Strength Analysis of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Tensile strength of Y₂O₃-stabilized ZrO₂ polycrystals (Y-TZP) was measured by a newly developed tensile testing method with a rectangular bar. The tensile strength of Y-TZP was lower than that of the three-point bend strength, and the shape of the tensile strength distribution was quite different from that of the three-point bend strength distribution. It was difficult to predict the distribution curve of the tensile strength using the data of the three-point bend strength by one-modal Weibull distribution. The distribution of the tensile strength was analyzed by two- or three-model Weibull distribution coupled with an analysis of fracture origins. The distribution curve of the three-point bend strength which was estimated by multimodal Weibull distribution agreed favorably with that of the measured three-point bend strength values. A two-modal Weibull distribution function was formulated approximately from the distributions of the tensile and three-point bend strengths, and the estimated two-modal Weibull distribution function for the four-point bend strength agreed well with the measured four-point bend strength.     

Tensile Strength of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Tensile strengths of 2.0 to 5.0 mol% Y₂O₃-stabilized ZrO₂ polycrystals were described using the newly developed tensile testing method. The tensile test was conducted by attaching three strain gauges on both sides of a rectangular bar that was 10 mm by 1 mm by 200 mm. The tensile strength of tetragonal ZrO₂ polycrystals (TZP) containing 2.0 mol% Y₂O₃ showed 745 MPa, whereas the bend strength of this material was 1630 MPa. Inelastic behavior of the stress-strain curve was observed at critical stresses and strains of 500 to 700 MPa and 0.25% to 0.35%, respectively. Although deviation from proportionality was observed to be small, it increased with the increase of temperature from −100° to 200°C.     

Slip Casting of Yttria-Stabilized Tetragonal Zirconia Polycrystals

The rheological and casting parameters of 3-mol%-yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP) powder obtained by a wet-chemical coprecipitation route have been studied. Colloidal stability has been studied through zeta potential measurements. An organic surfactant has been used as deflocculant. Viscosity, casting rate, and green densities have been determined for suspensions with 28.2, 33.6, and 40.3 vol% solids content. Relative density, grain size, and t -ZrO₂ evolution versus temperature and soaking time are also reported.     

Spherical and Vickers Indentation Damage in Yttria-Stabilized Tetragonal Zirconia Polycrystals

Damage induced in an yttria-stabilized tetragonal zirconia polycrystal by spherical and Vickers indentations was investigated. Scanning acoustic microscopy revealed that, as indentation stress increased, the spherical indentation gradually developed subsurface damage, until it experienced a transition to a fully plastic state, characterized by a highly anisotropic variation in the leaky Rayleigh wave velocity, v _R, and very similar to that for Vickers indentation. The transition was a result of the formation of a microcracked core beneath the contact. Indenter geometry had an appreciable effect only within the core; the distribution of microcracks differed depending on the indenter used, as confirmed by direct observations using a scanning electron microscope. In contrast, the residual stresses in the elastic-plastic zone were insensitive to indenter geometry. The resulting plastic zone was not hemispherical but rather cylindrical, irrespective of indenter geometry.     

Evaluation of Tensile Strength and Fracture Toughness of Yttria-Stabilized Zirconia Polycrystals with Fracture Surface Analysis

The tensile strength of yttria-stabilized tetragonal zirconia polycrystals (Y-TZPs) was measured and the fracture surfaces were analyzed with the scanning electron microscope and X-ray microanalyzer. The fracture origins of the pressureless-sintered samples were voids or inclusions such as A1₂O₃, A1₂O₃ with SiO₂, and cubic-ZrO₂, while the fracture origins of the hot isostatically pressed samples were inclusions; no voids were detected at fracture origins. The higher strengths of the hot isostatically pressed samples versus those of the pressureless-sintered samples were consistent with the change in fracture origins. The fracture toughness of the samples calculated from the tensile strength and analysis of the fracture origins was 3.4 to 3.7 MPa √m. These values are lower than those measured with the SEPB method. These discrepancies might be caused by the difference in the state of the fracture origin and its neighborhood, such as the size of the fracture origin and interaction between two surfaces in the precrack.     

