High-Temperature Creep of Y2O3-Stabilized ZrO2

The compression creep behavior of Y₂O₃-stabilized ZrO₂ (YSZ) was studied at temperatures to 2000 ° C. The function of Y₂O₃ content and grain size was tested in specimens with various impurity concentrations and porosity distributions. For relatively fine-grained specimens, creep rates increased with the 1.5 power of the applied stress at low stresses and with the third power at high stresses. The results for coarse-grained specimens can, in general, be fit by the cube dependence. The 1.5 power can be reduced to a linear dependence by correcting for an apparent threshold stress, which decreases with increasing temperature. Creep activation energies for YSZ are 128 ± 10 kcal/mol, independent of Y₂O₃ content, impurity level, grain size, and porosity distribution. In addition, over a broad range of temperatures and stresses the absolute values of the steady-state creep rates are influenced only by grain size and O₂ partial pressure.     

Lattice Parameters and Density for Y2O3-Stabilized ZrO2

Lattice parameter and density data were compiled for Y₂O₃-Stabilized ZrO₂, both from the literature and from experimental measurements. The data are described very well over a wide range of composition by the model of Aleksandrov et al. , which assumes Y substitution for Zr in the unit cell with compensating anion vacancies. Effects are noted in two-phase cubic-tetragonal materials which indicate significant lattice strains in the two-phase materials.     

Deformation of Monoclinic ZrO2 Polycrystals and Y2O3-Stabilized Tetragonal ZrO2 Polycrystals below the Monoclinic–Tetragonal Transition Temperature

Ultrafine-grained monoclinic ZrO₂ polycrystals (MZP) and 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystals (3Y-TZP) were obtained by hot isostatic pressing (HIP). Both MZP and TZP were "high-purity" materials with impurities less than 0.1 wt%. The deformation behavior was studied at 1373 K, which was lower than the monoclinic ↔ tetragonal transition temperature. The stress exponent of 3Y-TZP with grain size of 63 nm was 3 in the higher stress region, and increased from 3 to 4 with decreasing stress. The deformation of MZP was characterized by a stress exponent of 2.5 over a wide stress range. The strain rate of 3Y-TZP was slower than that of MZP by 1 order of magnitude. It was suggested that either the doped yttrium or the difference in the crystal structure affected the diffusion coefficients of ZrO₂.     

A Novel Method for Fabrication of Y2O3-Stabilized ZrO2 Electrolyte Films

Gas-tight Y₂O₃-stabilized ZrO₂ (YSZ) films were prepared on NiO–YSZ and NiO–SDC (Sm_0.2Ce_0.8O_1.9) anode substrates by a novel method. A cell, Ni–YSZ/YSZ(10 μm)/LSM–YSZ, was tested with humidified hydrogen as fuel and ambient air as oxidant. The maximum power densities of 1.64, 1.40, 1.06, and 0.60 W/cm² were obtained at 850°, 800°, 750°, and 700°C, respectively. With methane as fuel, a cell of Ni–SDC/YSZ (12 μm)/LSM–YSZ exhibited the maximum power densities of 1.14, 0.82, 0.49, and 0.28 W/cm² at 850°, 800°, 750°, and 700°C, respectively. The impedance results showed that the performance of the cell was controlled by the electrode polarization rather than the resistance of YSZ electrolyte film.     

Synthesis and Evaluation of Doped Y2O3-Stabilized ZrO2 for the Production of Hydrogen

The preparation and characterization of single-phase sintered ceramic materials based on Y₂O₃-stabilized ZrO₂ with oxides of Ti, Zn, Ce, Cr, Mn, and U/Fe as third-component additives are described. These materials were prepared for a process to produce high-purity hydrogen and were evaluated for this process via measurements of electrical conductivity, stability, and transport number. Compositions with oxides of Ce and Cr in Y₂O₃-stabilized ZrO₂ are shown to be the most promising candidates.     

Electrophoretic Deposition of Y2O3-Stabilized ZrO2 Electrolyte Films in Solid Oxide Fuel Cells

An electrophoretic deposition (EPD) method was applied for the preparation of yttria-stabilized zirconia (YSZ) films for solid oxide fuel cell (SOFC) applications. Dense YSZ films with uniform thickness can be readily prepared with the EPD method by using acetylacetone or acetone as a solvent. The open-circuit voltages of SOFC, for which the YSZ films were prepared by the EPD method, increased with increasing repetitions of deposition and sintering. It was found that the open-circuit voltage exceeded 1.0 V after five repetitions. When the planar SOFC was fabricated using La_0.6Sr_0.4MnO₃ as a cathode, and electroless plating Pt as an anode, the open-circuit voltage and the maximum power density attained were 1.03 V and 1.84 W·cm⁻², respectively. Consequently, it became evident that the electrophoretic deposition was a suitable processing route for the formation of gas-tight YSZ films with thickness less than 10 μm.     

