Ta2O5/Nb2O5 and Y2O3 Co-doped Zirconias for Thermal Barrier Coatings

Zirconia doped with 3.2–4.2 mol% (6–8 wt%) yttria (3–4YSZ) is currently the material of choice for thermal barrier coating topcoats. The present study examines the ZrO₂-Y₂O₃-Ta₂O₅/Nb₂O₅ systems for potential alternative chemistries that would overcome the limitations of the 3–4YSZ. A rationale for choosing specific compositions based on the effect of defect chemistry on the thermal conductivity and phase stability in zirconia-based systems is presented. The results show that it is possible to produce stable (for up to 200 h at 1000°–1500°C), single (tetragonal) or dual (tetragonal + cubic) phase chemistries that have thermal conductivity that is as low (1.8–2.8W/m K) as the 3–4YSZ, a wide range of elastic moduli (150–232 GPa), and a similar mean coefficient of thermal expansion at 1000°C. The chemistries can be plasma sprayed without change in composition or deleterious effects to phase stability. Preliminary burner rig testing results on one of the compositions are also presented.     

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.     

The System CaO-Al2O3-H2O

Phase equilibria have been determined in the system CaO-Al₂O₃-H₂O in the temperature range 100° to 1000°C. under water pressures of up to 3000 atmospheres. Only three hydrated phases are formed stably in the system: Ca(OH)₂, 3CaO·Al₂O₃·6H₂O, and 4CaO·3Al₂O₃-3H₂O. Pressure-temperature curves delineating the equilibrium decomposition of each of these phases have been determined, and some ther-mochemical data have been deduced therefrom. It has been established that both the compounds CaO·Al₂O₃ and 3CaO·Al₂O₃ have a minimum temperature of stability which is above 1000°C. The relevance of the new data to some aspects of cement chemistry is discussed.     

Microstructure, Conductivity, and NO2 Sensing Characteristics of α-Al2O3-Doped (8 mol% Sc2O3)ZrO2 Composite Solid Electrolyte

α-Al₂O₃-doped (8 mol % Sc₂O₃)ZrO₂ composite solid electrolyte has been investigated in the fabrication of solid-state ceramic gas sensors. The microstructure and electrical conductivity of the composite solid electrolyte have been measured over a range of temperature from 240°C to 596°C. The composite solid electrolyte has been found to exhibit a higher conductivity compared with the commonly used (8 mol% Y₂O₃)ZrO₂ at temperatures above ∼448°C. The sensing characteristics for NO₂ detection have been studied in the temperature range of 500–650°C at the low concentration from 10 to 30 ppm and at high concentration from 100 to 500 ppm of NO₂. The NO₂ sensor was found to respond reproducibly and rapidly to the variations of NO₂, concentration, indicating that the composite solid electrolyte has promising application as a solid electrolyte for on-board exhaust gas monitoring.     

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.     

High Electrical Conductivity and High Fracture Strength of Sc2O3-Doped Zirconia Ceramics with Submicrometer Grains

The microstructure, crystal phase, electrical conductivity, and mechanical strength of less than 7-mol%-Sc₂O₃-doped zirconia ceramics fabricated by comparatively low-temperature sintering at 1200–1300°C for 1 h were investigated. Zirconia ceramics having a uniform microstructure (grain size < 0.5 μm) stabilized with 6 mol% Sc₂O₃ showed high electrical conductivity (0.15 S/cm at 1000°C) and high fracture strength (660 MPa). With the increase of Sc₂O₃ content from 3.5 to 7 mol%, the grain size, fracture strength, and electrical conductivity at 1000°C changed from 0.2 to 0.5 μm, 970 to 440 MPa, and 0.07 to >0.2 S/cm, respectively. Sc₂O₃-doped zirconia polycrystals with high fracture strength and high electrical conductivity are promising candidates for the electrolyte material of solid oxide fuel cells.     