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.     

Dynamic Grain Growth During Superplastic Deformation of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Both static and dynamic grain growth were studied during superplastic deformation of fine-grained yttria-stabilized tetragonal zirconia. It was found that significant grain growth does not take place below 1300°C. Both static and dynamic growth were found to obey a similar equation of the form D³−D³₀=kt, where D and D₀ are the instantaneous and initial grain sizes, respectively, t is the annealing time, and k is the kinetic constant for either static or dynamic grain growth. The activation energies were approximately 580 and 520 kJ/mol for static and dynamic grain growth, respectively.     

Improved Low-Temperature Environmental Degradation of Yttria-Stabilized Tetragonal Zirconia Polycrystals by Surface Encapsulation

An encapsulating layer was deposited on the surface of tetragonal zirconia polycrystals doped with 3 mol% of yttria (3Y-TZP), to prevent low-temperature environmental degradation (aging) of the material. The layer, which was composed of silica and zircon, was formed on the surface by exposing the specimens next to a bed of silicon carbide powder in a flowing hydrogen atmosphere that contained ∼0.1% water vapor at 1450°C. The layer was ∼0.5 µm thick and is expected to be under strong residual compressive stress. This encapsulation process remarkably improved the low-temperature degradation of the material. The strength of the specimens also was improved by this process.     

Effect of Cation Doping on the Superplastic Flow in Yttria-Stabilized Tetragonal Zirconia Polycrystals

The superplastic characteristics of various cation-doped yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) were examined. For 1 mol% cation doping the true stress of Y-TZP is very dependent on the ionic radii of the doped cations; for instance, smaller cation radii give rise to lower true stress when compared with the other compositions for the same grain size, strain rate, and testing temperature. The altered true stress level must be due to the change in diffusivity of the accommodation process for grain boundary sliding caused by the addition of cations in ZrO₂. The strain to failure of the doped zirconia is affected by both ionic radius and valence of the dopant cations.     

Influence of an Amorphous Second Phase on the Properties of Yttria-Stabilized Tetragonal Zirconia Polycrystals (Y-TZP)

Y-TZP ceramics with various amounts of glassy intergranular phase were fabricated in order to investigate the effect of this amorphous phase on the properties of TZP. The presence of a liquid silicate phase not only enhanced sintering but also controlled the evolution of distinctly different grain morphologies, dependent on the amount of liquid phase present. The influence of the glass phase on the transformability of grains is discussed with respect to the room-temperature fracture toughness and surface degradation at 250°C.     

Superplastic Flow of Fine-Grained Yttria-Stabilized Zirconia Polycrystals: Constitutive Equation and Deformation Mechanisms

Available deformation data for superplastic yttria-stabilized zirconia polycrystals with grain size <1 µm have been analyzed at temperatures between 1250° and 1450°C as a function of stress, grain size, and impurity content. The apparent stress exponent n for the higher-purity materials (residual impurity content <0.10 wt%) varies from 2 (region II) to greaterthan equal to3 (region I), and then toward 1 when the stress is decreased. The stress for transition between region II and region I decreases when the temperature and/or grain size is increased. The activation energy Q for flow in region II is 460 kJ/mol, which is approximately that for cation lattice diffusion. The grain-size exponent p decreases continuously and Q increases continuously with decreasing stress in region I. The constitutive equation for superplastic flow in region II is identical to that for metallic systems when lattice diffusion is the rate-controlling mechanism. The experimental results have been correlated with a single deformation process that incorporates a threshold stress, below which grain-boundary sliding does not contribute to strain. The threshold stress may result from yttrium segregation at grain boundaries and its interaction with grain-boundary dislocations. A single deformation regime with n = 2 exists for low-purity materials (impurity content >0.10 wt%) over the entire stress range. The strain-rate enhancement with respect to high-purity materials is related to the grain-boundary amorphous phase present in such materials.     

