Electrical Properties and Defect Structure of Y2O3

Guarded measurements of the electrical conductivity of high-purity, polycrystalline Y₂O₃ in thermodynamic equilibrium with the gas phase were made under controlled temperature and oxygen partial pressure conditions. Data are presented as isobars from 1200° to 1600°C, and as isotherms from oxygen partial pressures of 10⁻¹ to 10⁻¹⁷ atm. The ionic contribution to the total conductivity, determined by the blocking electrode polarization technique, was less than 1% over the entire range of temperatures and oxygen partial pressures studied. Yttria is shown to be an amphoteric semiconductor with the region of predominant hole conduction shifting to higher pressures at higher temperatures. In the region of p -type conduction, the conductivity is represented by the expression σ= 1.3 × 10³ p O₂^3/16 exp (-1.94/kT). The observed pressure dependence is attributed to the predominance of fully ionized yttrium vacancies. Yttria is shown to be a mixed conductor below 900°C.     

Eutectic Composition in the Pseudobinary of Y4Al2O9 and Y2O3

The eutectic composition between Y₄Al₂O₉ and Y₂O₃ was determined using electron probe microanalysis (EPMA) on directionally solidified specimens with hypo- and hypereutectic compositions. The microstructures of the specimens as a function of composition differ considerably with small deviation from the eutectic composition (70.5 mol% Y₂O₃ and 29.5 mol% Al₂O₃). Based on the current results and other published data, the pseudobinary system between Al₂O₃ and Y₂O₃ is revised.     

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.     

Cation Self-Diffusion in Polycrystalline Y2O3 and Er2O3

A tracer sectioning technique was used to measure cation self-diffusion coefficients in fully dense polycrystalline Y_aO₃ and Er₂O_s under oxidizing conditions. The results are described by the relations for Y₂O₃ (1400° to 1670°C), and for Er₂O₃ (1400° to 1700°C). The greater activation energy for erbium diffusion in erbia may be partly attributable to a mass effect.     

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.     

Improvement of Mechanical Properties and Corrosion Resistance of Porous β-SiAlON Ceramics by Low Y2O3 Additions

Addition of Y₂O₃ as a sintering additive to porous β-SiAlON (Si_{6− z} Al _z O _z N_{8− z} , z = 0.5) ceramics has been investigated for improved mechanical properties. Porous SiAlON ceramics with 0.05–0.15 wt% (500–1500 wppm) Y₂O₃ were fabricated by pressureless sintering at temperatures of 1700°, 1800°, and 1850°C. The densification, microstructure, and mechanical properties were compared with those of Y₂O₃-free ceramics of the same chemical composition. Although this level of Y₂O₃ addition did not change the phase formation and grain size, the grain bonding appeared to be promoted, and the densification to be enhanced. There was a significant increase in the flexural strength of the SiAlON ceramics relative to the Y₂O₃-free counterpart. After exposure in 1 M hydrochloric acid solution at 70°C for 120 h, no remarkable weight loss and degradation of the mechanical properties (flexural and compression strength) was observed, which was attributed to the limited grain boundary phase, and with the minor Y₂O₃ addition the supposed formation of Y-α-SiAlON.     

Field-Assisted Densification of Superhard B6O Materials with Y2O3/Al2O3 Addition

B₆O is a possible candidate of superhard materials with a hardness of 45 GPa measured on single crystals. Up to now, densification of these materials was only possible at high pressure. However, recently it was found that Al₂O₃ can be utilized as an effective sintering additive, similar to the addition of Y₂O₃/Al₂O₃ that was used in this work. The densification behavior of the material as a function of applied pressure, its microstructure evolution, and the resulting mechanical properties were investigated. A strong dependence of the densification with increasing pressure was found. The material revealed characteristic triple junctions filled with amorphous residue composed of B₂O₃, Al₂O₃, and Y₂O₃, while no amorphous grain-boundary films were observed along internal interfaces. Mechanical testing revealed on average a hardness of 33 GPa, a fracture toughness of 4 MPa·m^1/2, and a strength value of 520 MPa.     

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.     

Oxygen Self-Diffusion in Single-Crystal Y2O3

Self-diffusion coefficients of the oxygen ion in single-crystal Y₂O₃ were determined by the gas-solid isotope exchange technique. The results in the range 1100° to 1500°C are described by D=7.3 X 10^-6 exp [-19l(kJ/mol)/RT] cm²/s. Comparison of the results with those for oxides with the fluorite-type structure indicates that the regularly arranged vacant anion sites in the C-type structure do not contribute eflectively to oxygen ion diffusion .     

Stable and Metastable Equilibria in the Systems Y2O2-Al2O3, and Gd2O3-Fe2O3

The phase equilibrium relations in the systems Y₂O₃-Al₂O₃ and Gd₂O₃-Fe₂O₃ were examined. Each system has two stable binary compounds. A 3:s molar ratio garnet-type compound exists in both systems. The 1:1 distorted perovskite structure is stable in the system Gd₂O₃-Fe₂O₃ but only metastable in the system Y₂O₃-AI₂O₃. This interesting example of metastable formation and persistence of a compound with ions of high Z/r values explains the discrepancies in the literature on the structure of the composition YA1O₃. A new 2:1 molar ratio cubic phase has been found in the system Y₂O₃-A1₂O₃. Since silicon can be completely substituted for aluminum in this compound, the aluminum ions are presumably in fourfold coordination.     

Fabrication of Transparent, Sintered Sc2O3 Ceramics

We report here the fabrication of transparent Sc₂O₃ ceramics via vacuum sintering. The starting Sc₂O₃ powders are pyrolyzed from a basic sulfate precursor (Sc(OH)_2.6(SO₄)_0.2·H₂O) precipitated from scandium sulfate solution with hexamethylenetetramine as the precipitant. Thermal decomposition behavior of the precursor is studied via differential thermal analysis/thermogravimetry, Fourier transform infrared spectroscopy, X-ray diffractometry, and elemental analysis. Sinterability of the Sc₂O₃ powders is studied via dilatometry. Microstructure evolution of the ceramic during sintering is investigated via field emission scanning electron microscopy. The best calcination temperature for the precursor is 1100°C, at which the resultant Sc₂O₃ powder is ultrafine (∼85 nm), well dispersed, and almost free from residual sulfur contamination. With this reactive powder, transparent Sc₂O₃ ceramics having an average grain size of ∼9 μm and showing a visible wavelength transmittance of ∼60–62% (∼76% of that of Sc₂O₃ single crystal) have been fabricated via vacuum sintering at a relatively low temperature of 1700°C for 4 h.     

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.