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.     

Defects and Charge Transport in β-Ta2O5: II, Analysis of the Conductivity of Nb2O5-doped β-Ta2O5

The model proposed to explain the defect behavior of nominally pure β-Ta₂O₅ was extended to the case of defect equilibria and charge transport in β-Ta₂O₅ doped with a multivalent cation, i.e., Nb₂O₅-doped P-Ta₂O₅. This case is of practical interest in the electronics industry, where Nb₂O₅, is a dominant impurity in capacitor-grade β-Ta₂O₅.     

Electrical Conduction in Sintered α-Sb2O4

Electrical conductivity and thermoelectric power were measured on sintered α-Sb₂O₄ at 250° to 780°C. Oxygen partial pressure dependence of the conductivity and sign of the Seebeck coefficient showed α-Sb₂O₄ to be a p -type semiconductor above 600°C in the oxygen pressure range of lo⁵ to 10² Pa. A hopping conduction was proposed from very small hole mobility with an activation energy of 18 kJ/mol.     

Defects and Charge Transport in β-Ta2O5: I, Analysis of the Conductivity Observed in Nominally Pure β-Ta2O5

Simple ionic defect theory has not been successful in describing the observed defect and transport behavior in β-Ta₂O₅. The available data were reviewed, and a revised model is proposed which more adequately describes the defect behavior of nominally pure or lightly doped β-Ta₂O₅.     

Mixed Protonic–Electronic Conduction in "α-Al2O3": An Alternative Hypothesis

As an alternative, the voltage data of Kurita et al . recently published on galvanic cells with commercial α-Al₂O₃ as a solid electrolyte and with O₂, H₂O/α-Al₂O₃ as well as H₂, H₂O/α-Al₂O₃ as electrodes can be quantitatively described by assuming that α-Al₂O₃ represents a mixed sodium ionic–electronic conductor rather than a protonic–electronic conductor. From the evaluation of the experimental data, numerical values for the p -type electronic conduction parameter are obtained that agree sufficiently well with the data known to date for the sodium ion conductor Na-beta-Al₂O₃.     

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.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

Atomistic Simulation of Defect Structures and Ion Transport in α-Fe2O3 and α-Cr2O3

Computer-modelling techniques are applied to the calculation of defect formation and migration energies in α-Fe₂O₃ and α-Cr₂O₃: both electronic and lattice defects are considered. The results are used to predict Arrhenius energies for cation and anion migration in different composition and temperature regimes and show reasonable agreement with experimental data where these are available.     

Low-Activation-Energy Conduction in Polycrystalline α-AI2O3 Doped with Si and Na

Polycrystalline AI₂O₃ containing a glassy aluminosilicate second phase displays a low-activation-energy conductivity when Na is present. The conductivity is ionic in nature at high oxygen pressure and electronic at low oxygen pressure and is attributed to the migration of Na⁺ ions and electrons through the second phase present at triple junctions. A smaller low-activation-energy conductivity is found in the absence of sodium, but in that case the low-activation-energy branch has different properties. AI₂O₃:Na without silicon bas no low-temperature low-activation-energy branch.     

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.     

Anion Diffusion in α-Cr2O3

Oxygen-18 exchange between gaseous oxygen, held at a pressure of 125 mm Hg in a Pt10Rh chamber, and spheres of α-Cr₂O₃ containing three or less grains was determined from 1100° to 1450°C. Isotope equilibrium on crystal surfaces appears to be quickly established, and the rate-determining factor is self-diffusion conforming to the relation D = 15.9 exp(-101,000/ RT) cm²sec⁻¹. Changing sphere diameters caused no detectable variation in diffusion coefficients. Anions are the much slower diffusing species in this oxide.     

High-Temperature Phase Relations in the System Gd2O3-Ta2O5

The Phase relations of the system Gd₂O₃-Ta₂O₅ in the composition range 50 to100 mol% Gd2O3 was studied by solidstate reactions at 1350°, 1500°, or 1700°C and by thermal analyses up to the melting temperatures. Weberite-type orthorhombic phase (W2 phase, space group C2221) with the composition of Gd3 TaO7 seems to melt incongruently; at about 2040°C, although this Gd₃TaO₇ Phase was previously reported to melt congruently. A new fluorite-type cubic phase (F phase, space group Fm3m ) was found for the first time above 1500°C in the system. It melts congruently with the composition of about 80mol% Gd2O3at 2318° 3°C. A phase diagram was proposed for the system Gd₂O3–Ta2O₅ in the Gd₂O₃–rich portion     