Microstructures of Y2O3-Stabilized ZrO2 Electron Beam-Physical Vapor Deposition Coatings on Ni-Base Superalloys

The microstructures of ZrO₂–20 wt% Y₂O₃ thermal barrier coatings formed by electron beam-physical vapor deposition on a Nibase superalloy have been studied by transmission electron microscopy. The coating systems consist of several layers, including a superalloy substrate, a bond coat, an Al₂O₃ scale, and the PVD coating. The overall ceramic thermal barrier coatings were characterized, with special emphasis being given to the α-Al₂O₃ scale which forms between the bond coat and the ZrO₂₋Y₂O₃ coating. The oxide scale exhibited various morphologies in different coating systems; the majority of the porosity formed in this region for all coatings.     

Mechanical Properties of Y2O3-Stabilized Tetragonal ZrO2 Polycrystals After Ageing at High Temperature

Yttria-partially-stabilized zirconia (Y-PSZ) materials containing 2.5, 3.0, and 5.0 mol% of Y₂O₃ prepared by hot pressing were subjected to ageing in air for >10 h at temperatures in the range of 800°C and 1200°C. The sintered materials were measured to determine the mechanical properties and microstructures and analyzed for trace elements. A sharp reduction in bending strength was observed after the ageing, the cause for which was suggested to be the formation of cavities produced by the oxidation of carbon.     

High-Strain-Rate Superplasticity in Y2O3-Stabilized Tetragonal ZrO2 Dispersed with 30 vol% MgAl2O4 Spinel

High-strain-rate superplasticity is attained in a 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (3Y-TZP) dispersed with 30 vol% MgAl₂O₄ spinel: tensile elongation at 1823 K reached >300% at strain rates of 1.7 × 10⁻²– 3.3 × 10⁻¹ s⁻¹. The flow behavior and the microstructure of this material indicate that the MgAl₂O₄ dispersion should enhance accommodation processes necessary for grain boundary sliding. Such an effect is assumed to arise from an enhancement of the cation diffusion by the dissolution of Al and Mg ions into the ZrO₂ matrix and from stress relaxation due to the dispersed MgAl₂O₄ grains.     

Effect of Nb2O5 Alloying on Thermal Expansion Anisotropy of 2 mol% Y2O3-Stabilized Tetragonal ZrO2

Tetragonal ZrO₂ ( t -ZrO₂) solid solutions were prepared with addit ons of 2 mol% Y₂O₃ plus up to 0.45 mol% Nb₂O₅. The thermal expansion coefficients in both the a- and c -axis lattice directions increased with Nb₂O₅ alloying and the thermal expansion in the c -axis direction was greater than that in the a -axis direction over the entire composition range. This anisotropic thermal expansion behavior was related to the 4-fold coordination of Nb⁵⁺ with oxygen ions in t -ZrO₂ solid solutions in the system ZrO₂–Y₂O₃–Nb₂O₅. The fracture toughness continuously increased with Nb₂O₅ alloying and suggested that the c/a axial ratio is a more significant factor than the internal stress that arises from the thermal expansion anisotropy, in the determination of the transformability of t -ZrO₂ in this system.     

Indentation Studies on Y2O2-Stabilized ZrO2: I, Development of Indentation-Induced Cracks

The development of Vickers indent-induced tracks with increasing indent load has been studied in two Y₂O₃-stabilizel ZrO₂ ceramics. Such cracks form as radial or Palmqvist cracks at low loads, assume "kidney" shapes at intermediate loads, and finally form median (half-penny) cracks at high loads. The plastic zone directly beneath the indent is uncracked; a significant portion of the plasticity induced by indentation occurs by martensitic transformation.     

Rhombohedral Phase in Y2O3-Partially-Stabilized ZrO2

Tetragonal-to-rhombohedral stress-induced phase transformation was studied by X-ray diffraction on the ground surfaces of tetragonal zirconia polycrystals and partially stabilized zirconia containing 2.0 to 5.0 mol% Y₂O₃ prepared by hot isostatic pressing. The rhombohedral phase increased with Y₂O₃ content and also with hot isostatic pressing temperature. The stability of the rhombohedral phase was studied with regard to surface finish and thermal annealing. The subsequent heat treatment of the specimens was found to cause the reverse rhombohedral-to-tetragonal transformation.     

