Subsolidus Phase Relations in the Ga2O3-In2O3-SnO2 System

Subsolidus phase relationships in the Ga₂O₃–In₂O₃–SnO₂ system were studied by X-ray diffraction over the temperature range 1250–1400°C. At 1250°C, several phases are stable in the ternary system, including Ga₂O₃( ss ), In₂O₃( ss ), SnO₂, Ga_{3− x} In_{5+ x} Sn₂O₁₆, and several intergrowth phases that can be expressed as Ga_{4−4 x} In_{4 x} Sn _{n −4}O_{2 n −2} where n is an integer. An In₂O₃–SnO₂ phase and Ga₄SnO₈ form at 1375°C but are not stable at 1250°C. GaInO₃ did not form over the temperature range 1000–1400°C.     

The System CaO-Ga2O3

CaO and Ga₂O₃ form three compounds: 3CaO-Ga₂O₃, CaO-Ga₂O₃, and CaO-2Ga₂O₃. 3CaO-Ga₂O₃ melts incongruently to CaO plus liquid at 1263°C.; CaO Ga₂O₃ and CaO 2Ga₂O₃ melt congruently at 1369° and 1504°C. respectively. Eutectics are located at the following temperatures and compositions (in mole% Ga₂O₃): between 3CaO Ga₂O₃ and CaO Ga₂O₃, 1245°C. and 37.5%; between CaO Ga₂O₃ and CaO-2Ga₂O₃,1323^oC. and 57.0%; and between CaO -2Ga₂O₃ and β-Ga₂O₃,1457°C. and 68.0%. There is a peritectic at 1263°C. and 36.0%. Three polymorphs of CaO Ga₂O₃ are described. Compositions from approximately 35 to 70 mole% Ga₂O₃ can be quenched to yield homogeneous glasses.     

Phase Relations and Lattice Constants in the MgO-Al2O3-Ga2O3 System at 1550°C

Phase relations and lattice constants in the MgO–Al₂O₃–Ga₂O₃ system at 1550°C have been determined experimentally. In a large part of this system, only a nonstoichiometric spinel is stable. Compositions as extreme as 12.5 mol% MgO–20.5 mol% Ga₂O₃–67 mol% Al₂O₃ for a homogeneous spinel are possible. In the bordering phase diagrams of MgO–Al₂O₃ and MgO–Ga₂O₃, the composition of the spinel is as high as 63 mol% Al₂O₃ or Ga₂O₃, respectively. The contributions of all simple ionic exchange reactions on the lattice constant of the spinel have been deduced from X-ray diffractometry data.     

Subsolidus Phase Relationships in the Ga2O3–Al2O3–TiO2 System

Subsolidus phase relationships in the Ga₂O₃–Al₂O₃–TiO₂ system at 1400°C were studied using X-ray diffraction. Phases present in the pseudoternary system include TiO₂ (rutile), Ga_{2−2 x} Al_{2 x} O₃ ( x ≤0.78 β-gallia structure), Al_{2−2 y} Ga_{2 y} O₃ ( y ≤0.12 corundum structure), Ga_{2−2 x} Al_{2 x} TiO₅ (0≤ x ≤1 pseudobrookite structure), and several β-gallia rutile intergrowths that can be expressed as Ga_{4−4 x} Al_{4 x} Ti _{n −4}O_{2 n −2} ( x ≤0.3, 15≤ n ≤33). This study showed no evidence to confirm that aluminum substitution of gallium stabilizes the n =7 β-gallia–rutile intergrowth as has been mentioned in previous work.     

Solid-State Phase Equilibria in the ZnS-Ga2S3 System

The ZnS-Ga₂S₃ equilibrium phase diagram has been determined to 50 mol% over the temperature range 700° to 900°C. Samples of various compositions were prepared via solid-state diffusion starting from powders of the pure components. The identification of the phases was determined by X-ray diffraction methods. The principal feature of the phase equilibria is the eutectoid transformation at 818 ± 5°C of hexagonal wurtzite containing 16 ± 1 mol% Ga₂S₃ to cubic ZnS and tetragonal ZnGa₂S₄. ZnGa₂S₄ is the equilibrium compound at 50 mol% Ga_zS₃, but it exists over a considerable range of stoichiometry. The solubility of Ga₂S₃ in ZnS increases with increasing temperature to a maximum of 9 ± 1 mol% at the eutectoid temperature.     

