In Situ Formation of Hexaferrite Magnets within a 3Y-TZP Matrix: La2O3–ZnO–Fe2O3 and BaO–Fe2O3 Systems

The in situ formation of magnetoplumbite-type (M-type) hexaferrites within a 3Y-TZP matrix was examined for the La₂O₃–ZnO–Fe₂O₃ and BaO–Fe₂O₃ systems. The formation of barium hexaferrite (Ba-M) was rapid enough at a temperature of 1300°C for 2 h to result in a uniform dispersion of fine Ba-M particles in a tetragonal zirconia polycrystal (TZP) matrix. However, the formation of lanthanum-substituted hexaferrite (La-M) was rather sluggish, despite the existence of a charge-compensating divalent oxide. The 3Y-TZP/20-wt%-BaFe₁₂O₁₉ in situ composite possessed good magnetic properties, as well as moderately good mechanical properties.     

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.     

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.     

Effect of Carbon Reduction on the Properties of 13 mol% Tio2─3 mol% Y2O3─84 mol% ZrO2

Fully tetragonal and sintered 13 mol% TiO₂─3 mol% Y₂O₃─84 mol% ZrO₂ was thermally treated at 1300°C for 1 h in argon in the presence of carbon. No phase changes occurred on the as-received surface and in the bulk of the material, but t → m transformation occurred on polished surfaces under reducing conditions, and it resulted in increased fracture toughness, Young's modulus, and modulus of rigidity. Deoxidation of the system occurred and 0.174 wt% of carbon was found in the sample. This seemed to stabilize the tetragonal phase.     

Microstructure and Short-Term Oxidation of Hot-Pressed Si3N4/ZrO2(+Y2O3) Ceramics

Composite ceramic materials based on Si₃N₄ and ZrO₂ stabilized by 3 mol% Y₂O₃ have been formed using aluminum isopropoxide as a precursor for the Al₂O₃ sintering aid. Densification was carred out by hot-pressing at temperatures in the range 1650° to 1800°C, and the resulting micro-structures were related to mechanical properties as well as to oxidation behavior at 1200°C. Densification at the higher temperatures resulted in a fibrous morphology of the Si₃N₄ matrix with consequent high room-temperature toughness and strength. Decomposition of the ZrO₂ grains below the oxidized surface during oxidation introduced radial stresses in the subscalar region, and from the oxidation experiments it is suggested that the ZrO₂ incorporated some N during densification.     

Effect of a liquid Phase on Superplasticity of 2-moI%-Y203-StabiIlzed Tetragonal Zirconla Polycrystals

A small addition of CuO to 2-mol%-Y₂O₃-stabilized tetragonal zirconia polycrystals significantly enhances superplasticity by forming an amorhous grain-boundary phase containing primarily Cu⁺, Y³⁺, Zr⁴⁺, and O²⁻. This phase apparently melts at around 1130°C, but it already provides a fast diffusion path even below the melting temperature. There are abrupt changes in stress exponent, activation energy, and grain size exponent across the melting temperature. Superplasticity is diffusion-controlled below the melting temperature and is interfaced-controlled above that.     

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.     

Low-Temperature Chemical Synthesis of Nanocrystalline MgAl2O4 Spinel Powder

Nanocrystalline MgAl₂O₄ spinel powder was synthesized by pyrolysis of complex compounds of aluminum and magnesium with triethanolamine (TEA). The soluble metal ion–TEA complexes formed the precursor material on complete dehydration of the complexes of aluminum–TEA and magnesium–TEA. Single-phase MgAl₂O₄ spinel powder resulted after heat treatment of the precursor material at 675°C. The precursor and the heat-treated powders were characterized by X-ray diffractometry (XRD), differential thermal and thermogravimetric analysis, and transmission electron microscopy (TEM). The average crystallite size as measured from the X-ray line broadening was around 14 nm and the average particle size from TEM studies was around 20 nm.     

