Assessment of the CaO-Al2O3 System

A thermodynamic assessment of the quasi-binary system CaO-Al₂O₃ has been made using a computerized CALPHAD (calculation of phase diagrams) technique. The actual optimization was carried out with a computer program for the optimization of parameters in thermodynamic models called PARROT. The liquid phase is described by a simple two-sublattice subregular solution model with Ca²⁺ and Al³⁺ as cationic species and O^2- as anionic species. All solid phases are treated as stoichiometric compounds. A consistent set of parameters describing the system is presented, and numerous comparisons with experimental data are made. There is a lack of accurate data in the high-alumina part of the system, and the importance of a better knowledge of the CaO·6Al₂O₃ phase is stressed.     

Stable and Metastable Phase Relationships in the System ZrO2–ErO1.5

Stable and metastable phase relationships in the system ZrO₂–ErO_1.5 were investigated using homogeneous samples prepared by rapid quenching of melts and by arc melting. The rapidly quenched samples were annealed in air for 48 h at 1690°C or for 8 months at 1315°C. Two tetragonal phases ( t - and t '-phases) were observed after quenching samples heated at 1690°C to a room temperature, whereas one t -phase and cubic ( c -) phase were found in those treated at 1315°C. Since the t '-phase is obtained through a diffusionless transformation during cooling from a high-temperature c -phase, t - and c -phases can coexist at high temperature. The t - and c -phases field spans from 4 to 10 mol% ErO_1.5 at 1690°C and from 3 to 15 mol% ErO_1.5 at 1315°C. The equilibrium temperature T ^t-m ₀ between the t - and monoclinic ( m -) phases estimated from A_s and M_s temperatures decreased with increasing ErO_1.5 contents.     

Phase Diagram of the System KF–AlF3

The system KF–AlF₃ was reinvestigated precisely by differential thermal analysis, X-ray diffractometry, and visual observation. All of the samples for the present investigation were prepared by solution synthesis. The results verified the existence of 2KF·AlF₃ (K₂AlF₅) and KF·4AlF₃ in the phase diagram; both compounds were orthorhombic. The cell parameters of the compounds were, respectively, a = 10.87 ± 0.03 Å, b = 10.36 ± 0.01 Å, c = 7.83 ± 0.03 Å, and a = 7.89 ± 0.01 Å, b = 7.57 ± 0.01 Å, c = 6.94 ± 0.01 Å. KAlF₄ was confirmed to melt congruently at 575°± 2°C by careful examination.     

CeO2−CoO Phase Diagram

Phase equilibria in the CeO₂−CoO system at temperatures above 1500°C were investigated. The microstructures and the phase compositions of the DTA (differential thermal analysis) samples and the quenched solid pellets were analyzed using SEM (scanning electron microscope), EDX (energy dispersive X-ray), and WDX (wavelength dispersive X-ray). A eutectic reaction was found at 1645 ± 5°C. The eutectic point was calculated to be at 82 ± 1.5 mol% CoO. The eutectic phases were the CeO₂-rich phase (containing <5 mol% CoO) and the CoO-rich phase (containing ∼0.5 mol% CeO₂). At 1580°C, the solubility of CoO in CeO₂ was ∼3 mol%.     

Thermodynamic Assessment of the ZrO2─YO1.5 System

An optimal set of thermodynamic functions for the ZrO₂─YO_1.5 system are obtained using phase diagram and thermodynamic data. The liquid is described by a subregular solution model. Both cubic ZrO₂ and YO_1.5 solid solutions are regarded as one cubic solution, which is also treated as a subregular solution. The ordered Zr₃Y₄O₁₂ phase is treated as a stoichiometric compound. A regular solution model is applied to the other solid solutions. Tentative equilibrium boundaries between monoclinic and tetragonal ZrO₂ solid solutions are evaluated from information about the T ₀ line. The calculated phase diagram and thermodynamic functions agree well with experimental data.     

