Ion exchange equilibria between (Mn,Co)O solid solution and (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions at 1100oC

The compositions of the (Mn,Co)O solid solution with rock salt structure in equilibrium with (Mn,Co)Cr2O4 and (Mn,Co)Al2O4 spinel solid solutions have been determined by X-ray diffraction measurements at 1100° C and an oxygen partial pressure of 10–10 atm. The ion exchange equilibria are quantitatively analysed, using values for activities in the (Mn,Co)O solid solution available in the literature, in order to obtain activities in the spinel solid solutions. The MnAl2O4-CoAl2O4 solid solution exhibits negative deviations from Raoult's law, consistent with the estimated cation disorder in the solid solution, while the MnCr2O4-CoCr2O4 solid solution shows slightly positive deviations. The difference in the Gibbs free energy of formation of the two pure chromites and aluminates derived from the results of this study are in good agreement with recent results obtained from solid oxide galvanic cells and gas-equilibrium techniques.

Vapor pressure and dissociation energy of (In2O)

The vapor pressure of pure liquid indium, and the sum of pressures of (In) and (In2O) species over the condensed phase mixture {In} + , contained in a silica vessel, have been measured by Knudsen effusion and Langmuir free vaporization methods in the temperatue range 600 to 950°C. Mass spectrometric studies reported in the literature show that (In) and (In2O) are the important species in the vapor phase over the {In} + ; mixture. The vapor pressure of (In2O) corresponding to the reaction, deduced from the present measurements is given by the equation, The “apparent evaporation coefficient” for the condensed phase mixture is approximately 0.8. The energy for the dissociation (In2O) molecule into atoms calculated from the above equation is D°0 = 180.0 (± 1.0) kcal mol−1.

Vapor pressure and thermodynamic properties of MgIn2O4

The vapor pressure of pure indium, and the sum of the pressures of (In) and (In2O) species over the condensed phase mixture {In} + 〈MgIn2O4〉 + 〈MgO〉, have been measured by the Knudsen effusion technique in the temperature range 1095–1350 K. The materials under study were contained in a zirconia crucible, which had a Knudsen orifice along the vertical wall. The major vapor species over the condensed phase mixture were identified as (In) and (In2O) using a mass-spectrometer. The vapor pressure of (In2O) corresponding to the reaction,View the MathML source was deduced from the experimental results;View the MathML source The standard free energy of formation of the inverse spinel 〈MgIn2O4〉 from its component oxides, is given by,View the MathML source View the MathML source The entropy of transformation of 〈In2O3〉 from the C rare-earth structure to the corundum structure is evaluated from the measured entropy of formation of (MgIn2O4) and a semi-empirical correlation for the entropy of formation of spinel phases from component oxides with rock-salt and corundum structures.

Vapor pressure of liquid metals and alloys

The Gibbs-Bogoliubov formalism in conjunction with the pseudopotential theory is applied to the calculation of the vapour pressure of eight liquid metals from Groups I to IV of the periodic table and of alloys (Na-K). The calculated vapour pressure of the elements and their temperature dependencies, the partial pressures, activities and boiling points of the alloys are all found to be in reasonable agreement with measured data.

Physically consistent simulation of mesoscale chemical kinetics: The non-negative FIS-alpha method

Biochemical pathways involving chemical kinetics in medium concentrations (i.e., at mesoscale) of the reacting molecules can be approximated as chemical Langevin equations (CLE) systems. We address the physically consistent non-negative simulation of the CLE sample paths as well as the issue of non-Lipschitz diffusion coefficients when a species approaches depletion and any stiffness due to faster reactions. The non-negative Fully Implicit Stochastic alpha (FIS alpha) method in which stopped reaction channels due to depleted reactants are deleted until a reactant concentration rises again, for non-negativity preservation and in which a positive definite Jacobian is maintained to deal with possible stiffness, is proposed and analysed. The method is illustrated with the computation of active Protein Kinase C response in the Protein Kinase C pathway. (C) 2011 Elsevier Inc. All rights reserved.

Thermodynamics and phase equilibria involving the spinel solid solution FexMg1-xCr2O4

Activities of FeCr2O4 in the spinel solid solutions Fe X Mg1−X Cr2O4 (0negative deviation from the ideal behavior, characterized by the regular solution parameter Ω s =−2260 (±200) J/mol. The lattice parameter of the spinel solid solutions quenched from 1200 K was found to obey Vegard’s law. The phase relations in the FeO-MgO-Cr2O3 system have been deduced from the results obtained in this study together with other relevant thermodynamic data from the literature. The tie-lines between the solid solutions with rock salt and spinel structures represent the influence of intercrystalline ion exchange. The tie-lines are skewed toward the FeCr2O4 corner, primarily because of the higher stability of FeCr2O4 compared to MgCr2O4, with respect to their component binary oxides. The oxygen partial pressure corresponding to the two three-phase regions, Fe + Fe X Mg1−X Cr2O4 + Cr2O3 and Fe + Fe Y Mg1−Y O + Fe X Mg1−X Cr2O4, have been evaluated as a function of composition at 1200 K.