Significance of Internal Stresses for the Martensitic Transformation in Yttria-Stabilized Tetragonal Zirconia Polycrystals During Degradation

Various aspects of the tetragonal ( t ) to monoclinic ( m ) transformation during degradation have been studied experimentally and theoretically in yttria-stabilized tetragonal zirconia polycrystals (Y-TZP), i.e., polycrystalline t -ZrO₂ containing Y₂O₃ in solution. Transmission electron microscopy (TEM) revealed that protruding grains at the surface of Y-TZP specimens do not transform under corrosive conditions (250°C, humid atmosphere) even after an annealing time of 168 h. Eigenstresses due to anistropic thermal expansion In and around protruding and bulk grains have been calculated for Y-TZP containing 2 and 3 mol% Y₂O₃. The prominent role of these stresses on subsequent transformation nucleation during degradation is shown to agree qualitatively with an established free energy concept. The lack of complete transformation of m -ZrO₂ is attributed to characteristics of the nucleation- and growth-controlled transformation process.     

Fatigue and Static Crack Propagation in Yttria-Stabilized Tetragonal Zirconia Polycrystals: Crack Growth Micromechanisms and Precracking Effects

The influence of precracking techniques in the crack growth behavior of yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) is investigated. Load-bridge and cyclic-compression precracking enhance subsequent tensile crack growth rates, in comparison to results that are found with precracks that are extended under four-point bending prior to testing. The actual influence of these precracking techniques in the near-threshold crack growth regime is remarkably different. Although load-bridge precracking produces a pattern of crack growth fluctuations for stress intensity factors, K , lower than the effective crack-growth threshold of the material, compression-fatigue precracks start to propagate under far-field tensile loads at very fast growth rates and for K values that are slightly higher than the effective threshold. Crack-tip shielding by tetragonal-to-monoclinic transformation develops gradually, influencing the crack growth behavior in Y-TZP. Proposed fatigue crack growth micromechanisms involve damage accumulation at the crack-tip region. For K _max > 3 MPa·m^1/2, fatigue crack growth rates are strongly affected by environmental interactions at the crack tip, and postulated fatigue micromechanisms include the cyclic degradation of crack-tip shielding.     

Solid-Solution Effects of a Small Amount of Nickel Oxide Addition on Phase Stability and Mechanical Properties of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Stability and mechanical properties of the tetragonal phase were investigated for NiO-doped yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) systems. Only 0.3 mol% of NiO in solid solution could be added to the Y-TZP while maintaining the tetragonal phase. Fracture toughness improved remarkably on addition of a small amount of NiO. Raman spectroscopy analysis around cracks introduced by Vickers indentation revealed that the amount of monoclinic phase transformed from tetragonal phase was increased. It was confirmed that fracture toughness improvement was due not only to increased grain size, but also to Y-TZP destabilization by solid solution of NiO.     

Chemical Interactions between La-Sr-Mn-Fe-O-Based Perovskites and Yttria-Stabilized Zirconia

Orthoferrite-based perovskites are of interest as materials for the cathode in solid oxide fuel cells (SOFCs). Therefore, the chemical compatibility between perovskites of the composition (La_1−xSr_x)_zFe_1−yMn_yO_3−δ (0 # x # 0.3; 0.2 # y # 1; z = 0.90, 0.95, 1.00) and the solid electrolyte zirconia (ZrO₂) doped with 8 mol% yttria (Y₂O₃) (8YSZ) has been investigated. Powder mixtures of the two materials have been annealed at different temperatures. The formation of monoclinic ZrO₂ at 1000°C, as well as of La₂Zr₂O₇ and SrZrO₃ at 1400°C, has been determined in some samples. The reactions that are observed are discussed, with respect to the thermodynamic activities, tolerance factor, and oxygen-ion migration energies. Some perovskite compositions seem to be compatible with Y₂O₃-stabilized ZrO₂ (YSZ), thereby offering the possibility to use orthoferrite-based perovskites in SOFCs with a solid electrolyte made of YSZ.     

