Fabrication, Microstructural Characterization, and Mechanical Properties of Polycrystalline t'-Zirconia

Large-grained (100- to 200-μm), yttria-doped, polycrystalline t '-zirconia ceramics were fabricated by heat-treating presintered samples at temperatures 2100°C. Polarized light microscopy revealed the ferroelastic domain structure in the t ' samples. XRD showed that no monoclinic phase was detected on as-polished, ground and fracture surfaces, or on surfaces while under a tensile stress as high as 400 MPa. By contrast, relative changes occurred in the tetragonal peak intensities, which were attributed to ferroelasatic domain switching. The higher toughness of 3-mol%-Y₂O₃-doped t ' samples (7.7 MPa · m^1/2) compared to that of 8 mol% Y₂O₃ cubic samples (2.4 MPa · m^1/2) was explained in part by ferroelastic domain switching.     

Phase Transformations of Plasma-Sprayed Zirconia–Ceria Thermal Barrier Coatings

Phase constituents and transformations of plasma-sprayed thermal barrier coatings (TBCs) with CeO₂-stabilized ZrO₂ (CSZ; 16–26 wt% CeO₂) have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy-dispersive spectroscopy (EDS). The as-coated CSZ coatings with 16 and 18 wt% CeO₂ consisted only of the nonequilibrium tetragonal ( t ') phase. A mixture of the t ' and the nonequilibrium cubic ( c ') phases was observed for the as-coated CSZ coatings containing 20–26 wt% CeO₂. During 65 min cyclic oxidation at 1135°C (45 min hold time) in air, the t ' or the mixture of the t ' and the c ' phases decomposed to the equilibrium tetragonal ( t ) and the equilibrium cubic ( c ) phases. Some of the t phase transformed to the monoclinic ( m ) phase on cooling. More m phase was observed to develop in the CSZ coating containing 16 wt% CeO₂ than in the other coatings. More m phase was observed on the top surface than on the bottom surface of the CSZ coating. Spalling of the plasma-sprayed CSZ coating during thermal cycling occurred after 230 cycles for the CSZ coating containing 16 wt% CeO₂, whereas the lifetime of the CSZ coatings with 18–26 wt% CeO₂ ranged between 320 and 340 cycles.     

Microstructural Characterization and Fracture Toughness of Cordierite-ZrO2 Glass-Ceramics

Crystallization of an MgO-Al₂O₃-SiO₂-ZrO₂ sintered glass frit was studied. Heat treatment at 850° or 900°C caused initial crystallization of μ-cordierite and tetragonal ( t ) ZrO₂. The t -ZrO₂ crystallized with an irregular dendritic morphology and could be transformed to monoclinic ( m ) symmetry under certain conditions; the cordierite underwent the μ→α a transformation with extended annealing. Heat treatments at 1000°C caused crystallization of t -ZrO₂ rods and spheroids in an α-cordierite matrix; these ZrO₂ crystals, however, are resistant to transformation to m -ZrO₂. The beneficial effects of ZrO₂ on the fracture toughness of cordierite-based glass-ceramics are described.     

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.     

Phase Transformation of Hydrous-Zirconia Fine Particles Containing Cerium Hydroxide

Monoclinic hydrous-zirconia fine particles that contained cerium(IV) hydroxide (Ce(OH)₄) were heated from 200°C to 600°C, to investigate the phase transformation to CeO₂-doped tetragonal ZrO₂. Both ZrOCl₂·8H₂O and CeCl₃·7H₂O were dissolved in aqueous solutions and then boiled to prepare the hydrous-zirconia particles. The Ce(OH)₄-containing hydrous-zirconia particles were prepared by adding aqueous ammonia into the boiled solutions. The monoclinic-to-tetragonal ( m right arrow t ) phase transformation of the Ce(OH)₄-containing hydrous zirconias was observed at 300°C using X-ray diffraction (XRD). XRD and Brunauer-Emmett-Teller (BET) specific surface area measurements revealed that the Ce(OH)₄-containing hydrous zirconias had a tendency to transform from the monoclinic phase to the tetragonal phase at lower temperatures as the primary particle size of the hydrous zirconia decreased and the Ce(OH)₄ content increased. These tendencies for the m right arrow t phase transformation agree with the conclusions that have been derived from thermodynamic and kinetic considerations.     