Internal displacement reactions in multicomponent oxides: Part I. Line compounds with narrow homogeneity range

Structure and phase transition of LaO1−xF1+2x, prepared by solid-state reaction of La2O3 and LaF3, was investigated by X-ray powder diffraction and differential scanning calorimetry for both positive and negative values of the nonstoichiometric parameter x. The electrical conductivity was investigated as a function of temperature and oxygen partial pressure using AC impedance spectroscopy. Fluoride ion was identified as the migrating species in LaOF by coulometric titration and transport number determined by Tubandt technique and EMF measurements. Activation energy for conduction in LaOF was 58.5 (±0.8) kJ/mol. Conductivity increased with increasing fluorine concentration in the oxyfluoride phase, suggesting that interstitial fluoride ions are more mobile than vacancies. Although the values of ionic conductivity of cubic LaOF are lower, the oxygen partial pressure range for predominantly ionic conduction is larger than that for the commonly used stabilized-zirconia electrolytes. Thermodynamic analysis shows that the oxyfluoride is stable in atmospheres containing diatomic oxygen. However, the oxyfluoride phase can degrade with time at high temperatures in atmospheres containing water vapor, because of the higher stability of HF compared with H2O.

Structural and electrical properties of low pressure metalorganic chemical vapor deposition grown Eu2O3 films on Si(100)

Structural and electrical properties of Eu2O3 films grown on Si(100) in 500–600 °C temperature range by low pressure metalorganic chemical vapor deposition are reported. As-grown films also possess the impurity Eu1−xO phase, which has been removed upon annealing in O2 ambient. Film’s morphology comprises uniform spherical mounds (40–60 nm). Electrical properties of the films, as examined by capacitance-voltage measurements, exhibit fixed oxide charges in the range of −1.5×1011 to −6.0×1010 cm−2 and dielectric constant in the range of 8–23. Annealing has resulted in drastic improvement of their electrical properties. Effect of oxygen nonstoichiometry on the film’s property is briefly discussed.

Ion-Acoustic Solitary Waves in Multicomponent Plasmas with Negative Ions

By using the perturbation technique, a Kortewege-de-Vries (K-dV) equation for a multicomponent plasma with negative ions and isothermal electrons has been derived. We have discussed the stationary solutions of K-dV equation and it has shown that in the presece of multiple ions, the amplitude of solitons exhibits interesting behaviour, especiallY when the negative ions are present.

Temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation in FCC metallic nanowire: a molecular dynamic study

Atomistic simulation of initial < 100 > oriented FCC Cu nanowires shows a novel coupled temperature-pressure dependent reorientation from < 100 > to < 110 > phase. A temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram is generated for Cu nanowire with varying cross-sectional sizes. A critical pressure is reported for Cu nanowires with varying cross-sectional sizes, above which an initial < 100 > oriented nanowire shows temperature independent reorientation into the < 110 > phase. The effect of surface stresses on the < 100 > to < 110 > reorientation is also studied. The results indicate that above a critical cross-sectional size for a given temperature-pressure, < 100 > to < 110 > reorientation is not possible. It is also reported here that for a given applied pressure, an increase in temperature is required for the < 100 > to < 110 > reorientation with increasing cross-sectional size of the nanowire. The temperature-pressure-induced solid-solid < 100 > to < 110 > reorientation diagram reported in the present paper could further be used as guidelines for controlling the reorientations/shape memory in nano-scale applications of FCC metallic nanowires.

Surface pressure and heat transfer measurements in the unsteady separated hypersonic flow field over double cones

Reliable bench mark experimental database in the separated hypersonic flow regime is necessary to validate high resolution CFD codes. In this paper we report the surface pressure and heat transfer measurements carried out on double cones (first cone semi-apex angle = 15, 25 deg.; second cone semi-apex angle= 35, 68 deg.) at hypersonic speeds that will be useful for CFD code validation studies. The surface pressure measurements are carried out at nominal Mach number of 8.35 in the IISc hypersonic wind tunnel. On the other hand the surface heat transfer measurements are carried out at a nominal Mach number of 5.75 in the IISc hypersonic shock tunnel. The flow separation point on the first cone, flow reattachment on the second cone and the wild fluctuation of the transmitted shock on the second cone surface (25/68 deg. double cone) in the presence of severe adverse pressure gradient are some of the flow features captured in the measurements. The results from the CFD studies indicate good agreement with experiments in the attached flow regime while considerable differences are noticeable in the separated flow regime.

A comparative study of erbium oxide and gadolinium oxide high-k dielectric thin films grown by low-pressure metalorganic chemical vapour deposition (MOCVD) using beta-Diketonates as precursors

In this paper, a comparative study of thin films of Er2O3 and Gd2O3 grown on n-type Si(100) by low-pressure metalorganic chemical vapour deposition (MOCVD) under the identical conditions has been presented. beta-Diketonate complex of rate earth metals was used as precursor. Description on the evolution of the morphology, structure, optical, and electrical characteristics of films with respect to growth parameters and post-deposition annealing process has been presented. As-gown Gd2O3 films grow with <111> texture, whereas the texture of Er2O3 films strongly depends on the growth temperature (either <100> or <111>). Compositional analysis reveals that the Gd2O3 films grown at or above 500degreesC are carbon free whereas Er2O3 films at upto 525degreesC show the presence of heteroatoms and Er2O3 films grown above 525degreesC are carbon five. The effective dielectric constant is in the range of 7-24, while the fixed charge density is in the range - 10(11) to 10(10) CM-2 as extracted from the C-V characteristics. DC I-V study was carried out to examine the leakage behaviour of films. It reveals that the as-grown Gd2O3 film was very leakey in nature. Annealing of the films in oxidizing ambient for a period of 20 min results in a drastic improvement in the leakage behaviour. The presence of heteroatoms (such as carbon) and their effect on the properties of films are discussed.