The System HfO2-Y2O3-Er2O3

A mathematical model of the liquidus surface based on a reduced polynomial method was proposed for the system HfO₂-Y₂O₃-Er₂O₃. The results of calculations according to this model agree fairly well with the experimental data. Phase equilibria in the system HfO₂-Y₂O₃-Er₂O₃ were studied on melted (as-cast) and annealed samples using X-ray diffraction (at room and high temperatures) and micro-structural and petrographic analyses. The crystallization paths in the system HfO₂-Y₂O₃-Er₂O₃ were established. The system HfO₂-Y₂O₃-Er₂O₃ is characterized by the formation of extended solid solutions based on the fluorite-type (F) form of HfO₂ and cubic (C) and hexagonal (H) forms of Y₂O₃ and Er₂O₃. The boundary curves of these solid solutions have the minima at 2370°C (15. 5 mol% HfO₂, 49. 5 mol% Y₂O₃) and 2360°C (10. 5 mol% HfO₂, 45. 5 mol% Y₂O₃). No compounds were found to exist in the system investigated.     

Energetics of La2O3–HfO2–SiO2 Glasses

A series of La₂O₃–HfO₂–SiO₂ glasses, approximately along the join 0.73SiO₂–0.27( x HfO₂–(1− x )La₂O₃), 0< x <0.3), was prepared using containerless processing techniques (aerodynamic levitation combined with laser heating in oxygen). The enthalpy of formation and enthalpy of vitrification at 25°C were obtained from drop solution calorimetry of these glasses and appropriate crystalline compounds in a molten lead borate (2PbO–B₂O₃) solvent at 702°C. The enthalpy of formation from crystalline oxides was exothermic and became less exothermic with increasing HfO₂ content. Heat contents were measured by transposed temperature drop calorimetry and depended linearly on the HfO₂ content. Differential scanning calorimetry showed that both the onset glass transition and the onset crystallization temperature of these glasses increased with increasing HfO₂ content. Upon slow cooling in air, the glasses crystallized to a mixture of baddeleyite, cristobalite, lanthanum disilicate, and hafnon.     

Phase Equilibria in the Hafnia–Yttria–Lanthana System

The HfO₂–Y₂O₃–La₂O₃ system was studied in the wide range of temperatures (1250°–2800°C) and concentrations by methods of X-ray analysis at 20°C, petrography, differential thermal analysis in helium at temperatures to 2500°C, thermal analysis in air using a solar furnace at temperatures to 3000°C, and electron microprobe X-ray analysis. The complete phase diagram was constructed. The liquidus and solidus projections, crystallization paths for the alloys, isothermal (1250°, 1600°, and 1900°C) and polythermal sections are presented. The structure of the boundary binary systems defines the phase equilibria in the ternary system. No ternary compounds were found. Ternary solid-solution regions were determined based on constituent oxides and intermediate phases.     

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.     

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.     

Experimental Investigation and Thermodynamic Assessment of the Nd2O3–Y2O3 System

The phase relations in the Nd₂O₃–Y₂O₃ system were experimentally studied in the 1300°–1600°C range. X-ray diffraction, scanning electron microscopy, and electron probe microanalysis were applied to analyze the phase composition of annealed Nd₂O₃–Y₂O₃ mixtures with varying Y₂O₃ content. A thermodynamic assessment was conducted using the experimental data obtained. The excess Gibbs energies of the solution phases were described based on a simple substitutional solution model. A consistent set of optimized interaction parameters was derived for the Gibbs energy of the constituent phases, resulting in a good match between calculated and experimental data.     

Phase Equilibrium Relationships at Liquidus Temperatures in the System FeO–Fe2O3–Al2O3–SiO2

Phase equilibrium data at liquidus temperatures are presented for mixtures in the system FeO–Fe₂O₃–Al₂O₃–SiO₂. The volume located between the 1 and 0.2 atm. O₂ isobaric surfaces of the tetrahedron representing this system was studied in detail. Scattered data were obtained at lower O₂ pressures. Results obtained in the present investigation were combined with data in the literature to construct a phase equilibrium diagram, at liquidus temperatures, for the entire system FeO–Fe₂O₃–Al 2 O₃–SiO₂. Methods for interpretation of the diagram are explained.     

Sintering of Al2O3–TiC Composite in the Presence of Liquid Phase

The results obtained from the sintering of Al₂O₃–50TiC (in weight percent) composite in the temperature range from 1650° to 1800°C with addition of Y₂O₃ are presented. Densification is accelerated by the formation of liquid at temperatures above 1750°C, and 99% of theoretical density can be achieved by vacuum sintering at 1800°C for 15 min. The liquid presented at the sintering temperature is crystallized to YAG (Y₃Al₅O₁₂) during cooling.     