Thermodynamic Modeling of the Isomorphous Phase Diagrams in the Al2O3–Cr2O3 and V2O3–Cr2O3 Systems

The phase diagrams in the Al₂O₃–Cr₂O₃ and V₂O₃–Cr₂O₃ systems have been assessed by thermodynamic modeling with existing data from the literature. While the regular and subregular solution models were used in the Al₂O₃–Cr₂O₃ system to represent the Gibbs free energies of the liquid and solid phases, respectively, the regular solution model was applied to both phases in the V₂O₃–Cr₂O₃ system. By using the liquidus, solidus, and/or miscibility gap data, the interaction parameters of the liquid and solid phases were optimized through a multiple linear regression method. The phase diagrams calculated from these models are in good agreement with experimental data. Also, the solid miscibility gap and chemical spinodal in the V₂O₃–Cr₂O₃ system were estimated.     

Phase Equilibria in the Systems CaO–CuO and CaO-Bi2O3

New data are presented on the phase equilibria of the binary systems CaO-CuO and CaO-Bi₂O₃. Corrected compositions are reported for Ca.Bi₆O₁₃ and Ca₂Bi₂O₅ and a new metastable high-temperature phase is reported for a composition near Ca₆Bi₇O_16.5. The composition and decomposition temperatures for Ca_1–x.CuO₂ are given for both air and 1 atm of oxygen at 755 ± 5° and 835 ± 5°C, respectively.     

Phase Diagram Studies in the System Tl2O3–BaO–CaO–CuO–Ag

The phase relations within the system Tl₂O₃–BaO–CaO–CuO including Ag have been studied with emphasis on the high-temperature superconducting phases TlBa₂Ca₂Cu₃O_8.5 (1223 phase), Tl₂Ba₂Ca₂Cu₃O₁₀ (2223 phase), TlBa₂CaCu₂O_6.5 (1212 phase), and Tl₂Ba₂CaCu₂O₈ (2212 phase) at 890°C in an oxygen atmosphere. 1223 has been found to be in equilibrium with a liquid phase that is Tl poor. 2223 and 2212 exhibit varying Tl/(Ba + Ca) ratios. The three-phase field 1223 + 2223 + 2212 has been identified. The results of this study emphasize that multiphase samples can be prepared which consist of three superconducting phases, each exhibiting a critical temperature of 100 K or above.     

Tentative Phase Relationships in the System CaHfTi2O7-Gd2Ti2O7 with up to 15 mol% Additions of Al2TiO5 and MgTi2O5

The phase relationships in the CaHfTi₂O₇-Gd₂Ti₂O₇ (zirconolite-pyrochlore) pseudobinary system were investigated, after heating at 1500°C, because of their importance in the design of pyrochlore-rich titanate ceramics for immobilization of impure surplus plutonium. Up to 15 mol% of MgTi₂O₅ and Al₂TiO₅ were added to CaHfTi₂O₇-Gd₂Ti₂O₇ compositions to elucidate the effects of divalent and trivalent impurities on the phase stability within these systems. From X-ray diffractometry analysis, scanning electron microscopy, and energy dispersive X-ray spectrometry, phase formation and compositional stability limits were evaluated. The main phases observed in these systems were pyrochlore, perovskite, and polytypes of zirconolite. The formation of the 2 M -, 4 M -, and 3 O -zirconolite polytypes was dependent on the amount of aluminum or magnesium present. In the magnesium system, a large area of pyrochlore-only was observed, which indicated that divalent impurities of appropriate ionic size could be readily incorporated in the eightfold site of the pyrochlore. The locations of the tentative phase boundaries are discussed with respect to the chemical composition.     

Thermodynamic Calculation of the ZrO2–YO1.5–MgO System

A thermodynamic evaluation of the ZrO₂-MgO system has been developed and combined with previous assessments of the ZrO₂–YO_1.5 and YO_1.5–MgO systems to describe the ZrO₂–YO_1.5-MgO Systems to describe the ZrO₂–YO_1.5-MgO system by means of Bonnier's equation. The calculated results are shown by isothermal and vertical sections, a projection of the liquidus surfaces, and the reaction scheme. Comparisons between calculated and experimental diagrams demonstrate that the calculations satisfactorily account for most of the available experimental data.     

