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.     

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.     

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.     

Mechanism of Thermal Transport in Zirconia and Yttria-Stabilized Zirconia by Molecular-Dynamics Simulation

We present results of molecular-dynamics simulations of the thermal conductivity, κ, of ZrO₂ and Y₂O₃-stabilized ZrO₂ (YSZ). For both pure ZrO₂ and YSZ with low concentrations of Y₂O₃, we find that the high-temperature κ is typical of a crystalline solid, with the dominant mechanism being phonon-phonon scattering. With increasing Y₂O₃ concentration, however, the mechanism changes to one more typical of an amorphous system. In particular, phononlike vibrational modes with well-defined wave vectors appear only at very low frequencies. As in amorphous materials, the vast majority of vibrational modes, while delocalized, do not propagate like ordinary phonon modes but transport energy in a diffusive manner. We also find that the few highest frequency modes are localized and do not contribute to κ.     

Aqueous Degradation and Chemical Passivation of Yttria-Tetragonally-Stabilized Zirconia at 25°C

The objective of this study was to establish the mechanism(s) controlling degradation of yttria-tetragonally-stabilized zirconia (Y-TZP) powder in aqueous suspensions and determine the significance of this degradation to the aqueous physical chemistry of Y-TZP. Experiments were performed on commercially available Y-TZP powder placed in aqueous suspensions at 25°C. Experimental investigations included analysis of the aqueous chemistry of Y-TZP in water via ICP-MS, determination of the surface and bulk structure of the powder via XRD and solid-state NMR, and observation of changes in surface charges via zeta potential determinations. The goal of this study was to control the surface chemistry of Y-TZP in aqueous suspension to promote dispersion and permit aqueous processing of Y-TZP powders.     

Water Incorporation in Tetragonal Zirconia

Samples of 3 mol% Y₂O₃-stabilized tetragonal ZrO₂ ceramics were annealed at 250°C in atmospheres of water vapor pressures of 1 bar and 26 mbar. As demonstrated by the water uptake and the lattice expansion, water molecules were incorporated into the ZrO₂ lattice during annealing, and the amount of the incorporated water is determined by the water vapor pressure. Owing to the filling of oxygen vacancies by the incorporated water molecules, part of the tetragonal ZrO₂ transformed to the monoclinic structure, and protonic defects were induced. The expected proton conduction was confirmed by the polarity of the water vapor concentration cells.     

Fabrication of Highly Porous Yttria-Stabilized Zirconia by Acid Leaching Nickel from a Nickel-Yttria-Stabilized Zirconia Cermet

Porous Y₂O₃-stabilized ZrO₂ (YSZ) samples were synthesized by preparing NiO/YSZ composites by tape casting and calcining at 1800 K, reducing the NiO to nickel in H₂ at 973 K, and finally leaching the nickel out of the structure with 2.2 M HNO₃ at 353 K. Porous YSZ was prepared from NiO/YSZ composites containing 0, 20, 40, and 50 wt% NiO. Complete removal of the nickel was demonstrated by XRD, weight changes, and porosity increases. Porosities >75% could be achieved without structural collapse of the YSZ phase. Finally, the method was applied to the fabrication of a solid oxide fuel cell with a copper-based anode operating on H₂ and n -butane.     

Evaluation of the Cyclic Fatigue Life of 3-mol%-Yttria-Stabilized Zirconia Bioceramic Using Biaxial Flexion

The cyclic fatigue life of zirconia bioceramic was determined under biaxial flexion using disk-shaped specimens. The fatigue life was not reduced by subjecting the material to a simulated physiological environment nor was it affected by testing at different loading frequencies. Tests performed at different stress ratios produced a large degree of scatter in the data but a statistical analysis proved that there was no significant effect on the fatigue life of the material. Failure of disk specimens was initiated either by flaws introduced during manufacturing or by the more typical inherent flaws commonly observed in ceramics. The former generally resulted in premature, low-stress failures on initial loading whereas the latter acted as initiating defects for fatigue cracks that then propagated to failure. The distributions of the two categories of flaw were analyzed using two- and three-parameter Weibull probability functions. It became clear that the Weibull modulus for the fatigue failures was consistent with previously reported work on other ceramics.     