Ionic Mobilities and Association Energies from an Analysis of Electrical Impedance of ZrO2–Y2O3 Alloys

The dc conductivities of ZrO₂–Y₂O₃ ceramic alloys (in the range 3–12 mol% of Y₂O₃) have been obtained from ac impedance measurements at temperatures between 250° and 370°C. The Almond–West ac conductivity model has been applied to evaluate hopping rates in this system. The migration enthalpies were evaluated and shown to increase with yttria concentration, but all values determined were shown to be lower than the corresponding activation enthalpies for conductivity. The association enthalpies thus calculated were shown to be very small in 3 mol% Y₂O₃–ZrO₃ and to increase with yttria concentration until the yttria contents were high enough to form fully stabilized cubic zirconia. For these samples the association enthalpies are about 0.19 eV, and no longer sensitive to yttria content. The low hopping rate at high yttria concentration might be attributed to low entropy in the system, which might be attributed to the formation of vacancy clusters and/or an ordering of the structure.     

Determination of CaO–SiO2–MgO–Al2O3–CrOx Liquidus

In this work, the liquidus of synthetic CaO–SiO₂–MgO–Al₂O₃–CrO _x slags is evaluated in the industrially relevant compositional domain. Equilibrium experiments are carried out at 1500°C and partial oxygen pressure ( p _O2) 10^−11.04 atm, and at 1600°C and p _O2=10^−10.16 and 10^−9.36 atm. The studied basicities (CaO/SiO₂) are 1.2 and 0.5. Al₂O₃ levels range from 0 to 30 wt%. Oversaturated liquid is sampled and phase relations are measured with quantitative electron probe microanalysis–wavelength dispersive spectroscopy (EPMA–WDS). The results are compared with the commercially available FactSage thermodynamic databases. Qualitative agreement is always obtained. Also a good quantitative agreement is found at the higher basicity, especially for the spinel liquidus. A minor but systematic deviation can be observed for the eskolaite liquidus. At the lower basicity, the calculated phase diagram deviates strongly from the experimental results, probably due to missing ternary interactions in the database.     

Thermodynamic Evaluation for the Y2O3–BaO–CuOx System

The thermodynamic data for the Y₂O₃–BaO–Cu₂O–CuO quaternary system were optimized from measured thermodynamic data. A two-sublattice model for ionic solution was used to express the Gibbs free energy of the liquid phase, and a two-sublattice regular solution model was used for the nonstoichiometric YBa₂Cu₃O_6+δ superconducting compound. The optimized thermodynamic data were used to calculate the phase diagrams of the Cu₂O–CuO binary system and the CuO _x –Y₂Cu₂O₅ and CuO _x –BaCuO₂ quasi-binary systems. The results were in good agreement with reported measured data. The liquidus projection and isothermal and vertical sections of the Y₂O₃–BaO-CuO _x quasi-ternary system were calculated. The effect of oxygen pressure on some reaction temperatures was predicted by calculating them at various oxygen pressures, and the oxygen contents (6 +δ) in YBa₂Cu₃O_6+δ were calculated at various temperatures and oxygen pressures. The results were compared with experimental data.     

Ionic Conductivity of Cubic Solid Solutions in the System CaO—Y2O3—ZrO2

The ionic conductivity of cubic solid solutions in the system CaO -Y₂O₃-ZrO₂ was examined. Particular Y₂O₃-ZrO₂ binary compositions were more conductive at elevated temperatures (>600°C) than either CaO-ZrO₂ binary or CaO-Y₂O₃-ZrO₂ ternary compositions. The higher ionic conductivity appears to be related to a lower activation energy rather than to the number of oxygen vacancies dictated by composition. Those compositions of highest conductivity lie close to the cubic-monoclinic solid-solution phase boundary. Conductivity-temperature data are presented that indicate a reversible order-disorder transition for Y₂O₃-ZrO₂ cubic solid solutions containing 20 and 25 mole % Y₂O₃. The transference number for the oxygen ion at 1000°C for Y₂O₂-ZrO₂ cubic solid solutions is greater than 0.99.     

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.     

Subsolidus Phase Relationships in the System Fe2O3–Al2O3–TiO2 between 1000° and 1300°C

Subsolidus phase equilibria in the system Fe₂O₃–Al₂O₃–TiO₂ were investigated between 1000° and 1300°C. Quenched samples were examined using powder X-ray diffraction and electron probe microanalytical methods. The main features of the phase relations were: (a) the presence of an M₃O₅ solid solution series between end members Fe₂TiO₅ and Al₂TiO₅, (b) a miscibility gap along the Fe₂O₃–Al₂O₃ binary, (c) an α-M₂O₃( ss ) ternary solid-solution region based on mutual solubility between Fe₂O₃, Al₂O₃, and TiO₂, and (d) an extensive three-phase region characterized by the assemblage M₃O₅+α-M₂O₃( ss ) + Cor( ss ). A comparison of results with previously established phase relations for the Fe₂O₃–Al₂O₃–TiO₂ system shows considerable discrepancy.     