Ternary System Al2O3—MgO—CaO: Part II, Phase Relationships in the Subsystem Al2O3—MgAl2O4—CaAl4O7

Solid-state compatibility and melting relationships in the subsystem Al₂O₃—MgAl₂O₄—CaAl₄O₇ were studied by firing and quenching selected samples located in the isopletal section (CaO·MgO)—Al₂O₃. The samples then were examined using X-ray diffractomtery, optical microscopy, and scanning and transmission electron microscopies with wavelength- and energy-dispersive spectroscopies, respectively. The temperature, composition, and character of the ternary invariant points of the subsystem were established. The existence of two new ternary phases (Ca₂Mg₂Al₂₈O₄₆ and CaMg₂Al₁₆O₂₇) was confirmed, and the composition, temperature, and peritectic character of their melting points were determined. The isothermal sections at 1650°, 1750°, and 1840°C of this subsystem were plotted, and the solid-solution ranges of CaAl₄O₇, CaAl₁₂O₁₉, MgAl₂O₄, Ca₂Mg₂Al₂₈O₄₆, and CaMg₂Al₁₆O₂₇ were determined at various temperatures. The experimental data obtained in this investigation, those reported in Part I of this work, and those found in the literature were used to establish the projection of the liquidus surface of the ternary system Al₂O₃—MgO—CaO.     

Stabilization of Tetragonal ZrO2 in ZrO2–SiO2 Binary Oxides

Gel-glasses of various compositions in the x ZrO₂^.(10 – x )SiO₂system were fabricated by the sol–gel process. Precipitation due to the different reactivities between tetraethyl orthosilicate (TEOS) and zirconium(IV) n -propoxide has been eliminated through the use of 2-methoxyethanol as a chelating agent. Thermal treatment of these gels produced crystalline ZrO₂particles. While monoclinic is the stable crystalline phase of zirconia at low temperatures, the metastable tetragonal phase is usually the first crystalline phase formed on heat treatment. However, stability of the tetragonal phase is low, and it transforms to the monoclinic phase on further heat treatment. In this study, it has been found that the transformation temperature increases as the SiO₂content in the ZrO₂–SiO₂ binary oxide increases. The most significant results were from samples containing only 2 mol% SiO₂, where the metastable tetragonal phase formed at low temperatures and remained stable over a broad temperature range. X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to elucidate the structure of these binary oxides as a function of temperature.     

Effect of a liquid Phase on Superplasticity of 2-moI%-Y203-StabiIlzed Tetragonal Zirconla Polycrystals

A small addition of CuO to 2-mol%-Y₂O₃-stabilized tetragonal zirconia polycrystals significantly enhances superplasticity by forming an amorhous grain-boundary phase containing primarily Cu⁺, Y³⁺, Zr⁴⁺, and O²⁻. This phase apparently melts at around 1130°C, but it already provides a fast diffusion path even below the melting temperature. There are abrupt changes in stress exponent, activation energy, and grain size exponent across the melting temperature. Superplasticity is diffusion-controlled below the melting temperature and is interfaced-controlled above that.     

Contribution to the Phase Diagram Al4C3-AIN-SiC

Compositions on the join A1₄C₃·2AIN-A1₄C₃.2SiC were investigated using X-ray diffraction and thermal analysis of hot-pressed bodies prepared from materials of various purities. The quaternary phase A1₄C₃· AIN · SiC was observed in samples prepared from the high-purity elements, but the ternary phases A1₄C₃·2AIN and A1₄C₃·2SiC were observed only in samples containing significant impurities. A projection onto the base triangle at 1860°C for the pseudoternary system Al₄C₃-AlN-SiC was constructed using X-ray diffraction, thermal analysis, and existing information in the literature.     

Quaternary System Al2O3–CaO–MgO–SiO2: I, Study of the Crystallization Volume of Al2O3

Compatibility relations of Al₂O₃ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching followed by microstructural and energy-dispersive X-ray examination. A projection of the liquidus surface of the primary phase volume of Al₂O₃ was constructed in terms of the CaO, SiO₂, and MgO contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, were defined, and the positions of the isotherms were tentatively established. The effect of SiO₂, MgO, and CaO impurities on Al₂O₃ growth also was studied.