Atomistic Simulation of the Surface Energy of Spinel MgAl2O4

Atomistic simulations with atomic potentials including anion polarizibility have been performed for the low-index surfaces of spinel MgAl₂O₄ with various terminations. The calculations show that for the most stable surface the surface energy is 2.27 J/m² for the {100}, about 2.85 J/m² for the {110}, and 3.07 J/m² for the {111} orientation. The ratio between the experimental values to the calculated relaxed surface energies is about 1.5. Strong surface relaxation was found for the {110} and {111} orientation but only moderate surface relaxation for the {100} surface.     

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.     

Preparation of MgAl2O4 Spinel Powders via Freeze-Drying of Alkoxide Precursors

High-sinterability MgAl₂O₄ powder has been produced from alkoxide precursors via a freeze-drying method. Clear alumina sol and magnesium methoxide were used as starting materials in the process. The spinel powders were characterized by various techniques, such as thermal analysis, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The tap density and sinterability of the spinel power are affected by the ball-milling techniques. Highly dense, transparent, polycrystalline MgAl₂O₄ has been obtained from these powders by sintering and hot isostatic pressing. Bimodal grain-size microstructure is observed in a HIPed sample.     

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.     

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.     

Computer Simulation of Dissociative Adsorption of Water on the Surfaces of Spinel MgAl2O4

Atomistic simulation techniques have been used to model the dissociative adsorption of water onto the low-index {100}, {110}, and {111} surfaces of spinel MgAl₂O₄. The Born model of solids and the shell model for oxygen polarization have been used. The resulting structures and chemical bonding on the clean and hydrated surfaces are described. The calculations show that the dissociative adsorption of water on the low-index surfaces is generally energetically favorable. For the {110} and {111} orientations, the surfaces cleaved between oxygen layers show high absorption and stability. The calculations also show that, for the {111} orientation, the surfaces may absorb chemically water molecules up to ∼90% coverage and have the highest stability. It is suggested that, during fracture, only partial hydration occurs, leading to cleavage preferentially along the {100} orientation.     

Phase Stability and Physical Properties of Cubic and Tetragonal ZrO2 in the System ZrO2–Y2O3–Ta2O5

The cubic ( c -ZrO₂) and tetragonal zirconia ( t -ZrO₂) phase stability regions in the system ZrO₂–Y₂O₃–Ta₂O₅ were delineated. The c -ZrO₂ solid solutions are formed with the fluorite structure. The t -ZrO₂ solid solutions having a c/a axial ratio (tetragonality) smaller than 1.0203 display high fracture toughness (5 to 14 MPa · m^1/2), and their instability/transformability to monoclinic zirconia ( m -ZrO₂) increases with increasing tetragonality. On the other hand, the t -ZrO₂ solid solutions stabilized at room temperature with tetragonality greater than 1.0203 have low toughness values (2 to 5 MPa · m^1/2), and their transformability is not related to the tetragonality.     

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.     

Neutron Diffraction Study of Ferroelasticity in a 3 mol% Y2O3–ZrO2

In situ neutron diffraction patterns were recorded from a 3Y-TZP sample during a complete loading–unloading cycle at compressive loads up to 2.3 GPa. The macroscopic stress–strain diagram shows elastic behavior to 1.7 GPa followed by volume conserving plastic strains of ∼1.6 × 10⁻³. There were no signs of t → m transformation in the neutron diffraction patterns, and intensity changes in the pattern show that the plasticity is due to ferroelastic switching of tetragonal zirconia crystals. Quantification of the degree of switching gives good agreement with the macroscopic strains. The ferroelastic switching is completely reversed by a process akin to creep relaxation on unloading. Lattice parameters, elastic constants, and structural changes as a function of load are also discussed.     

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.     

Plastic Deformation and Solid-Solution Hardening of Y2O3-Stabilized ZrO2

Fully stabilized cubic ZrO₂ single crystals containing various Y₂O₃ concentrations were deformed at 1400°C in air. The orientation chosen favored (001)(110) slip, which was confirmed by slip-trace analysis and transmission electron microscopy; (111)(110) slip could also be activated. The yield and flow stresses increased with increasing Y₂O₃ concentration, and stress-strain curves were dominated by a region of zero work hardening from very small strains for all compositions.     

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.