Crystallization and Transformation of Zirconia Under Hydrothermal Conditions

During constant-rate heating to 350°C in concentrated NaOH solutions, cubic ZrO₂ crystallized at ∼120°C from hydrated amorphous ZrO₂; these One cubic ZrO₂ particles abruptly changed into needlelike monoclinic ZrO₂ single crystals at 300°C. Crystallization and phase transformation were studied by XRD, TEM, and EPMA. Cubic ZrO₂ appears to crystallize via collapse of the ZrO₂−nH₂O structure and subsequent slight rearrangement of the lattice. The abrupt formation of mono-clinic ZrO₂ was considered to result when the very fine cubic ZrO₂ particles coagulated in a highly oriented fashion.     

Cubic-to-Tetragonal Displacive Transformation in Gd2O3–Bi2O3 Ceramics

Gd₂O₃-doped Bi₂O₃ polycrystalline ceramics containing between 2 and 7 mol% Gd₂O₃ were fabricated by pressureless sintering powder compacts. The as-sintered samples were tetragonal at room temperature. Hightemperature X-ray diffraction (XRD) traces showed that the samples were cubic at elevated temperatures and transformed into the tetragonal polymorph during cooling. On the basis of conductivity measurements as a function of temperature and differential scanning calorimetry (DSC), the cubic → tetragonal as well as tetragonal → cubic → teansition temperatures were determined as a function of Gd₂O₃ concentration. The cubic → tetragonal transformation appears to be a displacive transformation. It was observed that additions of ZrO₂ as a dopant, which is known to suppress cation interdiffusion in rare-earth oxide–Bi₂O₃ systems, did not suppress the transition, consistent with it being a displacive transition. Annealing of samples at temperatures 660°C for several hundred hours led to decomposition into a mixture of monoclinic and rhombohedral phases. This shows that the tetragonal polymorph is a metastable phase.     

Precipitation in Partially Stabilized Zirconia

Transmission electron microscopy was used to study the sub-structure of partially stabilized ZrO₂ (PSZ) samples, i.e. 2-phase "alloys" containing both cubic and monoclinic modifications of zirconia, after various heat treatments. Monoclinic ZrO₂ exists as (1) isolated grains within the polycrystalline aggregate (a grain-boundary phase) and (2) small plate-like particles within cubic grains. These intragranular precipitates are believed to contribute to the useful properties of PSZ via a form of precipitation hardening. These precipitates initially form as tetragonal ZrO₂, with a habit plane parallel to the {100} matrix planes. The orientation relations between the tetragonal precipitates and the cubic matrix are
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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.     

Microstructures of Simulated Nuclear Waste

The microstructures of simulated tailored ceramic forms for the Idaho Chemical Processing Plant (ICPP) high-level waste were characterized by TEM. The ceramic forms were consolidated from simulated ICPP waste calcines with either silicayttria-based or silica–lithia-based additives by hot isostatic pressing. The hot isostatically pressed ceramic waste forms are composed of cubic CaF₂, monoclinic ZrO₂, stabilized cubic ZrO₂, tetragonal ZrSiO₄, and amorphous silicate phases which can be phase separated. The phaseseparated glass is a result of phase immiscibility in the soda aluminosilicate glass to the compositions of albite and mullite.     

Na-Modified Cubic Zirconia—Link Between Sodium Zirconate and Zirconia in the Na2O–ZrO2 Phase Diagram

Solid-state electrochemical and XRD studies reveal that the phase relation between Na₂ZrO₃(s) and ZrO₂(s) is governed by the existence of non-stoichiometric Na-modified cubic ZrO₂. It leads to the splitting of the nominal Na₂ZrO₃/ZrO₂ (NZO) equilibrium system into two systems: . The causes extended single-phase region in between the thermodynamic stability in the temperature interval 400°–600°C to change steadily upon varying the composition of the phase mixture. As a consequence, previous data on the thermodynamic stability of the NZO system have to be considered with caution.     