Phase Formation and Stability in Reactively Sputter Deposited Yttria-Stabilized Zirconia Coatings

Yttria-stabilized zirconia (YSZ) coatings were produced by reactively cosputtering metallic zirconium and yttrium targets in an argon and oxygen plasma using a system with multiple magnetron sputtering sources. Coating crystal structure and phase stability, as functions of Y₂O₃ content, substrate bias, and annealing temperature, were investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Results demonstrated that highly (111)-oriented tetragonal and cubic zirconia structures were formed in 2 and 4.5 mol% Y₂O₃ coatings, respectively, when the coatings were grown with an applied substrate bias. Conversely, coatings deposited with no substrate bias had random tetragonal and cubic structures. XRD analysis of annealed coatings showed that the cubic zirconia in 4.5 mol% Y₂O₃ coatings exhibited structural stability at temperatures up to 1200°C. Transformation of the tetragonal to monoclinic phase occurred in 2 mol% Y₂O₃ coating during high-temperature annealing, with the fraction of transformation dependent on bias potential and annealing temperature.     

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.     

Nonisothermal Synthesis of Yttria-Stabilized Zirconia Nanopowder through Oxalate Processing: II, Morphology Manipulation

A novel, nontraditional route for controlling the morphology of yttria-stabilized zirconia nanopowders is explained. For understanding the real nature of yttrium zirconium oxalate nonisothermal decomposition and for the development of nanosize 3 mol% Y₂O₃·97mol% ZrO₂, mass spectrometry, X-ray, and TEM investigation were used. Characteristics of zirconia crystallization under nonisothermal heating conditions were studied. Morphology evolution during Y-Zr oxalate nonisothermal decomposition was investigated to optimize the heating schedule of calcination. The nonlinear heating regime has been used to produce nanosized Y₂O₃-stabilized tetragonal ZrO₂ powder with the finest primary crystallites and narrowest secondary aggregate size distribution.     

Thermodynamic Model of the Cubic → Tetragonal Transition in Nonstoichiometric Zirconia

Nonstoichiometric zirconia is described with a model recently developed for ZrO₂—Y₂O₃ alloys. It is thus possible to rationalize the experimental information on the cubic/tetragonal phase boundaries in zirconia.     

Fracture Resistance and Stable Crack-Growth Behavior of 8-mol%-Yttria-Stabilized Zirconia

The crack-growth behavior of a yttria-stabilized zirconia ceramic (8 mol% of cubic-phase yttria) was studied at room temperature. Double-cantilever-beam specimens were loaded with pure bending moments in a specially designed loading fixture inside an environmental scanning electron microscope. Crack-growth data were obtained from truly sharp (arrested) cracks, bypassing interpretation problems that involve crack initiation from a machined notch. The crack-growth study was conducted over a range of applied energy-release rates that allowed crack arrest on one hand and fast fracture on the other. Three energy-release-rate values were relevant: initiation of crack growth (3.5 J/m²), crack arrest (2.8 J/m²), and fast fracture (8.0 J/m²). At the macroscopic scale, subcritical crack growth occurred as a continuous process. In situ observations revealed that, at the microscopic scale, crack growth occurred in small jumps. The fracture mode for stable crack growth was identified to be transgranular.     

Effect of Preparation Methods and Condition of Precursors on the Phase Composition of Yttria-Stabilized Zirconia Powders

An yttria-stabilized zirconia powder, free of monoclinic phase, may be prepared by an oxalate method in an ethanol solution at strong acidity. This study demonstrates that the control of pH in the preparation of precursors has a significant effect on the ability of precursors to crystallize and hence plays an important role in determining the formation and fraction of various crystalline phases in the resulting yttria-stabilized zirconia powder. With the increase of pH, a precursor with a certain crystalline form may be transformed into an amorphous precursor, and a monoclinic phase appers in the phase composition of the resulting powder. The results of XRD analysis and Raman spectroscopy are discussed.     

