Thermodynamics Of Aluminum Strontium Alloys

The activity of strontium in liquid Al-Sr alloys (X(Sr) less-than-or-equal-to 0.17) at 1323 K has been determined using the Knudsen effusion-mass loss technique. At higher concentrations (X(Sr) greater-than-or-equal-to 0.28), the activity of strontium has been determined by the pseudoisopiestic technique. Activity of aluminium has been derived by Gibbs-Duhem integration. The concentration - concentration structure factor of Bhatia and Thornton at zero wave vector has been computed from the thermodynamic data. The behaviour of the mean square thermal fluctuation in composition and the thermodynamic mixing functions suggest association tendencies in the liquid state. The associated solution model with Al2Sr as the predominant complex can account for the properties of the liquid alloy. Thermodynamic data for the intermetallic compunds in the Al-Sr system have been derived using the phase diagram and the Gibbs' energy and enthalpy of mixing of liquid alloys. The data indicate the need for redetermination of the phase diagram near the strontium-rich corner.

Vapor-Pressure Of Calcium Corresponding To The Reduction Of Calcia By Aluminum

The equilibrium pressure of calcium corresponding to the reduction reaction 6CaO (s) + 2Al (l) half-arrow-right-over-half-arrow-left 3CaO.Al2O3 (s) + 3Ca (g) has been measured by Knudsen effusion - mass loss analysis in the temperature range 1190 - 1500 K. The measured vapour pressure can be expressed as a function of temperature by the relation: log p(Ca) (Pa) = -10,670/T + 9.267 The calcium generated is partially absorbed by aluminium to form an alloy. The equilibrium composition of the alloy at 1373 K was found to be 22 mol% Ca - 78 mol% Al. The measured vapour pressure is in good agreement with that computed from thermodynamic data.

Thermodynamic Properties of Niobium Oxides

Thermodynamic properties of three oxides of niobium have been measured using solid state electrochemical cells incorporating yttria-doped thoria (YDT) as the electrolyte in the temperature range T = (1000 to 1300) K. The standard Gibbs energies of formation of NbO, NbO2, and NbO2.422 from the elements can be expressed as: Delta(f)G(NbO)(o) +/- 547/J . mol(-1) = -414 986 + 86.861(T/K) Delta(f)G(NbO2)(o) +/- 548/J . mol(-1) = -779 864 + 164.438(T/K) Delta(f)G(NbO2.422)(o) +/- 775/J . mol(-1) = -911 045 + 197.932(T/K) The results are discussed in comparison with thermodynamic data reported in the literature. The new results refine data for NbO and NbO2 presented in standard data compilations. There are no data in thermodynamic compilations for NbO2.422 (Nb12O29). In the absence of the heat capacity and enthalpy of formation measurements, only the Gibbs energy of formation of NbO2.422 can be assessed. The free energy of formation of stoichiometric Nb2O5 is evaluated on the basis of measurements on NbO2.422 and information available in the literature on phase boundary compositions and isothermal variation of nonstoichiometric parameter with oxygen potential for Nb2O5-x. The results suggest a minor revision of data for Nb2O5. A minimum in the Gibbs energy of mixing for the system Nb-O occurs in the nonstoichiometric domain of Nb2O5-x with x = 0.036.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

Thermal expansion of doped lanthanum gallates

Thermal expansion of several compositions of Sr and Mg-doped LaGaO3 including an A-site deficient composition (La0.9Sr0.1)(0.98)(Ga0.8Mg0.2)O-2.821 were measured in the temperature range from 298 to 1273 K. The effect of doping on thermal expansion was studied by varying the composition at one site of the perovskite structure (either A or B), while keeping the composition at the other site invariant. Thermal expansion varied nonlinearly with temperature and exhibited an inflexion between 550 and 620 K, probably related to the change in crystal structure from orthorhombic to rhombohedral. The dependence of average thermal expansion coefficient (alpha (av)) on the dopant concentration on either A or B site of the perovskite structure was found to be linear, when the composition at the other site was kept constant. Mg doping on the B-site had a greater effect on the average thermal expansion coefficient than Sr doping on the A-site. Cation deficiency at the A-site decreases thermal expansion when compositions at both sites are held constant.