Influence of Annealing on the Electrical Conductivity of Polycrystalline ZrO2+8 Wt% Y2O3

The electrical conductivity of partially stabilized zirconia was investigated as a function of frequency (2 Hz to 100 kHz) and temperature (400° to 1000°C) by measuring ac admittance on a 2-probe cell using Lissajous figures. The dependence of the conductivity on annealing time was investigated with in situ conductivity measurements for prolonged annealing at 800°, 900°, and 1000°C. The aging behavior of two commercial zirconias was studied. At higher temperatures (7<750°C) the decrease in total conductivity arises mainly from changes within the grains, whereas at lower temperatures the decrease arises principally from the grain boundaries. Differences in initial conductivity and aging rates between samples from the two sources were related to grain size and impurity effects.     

Defect Structure of TiTa2O7 at Elevated Temperatures

The electrical conductivity of polycrystalline TiTa₂O₇ was measured at 1000° and 1050°C as a function of oxygen partial pressure from 10⁻¹ to 10⁻²¹ MPa. In the apparent n-type region, the value of m in σ_n∝PO₂^−1/m was found to be ∼6 in the region >10⁻¹⁷ MPa and ∼4from 10⁻¹⁶ to 10⁻⁹ MPa. The conductivity appeared to be p-type for P₀₂<10⁻⁵ MPa. The measured data are explained on the basis of the presence of small amounts of acceptor impurities in the undoped sample.     

Tentative Phase Relationships in the System CaHfTi2O7-Gd2Ti2O7 with up to 15 mol% Additions of Al2TiO5 and MgTi2O5

The phase relationships in the CaHfTi₂O₇-Gd₂Ti₂O₇ (zirconolite-pyrochlore) pseudobinary system were investigated, after heating at 1500°C, because of their importance in the design of pyrochlore-rich titanate ceramics for immobilization of impure surplus plutonium. Up to 15 mol% of MgTi₂O₅ and Al₂TiO₅ were added to CaHfTi₂O₇-Gd₂Ti₂O₇ compositions to elucidate the effects of divalent and trivalent impurities on the phase stability within these systems. From X-ray diffractometry analysis, scanning electron microscopy, and energy dispersive X-ray spectrometry, phase formation and compositional stability limits were evaluated. The main phases observed in these systems were pyrochlore, perovskite, and polytypes of zirconolite. The formation of the 2 M -, 4 M -, and 3 O -zirconolite polytypes was dependent on the amount of aluminum or magnesium present. In the magnesium system, a large area of pyrochlore-only was observed, which indicated that divalent impurities of appropriate ionic size could be readily incorporated in the eightfold site of the pyrochlore. The locations of the tentative phase boundaries are discussed with respect to the chemical composition.     

Sol–Gel Synthesis of λ–Na2O·xAl2O3 Films

Na₂O· x Al₂O₃ ( x = 9, 11)films have been obtained by sol–gel method. Crystallization processes during heat treatments have been investigated by X–ray diffraction analysis. A metastable phase with the mullite structure, λ–Na₂O· x Al₂O₃, has been observed starting from 800°C. Films remained stable after a heat treatment at 1000°C for 250 h. Impedance spectroscopy measurements showed that the films of λ-Na₂O· x Al₂O₃ possess a large three–dimensional ionic conductivity at 400°C.     

Stability Diagram for the System Yba2Cu3O7–x

The dependence of the degree of nonstoichiometry of YBa₂Cu₃0_7–x (123) on temperature and oxygen pressure has been determined by thermogravimetric analysis (TGA) in the temperature range 400° to 950°C and the oxygen pressure range 10^–6 to 1 atm (1 atm = 10⁵ Pa). The nature of the decomposition of 123 in the temperature range 750° to 950°C and the oxygen pressure range 10^–6 to 10^–2 atm has been determined by TGA and X-ray diffractometry (XRD). As the oxygen pressure decreases, the decomposition of 123 follows the sequence 123→ Y₂BaCuo₅ (211) + BaCuO₂° Cu₂O→ 211 ° BaCuO₂° BaCu₂O₂→ 211 ° YBa₃Cu₂O_x (132) ° BaCu₂O₂→ 211 ° BaCu₂O₂°BaO. The incongruent melting temperatures have been determined in the oxygen pressure range 10^–6 to 1 atm by differential thermal analysis, and the phases formed on solidification have been identified by XRD. The stability diagram for the composition 123 has been constructed.     

