Twinning in YNbO4

The compound YNbO₄ is a 3–5 analogue of ZrO₂ with two polymorphs: low-temperature monoclinic and high-temperature tetragonal forms. YNbO₄ powder with a surface area of 40 m²/g was prepared from citrate complexes. The powder sintered to theoretical density at 1550°C. Unlike pure ZrO₂, YNbO₄ can be cooled through the tetragonal-to-monoclinic phase transformation without cracking. The phase transformation is gradual and takes place by shear, resulting in twinning.     

ZrO2-Transformation-Toughened Glass-Ceramics Prepared by the Sol-Gel Process from Metal Alkoxides

Glasses of composition 3ZrO₂O · 2SiO₂ were prepared by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by appropriate heat treatment at 1000° to 1200°C. The fracture toughness of these glass-ceramics increased with increasing crystallite size of the tetragonal ZrO₂, reaching ∼5.0 MN/m^3/2 at a size of ∼40 nm. The higher fracture toughness was attributed to tetragonal → monoclinic ZrO₂ transformation toughening.     

Zircon-Zirconia Ceramics Prepared from Plasma Dissociated Zircon

A ceramic consisting of a dispersion of ZrO₂ particles (∼25%) in zircon was prepared by sintering partially leached plasma dissociated zircon. ZrO₂ particles smaller than ∼150 nm were tetragonal inform; larger particles were monoclinic. The large increase in proportions of tetragonal ZrO₂ after sintering may be ascribed partly to a reduction in particle size by reaction to form zircon, and partly to a matrix effect on the tetragonal to monoclinic transformation.     

Strength-Toughness Relations in Sintered and Isostatically Hot-Pressed ZrO2-Toughened Al2O3

The fracture toughness of fine-grained undoped ZrO₂-toughened Al₂O₃ (ZTA) was essentially unchanged by postsintering hot isostatic pressing and increased monotonically with ZrO₂ additions up to 25 wt%. The strength of ZTA with 5 to 15 wt% tetragonal ZrO₂, which depended monotonically on the amount of ZrO₂ present before hot isostatic pressing, was increased by pressing but became almost constant between 5 and 15 wt% ZrO₂ addition. The strength appeared to be controlled by pores before pressing and by surface flaws after pressing; the size of flaws after pressing increased with ZrO₂ content. The strength of ZTA containing mostly monoclinic ZrO₂ (20 to 25 wt%) remained almost constant despite the noticeable density increase upon hot isostatic pressing because the strength was controlled by preexisting microcracks whose extent did not change on postsintering pressing. These strength-toughness relations in sintered and isostatically hot-pressed ZTA are explained on the basis of R -curve behavior. The importance of the contribution of microcracks to the toughness of ZTA is emphasized.     

Transformation of Yttria-Doped Tetragonal ZrO2 Polycrystals by Annealing in Water

Phase changes and the microstructure resulting from low-temperature annealing of yttria-doped tetragonal ZrO₂ polycrystals in water were investigated at 65° to 120°C. Tetragonal ZrO₂ on the surface of the sintered body transformed to the monoclinic phase, accompanied by microcracking. The transformation rate in water, which was much greater than that in air, was first order with respect to surface concentration of tetragonal ZrO₂. Nonaqueous solvents with a molecular structure containing a lone-pair electron orbital opposite a proton donor site also greatly enhanced the transformation.     

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.     

Synthesis of the Orthorhombic Phase of 2Y˙ZrO2

A mixture of tetragonal and monoclinic 2Y˙ZrO₂ (2 mol% Y₂O₃–ZrO₂) powder was treated from 400° to 800°C and from 4 to 7 GPa for 30 min. The products were identified by powder XRD, Raman spectroscopy, and TEM. Results indicated that an orthorhombic phase was synthesized at T=400° to 600°C and P>4 GPa. The lattice parameters were obtained as a=0.505, b=0.525, and c=0.509 nm; the density was 6.17 Mg/m³. The orthorhombic phase always coexisted with the tetragonal phase in the products. The amounts of the tetragonal phase before and after treatment remained largely unchanged, whereas the amount of new orthorhombic phase was nearly the same as the decreased amount of the monoclinic phase. It was assumed, therefore, that only the monoclinic phase transformed into the orthorhombic phase.     