Effect of Particle Size on the Room-Temperature Crystal Structure of Barium Titanate

The room-temperature tetragonal-to-cubic transformation in BaTiO₃ powders with decreasing particle size has been carefully studied, using materials prepared mainly by hydrothermal methods. Hydrothermal BaTiO₃ powders exhibited a more uniform particle size distribution than oxalate-route powders, with X-ray diffraction and electron microscopy indicating that powders 0.19 μm in size were fully cubic while powders 0.27 μ were completely tetragonal (within a 5% detection limit for cubic material) at room temperature. The tetragonal-to-cubic transformation temperature was also found to lie in the range of 121°± 3°C for BaTiO₃ powders with room-temperature ( c/a ) values > 1.008. No transformation could be detected using differential scanning calorimetry for BaTiO₃ particles with a ( c/a ) > 1.008 at room temperature. BaTiO₃ powder with a particle size just too small (0.19 μm) to be tetragonal at room temperature remained cubic down to 80 K. Different models for the cubic-to-tetragonal room-temperature transformation are discussed. Hydroxyl ions do not appear to greatly affect the cubic-to-tetragonal transformation, which appears to be essentially dependent on particle size. It is concluded that a model based on surface free energy, as previously discussed for the monoclinic-to-tetragonal transformation at room temperature of fine ZrO₂ particles, is consistent with the experimental data.     

Microindentation-Induced Transformation in 3.5-mol%-Yttria-Partially-Stabilized Zirconia Single Crystals

The temperature dependence of the Vickers microhardness was studied in 3.4-mol%-Y₂O₃-partially-stabilized ZrO₂ (Y-PSZ) single crystals up to 1000°C; the samples had previously been annealed at 1600°C for 150 h to develop "colony" precipitates of tetragonal ZrO₂ in the cubic ZrO₂ matrix. Indentation caused extensive stress-induced martensitic transformation of the colony precipitates to monoclinic symmetry in zones which extended in extreme cases up to several hundred micrometers from the indent. For indents made at 500°C and above, the M _d and M _f temperatures are 450° and 310°C, respectively; A _s is ∼600°C ( M _d is the temperature of initial transformation (the "martensite start temperature") in deformed samples; M _f is the temperature at which the final transformation occurs; A _s is the temperature at which the reverse (monoclinic → tetragonal) transformation begins). However, extensive transformation zones are also found for indents made at 200°, 300°, and 400°C. The dislocation density introduced during indentation is responsible for nucleating the transformation in a zone adjacent to the indent. However, the transformation zone extends further than the plastic zone around the indent, indicating extensive autocatalytic transformation. Transformation within the zone appeared to occur in individual plates with {110} habit planes. The plate dimensions (∼100 μm ×∼175 μm ×∼10 μm) are large compared to the size of the colony precipitates (∼2 μm in maximum dimension).     

Low-Temperature Phase Equilibria by the Flux Method and the Metastable–Stable Phase Diagram in the ZrO2–CeO2 System

Low-temperature phase equilibria ranging from 1000° to 1200°C in the ZrO₂–CeO₂ system were investigated by annealing compositionally homogeneous ZrO₂–CeO₂ solid solutions in a Na₂B₂O₇.1 NaF flux. The 5 mol% CeO₂ samples decomposed into monoclinic ( m ) and tetragonal ( t ) phases during annealing at 1100°2 and 1120°C, and the t -phase transformed diffusionlessly into monoclinic ( m ') symmetry during quenching. A eutectoid reaction, t → ( m + c ), was confirmed to occur at 1055°± 10°C, where the equilibrium compositions of the t -, m -, and c -phases were 11.2 ± 2.8, 0.9 ± 0.9, and 84 ± 1 mol% CeO₂, respectively. The equilibrium phase boundaries were almost independent of the annealing time and/or the flux:sample ratio, which indicates that the flux accelerates the reaction rate withouts affecting the equilibration. The previous data are discussed using metastable–stable phase diagrams. The discrepancies of the low-temperature phase diagram in the literature are attributable to either regarding the metastable phase boundaries as stable ones or ignoring the sluggish kinetics.     

Infiltration of Porous Alumina Bodies with Solution Precursors: Strengthening via Compositional Grading, Grain Size Control, and Transformation Toughening

Alumina powder compacts, partially densified with a lowtemperature heat treatment and then cut into bars, were infiltrated with liquid precursors that decomposed to either mullite (3Al₂O₃·2SiO₂), fully stabilized zirconia (cubic Zr(8Y)O₂), or partially stabilized zirconia (tetragonal Zr(4Y)O₂). The specimens were repeatedly infiltrated and pyrolyzed to achieve a higher concentration of the precursor near the surface. The infiltrated bodies were then densified at 1500°C/2 h. Residual stresses developed during cooling from the densification temperature because of the higher concentration of the second phase near the surface and their differential thermal expansion relative to the matrix material. At least 10 bars of each two-phase material were fractured in four-point bending to determine the effect of the second phase on strength. The alumina bars without a second phase had a larger grain size (∼7 μm) and a mean strength of 253 MPa. The intruded phases significantly reduced the Al₂O₃ grain size to ∼1 1μm. Despite their higher concentration near the surface and apparent surface tensile stress, both of the Zr(Y)O₂ phases increased the mean strength to 413 MPa ( c -Zr(8Y)O₂) and 582 MPa ( t -Zr(4Y)O₂, an apparent toughening agent). The mullite second phase produced a high mean strength of 588 MPa, apparently due to its concentration gradient creating a compressive surface stress.     

