Influence of Tetragonality on Tetragonal-to-Monoclinic Phase Transformation during Hydrothermal Aging in Plasma-Sprayed Yttria-Stabilized Zirconia Coatings

The influence of tetragonality, which is defined as the lattice parameter ratio c / a , on the tetragonal-to-monoclinic phase transformation during hydrothermal aging was investigated in yttria-stabilized zirconia coatings. The yttria content was adjusted in the range of 4–8 mass% (denoted as x YZ, where x = 4–8 and YZ represents the yttria-stabilized zirconia). The tetragonality of the zirconia in the as-sprayed coatings was less than that in the powders. To change the tetragonality for each yttria content, the coatings were annealed at 1273 K before aging. Without annealing, the phase transformation was prevented only in 8YZ. When annealing was applied, an increase of the tetragonality (i.e., recovery of the tetragonality) was observed, and transformation during hydrothermal aging was also suppressed in 6YZ. It was concluded that the increase in tetragonality that occurred without a change in the yttria content was suggested to be caused by the lattice relaxation of the tetragonal phase, and this relaxation is believed to cause a reduction of the critical yttria concentration, thus preventing the phase transformation.     

Tetragonal-to-Monoclinic Phase Transitions in Nanocrystalline Rare-Earth-Stabilized Zirconia Prepared by a Mild Hydrothermal Method

Nanocrystalline 4-mol%-Sc₂O₃-stabilized zirconia (4ScSZ) and 4-mol%-Y₂O₃-stabilized zirconia (4YSZ) powders were prepared by a mild urea-based hydrothermal method. The as-prepared 4ScSZ and 4YSZ powders behaved with different tetragonal–monoclinic ( t – m ) transitions on calcination at temperatures between 400° and 1400°C. For the as-calcined 4ScSZ samples, the monoclinic phase fraction varies discontinuously with increasing temperature, i.e., first increases, then decreases, and finally increases again; whereas the monoclinic phase content reduces monotonously for the as-calcined 4YSZ samples, and only tetragonal phase is present over 1000°C. Such interesting results can be explained satisfactorily by considering the combined influences of crystallite size effect, microstrain, and the stabilization effect of the dopant. The microstrain relaxation is mainly responsible for the unusual phase transition in the 4ScSZ samples, while for the 4YSZ samples, the microstrain effect and crystallite size effect can be masked by the stabilization effect of the Y₂O₃ dopant due to its stronger stabilization capability.     

Cubic-to-Tetragonal (t') Transformation in Zirconia-Containing Systems

The coexistence of the cubic fluorite and tetragonal phases in rapidly quenched samples was studied in the ZrO₂-MO_1.5 systems for M = Sc, In, Y, and rare earths (R). Spontaneous transformation from metastable cubic phase was triggered at room temperature by a mechanical force. Isolated tetragonal platelets in the cubic matrix were bounded by [101] habit planes and contained anti-phase boundaries. The tetragonality decreased with stabilizer content and vanished at around 18 mol% for M = Y and R, 23 mol% for M = Sc, and 25 mol% for M = In, all at room temperature. With increasing temperature, the tetragonality initially increased because of anisotropic thermal expansion, then decreased rapidly, after reaching a maximum, as the temperature for the tetragonal-to-cubic transformation was approached. Being a first-order martensitic transformation, the cubic-to-tetragonal transformation is accompanied by a discontinuous change of tetragonality and a hysteresis loop as the temperature or composition passes through the equilibrium value.     

Metastability of the Martensitic Transformation in a 12 mol% Ceria-Zirconia Alloy: II, Grinding Studies

Observations of the grinding-induced transformation in singlephase Ce-TZP materials, referred to in an earlier paper, are presented. Two techniques were used to grind the surface: by hand in a slurry of abrasive particles and with a high-speed diamond-impregnated wheel. Significant differences in X-ray diffraction profiles between the two grinding methods was observed. Limited monoclinic ZrO₂ was detected on the machineground surface, along with the reversal of the tetragonal ZrO₂ (200) peak intensities. On the hand-ground surface, considerable monoclinic phase was observed. The disappearance of the monoclinic phase with heating was followed by X-ray diffraction, and the A _f was found to exceed 700°C, while the reversal in tetragonal (200) peak symmetry and intensity remained unaltered up to at least 1000°C. Transmission electron microscope studies at various depths below the ground surface were undertaken to identify the differences between these surfaces and fractured surfaces. A simple explanation is proposed for the reversal of the tetragonal peak intensities. This reversal has previously led to the notion of a ferroelastic toughening mechanism in similar TZP materials.     

