Stabilization of Tetragonal ZrO2 in ZrO2–SiO2 Binary Oxides

Gel-glasses of various compositions in the x ZrO₂^.(10 – x )SiO₂system were fabricated by the sol–gel process. Precipitation due to the different reactivities between tetraethyl orthosilicate (TEOS) and zirconium(IV) n -propoxide has been eliminated through the use of 2-methoxyethanol as a chelating agent. Thermal treatment of these gels produced crystalline ZrO₂particles. While monoclinic is the stable crystalline phase of zirconia at low temperatures, the metastable tetragonal phase is usually the first crystalline phase formed on heat treatment. However, stability of the tetragonal phase is low, and it transforms to the monoclinic phase on further heat treatment. In this study, it has been found that the transformation temperature increases as the SiO₂content in the ZrO₂–SiO₂ binary oxide increases. The most significant results were from samples containing only 2 mol% SiO₂, where the metastable tetragonal phase formed at low temperatures and remained stable over a broad temperature range. X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to elucidate the structure of these binary oxides as a function of temperature.     

Effect of YO1.5 Dopant on Unit-Cell Parameters of ZrO2 at Low Contents of YO1.5

The effect of YO_1.5 dopant on unit-cell parameters of ZrO₂ (YO_1.5=0 to 14.6 mol%) were examined by the X-ray whole-powder-pattern decom-position technique. The unit cell of monoclinic ZrO₂ has the largest expansion along the direction perpen-dicular to (100). The rate of increase of the unit-cell volume of monoclinic ZrO₂ with YO_1.5 content is greater than that of tetragonal ZrO₂ and comparable to that of cubic ZrO₂.     

Crack Resistance and Fatigue of Transforming Ceramics: II, CeO2-Stabilized Tetragonal ZrO2

Crack resistance characteristics and fatigue properties have been investigated in Ce-TZP ceramics with different grain sizes. The relatively low critical transformation stress allows the development of larger transformation zones (≦200 μm), leading to flaw-tolerant behavior. However, autocatalytic transformation processes are found to be bound to grain sizes beyond a critical value; transformation is then very limited in finer microstructures. Fatigue as a specific cyclic effect is more pronounced in microstructures with larger grains. Thus, damaging processes in the course of extensive t–m transformation are suspected to be intensified during cyclic loading.     

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.     

Microstructural Characterization of ZrO2 Particles Prepared by Reaction of Gaseous ZrCl4 with Fe2O3

The microstructure of ZrO₂ fine particles produced by a novel synthesis method at 450° and 950°C has been studied. The fundamentals of the synthesis method, which involves both chemical and diffusion phenomena, are presented. The method is based on mass transport through the gaseous phase between metallic zirconium and Fe₂O₃ powder. The mass-transporting chemical species are zirconium and iron chlorides. This article focuses on the microstructure and structure of ZrO₂ particles formed by the reaction between gaseous ZrCl₄ and solid Fe₂O₃, which is a relevant reaction step that occurs during the synthesis process. The resulting ZrO₂ crystals grown on Fe₂O₃ particles have been analyzed using transmission electron microscopy. Microstructural characterization has been complemented by X-ray diffractometry analysis. Tetragonal-ZrO₂ is produced at 450°C and monoclinic-ZrO₂ single crystals are produced at 950°C.     

Core-Shell Structures in ZrO2-Modified BaTiO3 Ceramic

Pure BaTiO₃ exhibits a paraelectric-to-ferroelectric phase transition at 130°C. When stoichiometric BaTiO₃ is combined with 10 mol% ZrO₂, the relative permittivity (ε) changes to a broad, relatively insignificant temperature dependence, and the Curie point, T _c , is not sharply defined. However, the transition sharpens at T = 95°C when these samples are sintered for a longer period of 60 h. SEM, EDAX analysis coupled with TEM observation gives three types of core-shell structures of different microstructural characteristics which are related to the diffuse phase transition. Chemical inhomogeneity, due to Zr⁴⁺ distribution in the core-shell structure, is proposed to account for the diffuse phase transition behavior.     