Massive Transformation in the Y2O3-Bi2O3 System

Cubic solid solutions in the Y₂O₃-Bi₂O₃ system with ∼25% Y₂O₃ undergo a transformation to a rhombohedral phase when annealed at temperatures ≤ 700°C. This transformation is composition-invariant and is thermally activated, and the product phase can propagate across matrix grain boundaries, indicating that there is no special crystallo-graphic orientation relationship between the product and the parent phases. Based on these observations, it is proposed that cubic → rhombohedral phase transformation in the Y₂O₃-Bi₂O₃ system is a massive transformation. Samples of composition 25% Y₂O₃-75% Bi₂O₃ with and without aliovalent dopants were annealed at temperatures ≤ 700°C for up to 10000 h. ZrO₂ as a dopant suppressed while CaO and SrO as dopants enhanced the kinetics of phase transformation. The rate of cubic/rhombohedra1 interface migration (growth rate or interface velocity) was also similarly affected by the additions of dopants; ZrO₂ suppressed while CaO enhanced the growth rate. Diffusion studies further showed that ZrO₂ suppressed while CaO enhanced cation interdiffusion coefficient. These observations are rationalized on the premise that cation interstitials are more mobile compared to cation vacancies in cubic bismuth oxide. The maximum growth rate measured was ∼10⁻¹⁰ m/s, which is orders of magnitude smaller than typical growth rates measured in metallic alloys. This difference is explained in terms of substantially lower diffusion coefficients in these oxide systems compared to metallic alloys.     

Phase Relations in the System UO2-UO3– Y2O3

The phase relations in the system U02-U03-Yz03, particularly in the Y203-rich region, were examined by X-ray and chemical analyses of reacted powders heated at temperatures up to 1700°C in H₂, CO₂-CO₂ and air. Four phases were identified in the system at temperatures between 1000° and 1700°C: U308, face-centered cubic solid solution, body-centered cubic solid solution, and a rhombohedral phase of composition (U,Y)₇O₂ ranging from 52.5 to 75 mole % Y₂O₃. The rhombohedral phase oxidized to a second rhombohedral phase with a nominal composition (U,Y), at temperatures below 1000°C. This phase transformed to a face-centered cubic phase after heating in air above 1000° C. The solubility of UO, in the body-centered cubic phase is about 14 mole % between 1000° and 1700°C but decreases to zero as the uranium approaches the hexavalent oxidation state. The solubility of Yz03 in the face-centered cubic solid solution ranges from 0 to 50 mole % Y2O3 under reducing conditions and from 33 to 60 mole % Y2O3 under oxidizing conditions at 1000°C. At temperatures above 1000° C, the face-centered cubic solid solution is limited by a filled fluorite lattice of composition (U,Y)O₂. For low-yttria content, oxidation at low temperatures (<300°C) permits additional oxygen to be retained in the structure to a composition approaching (U,Y)O_2.25 A tentative ternary phase diagram for the system UO₂-UO₃-Y₂O₃ is presented and the change in lattice parameter and in cell volume for the solid-solution phases is correlated with the composition.     

Densification and Phase Transformation During Pressureless Sintering of Nanocrystalline ZrO2–Y2O3–CuO Ternary System

ZrO₂–Y₂O₃–CuO nanocrystalline powders have been synthesized using a chemical coprecipitation method. Nano-powders were compacted uniaxially and densified in a muffle furnace. Densification studies show that the presence of CuO accelerates the densification process of ZrO₂(3Y). A fully dense (>96%) pellet of ZrO₂(3Y)/5 mol% CuO was obtained after sintering at 900°C, with a very small grain size of 44 nm calculated by X-ray line broadening.     

Phase Transformation and Densification Behavior of Microwave-Sintered Si3N4–Y2O3–MgO–ZrO2 System

A 2.45 GHz microwave-sintered Si₃N₄–Y₂O₃–MgO system containing various amounts of ZrO₂ secondary additives have been studied with respect to phase transformation and densification behavior. The temperature dependent dielectric properties were measured from 25°C to 1400°C using a conventional cavity perturbation technique. Phase transformation behavior was studied using X-ray diffractometry. Microwave sintered results were compared with those of conventional sintered results. It has been found that α to β phase transformation was completed at a lower temperature in microwave-sintered samples than those of the conventionally sintered samples. Density of the microwave-sintered samples increased up to 2.5 wt% of ZrO₂ addition and thereafter it showed a tendency to decrease or remain constant. The decrease in density is attributed to the pore generation caused by decomposition due to the localized over heating.     

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.