Massive Transformation in the Y2O3-Bi2O3 System

Cubic solid solutions in the Y₂O₃-Bi₂O₃ system with ∼25% Y₂O₃ undergo a transformation to a rhombohedral phase when annealed at temperatures ≤ 700°C. This transformation is composition-invariant and is thermally activated, and the product phase can propagate across matrix grain boundaries, indicating that there is no special crystallo-graphic orientation relationship between the product and the parent phases. Based on these observations, it is proposed that cubic → rhombohedral phase transformation in the Y₂O₃-Bi₂O₃ system is a massive transformation. Samples of composition 25% Y₂O₃-75% Bi₂O₃ with and without aliovalent dopants were annealed at temperatures ≤ 700°C for up to 10000 h. ZrO₂ as a dopant suppressed while CaO and SrO as dopants enhanced the kinetics of phase transformation. The rate of cubic/rhombohedra1 interface migration (growth rate or interface velocity) was also similarly affected by the additions of dopants; ZrO₂ suppressed while CaO enhanced the growth rate. Diffusion studies further showed that ZrO₂ suppressed while CaO enhanced cation interdiffusion coefficient. These observations are rationalized on the premise that cation interstitials are more mobile compared to cation vacancies in cubic bismuth oxide. The maximum growth rate measured was ∼10⁻¹⁰ m/s, which is orders of magnitude smaller than typical growth rates measured in metallic alloys. This difference is explained in terms of substantially lower diffusion coefficients in these oxide systems compared to metallic alloys.     

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.     

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.     

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.     

Phase Equilibria in the System ZrO2─InO1.5

Phase equilibria in the system ZrO₂─InO_1.5 have been investigated in the temperature range from 800° to 1700°C Up to 4 mol%, InO_1.5 is soluble in t -ZrO₂ at 1500°C. The martensitic transformation temperature m → t of ZrO₂ containing InO_1.5 is compared with that of ZrO₂ solid solutions with various other trivalent ions with different ionic radii. The diffusionless c → t ' A phase transformation is discussed. Extended solid solubility from 12.4 ± 0.8 to 56.5 ± 3 mol% InO_1.5 is found at 1700°C in the cubic ZrO₂ phase. The eutectoid composition and temperature for the decomposition of c -ZrO₂ solid solution into t -ZrO₂+InO_1.5 solid solutions were determined. A maximum of about 1 mol% ZrO₂ is soluble in bcc InO_1.5 phase. Metastable supersaturation of ZrO₂ in bcc InO _1.5 and conditions for phase separation are discussed.     

Phase Relationships in the ZrO2-Sc2O3 and ZrO2-In2O3 Systems

Zirconia-rich subsolidus phase relationships in the ZrO₂–Sc₂O₃ and ZrO₂–In₂O₃ systems were investigated. Phase inconsistencies in the ZrO₂–Sc₂O₃ system resulted from a diffusionless cubic-to-tetragonal ( t' ) phase transformation not being recognized in the past. Through three different measuring techniques, along with microstructural observations, the solubility limits of the tetragonal and cubic phases were determined.     

Phase Relations and Ordering in the System ZrO2-MgO

The Phase relationships in the system ZrO₂-MgO were reinvestigated over a wide range of temperatures and compositions. The extent of the cubic solid solution field was determined with precise lattice parameter measurements and a high-temperature X-ray furnace using analyzed samples. DTA results show that the addition of MgO to ZrO₂ decreases the transition temperature for monoclinic ⇌ tetragonal ZrO₂ and 1 mol% of MgO is soluble in the monoclinic zirconia at ∼1070°C.The invariant eutectiod point is at 13.5 ± 0.3 mol% MgO at 1406°± 7°C, which is in fair agreement with previous results by Grain. The ordered phase Mg₂Zr₅O₁₂ (δ-phase) can form metastably in cubic solid solutions at temperatures as low as 800°C after prolonged annealing. Evidence for the existence of the ordered phase MgZr₆O₁₃(γ-phase) was obtained by electron diffraction technique. Conditions for the formation of this phase are described. The ordered phases in this system are metastable and their formation is an intermediate step in the eutectoid decomposition of the cubic phase.     

Strength Improvement in Transformation-Toughened Alumina by Selective Phase Transformation

A1₂O₃-15 vol% ZrO₂ bar-shaped ceramic specimens were fabricated in the green state in such a way that the near surface regions consisted of A1₂O₃ and unstabilized ZrO₂ while the bulk consisted of A1₂O₃ and partially stabilized ZrO₂. After sintering, specimens had macroscopic residual compressive surface stresses and balancing interior tensile stresses due to the tetragonal-to-monoclinic phase transformation in the outer layers which occurs during cooling. The depth of the surface region was controlled during green forming. Residual surface compressive stresses at room temperature varied between 100 and 400 MPa depending on the outer-layer thickness. The increased strengths of the three-layer specimens were obtained in the as-fired unground condition, demonstrating that the stresses introduced are the result of transformation of tetragonal zirconia into monoclinic polymorph which occurred upon cooling from the sintering temperature. Specimens with residual surface compressive stresses were 200 MPa stronger at 750°C than monolithic specimens, demonstrating the viability of this approach for improving elevated-temperature mechanical properties.     