Chemical Interactions Promoting the ZrO2 Tetragonal Stabilization in ZrO2–SiO2 Binary Oxides

Metastable tetragonal ZrO₂ phase has been observed in ZrO₂–SiO₂ binary oxides prepared by the sol–gel method. There are many studies concerning the causes of ZrO₂ tetragonal stabilization in binary oxides such as Y₃O₂–ZrO₂, MgO–ZrO₂, or CaO–ZrO₂. In these binary oxides, oxygen vacancies cause changes or defects in the ZrO₂ lattice parameters, which are responsible for tetragonal stabilization. Since oxygen vacancies are not expected in ZrO₂–SiO₂ binary oxides, tetragonal stabilization should just be due to the difficulty of zirconia particles growing in the silica matrix. Furthermore, changes in the tetragonal ZrO₂ crystalline lattice parameters of these binary oxides have recently been reported in a previous paper. The changes of the zirconia crystalline lattice parameters must result from the chemical interactions at the silica–zirconia interface (e.g., formation of Si–O–Zr bonds or Si–O⁻ groups). In this paper, FT-IR and ²⁹Si NMR spectroscopy have been used to elucidate whether the presence of Si–O–Zr or Si–O⁻ is responsible for tetragonal phase stabilization. Moreover, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy have also been used to study the crystalline characteristics of the samples.     

Metastable Phase Selection and Partitioning in ZrO2—MgO Processed from Liquid Precursors

Aqueous mixtures of either zirconium acetate or zirconium nitrate and magnesium nitrate were dried and subsequently pyrolyzed at fast heating rates (upquenching) to form metastable crystalline phases of ZrO₂ with various degrees of MgO supersaturation. The crystallization temperature was determined to be 380°C for the zirconium acetate, and 270°C for the zirconium nitrate at a heating rate of 5°C/min. The crystalline structures were characterized as a function of MgO content and thermal history for specimens containing 0 to 30 mol% MgO. Upquenching to 900°C, where monoclinic ( m ) ZrO₂ and MgO are the equilibrium phases, yielded single-phase tetragonal ( t ) ZrO₂ (<8 mol% MgO), single-phase cubic ( c ) ZrO₂ (9 to 17 mol% MgO), and two-phase c -ZrO₂+ MgO structures (>17 mol% MgO). The composition for which T ₀( t/c ) = 900°C was estimated as 9 ± 1 mol% MgO. Compositions crystallizing as metastable t -ZrO₂ (<8 mol% MgO) partitioned at higher temperatures and/or longer times into two-phase mixtures, following the general sequence t → t + m → m + MgO. Similarly, compositions forming metastable c -ZrO₂ (10 to 30 mol% MgO) partitioned in the following sequence: c → c + t + MgO → t + MgO → t + m + Mgo → m + Mgo. The initial phase selection and subsequent partitioning sequence are discussed in light of phase hierarchies predicted from thermodynamic concepts and kinetic constraints which are introduced by the solute partitioning required to achieve equilibrium.     

Formation Mechanism of Hydrous-Zirconia Particles Produced by Hydrolysis of ZrOCl2 Solutions: II

The primary and secondary particle sizes of monoclinic hydrous-ZrO₂ particles produced by the hydrolysis of various ZrOCl₂ solutions, with and without the addition of NaCl, CaCl₂, or AlCl₃, were measured using X-ray diffraction and transmission electron microscopy in order to clarify the formation mechanisms of primary and secondary particles. The primary particle size of hydrous ZrO₂, under a constant ZrOCl₂ concentration, decreased monotonously with increasing Cl⁻-ion concentration. On the contrary, the secondary particle size increased monotonously with increasing Cl⁻-ion concentration. The present experimental results revealed that the primary and secondary particle sizes of hydrous ZrO₂ are controlled primarily by the concentrations of H⁺ and Cl⁻ ions produced during hydrolysis, and are independent of the type of added metal ions. The formation mechanisms of the primary and secondary particles of hydrous ZrO₂ were determined on the basis of the present experimental results.     

Thermodynamic Assessment of the ZrO2─YO1.5 System

An optimal set of thermodynamic functions for the ZrO₂─YO_1.5 system are obtained using phase diagram and thermodynamic data. The liquid is described by a subregular solution model. Both cubic ZrO₂ and YO_1.5 solid solutions are regarded as one cubic solution, which is also treated as a subregular solution. The ordered Zr₃Y₄O₁₂ phase is treated as a stoichiometric compound. A regular solution model is applied to the other solid solutions. Tentative equilibrium boundaries between monoclinic and tetragonal ZrO₂ solid solutions are evaluated from information about the T ₀ line. The calculated phase diagram and thermodynamic functions agree well with experimental data.     

Low-Temperature Sintering of Seeded Sol—Gel-Derived, ZrO2-Toughened Al2O3 Composites

Seeding a mixture of boehmite (AIOOH) and colloidal ZrO₂ with α-alumina particles and sintering at 1400°C for 100 min results in 98% density. The low sintering temperature, relative to conventional powder processing, is a result of the small alumina particle size (∼0.3 μm) obtained during the θ-to α-alumina transformation, homogeneous mixing, and the uniform structure of the sol-gel system. Complete retention of pure ZrO₂ in the tetragonal phase was obtained to 14 vol% ZTA because of the low-temperature sintering. The critical grain size for tetragonal ZrO₂ was determined to be ∼0.4 μm for the 14 vol% ZrO₂—Al₂O₃ composite. From these results it is proposed that seeded boehmite gels offer significant advantages for process control and alumina matrix composite fabrication.     