Synthesis of ZrO2 and Y2O3-Doped ZrO2 Thin Films Using Self-Assembled Monolayers

Undoped or Y₂O₃-doped ZrO₂ thin films were deposited on self-assembled monolayers (SAMs) with either sulfonate or methyl terminal functionalities on single-crystal silicon substrates. The undoped films were formed by enhanced hydrolysis of zirconium sulfate (Zr(SO₄)·4H₄O) solutions in the presence of HCl at 70°C. Typically, these films were a mixture of two phases: nanocrystalline tetragonal- ( t -) ZrO₂ and an amorphous basic zirconium sulfate. However, films with little or no amorphous material could be produced. The mechanism of film formation and the growth kinetics have been explained through a coagulation model involving homogeneous nucleation, particle adhesion, and aggregation onto the substrate. Annealing of these films at 500°C led to complete crystallization to t -ZrO₂. Amorphous Y₂O₃-containing ZrO₂ films were prepared from a precursor solution containing zirconium sulfate, yttrium sulfate (Y₂(SO₄)₃8·H₂O), and urea (NH₂CONH₂) at pH 2.2–3.0 at 80°C. These films also were fully crystalline after annealing at 500°C.     

Microstructural Evolution in a ZrO2 Wt% Y2O3 Ceramic

Several unusual microstructural features, i.e., 90° tetragonal ZrO₂ twins containing antiphase domain boundaries, tetragonal ZrO₂ precipitates in a colony morphology, and precipitate-free zones at the perimeter of cubic ZrO₂ grains containing fine tetragonal ZrO₂ precipitates, were observed in a single ZrO₂-12 wt% Y₂O₂ ceramic annealed at 1550°, 1400°, and 1250°C, respectively. The type of phase transformation responsible for each microstructural feature is described.     

High-Temperature Precipitation Hardening of Two-Phase Y2O3-Partially-Stabilized ZrO2 Single Crystals: A First Report

Precipitation hardening was observed in two-phase (cubic plus tetragonal) Y₂O₃-partia1ly-stabilized ZrO₂ single crystals deformed at 1400°C. Slip was activated on (001) 〈110〉, primarily in Luders bands.     

Effect of Ta2O5, Nb2O5, and HfO2 Alloying on the Transformability of Y2O3-Stabilized Tetragonal ZrO2

The addition of Ta₂O₅, Nb₂O₅, and HfO₂ enhanced the transformability of Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (Y-TZP), which was indicated by an increase in phase transformation temperatures and fracture toughness of Y-TZP. Comparison of the alloying effects of these oxides on the transformability and crystal structure of Y-TZP suggested that an alloying oxide which increases the c/a axial ratio (tetragonality) of TZP also increases the transformability. Empirical equations to predict the tetragonality are proposed. Calculated tetragonalities showed good agreement with measured values in the systems ZrO₂-Y₂O₃-Ta₂O₅, -Nb₂O₅, and -HfO₂.     

In Situ Laser Raman Determination of Electrochemical Reactions of Y2O3-Stabilized ZrO2 and Molten Na2SO4

When used as components of advanced energy conversion systems, oxide ion conductors and molten electrolytes may react or decompose according to various mechanisms. Understanding these mechanisms is important in improving system performance. In situ laser Raman spectroscopy was used successfully to study the reactions between an oxide ion conductor and a molten salt. Changes in the Raman spectrum of molten Na₂SO₄ were observed near Y₂O₃-stabilized ZrO₂ electrodes when they were polarized anodically in the molten salt. These changes were interpreted to indicate the formation of yttrium sulfate complexes.     

Indentation Studies on Y2O3-Stabilized ZrO2: II, Toughness Determination from Stable Growth of Indentation-Induced Cracks

Stable indentation cracks were grown in four-point bend tests to study the fracture toughness of two Y₂O₃-stabilized ZrO₂ ceramics containing 3 and 4 mol% Y₂O₃. By combining microscopic in situ stable crack growth observations at discrete stresses with crack profile measurements, the dependence of toughness on crack extension was determined from crack extension plots, which graphically separate the crack driving residual stress intensity and applied stress intensity factors. Both materials exhibit steeply rising R -curves, with a plateau toughness of 4.5 and 3.1 Mpa·m^1/2 for the 3- and 4-mol% materials, respectively. The magnitude of the plateau toughness reflects the fraction of tetragonal grains contributing to transformation toughening.     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

Anisotropic Thermal Expansion Coefficients of Y2O3-Stabilized Tetragonal Zirconia

The transformability of the grains in tetragonal zirconia polycrystals is determined by thermal stresses (eigenstresses) which develop because of anisotropic expansion behavior of the tetragonal grains on cooling. Anisotropic thermal expansion coefficients based on lattice parameter determinations at room temperature and 600° and 800°C are presented for tetragonal zirconia containing 2 and 3 mol% Y₂O₃. The sources of errors in these data are discussed.