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.     

Chemical Compatibility between Strontium-Doped Lanthanum Manganite and Yttria-Stabilized Zirconia

Equimolar powder mixtures and multilayer pellets of single-phase Sr-doped lanthanum manganite perovskite materials La_y-xSr_xMnO₃ with La content y = 1 and 0.95 and Sr content 0 ≤ x ≤ 0.5 were annealed in air with 8 mol% Y₂O₃-ZrO₂ at 1470 K, up to 400 h and at 1670 K. up to 200 h. X-ray diffraction and electron probe microanalysis confirmed the formation of La₂Zr₂O₇ or SrZrO₃ depending on the composition of the perovskites. No reaction products could be detected for La_0.95-xSr _xMnO₃ with 0.2 ≤ x ≤ 0.4 after annealing for 400 h at 1470 K, and for the perovskite La_0.65Sr_0.3MnO₃ even after annealing for 200 h at 1670 K. The results demonstrate the improved chemical compatibility of La-deficient perovskites against reaction with zirconia and can provide a basis for the selection of a sufficiently chemically stable material for the air electrode of solid oxide fuel cells.     

Mechanism of Reaction between Lanthanum Manganite and Yttria-Stabilized Zirconia

The reaction of La_{1- x} Ca _x MnO₃ ( x = 0, 0.1, 0.2) with ZrO₂-8 mol% Y₂O₃ (YSZ) has been investigated at temperatures ranging from 1300° to 1425°C in air. Substitution of Ca for La in LaMnO₃ depresses the reactivity with YSZ. A layer of La₂Zr₂O₇ is formed at the La_{1- x} Ca _x MnO₃/YSZ interface after an induction period, and its formation is accelerated when the La_{1- x} Ca _x MnO₃ phase is porous. The reaction proceeds by unidirectional diffusion of La, Mn, and/or Ca ions, mainly Mn ions, into YSZ. The diffusion coefficients of La and Mn ions in YSZ, which are estimated using a LaMnO₃/single-crystal YSZ couple, are much lower than that of oxygen ion. From the experimental data, a reaction mechanism is proposed.     

Strain Hardening in Superplastic Codoped Yttria-Stabilized Tetragonal-Zirconia Polycrystals

The superplastic characteristics of 3-mol%-yttria-stabilized tetragonal-zirconia polycrystals (3Y-TZP) were drastically improved by the combined addition of germanium oxide and other oxides (titanium, magnesium, and calcium), resulting in up to 1000% elongation under optimum conditions. Extensive work hardening of the codoped compositions for temperatures >1400°C was observed. Dynamic grain growth was not a sufficient mechanism to explain this anomalous high strain hardening. The appearance of a cubic phase that caused abnormal grain growth during testing may have resulted in increased flow stress, which resulted in exaggerated work hardening.     

Subeutectoid Degradation of Yttria-Stabilized Tetragonal Zirconia Polycrystal and Ceria-Doped Yttria-Stabilized Tetragonal Zirconia Polycrystal Ceramics

Yttria-doped tetragonal zirconia containing 2 and 3 mol% Y₂O₃ (Y-TZP), and CeO₂-doped Y-TZP containing 0 to 12 mol% CeO₂ were sintered at 1350°C in a tetragonal single-phase field for 2 h in air, and the degradation behavior at low temperature in air and in hot water was observed. X-ray photoelectron spectroscopy studies on the surface of hydrothermally treated samples show evidence for the formation of a YO(OH) species, along with the simultaneous formation of purely tetragonal zirconia nuclei that retain their coherence in the Y-TZP matrix. Above a critical size, the tetragonal nuclei spontaneously transform to a monoclinic structure, giving rise to macro- and microcracking. The strong tetragonal grains degrade to produce a spalling phenomenon that facilitates further degradation. Y-TZP ceramics alloyed with adequate amounts of CeO₂ show no tetragonal-to-monoclinic transformation after hydrothermal treatment.