Metastable Alumina Structures in Melt-Extracted Alumina–25 wt% Zirconia and Alumina–42 wt% Zirconia Ceramics

Microstructures are examined of rapidly solidified hypoeutectic Al₂O₃–25 wt% ZrO₂ and eutectic Al₂O₃–42 wt% ZrO₂ ceramic alloys by using transmission electron microscopy and scanning transmission electron microscopy. Structures observed in the hypoeutectic alloy were dendritic. Three different types of dendrite morphologies were observed. These are believed to be the stable α- and metastable γ- and δ- modifications of alumina. The cores of the γ-alumina dendrites were somewhat richer in ZrO₂ than those of α-alumina dendrites; δ-alumina dendrites were substantially enriched in ZrO₂. The lamellar structure of the eutectic in the Al₂O₃–42 wt% ZrO₂ alloy became increasingly finer with increasing cooling rate and at the highest cooling rates was replaced by a fully amorphous structure (except in some instances a ZrO₂-rich needlelike phase identifiable as δ-alumina was found in the amorphous matrix). An interpretation is given of the results obtained, based on assumed metastable free energy curves and dendrite growth theory.     

Subsolidus Phase Relations in the Pseudoternary System ZrO2-YO1.5-CrO1.5 in Air

The pseudoternary system ZrO₂-YO_1.5CrO_1.5 was studied between 1300° and 1600C in air by °a quenching method. No ordered phase of the type ZrY₆O₁₁ was detected, but an ordered Zr₃Y₄O₁₂ phase at 1300°C and YCrO₃ were observed as intermediate compounds. Solid solutions ofZrO₂ and YO_1.5 coexisting with CrO_1.5 and/or YCrO₃ formed; the apex occurred between 26.5 and 27.5 wt% YO_1.5 for the cubic ZrO₂+CrO_1.5+YCrO₃, three-phase region; CrO_1.5 is slightly soluble in ZrO₂(ss).     

Stress-Induced Transformation During Subcritical Crack Growth in Partially Stabilized Zirconia

Fracture surfaces of a commercial partially stabilized ZrO₂ that had undergone subcritical crack growth in H₂0 were characterized by scanning and transmission electron microscopy. At high stress intensities (≥4.6 MPa·m^−1/2), fracture was primarily trans granular, and coherent tetragonal ZrO₂ precipitates had undergone a martensitic transformation to monoclinic symmetry. At lower stress intensities, where power-law crack growth occurred, fracture suflaces were primarily inter-granular, and the tetragonal ZrO₂ had transformed to a new ZrO₂ polymorph with orthorhombic symmetry.     

Energy Crossovers in Nanocrystalline Zirconia

The synthesis of nanocrystalline powders of zirconia often produces the tetragonal phase, which for coarse-grained powders is stable only at high temperatures and transforms into the monoclinic form on cooling. This stability reversal has been suggested to be due to differences in the surface energies of the monoclinic and tetragonal polymorphs. In the present study, we have used high-temperature oxide melt solution calorimetry to test this hypothesis directly. We measured the excess enthalpies of nanocrystalline tetragonal, monoclinic, and amorphous zirconia. Monoclinic ZrO₂ was found to have the largest surface enthalpy and amorphous zirconia the smallest. Stability crossovers with increasing surface area between monoclinic, tetragonal, and amorphous zirconia were confirmed. The surface enthalpy of amorphous zirconia was estimated to be 0.5 J/m². The linear fit of excess enthalpies for nanocrystalline zirconia, as a function of area from nitrogen adsorption (BET) gave apparent surface enthalpies of 6.4 and 2.1 J/m², for the monoclinic and tetragonal polymorphs, respectively. Due to aggregation, the surface areas calculated from crystallite size are larger than those measured by BET. The fit of enthalpy versus calculated total interface/surface area gave surface enthalpies of 4.2 J/m² for the monoclinic form and 0.9 J/m² for the tetragonal polymorph. From solution calorimetry, the enthalpy of the monoclinic to tetragonal phase transition for ZrO₂ was estimated to be 10±1 kJ/mol and amorphization enthalpy to be 34±2 kJ/mol.     

Stabilization of Zirconia Sintered with Titanium

Electron and X-ray diffraction studies show that zirconia sintered with 5 to 15 mol% titanium under a vacuum of 10⁻¹ to 10⁻² torr (∼13 to 1.3 Pa) was partially stabilized as cubic and tetragonal phases, whose amounts increase with increasing Ti content. The stabilization of ZrO₂ is due to the dissolution of TiO which forms as a second phase in the sintered specimen. The grain size of ZrO₂ decreases with increase in Ti. The improvements in strength and thermal shock resistance of ZrO₂ sintered with Ti are attributed to the reduction in ZrO₂ grain size and the effect of partial stabilization.     

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.