Properties of Ionic-Conducting β-Bi2O3 Containing Mixed Dopants

β-Bi₂O₃ compositions were prepared to evaluate the effect on properties of using mixed dopants. Baseline compositions containing 28 mol% of the alkaline-earth oxides CaO, SrO, or BaO were used for comparison. When the alkaline earths were combined in pairs to dope the bismuth oxide, the resulting properties were intermediate between the baseline end members. The data suggest that the transformation temperature for forming the high-conductivity β₁ phase can be varied continuously over a temperature range of about 565° to 750°C. Utilization of additional additives having different ionic size or valence charge compared with the alkaline earths resulted in no observed property changes that could be attributed to the additive alone. The most important variables influencing the conductivity level and phase transformation temperature of β-Bi₂O₃ were the type and the amount of the alkaline-earth dopant in the composition.     

Depolymerization of GeO2 and B2O3-GeO2 Network Glasses by Sb2O3

Binary Sb₂O₃-GeO₂ glasses containing 45 mol% Sb₂O₃ and ternary Sb₂O₃-B₂O₃-GeO₂ glasses containing 50 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined, and their colors and high-temperature viscosities were estimated visually. Small amounts of Sb₂O₃ (∼10 mol%) appear to perturb neither the Ge-O-Ge network nor those B-O-Ge networks with small B/Ge ratios (∼0.2). The B-O-Ge networks with larger B/Ge ratios (∼1.0) depolymerize in the presence of even less Sb₂O₃. Amounts of Sb₂O₃ >10 mol% appear to depolymerize the Ge-O-Ge and Ge-O-B networks progressively, possibly with the formation of chains. A structurally sensitive ir isofrequency contour technique developed for ternary glass systems was applied successfully to these Sb₂O₃-B₂O₃-GeO₂ glasses. These contours can thus readily detect significant network depolymerization in the absence of the usual network modifiers.     

The Influence of Sb2O3 Addition on the Properties of Low-melting ZnO–P2O5 Glasses

The influence of 0–16 mol% Sb₂O₃ substitution for P₂O₅ on the properties of ZnO–P₂O₅ glasses has been investigated. It was shown that Sb₂O₃ could participate in the glass network and thermal stability of the glasses decreased with increasing Sb₂O₃ content. Glass transition temperature T _g, softening temperature T _s, and water durability all decreased firstly (up to 6 mol% Sb₂O₃ added) and then increased. Substitution of 12 mol% Sb₂O₃ led to a 16°C decrease in T _g and 30°C decrease in T _s, and weight loss of the glass was only 0.42 mg/cm², which is ∼11 times lower than that of the glass without Sb₂O₃ after immersion in deionized water at 90°C for 1 day. The glass containing 12 mol% Sb₂O₃ might be a substitute for Pb-based glasses in some applications.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Phase Equilibria in the Ga2O3In2O3 System

Subsolidus phase relationships in the Ga₂O₃–In₂O₃ system were studied by X-ray diffraction and electron probe microanalysis (EPMA) for the temperature range of 800°–1400°C. The solubility limit of In₂O₃ in the β-gallia structure decreases with increasing temperature from 44.1 ± 0.5 mol% at 1000°C to 41.4 ± 0.5 mol% at 1400°C. The solubility limit of Ga₂O₃ in cubic In₂O₃ increases with temperature from 4.X ± 0.5 mol% at 1000°C to 10.0 ± 0.5 mol% at 1400°C. The previously reported transparent conducting oxide phase in the Ga-In-O system cannot be GaInO₃, which is not stable, but is likely the In-doped β-Ga₂O₃ solid solution.     

Ionic Conductivity of the Fluorite-Type Hafnia–R2O3 Solid Solutions

The ionic conductivity of the hafnia-scandia, hafnia-yttria, and hafnia-rare earth solid solutions with high dopant concentrations of 8, 10, and 14 mol% was measured in air at 600° to 1050°C. Impedance spectroscopy was used to obtain lattice conductivity. A majority of the investigated samples exhibited linear Arrhenius plots of the lattice conductivity as a function of temperature. For all investigated dopant concentrations the ionic conductivity was shown to decrease as the dopant radius increased. The activation enthalpy for conduction was found to increase with dopant ionic radius. The fact that the highest ionic conductivity among 14-mol%-doped systems was obtained with HfO₂─Sc₂O₃ suggested that the radius ratio approach should be used to predict the electrical conductivity behavior of HfO₂─R₂O₃ systems. A qualitative model based on the Kilner's lattice parameter map does not seem to apply to these systems. For the three systems HfO₂─Yb₂O₃, HfO₂─Y₂O₃, and Hf₂O₃─Sm₂O₃ a conductivity maximum was observed near the dopant concentration of 10 mol%. Deep vacancy trapping is responsible for the decrease in the ionic conductivity at high dopant concentrations. Formation of microdomains of an ordered compound cannot explain the obtained results. A comparison between the ionic conductivities of doped HfO₂ and ZrO₂ systems indicated that the ionic conductivities of HfO₂ systems are 1.5 to 2.2 times lower than the ionic conductivities of ZrO₂ systems.     