Phase relationships in the system Ni-W-O and thermodynamic properties of NiWO,

The phase diagram of the Ni-W-O system at 1200 K was established by metallographic and X-ray identification of the phases present after equilibration at controlled oxygen potentials. The oxygen partial pressures over the samples were fixed by metered streams of CO+CO2 gas mixtures. There was only one ternary oxide, nickel tungstate (NiWO4), in the Ni-W-O system at a total pressure of 1 atm, and this compound decomposed to a mixture of Ni+WO2.72 on lowering the oxygen potential. The Gibbs' free energy of formation of NiWO4 was determined from the measurement of the e.m.f. of the solid oxide galvanic cell, Pt, Ni+NiWO4+WO2.72/CaO-ZrO2/Ni+NiO, Pt and thermodynamic properties of tungsten and nickel oxides available in the literature. For the reaction, NiO(s)+WO3(s)rarrNiWO4(s) DeltaG°=–10500–0.708 T (±250) cal mol–1.

The mobility of oxygen ions in CaF2

The a.c. conductivity of CaF2 samples containing a fine dispersion of CaO particles has been measured in the temperature range 630 to 1100 K. The conductivity of the dispersed solid electrolyte is two orders of magnitude higher than that for pure polycrystalline CaF2 in the middle of the temperature range. Transport measurements on pure single crystals of CaF2 and polycrystalline samples, with and without CaO dispersion, using Fe+FeO and pure Fe as electrodes, clearly indicate that fluorine ions are the only migrating ionic species with a transport number of almost unity, contrary to the suggestion of Chou and Rapp [1, 2]. The enhanced conductivity of the dispersed solid electrolyte probably arises from two effects. A small solubility of oxygen in CaF2 results in an increase in the fluorine vacancy concentration and conductivity. Adsorption of fluorine ions on the surface of the dispersed particles of CaO results in a space charge region around each particle with enhanced conductivity. Measurements on a galvanic cell incorporating CaF2 as the solid electrolyte and oxide electrodes show that the e.m.f. is a function of the activity of CaO at the electrode/electrolyte interface. The response to an oxygen potential gradient is, therefore, through an exchange reaction, which establishes an equivalent fluorine potential at the electrode/electrolyte interface.

Solid State Electrochemical Sensors in Process Control

The basic principles of operation of gas sensors based on solid-state galvanic cells are described. The polarisation of the electrodes can be minimised by the use of point electrodes made of the solid electrolyte, the use of a reference system with chemical potential close to that of the sample system and the use of graded condensed phase reference electrodes. Factors affecting the speed of response of galvanic sensors in equilibrium and non-equilibrium gas mixtures are considered with reference to products of combustion of fossil fuels. An expression for the emf of non-isothermal galvanic sensors and the criterion for the design of temperature compensated reference electrodes for non-isothermal galvanic sensors are briefly outlined. Non-isothermal sensors are useful for the continuous monitoring of concentrations or chemical potentials in reactive systems at high temperatures. Sensors for oxygen, carbon, and alloying elements (Zn and Si) in liquid metals and alloys are discussed. The use of auxiliary electrodes permits the detection of chemical species in the gas phase which are not mobile in the solid electrolyte. Finally, the cause of common errors in galvanic measurements, and tests for correct functioning of galvanic sensors are given. 60 ref.--AA

On the evaluation of stability of rare earth oxides as face coats for investment casting of titanium

Attempts have been made to evaluate the thermal stability of rare earth oxide face coats against liquid titanium. Determination of microhardness profiles and concentration profiles of oxygen and metallic constituents of oxide in investment cast titanium rods has allowed grActation of relative stability of rare earth oxides. The relative stability of evaluated oxides in the order of increasing stability follows the sequence CeO2 — ZrO2 — Gd2O3 — didymium oxide — Sm2O3 —Nd2O3 — Y2O3. The grading does not follow the free energy data of the formation of these oxides. A better correlation with the experimental observations is obtained when the solubility of the metallic species in titanium is also taken into consideration.

Phase Relations in the System CaO-Fe2O3-Y2O3 at 1273 K and Compatibility Between Y1-xCaxFeO3-0.5x and Stabilized Zirconia

Phase relations in the system CaO-Fe2O3-Y2O3 in air (P-O2/P-o = 0.21) were explored by equilibrating samples representing eleven compositions in the ternary at 1273 K, followed by quenching to room temperature and phase identification using XRD. Limited mutual solubility was observed between YFeO3 and Ca2Fe2O5. No quaternary oxide was identified. An isothermal section of the phase diagram at 1273 K was constructed from the results. Five three-phase regions and four extended two-phase regions were observed. The extended two-phase regions arise from the limited solid solutions based on the ternary oxides YFeO3 and Ca2Fe2O5. Activities of CaO, Fe2O3 and Y2O3 in the three-phase fields were computed using recently measured thermodynamic data on the ternary oxides. The experimental phase diagram is consistent with thermodynamic data. The computed activities of CaO indicate that compositions of CaO-doped YFeO3 exhibiting good electrical conductivity are not compatible with zirconia-based electrolytes; CaO will react with ZrO2 to form CaZrO3.