Phase Diagram and Oxygen-Ion Conductivity in the Y2O3-Nb2O5 System

The phase equilibria in the Y₂O₃-Nb₂O₅ system have been studied at temperatures of 1500° and 1700°C in the compositional region of 0-50 mol% Nb₂O₅. The solubility limits of the C-type Y₂O₃ cubic phase and the YNbO₄ monoclinic phase are 2.5 (±1.0) mol% Nb₂O₅ and 0.2 (±0.4) mol% Y₂O₃, respectively, at 1700°C. The fluorite (F) single phase exists in the region of 20.1-27.7 mol% Nb₂O₅ at 1700°C, and in the region of 21.1-27.0 mol% Nb₂O₅ at 1500°C, respectively. Conductivity of the Y₂O₃- x mol% Nb₂O₅ system increases as the value of x increases, to a maximum at x = 20 in the compositional region of 0 ≤ x ≤ 20, as a result of the increase in the fraction of F phase. In the F single-phase region, the conductivity decreases in the region of 20-25 mol% Nb₂O₅, because of the decrease in the content of oxygen vacancies, whereas the conductivity at x = 27 is larger than that at x = 25. The conductivity decreases as the value of x increases in the region of 27.5 ≤ x ≤ 50, because of the decrease in the fraction of F. The 20 mol% Nb₂O₅ sample exhibits the highest conductivity and a very wide range of ionic domain, at least up to log p _O2=−20 (where p _O2 is given in units of atm), which indicates practical usefulness as an ionic conductor.     

High-Temperature Phase Relations in the Sc2O3-Ta2O5 System

The phase relations for the Sc₂O₃-Ta₂O₅ system in the composition range of 50-100 mol% Sc₂O₃ have been studied by using solid-state reactions at 1350°, 1500°, or 1700°C and by using thermal analyses up to the melting temperatures. The Sc_5.5Ta_1.5O₁₂ phase, defect-fluorite-type cubic phase (F-phase, space group Fm 3 m ), ScTaO₄, and Sc₂O₃ were found in the system. The Sc_5.5Ta_1.5O₁₂ phase formed in 78 mol% Sc₂O₃ at <1700°C and seemed to melt incongruently. The F-phase formed in ∼75 mol% Sc₂O₃ and decomposed to Sc_5.5Ta_1.5O₁₂ and ScTaO₄ at <1700°C. The F-phase melted congruently at 2344°± 2°C in 80 mol% Sc₂O₃. The eutectic point seemed to exist at ∼2300°C in 90 mol% Sc₂O₃. A phase diagram that includes the four above-described phases has been proposed, instead of the previous diagram in which those phases were not identified.     

Exsolution of β-Ga2O3 Crystalline Solutions in the System MgAl2O3-Ga2O3

The subsolidus phase equilibrium diagram for the pseudobinary join MgAl₂O₄-Ga₂O₃ was determined. The shape of the exsolution boundary was obtained by heat-treating samples pre- equilibrated at 1600°C. Crystalline solubility of Ga₂O₃ in MgAl₂O₄ decreased from 73 mole % at 1600°C to 55 mole % at 1200°C. The crystalline solution was formed by the replacement of Mg²⁺ions by Ga³⁺ ions to produce a cation defect spinel. The phase precipitated was the mono-clinic δ-Ga₂O₃ (=δ-Al₂O₃ structure). Changes in the ratios of relative X-ray diffraction intensities indicated that the crystalline solutions also disorder with temperature.     

Subsolidus Relations in the La2O3─CuO─CaO Phase Diagram and the La2O3─CuO Binary Join

The phase diagram for the CuO-rich part of the La₂O₃─CuO join was redetermined. La₂Cu₂O₅ was found to have a lower limit of stability at 1002°± 5°C and an incongruent melting temperature of ∼1035°C. LagCu₇O₁₉ had both a lower (1012°± 5°C) and an upper (1027°± 5°C) limit of stability. Subsolidus phase relations were studied in the La₂O₃─CuO─CaO system at 1000°, 1020°, and 1050°C in air. Two ternary phases, La_1.9Ca_1.1Cu₂O_5.9 and LaCa₂Cu₃O_8.6, were stable at these temperatures, with three binary phases, Ca₂CuO₃, CaCu₂O₃, and La₂CuO₄. La₂Cu₂O₅ and La₈Cu₇O₁₉ were stable only at 1020°C, and did not support solid-solution formation.     