Stable and Metastable Phase Relationships in the System ZrO2–ErO1.5

Stable and metastable phase relationships in the system ZrO₂–ErO_1.5 were investigated using homogeneous samples prepared by rapid quenching of melts and by arc melting. The rapidly quenched samples were annealed in air for 48 h at 1690°C or for 8 months at 1315°C. Two tetragonal phases ( t - and t '-phases) were observed after quenching samples heated at 1690°C to a room temperature, whereas one t -phase and cubic ( c -) phase were found in those treated at 1315°C. Since the t '-phase is obtained through a diffusionless transformation during cooling from a high-temperature c -phase, t - and c -phases can coexist at high temperature. The t - and c -phases field spans from 4 to 10 mol% ErO_1.5 at 1690°C and from 3 to 15 mol% ErO_1.5 at 1315°C. The equilibrium temperature T ^t-m ₀ between the t - and monoclinic ( m -) phases estimated from A_s and M_s temperatures decreased with increasing ErO_1.5 contents.     

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.     

Nanometer-Sized ZrO2 Particles Prepared by a Sol–Emulsion–Gel Method

ZrO₂ powder was prepared by a sol–emulsion–gel method at temperatures below 140°C from ZrO(NO₃)₂· n H₂O. The asprepared powder was amorphous, but crystallized into the tetragonal structure by 600°C. The metastable tetragonal powder (600°C) was comprised of ultrafine 4- to 6-nm size particles. On heat treatment, the tetragonal form completely transformed into the monoclinic state at 1100°C. Preliminary studies indicate good sinterability with densities greater than 94% at 1100°C and with a grain size of 0.25 μ.     

Reversible Transformation and Elastic Anisotropy in Mg-ZrO2

Mechanical loading of polycrystalline ZrO₂ ceramics causes reversible, out-of-plane distortions at free surfaces that are parallel to the direction of applied stress. These distortions have been measured using optical interference microscopy, and the separate contributions due to elastic anisotropy and reversible mantensitic tranformation have been identified.     

Growth Mechanism of Monodispersed ZrO2 Particles

Monodispersed ZrO₂ seed particles which were prepared by hydrolysis of zirconium alkoxide solutions were allowed to grow by further addition of zirconium alkoxide and water under conditions in which new particles do not nucleate and grow. The particle growth mechanism is presumed to be a surface reaction in which the rate-determining step is a first-order polynuclearlayer growth mechanism. With this method of powder preparation, it is possible to precisely control the particle size, and it may be useful for applications in ceramic processing.     

Low-Temperature Equilibria Among ZrO2, Tho2, and UO2

Studies made on low-hafnium-content ZrO₂, show that the monoclinic-tetragonal inversion temperature is 1170°C., and it is raised to approximately 1190°C. in the "natural" ZrO², which contains approximately 2% HfO₂. No explanation could be found for the knownmarked hysteresis during cooling, when the reverse polymorphic transformation takes dace at 1040°C. In the system ZrO₂-ThO₂ the monoclinic-tetragonal ZrO₂, inversion temperature is lowered to 1000°C., although the maximum solid solution extent of ZrO₂, in Thon and vice versa is approximately only 2% at this temperature. Below about 400°C. under hydrothermal conditions it was possible to prepare a continuous, although metastable series of solid solutions with the fluorite structurewith compositions varying from ThO₂, to nearly pure ZrO₂. Contrary to earlier work only 8 mole ZrO₂, dissolves in UO₂ and less than 4 mole of UO, in ZrO₂ at temperatures up to 13OO0C. A continuous series of solid solutions could be made between Th₂ and UO₂ at 13OO°C., and extensive defect fluorite solid solutions could be prepared between Tho₂ and U₃O₈; there is some evidence for exsolution into uranium-rich and thorium-rich members at low temperatures.     

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.     

Sol–Gel Preparation of BaTi4O9 and Ba2Ti9O20

BaTi₄O₉ and Ba₂Ti₉O₂₀ precursors were prepared via a sol–gel method, using ethylenediaminetetraacetic acid as a chelating agent. The sol–gel precursors were heated at 700°–1200°C in air, and X-ray diffractometry (XRD) was used to determine the phase transformations as a function of temperature. Single-phase BaTi₄O₉ could not be obtained, even after heating the precursors at 1200°C for 2 h, whereas single-phase Ba₂Ti₉O₂₀ (as determined via XRD) was obtained at 1200°C for 2 h. Details of the synthesis and characterization of the resultant products have been given.     

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.