Influence of Sintering Temperature on Grain Growth and Phase Structure of Compositionally Optimized High-Performance Li/Ta-Modified (Na,K)NbO3 Ceramics

Microstructure characteristics, phase transition, and electrical properties of (Na_0.535K_0.485)_0.926Li_0.074(Nb_0.942Ta_0.058)O₃ (NKN-LT) lead-free piezoelectric ceramics prepared by normal sintering are investigated with an emphasis on the influence of sintering temperature. Some abnormal coarse grains of 20–30 μm in diameter are formed in a matrix consisting of about 2 μm fine grains when the sintering temperature was relatively low (980°C). However, only normally grown grains were observed when the sintering temperature was increased to 1020°C. On the other hand, orthorhombic and tetragonal phases coexisted in the ceramics sintered at 980°–1000°C, whereas the tetragonal phase becomes dominant when sintered above 1020°C. For the ceramics sintered at 1000°C, the piezoelectric constant d ₃₃ is enhanced to 276 pC/N, which is a high value for the Li- and Ta-modified (Na,K)NbO₃ ceramics system. The other piezoelectric and ferroelectric properties are as follows: planar electromechanical coupling factor k _p=46.2%, thickness electromechanical coupling factor k _t=36%, mechanical quality factor Q _m=18, remnant polarization P _r=21.1 μC/cm², and coercive field E _c=1.85 kV/mm.     

Stability of Ultrafine Tetragonal ZrO2 Coprecipitated with Al2O3 by the Spray-ICP Technique

The transformation of ultrafine powders (particle size, 0.01 to 0.04 μm) of the system ZrO_2–Al₂O₃, prepared by spraying their corresponding nitrate solutions into an inductively coupled plasma (ICP) of ultrahigh temperature, was investigated. The powders were composed of metastable tetragonal ZrO₂ ( mt- ZrO₂) and γ-Al₂O₃. On heating, the mt- ZrO₂ (or tetragonal ZrO₂, t -ZrO₂) was retained up to 1200°C. At 1380°C the transformation to monoclinic ZrO₂ ( m -ZrO₂) occurred and the amount of the m -ZrO₂ decreased with the increase in Al₂O₃ content, thus indicating the stabilization of the t -ZrO₂ by the Al₂O₃, which seems to be explained in terms of the retardation of grain growth.     

Cation Interdiffusion and Phase Stability in Polycrystalline Tetragonal Ceria–Zirconia–Hafnia Solid Solution

Zr–Hf interdiffusions were carried out at 1350° to 1520°C for polycrystalline tetragonal solid solutions of 14CeO₂·86(Zr_{1- x} Hf _x )O₂ with X = 0.02 and 0.10. Lattice and grain-boundary interdiffusion parameters were calculated from the concentration distributions by using Oishi and Ichimura's equation. Lattice interdiffusion coefficients were described by D = 3.0 × 10³ exp[-623 (kJ/mol)/ RT ] cm²/s and grain-boundary interdiffusion parameters by δ D ' = 0.29 exp[-506 (kJ/mol)/ RT ] cm³/s. The cation diffusivity was lower than the anion diffusivity. The results were compared with diffusivities in the fluorite-cubic solid solution. The critical grain radii for stabilization of the tetragonal phase in CeO₂-doped ZrO₂ were 11 and 6 μm for the solutions with 2 and 10 mol% HfO₂ substitution, respectively, both of which are much greater than in the Y₂O₃-doped ZrO₂ solid solution.     

The System Zirconia-Scandia

The system zirconia-scandia was investigated using X-ray diffraction analysis, differential thermal analysis, metallographic analysis, and melting point studies. Results reveal the monoclinic α₁ phase (0 to 2 mol% Sc₂O₃), the tetragonal α₂'phase (5 to 8% Sc₂O₃), the rhombohedral β phase (9 to 13% Sc₂O₃), the rhombohedral γ phase (15 to 23% Sc₂O₃), the rhombohedral δ phase (24 to 40% Sc₂O₃), and the cubic % phase (77.5 to 100% Sc₂O₃). The monoclinic α₁ phase and the tetragonal α₂'phase were found to transform to the tetragonal α₂ phase over a wide temperature range depending on composition. The β, γ, and α phases transformed to a cubic phase at temperatures of %600^%, 1100^%, and 1300^%C, respectively. A maximum melting point of %2870^%C was found at %10% Sc₂O₃ and a eutectic at %2400^%C at 55% Sc₂O₃.     