Phase Equilibria and Ordering in the System ZrO2-Y2O3

The phase diagram for the system ZrO₂-Y₂O₃ was redetermined. The extent of the fluorite-type ZrO₂-Y_zO₃ solid solution field was determined with a high-temperature X-ray furnace, precise lattice parameter measurements, and a hydrothermal technique. Long range ordering occurred at 40 mol% Y₂O₃ and the corresponding ordered phase was Zr₃Y₄OL₁₂. The compound has rhombohedra1 symmetry (space group R 3), is isostructural with UY₆O_l2 and decomposes above 1250±50°C. The results indicate that the eutectoid may occur at a temperature <400°C at a composition between 20 and 30 mol% Y₂O₃ Determination of the liquidus line indicated a eutectic at 83± 1 mol% Y₂O₃ and a peritectic at 76 ± 1 mol% Y₂O₃.     

Subsolidus Phase Equilibria and Ordering in the System ZrO2-Y2O3

The subsolidus phase relations in the entire system ZrO₂-Y₂O₃ were established using DTA, expansion measurements, and room- and high-temperature X-ray diffraction. Three eutectoid reactions were found in the system: ( a ) tetragonal zirconia solid solution→monoclinic zirconia solid solution+cubic zirconia solid solution at 4.5 mol% Y₂O₃ and ∼490°C, ( b ) cubic zirconia solid solutiow→δ-phase Y₄Zr₃O₁₂+hexagonalphase Y₆ZrO₁₁ at 45 mol% Y₂O₃ and ∼1325°±25°C, and ( c ) yttria C -type solid solution→wcubic zirconia solid solution+ hexagonal phase Y₆ZrO₁₁ at ∼72 mol% Y₂O₃ and 1650°±50°C. Two ordered phases were also found in the system, one at 40 mol% Y₂O₃ with ideal formula Y₄Zr₃O₁₂, and another, a new hexagonal phase, at 75 mol% Y₂O₃ with formula Y₆ZrO₁₁. They decompose at 1375° and >1750°C into cubic zirconia solid solution and yttria C -type solid solution, respectively. The extent of the cubic zirconia and yttria C -type solid solution fields was also redetermined. By incorporating the known tetragonal-cubic zirconia transition temperature and the liquidus temperatures in the system, a new tentative phase diagram is given for the system ZrO₂-Y₂O₃.     

Phase Relations in the System CoNb2O6–CoTa2O6

The pseudobinary system CoNb₂O₅–CoTa₂O₆ was investigated. CoNb₂O₆ crystallizes in either the columbite or rutile structure, whereas CoTa₂O₆ assumes only the trirutile structure. In an argon atmosphere at about 1400°C, CoNb₂O₆ undergoes a phase transition from columbite or rutile. Between 1000° and 1400°C the solubility of CoTa₂O₆ in CoNb₂O₆ is about 10 mole %; in the same temperature region the solubility of CoNb₂O₆ in CoTa₂O₆ varies from about 40 to 70 mole %. The extensive solubility of CoNb₂O₆ in CoTa₂O₆ is explained by the ability of niobium to induce some disorder in the trirutile phase. The columbite to rutile transformation is also discussed on this basis.     

The Al2O3-Nd2O3 Phase Diagram

A tentative phase diagram for the system Al₂0₃-Nd₂O₃ is presented. Three compounds were obtained: a β -A1₂O₃-type compound, the perovskite NdAlO₃, and Nd₄Al₂O₉. The perovskite melts congruently (mp 2090°C), and the two other compounds exhibit incongruent melting behavior: β -Nd/Al₂O₃, mp 1900°C; Nd₄Al₂O₉, mp 1905°C. Two eutectics exist with the following compositions and melting points: 80 mol% Al₂O₃, 1750°C; 23 mol% Al₂O₃,1800°C. Nd₄Al₂O9 decomposes in the solid state at 1780°C.     

Phase Relations in the System Bi2O3-WO3

Phase relations in the system Bi₂O₃-WO₃ were studied from 500° to 1100°C. Four intermediate phases, 7Bi₂O₃· WO₃, 7Bi₂O₃· 2WO₃, Bi₂O₃· WO₃, and Bi₂O₃· 2WO₃, were found. The 7B₂O · WO₃ phase is tetragonal with a ₀= 5.52 Å and c ₀= 17.39 Å and transforms to the fcc structure at 784°C; 7Bi₂O₃· 2WO₃ has the fcc structure and forms an extensive range of solid solutions in the system. Both Bi₂O₃· WO₃ and Bi₂O₃· 2WO₃ are orthorhombic with (in Å) a ₀= 5.45, b ₀=5.46, c ₀= 16.42 and a ₀= 5.42, b ₀= 5.41, c ₀= 23.7, respectively. Two eutectic points and one peritectic exist in the system at, respectively, 905°± 3°C and 64 mol% WO₃, 907°± 3°C and 70 mol% WO₃, and 965°± 5°C and 10 mol% WO₃.     