On the Thermoelastic Martensitic Transformation in Tetragonal Zirconia

Recent evidence is summarized showing that the tetragonal ( t ) → monoclinic ( m ) martensitic transformation in ZrO₂ can occur thermoelastically in certain ZrO₂-containing ceramics, and that microcracking accompanying the transformation is more common than had previously been recognized. The implications of these new data for the conditions under which the stress-induced transformation is irreversible, and for the particle size dependence of the transformation start ( M _s), temperature, are discussed.     

Martensitic Relief Observation by Atomic Force Microscopy in Yttria-Stabilized Zirconia

The tetragonal to monoclinic (t–m) phase transformation of zirconia has been the object of extensive investigations of the past 20 years and is now recognized as being of martensitic nature. However, martensitic transformation has only been observed by transmission electron microscopy or indirect methods. Though the benefit on the fracture toughness and crack resistance was the main interest, the transformation is now considered for its consequences on the degradation of the material. The use of atomic force microscopy reported here allowed the observation of the first stages of martensite relief growth and of new martensitic features.     

Surface Relief Induced by Martensitic Transformation in Phosphorus-Bearing Dicalcium Silicate

Crystals of (Ca_1.955□_0.045)(Si_0.91P_0.09)O₄, where □ denotes a vacancy, have been prepared and examined by XRD, optical microscopy, SEM, and AFM. At 20°C, the crystals are composed of 38%α' _L and 62%β phases. Upon cooling to −185°C, the α' _L - to β-phase transformation occurs, which increases the β-phase composition to 72%. The transformation is also accompanied by the formation of platelike surface reliefs. The surface relief angles have been determined from observations (7.9°± 0.2°) and calculations based on a phenomenological analysis (7.84°). The fair agreement of these values indicates that the transformation is martensitic and mainly governed by a shear mechanism.     

Size driven thermodynamic crossovers in phase stability in zirconia and hafnia

Hafnia (HfO₂) and zirconia (ZrO₂) are of great interest in the quest for replacing silicon oxide in semiconductor field effect transistors because of their high permittivity. Both exhibit extensive polymorphism and understanding the energetics of their transitions is of major fundamental and practical importance. In this study, we present a systematic thermodynamic summary of the influence of particle size on thermodynamic phase stability in hafnia and zirconia using recently measured enthalpy data from the literature. The amorphous phase is found to be the most energetically stable above 165 and 363 m²/g of surface area for HfO₂ and ZrO₂, respectively. Below 16 and 20.3 m²/g of surface area, respectively, the monoclinic phase is the most energetically stable for HfO₂ and ZrO₂. At intermediate sizes there are closely balanced energetics among monoclinic, tetragonal, and cubic phases. The energy crossovers reflect decreasing surface enthalpy in the order monoclinic, tetragonal, cubic and amorphous for both hafnia and zirconia.     

Tetragonal-to-Monoclinic Transformation in Mg-PSZ Studied by in Situ Neutron Diffraction

The deformation of 9.4 mol% magnesia-partially-stabilized zirconia under compressive loads up to 1225 MPa was studied using mechanical testing with in situ neutron diffraction. The material shows obvious plastic deformation at applied stresses in excess of an estimated critical stress of 925 ± 20 MPa. Most of the accumulated strain occurred by transient room-temperature creep. Plastic deformation was associated with considerable stress-induced tetragonal-to-monoclinic transformation. The volume change calculated from the strain gauges correlates well with the amount of t → m transformation observed. Unlike previous studies of Ce-TZP and Y-TZP, ferroelasticity was not observed, nor was the t → o transformation observed. Minor microstructural changes were noted, including an increase in the root mean square internal strain of 0.05%, commensurate with an increase in internal stress of ∼100 MPa. It would appear that transformation selectivity was exercised with the transformation occurring first in tetragonal crystallites favorably oriented to the applied stress. The stress-induced monoclinic phase therefore exhibits a strong preferred orientation. Comparison is made with the other commercially interesting zirconia ceramics, Ce-TZP and Y-TZP, which have been studied using the same techniques.     