Electrical Conductivity of the High-Temperature Proton Conductor BaZr0.9Y0.1O2.95

The impedance of the cubic perovskite BaZr_0.9Y_0.1O_3-δ has been systematically investigated in dry and wet atmospheres at high and low oxygen partial pressures. In the grain interior, conductivity contributions from oxygen ions, electron holes, and protons can be identified. Below 300°C, proton conduction dominates and increases linearly with the frozen-in proton concentration. The proton mobility, with an activation energy of 0.44 ± 0.01 eV is among the highest ever reported for a perovskite-type oxide proton conductor. For dry oxygen atmos-pheres, electron hole conduction dominates with an activation energy of ∼0.9 eV. At temperatures <500°C, the grain-boundary conductivity can be separated and increases upon incorporation of protons. The high electrical conductivity and chemical stability make acceptor-doped barium zirconate a good choice for application as a high-temperature proton conductor.     

Mineralizing Effect of Li2B4O7 and Na2B4O7 on Magnesium Aluminate Spinel Formation

Lithium borate (Li₂B₄O₇) and sodium borate (Na₂B₄O₇) mineralize spinel formation from stoichiometric MgO and Al₂O₃ between 1000° and 1100°C. Mineralization with both compounds is shown to be mediated by B-containing liquids which form glass on cooling. However, the liquid compositions depend on the type of mineralizer and temperature, suggesting that templated grain growth or dissolution–precipitation mechanisms are operating, one dominating over the other under certain conditions. Na₂B₄O₇-mineralized compositions show predominantly templated grain growth at 1000°C, which changes to dissolution–precipitation at 1100°C, whereas Li₂B₄O₇-mineralized compositions show dissolution–precipitation from 1000°C. Li₂B₄O₇ is a stronger mineralizer as spinel formation is complete with 3 wt% Li₂B₄O₇ at 1000°C and with ≥1.5 wt% addition at 1100°C, whereas Na₂B₄O₇-mineralized compositions are found to retain some unreacted corundum even at 1100°C.     

Defect Structure of Ta2O5

Electrical conductivity, thermoelectric power, and weight change were measured for polycrystalline Ta₂O₅ from 900° to 1400°C. The predominant ionic and electronic defects in this temperature range are oxygen vacancies and electrons. The oxygen-vacancy and electron mobilities are 8.1 × 10³exp (−1.8 eV/ k T) and ∼0.05 cm²/V-s, respectively. At O₂ partial pressures near 1 atm, the ionic-defect concentration is essentially fixed by the presence of lower-valence cation impurities, and the total electrical conductivity is predominantly ionic, whereas at low P _o2's the conductivity is electronic and proportional to P P _o2^−1/6.     

Formation and Stability of Ferroelectric BaTi2O5

BaTi₂O₅ (BT₂) is thermodynamically stable over a very narrow temperature range between 1220° and 1230°C: a modification to the BaO–TiO₂ phase diagram is proposed. This thermodynamic stability was shown by constructing a time–temperature transformation diagram for the decomposition of BT₂. Once formed, BT₂ appears to be stable indefinitely at 1220°–1230°C; at higher temperatures, the decomposition rate increases with temperature; at lower temperatures, the decomposition rate increases with decreasing temperature and passes through a maximum at ∼1200°C; below ∼1150°C, BT₂ has long-lived kinetic stability. Kinetic considerations show a nucleation and growth mechanism for decomposition, with a nucleation induction period that is very temperature dependent. BT₂ can be prepared by various routes, including solid-state reaction of oxides below ∼1100°C; because it is metastable at all temperatures other than 1220°–1230°C, its formation is an example of Ostwald's rule of successive reactions. Discrepancies in the literature concerning the reported stability range of BT₂ can be explained by the complex dependence on temperature and time of both its formation and decomposition, for both of which, the nucleation stage is rate limiting.     