High-Temperature Phase Relations in the System Y2O3-Ta2O5

The phase relations for the system y₂o₃–Ta₂o₅ in the composition range 50 to 100 mol% Y₂O₃ have been studied by solid-state reactions at 1350°, 1500°, or 17000C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phases (W2 phase, space group C222₁), fluorite-type cubic phases (F phase, space group Fm3m )and another orthorhombic phase (O phase, space group Cmmm )are found in the system. The W2 phase forms in 75 mol% Y₂O₃ under 17000C and O phase in 70 mol% Y₂O₃ up to 1700°C These phases seem to melt incongruently. The F phase forms in about 80 mol% Y₂O₃ and melts congruently at 2454° 3°C. Two eutectic points seem to exist at about 2220°C 90 mol% Y²O₃, and at about 1990°C, 62 mol% Y₂O₃. A Phase diagram including the above three phases were not identified with each other.     

Phase Equilibria and Ionic Conductivity in the System ZrO2−Yb2O3−Y2O3

The phase equilibria in the zirconia-rich part of the system ZrO₂−Yb₂O₃−Y₂O₃ were determined at 1200°, 1400°, and 1650°C. The stabilizing effects of Yb₂O₃ and Y₂O₃ were found to be quite similar with <10 mol% of either being necessary to fully stabilize the cubic fluorite-structure phase at 1200°C. The two binary ordered phases, Zr₃Yb₄O₁₂ and Zr₃Y₄O₁₂, are completely miscible at 1200°C. These were the only binary or ternary phases detected. The ionic conductivities of ternary specimens in this system were measured using the complex impedance analysis technique. For a given level of total dopant, the substitution of Yb₂O₃ for Y₂O₃ gives only minor increases in specimen conductivity.     

Phase Equilibria in the System Nd2O3-P2O5

The phase diagram for the system NdI₂O₃-P₂O₅ was constructed. Six intermediate compounds, having molar Nd₂O₃: P₂O₅ ratios of 3:1, 7:3, 1:1, 1:2, 1:3, and 1:5, were identified. The 3:1, 7:3, and 1:1 compounds are stable to at least 1500°C. The 1:2 compound decomposes to 1:1 and 1:3 at 730 ± 5°C. The 1:3 and 1:5 compounds melt congruently at 1280 ± 5° and 1055 ± 5°C, respectively. None of the neodymium phosphates show lower temperature limits of stability.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Phase Relations in the System Fe2O3–Fe3O4–YFeO3 in Air

Measurements were made of temperature and ternary composition for coexisting liquid and crystalline phases on the air isobar in the system Fe₂O₃-Fe₃O₄-YFeO₃ with particular regard to the stability range and compositional limits of yttrium iron garnet. Phase equilibrium relations were determined by conventional quenching techniques combined with measurements of loss in weight at the reaction temperature to locate true ternary compositions. The intersection of the air isobar with the ternary univariant boundary curve for coexisting magnetite, garnet, and liquid phases results in a eutectic-type situation at the composition Y_0.27Fe_1.73 O_2.87 and 1469°± 2°C. A similar intersection of the isobar with the boundary curve for coexisting garnet, orthoferrite, and liquid phases gives rise to a peritectic-type reaction at 1555° 3°C. and Y_0.44Fe_1.56 O_2.89 The yttrium iron garnet crystallizing from liquids within these temperature and composition limits contains up to 0.5 mole % iron oxide in excess of the stoichiometric formula in terms of the starting composition 37.5 mole % Y₂O₃, 62.5 mole % Fe₂O₃. At 1470° C. the garnet phase in equilibrium with oxide liquid contains 2 mole % FeO in solid solution. The small solubility of excess of iron oxide and partial reduction of the garnet phase in air are unavoidable during equilibrium growth from the melt.     

The System Sc2O3-WO3

Phase relations in the system Sc₂O₃-WO₃ were characterized. Two stable binary compounds were, found. The 1:3 compound, SC₂(WO₄)₃, melts congruently at 1640°±10°C and forms a simple eutectic with WO₃ at ∼90 mol% WO₃ and 1309°+10°C. The 3 : 1 compound, Sc₆WO₁₂, forms a simple eutectic with the 1:3 compound at -69 mol% WO₂, and 1580°+10°C. The melting temperature of SC₆WO₁₂ was >1600°C.