Activities in the spinel solid solution FeXMg1−XAl2O4

Abstract: Activities in the spinel solid solution FexMg1-xAl2O4 saturated with alpha-Al2O3 have been measured for the compositional range 0 < X < 1 between 1100 and 1350 K using a bielectrolyte solid-state galvanic cell, which may be represented as Pt, Fe + FexMg1-xAl2O4 + alpha-Al2O3//(Y2O3)ThO2/ (CaO)ZrO2//Fe + FeAl2O4 + alpha-Al2O3, Pt Activities of ferrous and magnesium aluminates exhibit small negative deviations from Raoult's law. The excess free energy of mixing of the solid solution is a symmetric function of composition and is independent of temperature: Delta G(E) = -1990 X(1 - X J/mol. Theoretical analysis of cation distribution in spinel solid solution also suggests mild negative deviations from ideality. The lattice parameter varies linearly with composition in samples quenched from 1300 K. Phase relations in the FeO-MgO-Al2O3 system at 1300 K are deduced from the results of this study and auxiliary thermodynamic data from the literature. The calculation demonstrates the influence of intracrystalline ion exchange equilibrium between nonequivalent crystallographic sites in the spinel structure on intercrystalline ion exchange equilibrium between the monoxide and spinel solid solutions (tie-lines). The composition dependence of oxygen partial pressure at 1300 K is evaluated for three-phase equilibria involving the solid solutions Fe + FexMg1-xAl2O4 + alpha-Al2O3 and Fe + FeyMg1-yO + FexMg1-xAl2O4. Dependence of X, denoting the composition of the spinel solid solution, on parameter Y, characterizing the composition of the monoxide solid solution with rock salt structure, in phase fields involving the two solid solutions is elucidated. The tie-lines are slightly skewed toward the MgAl2O4 corner.

Low-temperature specific heat of antiferromagnetic EuNi5P3 and mixed-valent EuNi2P2 in magnetic fields to 7 T

he specific heats of EUNi(5)P(3), an antiferromagnet, and EuNi2P2, a mixed-valence compound, have been measured between 0.4 and 30 K in magnetic fields of, respectively, 0, 0.5, 1, 1.5, 2.5, 5, and 7 T, and 0 and 7 T. In zero field the specific heat of EuNi5P3 shows a h-like anomaly with a maximum at 8.3 K. With increasing field in the range 0-2.5 T, the maximum shifts to lower temperatures, as expected for an antiferromagnet. In higher fields the antiferromagnetic ordering is destroyed and the magnetic part of the specific heat approaches a Schottky anomaly that is consistent with expectations for the crystal-field/Zeeman levels. In low fields and for temperatures between 1.5 acid 5 K the magnetic contribution to the specific heat is proportional to the temperature, indicating a high density of excited states with an energy dependence that is very unusual for an antiferromagnet. The entropy associated with the magnetic ordering is similar to R In8, confirming that only the Eu2+-with J=7/2, S=7/2, L=0-orders below 30 R. In zero field approximately 20% of the entropy occurs above the Neel temperature, consistent. with the usual amount of short-range order observed in antiferromagnets. The hyperfine magnetic field at the Eu nuclei in EUNi(5)P(3) is 33.3 T, in good agreement with a value calculated from electron-nuclear double resonance measurements. For EuNi2P2 the specific heat is nearly field independent and shows no evidence of magnetic ordering or hyperfine fields. The coefficient of the electron contribution to the specific heat is similar to 100 mJ/mol K-2.

Passive pressure coefficients, critical failure surface and its kinematic admissibility

Using a combination of a logarithmic spiral and a straight line as a failure surface, comprehensive charts have been developed to determine the passive earth pressure coefficients and the positions of the critical failure surface for positive as well as negative wall friction angles. Translational movement of the wall has been examined in detail, considering the soil as either an associated flow dilatant material or a non-dilatant material, to determine the kinematic admissibility of the limit equilibrium solutions.

Pressure-induced charge transfer in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) and analogies to composition-driven charge transfer in dilanthanum cuprate (La2CuO4): an infrared study

A reversible pressure-induced phase transition in lanthanum nickel ferrate (LaNi0.5Fe0.5O3) manifests itself in the infrared spectrum of the transition metal-oxygen stretching (nu(TM-O)) modes by the emergence of new peaks at pressures greater than similar to 1.4 x 10(9) Pa. Analogies to this transition are made by considering charge transfer in dilanthanum cuprate (La2CuO4) and its modification by partial substitution of copper ions by chromium ions.