Degradation During Aging of Transformation-Toughened ZrO2-Y2O3 Materials at 250°C

The detrimental aging phenomenon observed in ZrO₂-Y₂O₃ materials, which causes tetragonal ZrO₂ to transform to its monoclinic structure at temperatures between 150 and 400°C, was investigated with respect to the gaseous aging environment and the Y₂O₃ and SiO₂ content of the material. It is shown that the aging phenomenon is caused by water vapor and that inter-granular silicate glassy phases play no significant role. Transmission electron microscopy of thin foils, before and after aging, showed that the water vapor reacted with yttrium in the ZrO₂ to produce clusters of small (20 to 50 nm) crystallites of α-Y(OH)₃. It is hypothesized that this reaction produces a monoclinic nucleus (depleted of Y₂O₃) on the surface of an exposed tetragonal grain. Monoclinic nuclei greater than a critical size grow spontaneously to transform the tetragonal grain. If the transformed grain is greater than a critical size, it produces a microcrack which exposes subsurface tetragonal grains to the aging phenomenon and results in catastrophic degradation. Degradation can be avoided if the grain size is less than the critical size required for microcracking.     

Stability of ZrO2 Phases in Ultrafine ZrO2-Al2O3 Mixtures

Mixtures of ultrafine monoclinic zirconia and aluminum hydroxide were prepared by adding NH₄OH to hydrolyzed zirconia sols containing varied amounts of aluminum sulfate. The mixtures were heat-treated at 500° to 1300°C. The relative stability of monoclinic and tetragonal ZrO₂ in these ultrafine particles was studied by X-ray diffractometry. Growth of ZrO₂ crystallites at elevated temperatures was strongly inhibited by Al₂O₃ derived from aluminum hydroxide. The monoclinic-to-tetragonal phase transformation temperature was lowered to ∼500°C in the mixture containing 10 vol% Al₂O₃, and the tetragonal phase was retained on cooling to room temperature. This behavior may be explained on the basis of Garvie's hypothesis that the surface free energy of tetragonal ZrO₂ is lower than that of the monoclinic form. With increasing A1₂O₃ content, however, the transformation temperature gradually increased, although the growth of ZrO₂ particles was inhibited; this was found to be affected by water vapor formed from aluminum hydroxide on heating. The presence of atmospheric water vapor elevates the transformation temperature for ultrafine ZrO₂. The reverse tetragonal-to-monoclinic transformation is promoted by water vapor at lower temperatures. Accordingly, it was concluded that the monoclinic phase in fine ZrO₂ particles was stabilized by the presence of water vapor, which probably decreases the surface energy.     

Tape Casting and Properties of Mullite and Zirconia–Mullite Ceramics

Mullite and ZrO₂-mullite ceramics have been prepared by tape casting mixtures of Al₂O₃, quartz, and ZrO₂ powders and subsequent reaction sintering. Tape casting leads to homogeneous, high-density green materials with good sinterability. The design of a thermal cycle which favors densification with respect to mullitization allows the preparation of nearly dense, nearly fully reacted materials at sintering temperatures below 1600°C. ZrO₂ additions limit grain growth, but the ZrO₂ content must not be too high when a high tetragonal:monoclinic ratio is required.     

Fracture Toughness of Al2O3 with an Unstabilized ZrO2Dispersed Phase

The fracture toughness of Al₂O₃ is considerably increased by the incorporation of fine monoclinic ZrO₂ particles. Hot-pressed composites containing 15 vol % ZrO₂ yield K_lcvalues of ∼ 10 MN/m^3/2, twice that of the A1₂O₃ matrix. It is hypothesized that this increase results from a high density of small matrix microcracks absorbing energy by slow propagation. The microcracks are formed by the expansion of ZrO₂during the tetragonal → monoclinic transformation. Since extremely high tensile stresses develop in the matrix, very small ZrO2 particles can act as crack formers, thus limiting the critical flaw size to small values.     

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.     

Effect of MgO Addition on the Microstructure Development of 3 mol% Y2O3—ZrO2

MgO addition to 3 mol% Y₂O₃–ZrO₂ resulted in enhanced densification at 1350°C by a liquid-phase sintering mechanism. This liquid phase resulted from reaction of MgO with trace impurities of CaO and SiO₂ in the starting powder. The bimodal grain structure thus obtained was characterized by large cubic ZrO₂ grains with tetragonal ZrO₂ precipitates, which were surrounded by either small tetragonal grains or monoclinic grains, depending on the heat-treatment schedule.     