Oxygen Mobility in Polycrystalline NiCr2O4 and α-Fe2O3

Oxygen diffusion coefficients have been determined for polycrystalline samples of NiCr₂O₄ and α-Fe₂O₃ by exchange measurements with oxygen gas containing the stable isotope¹⁸O, using mass spectrometer analysis. Oxygen diffusion in NiCr₂O₄ can be represented by the equation D = 0.017 exp (-65,400/RT); oxygen diffusion in α-Fe₂O₃ can be represented by the equation D = 1 × 10¹¹ exp (-146,000/RT). The large difference between D₀ and activation energy for these materials suggests that different diffusion mechanisms are involved.     

Initial Sintering of α-Cr2O3

Since the difference between oxygen-ion and cation diffusion coefficients is greater for α-Cr₂O₃ than for α-Fe₂O₃ or α-Al₂O₃, a study of initial-sintering kinetics was undertaken to show unequivocally which species is rate controlling. Fine powders of α-Cr₂O₃, obtained by thermal decomposition of reagent-grade (NH₄)₂Cr₂O₇, were lightly compacted and their isothermal rates of shrinkage were determined between 1050° and 1300°C. Resultant data follow volume-diffusion sintering models, and calculated diffusion coefficients agree with, those measured for oxygen ions in α-Cr₂O₃. There is little evidence that oxygen diffusion along grain boundaries becomes so enhanced that chromium ions are left in control of the process.     

Refractory α-SiAlON Containing La2O3

Refractory Y-α-SiAlON with elongated grain morphology was obtained by utilizing La₂O₃ as a densification aid, which resulted in excellent room-temperature and high-temperature strength. Room-temperature strength of 1000 MPa was achieved when La₂O₃ was augmented by adding Y₂O₃ or removing AlN. With only La₂O₃, a temperature-independent strength of 800–950 MPa was maintained up to 1100°C, then gradually decreasing by 25% when reaching 1300°C. The R-curve measurements of fracture toughness showed relatively little dependence on microstructure, consistent with a strong interface that suppresses grain boundary decohesion. Compared with other densification aids such as SiO₂, Al₂O₃, Sc₂O₃, Y₂O₃, and Lu₂O₃, a finer microstructure was obtained by using La₂O₃. High nitrogen content in the residual La–Si–Al–O–N glass in equilibrium with the nitrogen-rich α-SiAlON is suggested to be the cause of these findings.     

Nanocrystalline α-Al2O3 Using Sucrose

Nanocrystalline α-Al₂O₃ ceramic powders have been prepared from an aqueous solution of aluminum nitrate and sucrose. Soluble Al ion-sucrose solution forms the precursor material once it is completely dehydrated. Heat treatment of the dehydrated precursors at low temperature (600°C) results in the formation of porous single-phase α-Al₂O₃. The precursor and heat-treated powders have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and BET surface area analysis. The phase-pure nanocrystalline α-Al₂O₃ particles had an average specific surface area of >190 m²/g, with an average pore size between 18 and 25 nm.     

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.     

Electrical Conduction in β-Bi2O3 Doped with Sb2O3

Electrical conduction in tetragonal β-Bi₂O₃ doped with Sb₂O₃ was investigated by measuring electrical conductivity, ionic transference number, and Seebeck coefficient. The β-Bi₂O₃ doped with 1 to 10 mol% Sb₂O₃ was stable up to 600°C and showed an oxygen ionic and electronic mixed conduction, where the electron conduction was predominant at low oxygen pressures. The oxygen-ion conductivity showed a maximum at 4 mol% Sb₂O₃, whereas the activation energy for the ionic conduction remained unchanged for 4 to 10 mol% Sb₂O₃-doped specimens. These results were interpreted in terms of the oxygen vacancy concentration and the distortion of the tetragonal structure. The electron conductivity and its oxygen pressure dependence decreased with increasing Sb₂O₃ content. The fact that Sb⁵⁺ is partially reduced by excess electrons in heavily doped β specimens at low oxygen pressures is explained.     

Oxygen Diffusion in MgO and α-Fe2O3

Oxygen-diffusion coefficients were determined in single crystals of MgO and α-Fe₂O₃ by exchanging the samples with ¹⁸O enriched gas at 1 atm and measuring ¹⁸O profiles using a proton activation technique. For MgO, in the temperature range 1580 to 1820 K, the diffusion coefficient is represented by: