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.     

Compression Creep Characteristics of 8-mol%-Yttria-Stabilized Cubic-Zirconia

Constant stress compression creep tests were conducted on 8-mol%-yttria-stabilized cubic-zirconia (8YCZ) over stress (ς), temperature, and grain-size ranges from ∼20 to 300 MPa, 1673 to 1773 K, and 4 to 8 μm, respectively. Creep data were analyzed in terms of the relationship [epsivdot] ∝ς ⁿ , where [epsivdot] is the strain rate and n the stress exponent. Although the experimental data yielded a stress exponent of n & 2, analysis of the results with compensation of significant concurrent grain growth revealed that the true stress exponent was n ∼ 1. The results were consistent with deformation by the Coble creep mechanism. Experiments at stresses greater than ∼100 MPa revealed a transition from grain-size-dependent Coble diffusion creep to grain-size-independent intragranular dislocation creep.     

Cyclic Fatigue Life and Crack-Growth Behavior of Microstructurally Small Cracks in Magnesia-Partially-Stabilized Zirconia Ceramics

Cyclic fatigue stress/life ( S / N ) and crack-growth properties are investigated in magnesia-partially-stabilized zirconia (Mg-PSZ), with particular reference to the role of crack size. The material studied is subeutectoid aged to vary the steady-state fracture toughness, K_c , from ∼3 to 16 MPa · m^1/2· S / N data from unnotched specimens show markedly lower lives under tension—compression compared with tension—tension loading; "fatigue limits"(at 10⁸ cycles) for the former case approach 50% of the tensile strength. Under tension—tension loading, cyclic crack-growth rates of "long"(> 3 mm) cracks are found to be power-law dependent on the stress-intensity range, Δ K , with a fatigue threshold, Δ K _TH, of order 50% of K_c . Conversely, naturally occurring "small"(1 to 100 μm) surface cracks are observed to grow at Δ K levels 2 to 3 times smaller than Δ K _TH, similar to behavior widely reported for metallic materials. The observed small-crack behavior is rationalized in terms of the restricted role of crack-tip shielding (in PSZ from transformation toughening) with cracks of limited wake, analogous to the reduced role of crack closure with small fatigue cracks in metals. The implications of such data for structural design with ceramics are briefly discussed.     

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.     

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.     

Indentation-Induced Cracks and the Toughness Anisotropy of 9.4-mol%-Yttria-Stabilized Cubic Zirconia Single Crystals

The crack systems associated with room-temperature Vickers indentations on {001} surfaces in 9.4-mol%-Y₂O₃-stabilized cubic ZrO₂ single crystals are examined. The indentation-induced radial cracks are not always perpendicular to the free surface, as is usually assumed, and the surface traces are therefore not a reliable guide to the nature of the cracking. In fact, indentations with 〈100〉 diagonals do not form cracks on {010}, but form secondary radial cracks on inclined planes and noncoplanar median cracks on (110) or (1 1 0).     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

Structural Changes by Compressive Stresses of 2.0-mol%-Yttria-Stabilized Tetragonal Zirconia Polycrystals

Reorientation of the tetragonal (002) peak in tetragonal ZrO₂ polycrystals (TZP) (so-called domain switching) was studied by XRD and residual stress measurement using TZP specimens containing 2.0 mol% Y₂O₃ that had undergone mechanical and thermal treatments and compressive stress. The observed domain switching was due to a preferred transformation of the tetragonal phase caused by compressive stress above 70 MPa leading to a remnant c-axis orientation normal to the compressive direction. Domain switching did not depend on thermal stress but arose directly from the tetragonal phase with little relation to monoclinic phase.     

Solid Yttria-Stabilized Zirconia Films by Pulsed Chemical Vapor Deposition from Metal-organic Precursors

A pulsed chemical vapor deposition from metal-organic precursors (MOCVD) system was used to produce solid zirconia, and yttria-stabilized zirconia (YSZ) films. A total of six candidate metal-organic precursors for zirconia and three for yttria were investigated. Three precursor solutions for YSZ proved suitable for pulsed-MOCVD processing. Layers were deposited on metal, alumina, and porous nickel cermet substrates. Under optimal deposition conditions, precursor conversion efficiency of 90% was achieved using a solution of 3.74 vol% zirconium 2-methyl-2-butoxide + 0.42% yttium methoxyethoxide in toluene. The film growth rate was 7.5 μm·h⁻¹ at 525°C deposition temperature. Two alkoxide precursors produced YSZ layers with material costs under $0.50/(μm·cm²).     

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.     

Nonisothermal Synthesis of Yttria-Stabilized Zirconia Nanopowder through Oxalate Processing: I, Characteristics of Y-Zr Oxalate Synthesis and Its Decomposition

To obtain powder with a composition of 3 mol% Y₂O₃–97 mol% ZrO₂, a process of Y-Zr oxalate powder production has been optimized, to produce an oxalate with minimal particle size. The methodology of the nonisothermal decomposition of Y-Zr oxalate has been explained. Characteristics of the nonisothermal decomposition of different oxalates have been studied. Nanocrystalline Y₂O₃-stabilized ZrO₂ (YSZ) powder with a narrow size distribution of primary particles and aggregates was produced. The zirconia powder that was obtained from the smallest oxalate powder via nonisothermal decomposition had a particle size of 8–10 nm. The YSZ powder was weakly aggregated, with a narrow aggregate-size distribution of 70–90 nm.     

Effect of Nitrogen Atmosphere on the Densification of a 3-mol%-Yttria-Doped Zirconia

The densification behavior of a 3-mol%-Y₂O₃-doped ZrO₂ (3Y-ZrO₂) has been investigated under N₂ and O₂ atmospheres. Powder compacts have been sintered at 1550° and 1400°C for various times. The density of the specimen sintered at 1550°C is higher in N₂ than in O₂, while the contrary result is obtained in the case of the specimen sintered at 1400°C. Such results can be explained in terms of nitrogen solubility and oxygen vacancy in a ZrO₂ matrix. Because nitrogen solubility into the ZrO₂ increases with an increase in heat-treatment temperature, leading to the formation of oxygen vacancy, the densification rate becomes higher. The present study thus shows evidence of nitrogen solubility into the ZrO₂ and its role on the densification behavior of 3Y-ZrO₂.     

Quantitative Analysis of Microstructural Homogeneity and Capacitance Correlations in Palladium/Yttria-Stabilized Zirconia Composites

Voronoi tessellation was applied to quantify the microstructural homogeneity of palladium particles in random Pd/cubic yttria-stabilized zirconia (YSZ) composites with the Pd concentration ranging from 0 to 30 vol%. Room-temperature impedance measurements were used to determine the capacitance of the composites. A fourfold enhancement in capacity near the percolation threshold of Pd was obtained. The percolation threshold was estimated at ∼30 vol% Pd using the normalized percolation theory (NPT). Data obtained from Voronoi diagrams resulted in a quantitative measure for the homogeneity of the dual-phase composite. The homogeneity was found to decrease with increasing Pd concentration in the composites. Near the theoretical value of the percolation threshold, the Pd phase appeared to be distributed too inhomogeneously for preparing insulating composites. No large increase in capacity as predicted by NPT could therefore be experimentally verified.