Effects of Oxygen Partial Pressure on the Nucleation Behavior and Morphology of Chemically-Vapor-Deposited Zirconia on Hi-Nicalon Fiber and Si

A ZrO₂ coating was prepared on Hi-Nicalon fiber and single-crystal Si by chemical vapor deposition (CVD) using ZrCl₄, CO₂, and H₂ as precursors at 1050°C. The effects of oxygen partial pressure on the nucleation behavior of the CVD-ZrO₂ coating were systematically studied by intentionally varying the controlled amount of O₂ into the CVD chamber. Characterization results suggested that the number density of tetragonal ZrO₂ nuclei apparently decreased with increasing the oxygen partial pressure from 4 × 10⁻³ to 1.6 Pa. Also, the coating layer became more columnar and contained larger monoclinic ZrO₂ grains. The observed relationships between the oxygen partial pressure and the nucleation and morphologic characteristics of the ZrO₂ coating were attributed to the grain size and oxygen deficiency effects, which have been previously reported to cause the stabilization of the tetragonal ZrO₂ phase in bulk ZrO₂ specimens.     

Phase Relations in the System ZrO2-Y2O3 at Low Y2O3 Contents

Subsolidus phase relations in the low-Y₂O₃ portion of the system ZrO_2-Y₂O₃ were studied using DTA with fired samples and X-ray phase identification and lattice parameter techniques with quenched samples. Approximately 1.5% Y₂O₃ is soluble in monoclinic ZrO₂, a two-phase monoclinic solid solution plus cubic solid solution region exists to ∼7.5% Y₂O₃ below ∼500°C, and a two-phase tetragonal solid solution plus cubic solid solution exists from ∼1.5 to 7.5% Y₂O₃ from ∼500° to ∼1600°C. At higher Y₂O₃ compositions, cubic ZrO₂ solid solution occurs.     

Preparation, Sintering, and Properties of Translucent Er2O3-Doped Tetragonal Zirconia

Tetragonal zirconia doped with 3 mol% Er₂O₃ was prepared by the gel-precipitation wet-chemical method. The compaction response of ultrafine (∼8.5 nm), calcined, deagglomerated powders was studied. Initial sintering was studied using both isothermal and nonisothermal techniques, and an activation energy of 270 ± 40 kJ/mol was obtained; therefore, grain-boundary diffusion was probably the predominant mechanism in the sintering stage. The microstructural development in the high-temperature-aged, sintered samples and its effect on density and mechanical properties were also studied. A theoretically dense body of tetragonal zirconia solid solution of 3 mol% Er₂O₃–ZrO₂, obtained from sintering below 1400°C, was translucent.     

Role of Water Vapor in Crystallite Growth and Tetragonal-Monoclinic Phase Transformation of ZrO2

The role of water vapor in crystallite growth and the tetragonal-to-monoclinic phase transformation of ZrO₂ was studied using three specially prepared samples: an ultrafine powder of monoclinic ZrO₂ obtained by hydrolysis of ZrOCI₂, an aggregated powder of tetragonal ZrO₂ obtained by thermal decomposition of Zr(OH)₄ under reduced pressure, and an ultrafine powder of tetragonal ZrO₂ obtained by thermal decomposition of zirconyl acetate dispersed in caramel. The samples were heat-treated up to 1000°C in dry and wet atmospheres saturated with water vapor at 90°C. It was found that water vapor markedly accelerated crystallite growth for both monoclinic and tetragonal ZrO₂ and facilitated the tetragonal-to-monoclinic phase transformation. Water vapor increases surface diffusion and thus enhances crystallite growth and decreases surface energy, which leads to stabilization of the tetragonal phase.     

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.     

Sintering and Characterization of Polycrystalline Monoclinic, Tetragonal, and Cubic Zirconia

Polycrystalline monoclinic ( m ), tetragonal ( t ), and cubic ( c ) ZrO₂, sintered at 1500°C, were annealed in the cubic stability field and rapidly cooled to permit the displacive c → t ' transformation to occur in compositions containing 0–6 mol% Y₂O₃. The bulk fracture toughness of coarse-grained (> 25 μm) m , t ', and c zirconias were compared with conventionally sintered, fine-grained (typically less than 1 μm) materials. The ferroelastic monoclinic and tetragonal zirconias were more than twice as tough as paraelastic cubic zirconia.     

Phase Relations in the ZrO2-MgO System

Phase relations were studied in the system ZrO₂-MgO with emphasis on the range 1350° to 1600°C. A phase relation was determined from samples, using precision lattice parameters, X-ray diffraction line intensities, and petrographic observations, and from dynamic observations of the phases present using high-temperature X-ray diffraction techniques. Limits were established for the solubility of MgO in tetragonal ZrO₂ and for the range of the cubic solid solution. The phase relations below 1240°C were complicated by hysteresis in the monoclinic to tetragonal inversion of ZrO₂.