Increase in Phase Transition Temperature of Activated Alumina with Nano-Zirconia Synthesized by Pulsed Wire Discharge

Activated alumina powders have been synthesized by using a novel dry process of pulsed wire discharge. The temperature of phase transition from activated alumina to α-alumina and its variation caused by adding zirconia have been investigated. A mixture of activated alumina and zirconia was formed by mixing zirconium plasma with aluminum plasma and cooling together in an oxygen atmosphere. It was found that the transition temperature increased when the zirconia content ratio was increased. On the other hand, results of X-ray diffraction and X-ray photoelectron spectroscopy analysis indicated no substitution of zirconium in an alumina lattice. Thus, most of the zirconium atoms were located in zirconia particles on the surface and/or the grain boundary of alumina grains. Thus, it appears that the increase in the phase transition was caused by retardation of atomic diffusion at zirconia particles.     

Phase Transformation in EB-PVD Yttria Partially Stabilized Zirconia Thermal Barrier Coatings during Annealing

Electron-beam physical-vapor-deposited thermal barrier coatings consisting of ZrO₂ stabilized by 7 wt% Y₂O₃ were investigated in regard to phase transformation after annealing. Free-standing ceramic layers were heat-treated in air, for up to 200 h, in the temperature range 1200°—1400°C and then analyzed by X-ray diffractometry. Based on information obtained from the {111} and {400} peaks, the phase composition and the Y₂O₃ content in the phases were calculated. At the start of transformation, small grains of a low-Y₂O₃ t phase and a c phase formed. After >30 h at 1300°C and at 1400°C, a mixture of a t phase deficient in Y₂O₃, an m phase, and a c phase formed after cooling, with the Y₂O₃ contents in the phases roughly predicted by the phase diagrams. The results of the present study are discussed here in detail and compared with data for plasma-sprayed coatings.     

Phase Transformation and Densification of an Attrition-Milled Amorphous Yttria-Partially-Stabilized Zirconia–20 mol% Alumina Powder

Phase transformations during consolidation treatments of an attrition-milled amorphous yttria-partially-stabilized zirconia (Y-PSZ: ZrO₂–3 mol% Y₂O₃)–20 mol% Al₂O₃ powder and the resulting microstructures have been investigated. A metastable cubic phase ( c -ZrO₂ solid solution) together with an α-Al₂O₃ phase is formed in the amorphous matrix by consolidation at temperatures below 1204 K. The metastable cubic phase transforms to a stable tetragonal phase ( t -ZrO₂ solid solution) with an increase in the consolidation temperature. Fully dense bulk samples consisting of extremely fine tetragonal grains together with a small amount of α-Al₂O₃ particles could be obtained by consolidation at temperatures above 1432 K. Important features concerned with the densification behavior are as follows: (1) Marked increase in the relative density occurs after cubic crystallization and subsequent cubic-to-tetragonal transformation. (2) All of the consolidated bulk samples show extremely fine grain structure with grain sizes of several tens of nanometers, irrespective of the consolidation temperature. (3) The regularity of the lattice fringe contrast in each tetragonal grain seems to be kept in the vicinity of grain boundaries. These results suggest that densification of the attrition-milled amorphous powder proceeds via superplastic flow and/or diffusional creep, rather than viscous flow of the initial amorphous phase before crystallization.     

Neutron Diffraction Studies of Phase Transformations between Tetragonal and Orthorhombic Zirconia in Magnesia-Partially-Stabilized Zirconia

Neutron powder diffraction and conventional dilatometry have been used to investigate the tetragonal-to-orthorhombic phase transformation and the orthorhombic-to-tetragonal reversion in a high-toughness magnesia-partially-stabilized zirconia. For this material, the onset temperature on cooling for the tetragonal-to-orthorhombic transformation (determined by dilatometry) was 192 K, and the reversion on subsequent heating occurred between 500 and 620 K. Neutron diffraction patterns were recorded at temperatures down to 19 K then up to 664 K, and analyzed by the multiphase Rietveld method to determine the amounts of different phases as well as their lattice parameters and unit-cell volumes. It is notable that, at its maximum, the orthorhombic phase amounted to 45% of the sample by weight. Length changes were measured, using pushrod dilatometers, in the temperature range 80 to 700 K. Length changes calculated from the neutron diffraction determinations of the proportions and unit-cell volumes of the different phases are in very good agreement with the directly measured values.     

