from sources such as solar, geothermal and industrial waste heat in the temperature range of 380-425 K can be converted to electrical energy with reasonable efficiency using isopentane and R-245fa. While the former is flammable and the latter has considerable global warming potential, their mixture in 0.7/0.3 mole fraction is shown to obviate these disadvantages and yet retain dominant merits of each fluid. A realistic thermodynamic analysis is carried out wherein the possible sources of irreversibilities such as isentropic efficiencies of the expander and the pump and entropy generation in the regenerator, boiler and condenser are accounted for. The performance of the system in the chosen range of heat source temperatures is evaluated. A technique of identifying the required source temperature for a given output of the plant and the maximum operating temperature of the working fluid is developed. This is based on the pinch point occurrence in the boiler and entropy generation in the boiling and superheating regions of the boiler. It is shown that cycle efficiencies of 10-13% can be obtained in the range investigated at an optimal expansion ratio of 7-10. (C) 2012 Elsevier Ltd. All rights reserved.