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).     

Pyrochlore Phase Formation in the System Bi2O3–ZnO–Ta2O5

The subsolidus phase diagram of the system Bi₂O₃–ZnO–Ta₂O₅ in the region of the cubic pyrochlore phase has been determined at 1050°C. This phase forms a solid solution area that includes the ideal composition P, Bi₃Zn₂Ta₃O₁₄; possible solid solution mechanisms are proposed, supported by density measurements of Zn-deficient solid solutions. The general formula of the solid solutions is Bi_{3+ y} Zn_{2− x} Ta_{3− y} O_{14− x − y} , based on the creation of Zn²⁺, O²⁻ vacancies in Zn-deficient compositions and a variable Bi/Ta ratio.     

La2Ti2O7 Ceramics

La₂Ti₂O₇ powders were prepared using three different techniques. Single-phase material was obtained at 1150°C by calcination of mixed oxides, at 1000°C by molten salt synthesis, and at 850°C by evaporative decomposition of solutions. Particle sizes and morphologies of the powders differed substantially, as did the sintered microstructures and dielectric properties. Very dense (99%), translucent, grain-oriented lanthanum titanate was fabricated by hot-forging at 1300°C under a 200-kg load. Anisotropy was demonstrated by X-ray diffraction, scanning electron microscopy, thermal expansion, and dielectric measurements.     

Preparation of an Alkali-Element-Doped CeO2-Sm2O3 System and Its Operation Properties as the Electrolyte in Planar Solid Oxide Fuel Cells

The ionic conductivity of the ceria-samaria (CeO₂-Sm₂O₃) system is higher than that of yttria-stabilized zirconia and other CeO₂-based oxides. In this study, a small amount of alkali-element-doped CeO₂-Sm₂O₃ solid solution was prepared. This solid solution was characterized by measuring the powder density and the chemical composition. Moreover, its electrochemical properties were investigated in the temperature range from 700° to 1000°C. It was found that a small amount of alkali-element-doped CeO₂ solid solution enhanced the ionic conductivity. The power density of an oxygen-hydrogen fuel cell for alkali-element-doped CeO₂-Sm₂O₃ ceramics exhibited high values at low temperatures such as 700° to 800°C. It is concluded that the improved fuel cell performance can be attributed to the high stability of this composition in the fuel atmosphere.     

Electrical Conductivity of Y2O3 as a Function of Oxygen Partial Pressure in Wet and Dry Atmospheres

The electrical conductivity of polycrystalline Y₂O₃ has been studied as a function of the partial pressure of oxygen (10^–14 to 10⁵ Pa) at 900° to 1500°C in atmospheres saturated with water vapor at 12°C or dried with P₂O₅. Yttria is a p -conductor at high oxygen activities. The p -conductivity increases with increasing P _O2 and decreases with increasing P_H2O. At low oxygen activities the oxide is a mixed ionic/electronic conductor. The ionic conductivity is approximately independent of P _O2 and increases with increasing P _H2O. In the Y₂O₃ samples, excesses of lower-valent cation impurities (in the 10 to 100 mol-ppm range) are the dominating negatively charged defects, and in the presence of water vapor they are compensated by interstitial protons. At high P _H2O levels additional protons are probably compensated by interstitial oxygen ions. At high temperatures (±1100°C) and for high P _O2 and low P _H2O, the protons are no longer dominant, and the lower-valent cations are mainly compensated by electron holes. The electrical conductivity exhibits hysteresis-like effects which are interpreted in terms of segregation/desegregation of impurities at grain boundaries. The mobility of electron holes in yttria at 1500°C is estimated to be of the order of magnitude of 0.05 cm². s^–1. V^–1