Nature of Intergranular Phase in Nonohmic ZnO Ceramics Containing 0.5 Mol% Bi2O3

The intergranular phase obtained by sintering a binary mixture of ZnO + 0.5 mol% Bi₂O₃ was isolated by using a dilute solution of HCIO₄, which etches ZnO preferentially. The combined results of selected-area electron diffraction and microscopy, microprobe analysis, and X-ray diffraction strongly indicate that the intergranular material is a polycrystalline phase of tetragonal β-Bi₂O₃ ( P 42₁ c ), rather than the amorphous ZnO-Bi₂O₃ phase reported earlier. It appears that the nonohmic behavior in this prototype metal-oxide varistor must be an interfacial property associated with the semiconducting ZnO grains separated by thin layers of high-resistivity Bi₂O₃.     

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.     

Polymer Mixtures in Na2O.Sb2O3.GeO2 Glasses

Ternary Na₂O.Sb₂O₃.GeO₂ glasses (with various [Na]/[Na + Sb] ratios) that contained ≥65 mol% GeO₂ were prepared. Their densities (volumes), refractive indices, and infrared spectra were determined and their colors noted. The ternary glasses with ≥88 mol% GeO₂ exhibit nearly additive volumes, refractivities, and frequencies for the main Ge-O vibration. Ternary glasses with lesser amounts of GeO₂ exhibit a variety of behaviors, depending on the [Na]/[Na + Sb] ratio. Small amounts of Sb₂O₃ cause significant volume and refraction deviations, as well as changes in ν_Ge-O, that can be associated with gradual elimination of GeO₆ octahedra. All the information supports a model for the glasses with 65 to 88 mol% GeO₂ that involves a degree of depolymerization that is greater when Na₂O and Sb₂O₃ are present together than when either is present alone.     

Electrical Conduction in Single-Crystal and Polycrystalline Al2O3 at High Temperatures

The electrical conductivity and ion/electron transference numbers in Al₃O₃ were determined in a sample configuration designed to eliminate influences of surface and gas-phase conduction on the bulk behavior. With decreasing O₂ partial pressure over single-crystal Al₂O₃ at 1000° to 1650°C, the conductivity decreased, then remained constant, and finally increased when strongly reducing atmospheres were attained. The intermediate flat region became dominant at the lower temperatures. The emf measurements showed predominantly ionic conduction in the flat region; the electronic conduction state is exhibited in the branches of both ends. In pure O₂ (1 atm) the conductivity above 1400°C was σ≃3×10³ exp (–80 kcal/ RT ) Ω⁻¹ cm⁻¹, which corresponds to electronic conductivity. Below 1400°C, the activation energy was <57 kcal, corresponding to an extrinsic ionic condition. Polycrystalline samples of both undoped hot-pressed Al₂O₃ and MgO-doped Al₂O₃ showed significantly higher conductivity because of additional electronic conduction in the grain boundaries. The gas-phase conduction above 1200°C increased drastically with decreasing O₂ partial pressure (below 10⁻¹⁰ atm).     

Dielectric Properties of the Fluorite-like Bi2O3–Nb2O5 Solid Solution and the Tetragonal Bi3NbO7

Our analysis of the microwave dielectric properties of the δ-Bi₂O₃–Nb₂O₅ solid solution (δ-BN_ss) showed a continuous increase in permittivity and dielectric losses with an increasing concentration of Nb₂O₅. The only discontinuity was found for the temperature coefficient of resonant frequency, which is negative throughout the entire homogeneity range but reaches a minimum value for the sample with 20 mol% Nb₂O₅. At the same composition there is a discontinuity in the grain size of the δ-BN_ss ceramics. For the sample containing 25 mol% Nb₂O₅ two structural modifications were observed. A single-phase tetragonal Bi₃NbO₇, in the literature referred to as a Type-III phase, is formed in a very narrow temperature range from 850° to 880°C. A synthesis performed below or above this temperature range resulted in the formation of the end member of the δ-BN_ss homogeneity range. Compared with the δ-BN_ss the Bi₃NbO₇ ceramics exhibit lower microwave dielectric losses, an increased conductivity, and a positive temperature coefficient of resonant frequency.     

Temperature/Composition Phase Diagram of the System Bi2O3-PbO

The Bi₂O₃-PbO phase diagram was determined using differential thermal analysis and both room- and high-temperature X-ray powder diffraction. The phase diagram contains a single eutectic at 73 mol% PbO and 635°C. A body-centered cubic solid solution exists above ∼600°C within a composition range of 30 to 65 mol% PbO. The compounds α-Bi₂O₃, σ5-Bi₂O₃, and γ-PbO (litharge) have wide solubility ranges. Four compounds, 6Bi₂O₃·PbO, 3Bi₂O₃·2PbO, 4Bi₂O₃,5PbO, and Bi₂O₃·3PbO, are formed in this system and the previously unreported X-ray diffraction patterns of the latter three compounds are reported. Diffraction patterns for some of these mixed oxides have been observed in ZnO-based varistors grown using Bi₂O₃ and PbO as sintering aids.     

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.     

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.     

Changes in Aging Behavior and Defect Structure of Yttria-Fully-Stabilized ZrO2 with Sc2O3 Doping

Methods of suppressing decreased conductivity in 8 mol% Y₂O₃-stabilized–92 mol% ZrO₂ (8YSZ) with aging were investigated. Different amounts of Sc₂O₃ were doped into 8YSZ. The electrochemical properties of Sc₂O₃-doped 8YSZ were measured, and the microstructural and local structural changes were characterized. The present results indicate that an appropriate amount of Sc₂O₃ doping, 3 or 4 mol%, effectively suppresses decreased conductivity with aging in 8YSZ.     

Spectroscopic Properties of Er3+-Doped Na2O–La2O3–Al2O3–SiO2 Glasses

Er³⁺-doped sodium lanthanum aluminosilicate glasses with compositions of (90− x )(0.7SiO₂·0.3Al₂O₃)· x Na₂O·8.2La₂O₃· 0.6Er₂O₃·0.2Yb₂O₃·1Sb₂O₃ (in mol%) ( x = 12, 20, 24, 40, 60 mol%) were prepared and their spectroscopic properties were investigated. Judd–Ofelt analysis was used to calculate spectroscopic properties of all glasses. The Judd–Ofelt intensity parameter Ω _t ( t = 2, 4, 6) decreases with increasing Na₂O. Ω₂ decreases rapidly with increasing Na₂O while Ω₄ and Ω₆ decrease slowly. Both the fluorescent lifetime and the radiative transition rate increase with increasing Na₂O. Fluorescence spectra of the ⁴ I _13/2 to ⁴ I _15/2 transition have been measured and the change with Na₂O content is discussed. It is found that the full width at half-maximum decreases with increasing Na₂O.     

Differences in Wetting Characteristics of Bi2O3 Polymorphs in ZnO Varistor Materials

Detailed analysis of the microstructure of grain boundaries, especially triple-grain and multiple-grain junctions, in ZnO varistor materials has been performed using transmission electron microscopy. Different polymorphs of Bi₂O₃ are shown to exhibit different wetting properties on ZnO interfaces. Recent investigations suggest that the equilibrium configuration consists of crystalline Bi₂O₃ in the triple-grain and multiple-grain junctions and an amorphous bismuth-rich film in the ZnO/ZnO grain boundaries. The present investigation supports this suggestion for δ-Bi₂O₃ and also adds to the microstructural image and wetting properties of α-Bi₂O₃.     

Formation and Transformation of δ-Ta2O5 Solid Solution in the System Ta2O5-Al2O3

In the system Ta₂O₃-Al₂O₅ solid solutions of metastable δ-Ta₂O₅ (hexagonal) are formed up to 50 mol% Al₂O₃ from amorphous materials prepared by the simultaneous hydrolysis of tantalum and aluminum alkoxides. The values of the lattice parameters decrease linearly with increasing Al₂O₃, content. The to β-Ta₂O₅ (orthorhombic, low-temperature form) transformation occurs at ∼950°C. The solid solution containing 50 mol% Al₂O₃ transforms at 1040° to 1100°C to orthorhombic TaAlO₄. Orthorhombic TaAlO₄ contains octahedral TaO₆ groups in the structure.     

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.     

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.