A molecular dynamics study and molecular level explanation of pressure dependence of ionic conductivity of potassium chloride in water

Experimental ionic conductivity of different alkali ions in water shows markedly different dependences on pressure. Existing theories such as that of Hubbard-Onsager are unable to explain these dependences on pressure of the ionic conductivity for all ions. We report molecular dynamics investigation of potassium chloride solution at low dilution in water at several pressures between 1 bar and 2 kbar. Two different potential models have been employed. One of the models successfully reproduces the experimentally observed trend in ionic conductivity of K+ ions in water over the 0.001-2 kbar range. We also propose a theoretical explanation, albeit at a qualitative level, to account for the dependence of ionic conductivity on pressure in terms of the previously studied Levitation Effect. It also provides a microscopic picture in terms of the pore network in liquid water.

Screw dynamo and the generation of nonaxisymmetric magnetic fields

A mechanism is presented here for the amplification of large-scale nonaxisymmetric magnetic fields as a manifestation of the dynamo effect. We generalize a result on restrictions of dynamo actions due to laminar flow originally derived by Zeldovich, Ruzmaikin, and Sokolov [Magnetic Fields in Astrophysics (Gordon and Breach, New York, 1983)]. We show how a screwlike motion having phi and z components of velocity can help to grow a magnetic field. This model postulates a large-scale flow having phi and z components with radial dependences (helical flow). Shear in the radial field, because of a near-flux-freezing condition, causes amplification of the phi component of the magnetic field. The radial and axial components grow due to the presence of turbulent diffusion. The shear in the large scale flow induces an indefinite growth of magnetic field without the a effect; nevertheless, turbulent diffusion forms an important part in the overall mechanism.

Micromechanical modeling of granular materials: effect of confining pressure on mechanical behavior

This paper reports the effect of confining pressure on the mechanical behavior of granular materials from micromechanical considerations starting from the grain scale level, based on the results of numerically simulated tests on disc assemblages using discrete element modeling (DEM). The two macro parameters which are influenced by the increase in confining pressure are stiffness (increases) and volume change (decreases). The lateral strain coefficient (Poisson's ratio) at the beginning of the test is more or less constant. The angle of internal friction slightly decreases with increase in confining pressure. The numerical results of disc assemblages indicate very clearly a non-linear Mohr-Coulomb failure envelope with increase in confining pressure. The increase in average coordination number and accompanying decrease of fabric anisotropy reduce the shear strength at higher confining pressures. Micromechanical explanations of the macroscopic behavior are presented in terms of the force and fabric anisotropy coefficients. (C) 1999 Elsevier Science Ltd. AII rights reserved.

Solutions of cubic equations in quadratic fields

Let K be any quadratic field with O-K its ring of integers. We study the solutions of cubic equations, which represent elliptic curves defined over Q, in quadratic fields and prove some interesting results regarding the solutions by using elementary tools. As an application we consider the Diophantine equation r + s + t = rst = 1 in O-K. This Diophantine equation gives an elliptic curve defined over Q with finite Mordell-Weil group. Using our study of the solutions of cubic equations in quadratic fields we present a simple proof of the fact that except for the ring of integers of Q(i) and Q(root 2), this Diophantine equation is not solvable in the ring of integers of any other quadratic fields, which is already proved in [4].

Study of the electrical properties of pulsed laser ablated (Ba0.5Sr0.5)TiO3 thin films