Effect of Heat Treatment on Grain Size, Phase Assemblage, and Mechanical Properties of 3 mol% Y-TZP

The effect of heat treatment on the grain size, phase assemblage, and mechanical properties of a 3 mol% Y-TZP ceramic was investigated. Specimens were initially sintered for 2 h at 1450°C to near theoretical density; some specimens were then heat-treated at 1550°, 1650°, 1750°, or 1850°C to coarsen the microstructure. The average grain size increased with heat treatment from <0.5 to ∼10 μ-m. Phase analyses revealed predominantly tetragonal and cubic phases below 1750°C, with a significant decrease in tetragonal content and increase in monoclinic content for temperatures >1750°C. The maximum fraction of tetragonal phase that transformed during fracture corresponded with the largest tetragonal grain size of ∼5–6 μm. Strength was on the order of 1 GPa, and was surprisingly insensitive to heat-treatment temperature and grain size, contrary to previous studies. The fracture toughness increased from 4 to 10 MPa.m^1/2 with increasing grain size, owing to an increasing transformation zone size. Grain sizes larger than 5–6 μm spontaneously transformed to monoclinic phase during cooling. Such critical grain sizes are much larger than those found in past investigations, and may be due to the greater fraction of cubic phase present which decreases the strain energy arising from crystallographic thermal expansion anisotropy of the tetragonal phase.     

'Polymorph Method' Determination of Monoclinic Zirconia in Partially Stabilized Zirconia Ceramics

The polymorph method, which provides phase analysis from a small number of integrated intensities in a powder diffraction scan, is adapted for the determination of monoclinic zirconia in a mixture with cubic, tetragonal. and orthorhombic zirconias and the γ-phase (Mg₂Zr₅O₁₂). Such a mixture is representative of Mg-PSZ after subeutectoid aging. The quantitative determination of the monoclinic depends in principle on a knowledge of the relative amounts of the other phases present in the mixture. It is demonstrated, however, that without this knowledge, even in complex mixtures, the traditional polymorph method analysis gives an acceptable estimate of the monoclinic fraction in the sample.     

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.     

Effect of Composition and Size of Crystallite on Crystal Phase in Lead Barium Titanate

Lead titanate, barium titanate, and lead barium titanate powders (>99.9% pure), the particle size of which varied from 0.03 to 0.15 μm depending on the calcination temperature and the composition, was prepared from barium lead titanyl oxalate, which was previously prepared by reacting high-purity ammonium titanyl oxalate with barium and lead acetate. The critical crystallite size of BaTiO₃ powder from the cubic to the tetragonal phase is around 1 μm. Pb_0.3Ba_0.7TiO₃ powder with an average size of 0.057 μm showed the tetragonal phase.     

Raman Scattering Study of Cubic–Tetragonal Phase Transition in Zr1−xCexO2 Solid Solution

A structural phase transition between the cubic (space group, Fm 3 m) and tetragonal (space group, P 4₂ /nmc) phases in a zirconia–ceria solid solution (Zr_1−xCe_xO₂) has been observed by Raman spectroscopy. The cubic–tetragonal ( c–t" ) phase boundary in compositionally homogeneous samples exists at a composition X₀ (0.8 < X₀ < 0.9) at room temperature, where t " is defined as a tetragonal phase whose axial ratio c/a equals unity. The axial ratio c/a decreases with an increase of ceria concentration and becomes 1 at a composition X'₀ (0.65 < X'₀ < 0.7) at room temperature. The sample with a composition between X₀ and X'₀ is t " ZrO₂. By Raman scattering measurements at high temperatures, the tetragonal ( t" ) → cubic and cubic → tetragonal phase transitions occur above 400°C in Zr_0.2 Ce_0.8O₂ solid solution.     

Measurement of the Crystallographically Transformed Zone Produced by Fracture in Ceramics Containing Tetragonal Zirconia

During fracture of ceramics containing tetragonal zirconia particles, a volume of zirconia material on either side of the crack irreversibly transforms to the monoclinic crystal structure. Transformation zone sizes, measured using Raman microprobe spectroscopy, are presented for three sintered ceramics. In a single-phase ZrO₂−3.5 mol% Y₂O₃ material, an upper bound measurement of 5 μm is obtained for the zone size. In the Al₂O₃/ZrO₂ composites studied, the zone size is deduced to correspond to ∼1 grain in diameter. On the basis of the monoclinic concentrations derived from the Raman spectra it is further concluded that only a fraction of the ZrO₂ grains within the transformation zone transform, providing indirect evidence for the effect of particle size on the propensity for transformation.     

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.