Thin Yttrium-Stabilized Zirconia Electrolyte Solid Oxide Fuel Cells by Centrifugal Casting

A centrifugal casting technique was developed for depositing thin 8-mol%-yttrium-stabilized zirconia (YSZ) electrolyte layers on porous NiO-YSZ anode substrates. After the bilayers were cosintered at 1400°C, dense pinhole-free YSZ coatings with thicknesses of ∼25 μm were obtained, while the Ni-YSZ retained porosity. After La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF)-Ce_0.9Gd_0.1O_1.95 (GDC) or La_0.8Sr_0.2MnO₃ (LSM)-YSZ cathodes were deposited, single SOFCs produced near-theoretical open-circuit voltages and power densities of ∼1 W/cm² at 800°C. Impedance spectra measured during cell tests showed that polarization resistances accounted for ∼70%–80% of the total cell resistance.     

In Situ Observation of Crack Behavior in Compressively Loaded Plasma-Sprayed 7-wt%-Yttria-Stabilized Zirconia

A plasma-sprayed 7-wt%-yttria-stabilized zirconia stand-alone tube was incrementally loaded in uniaxial compression inside a scanning electron microscope. Micrographs taken at each increment showed cracks perpendicular to the applied load to have partially closed and cracks parallel to the applied load to have opened. New cracks were observed to nucleate and then propagate in a direction parallel to the applied load.     

Strength and Toughness of Tape-Cast Yttria-Stabilized Zirconia

The biaxial flexural strength and fracture toughness of tape-cast yttria-stabilized zirconia, for application as the electrolyte in solid oxide fuel cells, have been measured at room temperature and at a typical operating temperature of 900°C. The flexural strength was measured in ring-on-ring loading and decreased from 416 MPa at room temperature to 265 MPa at 900°C. The fracture toughness was measured using two different techniques: indentation fracture and double-torsion loading. The latter was more reliable and gave a fracture toughness of 1.61 ± 0.12 MPa·m^1/2 at room temperature and 1.02 ± 0.05 MPa·m^1/2 at 900°C. The flexural strength and fracture toughness were quantitatively consistent with fracture being initiated at the observed surface defects. The lower fracture toughness at 900°C is partly due to a reduction in elastic modulus and partly due to a reduction in the work of fracture.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

Growth of Yttria-Stabilized Zirconia Thin Films on Textured Silver Substrates by Chemical Vapor Deposition

The effect of deposition conditions on the growth of yttria-stabilized zirconia (YSZ) films on textured silver substrates using the chemical vapor deposition (CVD) process was investigated. The crystalline structure of the YSZ film depended strongly on the deposition conditions, such as substrate temperature and deposition time. YSZ films prepared at 750°C using β-diketone chelate sources, which had an orientation of c -axis normal to the textured silver substrate surface. The YSZ surface was dense but not rough, and the YSZ film grew granular-like. The cross-sectional image of YSZ film showed the columnar growth feature; the growth rate was ∼20 nm/min.     

液相烧结Al2O3/3Y-TZP复相材料的致密化与力学性能

以CaO-MgO-SiO2玻璃为烧结助剂,用液相烧结法制备了氧化铝和3%氧化钇稳定四方氧化锆复相材料.研究了烧结助剂对材料致密化、显微结构及力学性能的影响.结果表明:由于CaO-MgO-SiO2玻璃具有较小的液相粘度,因而对材料的致密化有较大促进作用,可使材料在1 500℃获得致密.烧成温度和材料组成均对Al2O3和ZrO2的平均晶粒尺寸产生影响.显微结构中少量的Al2O3和ZrO2晶粒为晶内分布.引入烧结助剂降低了材料的烧结温度,使材料具有细晶结构,因而具有良好的力学性能,在最佳条件下,样品的抗弯强度可达到778 MPa.