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.     

Crystallization and Phase Transformation Process in Zirconia: An in situ High-Temperature X-ray Diffraction Study

Amorphous zirconia precursors were made by the precipitation of a zirconium tetrachloride solution with either slow (8 h) or rapid additions of ammonium hydroxide at a pH of 10.5. Following calcination at 500°C for 4 h, the rapidly precipitated precursor exhibited predominantly monoclinic ZrO₂ phase, while the slowly precipitated precursor produced the tetragonal ZrO₂ phase. The crystallization and phase transformations were followed by in situ high-temperature X-ray diffraction (HTXRD) for both specimens in helium and in air. Each amorphous precursor first crystallizes as the tetragonal phase at about 450°C. A tetragonal-to-monoclinic phase transformation of the rapidly precipitated material was observed on cooling at about 275°C. Surface impregnation of sulfate ions following precipitation inhibited the tetragonal-to-monoclinic transformation for the rapidly precipitated ZrO₂ sample. The crystallite size for the t -ZrO₂ of all samples, irrespective of whether they transform to monoclinic, was approximately 11 nm, indicating that the t → m transformation in these materials is not controlled by differences in crystallite size. It is therefore suggested that anionic vacancies control the tetragonal-to-monoclinic phase transformation on cooling, and that oxygen adsorption triggers this phase transformation.     

Strengthening of Ceria-Doped Tetragonal Zirconia Polycrystals by Reduction-Induced Phase Transformation

Phase-transformation-induced compressive surface stresses were introduced into ceria-doped tetragonal zirconia polycrystals by reduction of CeO₂. Four-point-bending strength of sintered ZrO₂ containing 12 mol% CeO₂ increased from 240 to 545 MPa after it was annealed at 1400°C for 2 h in nitrogen. The strength of the same material hot isostatically pressed in oxygen increased after it was annealed in nitrogen for 2 h at 1500°C from 430 to 595 MPa.     

Metastability of the Martensitic Transformation in a 12 mol% Ceria-Zirconia Alloy: I, Deformation and Fracture Observations

A single-phase tetragonal zirconia polycrystal containing 12 mol% cerium dioxide was found to readily undergo the tetragonal-to-monoclinic phase transformation on deformation, fracture, or cooling below 150 K. Deformation tests, primarily indentation studies, indicated that an extensive transformation zone developed about the impression. The transformation zone increased in dimension as the temperature approached the martensitic start temperature for the tetragonal-to-monoclinic transformation. Associated with flexure tests at room temperature "Luders"-like transformation bands propagated entirely across the tensile surface perpendicular to the applied stress. Transmission electron microscopy and X-ray diffraction were used to monitor the extent and form of the transformation. The reverse transformation was also examined using X-ray diffraction while heating and compared with in situ transmission electron microscopy observations.     

Edge-Crack Resistance Curves in Supercritical Ceramics

The growth of edge cracks in zirconia-reinforced ceramics is analyzed theoretically with the „supercritical” transformation model. The injection of an initial edge crack by a damage process is modeled in an approximate manner. Subsequent crack growth under the application of a remote tensiles stress models the evolution of the transformed region as the crack advances. For the range of initial crack sizes considered, „nominal” resistance curves depend strongly on a transformation-toughening parameter. The analysis may have a bearing on the indentation/bend method of testing fracture toughnesses.     

Phase Diagram of the BaO-CuO Binary System

The phase diagram of the BaO-CuO binary system has been investigated in air and in a mixed gas of Ar + 0.21 atm of O₂. The existence of two compounds, BaCuO₂ and Ba₂CuO₃, was confirmed. The phase transition of Ba₂CuO₃ from an orthorhombic to a tetragonal phase was observed to occur at 1083 K. The lattice constants of the tetragonal Ba₂CuO₃ phase were determined to be a = 1.2975 nm and b = 0.3992 nm. BaCuO₂ was shown to melt incongruently by a synthetic reaction at 1289 K. Furthermore, the existence of two eutectic reactions and a peritectic reaction in the present system was confirmed.