The laser ablated barium strontium titanate (BST) thin films were characterized in terms of composition, structure, microstructure and electrical properties. Films deposited at 300 degrees C under 50 mTorr oxygen pressure and 3 J cm(-2) laser fluence and further annealed at 600 degrees C in flowing oxygen showed a dielectric constant of 467 and a dissipation factor of 0.02. The room-temperature current-voltage characteristics revealed a space charge limited conduction (SCLC) mechanism, though at low fields the effect of the electrodes was predominant. The conduction mechanism was thoroughly-investigated in terms of Schottky emission at low fields, and bulk-limited SCLC at high fields. The change over to the bulk-limited conduction process from the electrode-limited Schottky emission was, attributed to the process of tunneling through the electrode interface at high fields resulting into the lowering of the electrode contact resistance and consequently giving rise to a bulk limited conduction process. The predominance of SCLC mechanism in the films suggests that the bulk properties are only revealed if the depletion width at the electrode interface is thin enough to allow the tunneling process to take place. This condition is only favorable if the him thickness is high or if the doping concentration is high enough. In the present case the film thickness ranged from 0.3 to 0.7 mu m which was suitable to show the transition mentioned above. (C) 1999 Elsevier Science S.A. All rights reserved.

Thermodynamic properties of the calcium ferrites CaFe2O4 and Ca2Fe2O5

The chemical potentials of CaO in the two-phase fields Fe2O3 + CaFe2O4 and CaFe2O4 + Ca2Fe2O5 of the pseudobinary system CaO - Fe2O3 have been measured in the temperature range from 975 to 1275 K, relative to pure CaO as the reference state, using solid state galvanic cells incorporating single-crystal CaF2 as the solid electrolyte. The cell was operated under pure oxygen at ambient pressure. The standard Gibbs energies of formation of calcium ferrites, CaFe2O4 and Ca2Fe2O5, were derived from the reversible emfs. The results can be summarized by the following equations:CaO + Fe2O3 --> CaFe2O4;Delta G degrees = - 37,480 + 1.16 T (+/- 250) J/mol 2 CaO + Fe2O3 --> Ca2Fe2O5;Delta G degrees = - 45, 280 - 13.51 T (+/- 275) J/mol These values are compared with thermodynamic data reported in the literature. The results of this study are in excellent agreement with heat capacity data, and in reasonable agreement with earlier measurements of enthalpy and Gibbs energy of formation, but suggest significant revision of enthalpies of formation of calcium ferrites given in current thermodynamic compilations.

An interesting feature of the vapour pressure curve

There exists a maximum in the products of the saturation properties such as T(p(c) - p) and p(T-c - T) in the vapour-liquid coexistence region for all liquids. The magnitudes of those maxima on the reduced coordinate system provide an insight to the molecular complexity of the liquid. It is shown that the gradients of the vapour pressure curve at temperatures where those maxima occur are directly given by simple relations involving the reduced pressures and temperatures at that point. A linear relation between the maximum values of those products of the form [p(r)(1 - T-r)](max) = 0.2095 - 0.2415 [T-r(1 - p(r))](max) has been found based on a study of 55 liquids ranging from non-polar monatomic cryogenic liquids to polar high boiling point liquids.

Constant pressure laminar, transitional and turbulent flows - An approximate unified treatment

A nondimensional number that is constant in two-dimensional, incompressible and constant pressure laminar and fully turbulent boundary, layer flows has been proposed. An extension of this to constant pressure transitional flow is discussed.

Converging swirling liquid jets from pressure swirl atomizers: Effect of inner air pressure

Converging swirling liquid jets from pressure swirl atomizers injected into atmospheric air are studied experimentally using still and cine photographic techniques in the context of liquid-liquid coaxial swirl atomizers used in liquid rocket engines. The jet exhibits several interesting flow features in contrast to the nonswirling liquid jets (annular liquid jets) studied in the literature. The swirl motion creates multiple converging sections in the jet, which gradually collapse one after the other due to the liquid sheet breakup with increasing Weber number (We). This is clearly related to the air inside the converging jet which exhibits a peculiar variation of the pressure difference across the liquid sheet, DeltaP, with We. The variation shows a decreasing trend of DeltaP with We in an overall sense, but exhibits local maxima and minima at specific flow conditions. The number of maxima or minima observed in the curve depends on the number of converging sections seen in the jet at the lowest We. An interesting feature of this variation is that it delineates the regions of prominent jet flow features like the oscillating jet region, nonoscillating jet region, number of converging sections, and so on. Numerical predictions of the jet characteristics are obtained by modifying an existing nonswirling liquid jet model by including the swirling motion. The comparison between the experimental and numerical measurements shows that the pressure difference across the liquid sheet is important for the jet behavior and cannot be neglected in any theoretical analysis. (C) 2002 American Institute of Physics.