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.     

Sliding Wear Properties of Self-Mated Yttria-Stabilized Tetragonal Zirconia Ceramics in Cryogenic Environment

The objective of the present work is to investigate the friction and wear of self-mated ZrO₂ ceramics in a cryogenic environment. Using a specially designed high-speed cryo-tribometer, fine-grained yttria-stabilized tetragonal ZrO₂ polycrystals (Y-TZP) were worn at varying loads (5–15 N) with sliding speed of 1.1 m/s in a cryogenic environment (liquid nitrogen, LN2). For comparison, the sliding tests were also conducted under selected operating conditions on self-mated Y-TZP under ambient conditions (room temperature (RT)), primarily to understand the difference in wear mechanisms for a given sliding condition. With these planned experiments, it was attempted to answer some important issues: (a) Can sliding in LN2 reduce the coefficient of friction (COF) of self-mated ZrO₂? (b) Does t-ZrO₂ transformation occur in a cryogenic environment and if it occurs, how does it affect the fracture behavior? (c) How does the mechanism of wear change from RT to LN2 temperature? In our experiments, high COF (0.35–0.75) and high wear rate of disks 10⁻⁴–10⁻⁶ mm³·(N·m)⁻¹ have been measured under the selected tribological testing conditions. Interestingly, X-ray diffraction analysis revealed the presence of o-ZrO₂ after sliding in a cryogenic environment, while no change in phase assemblage was recorded after sliding under identical conditions at RT. An important observation has been that severe plastic deformation (wider and deeper grooves) at RT and microcracking (“fish scale” pattern)-induced spalling of a damaged layer in an LN2 environment are the dominant wear mechanisms, respectively.     

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.     

Erosive Damage Depth in Ceramics: A Study on Metastable, Tetragonal Zirconia

A novel method is described for measuring the depth of erosion damage on ceramics that exhibit a stress-induced martensitic transformation. The technique is applied to metastable, tetragonal zirconia, eroded with silicon carbide particles. The damage depth data are compared with fracture depth predictions from single-particle studies, on the premise that the surface transformation zone can be attributed to the presence of impact fractures. The reasonable correlation obtained adds credence to the suggestion that single-particle tests are pertinent to erosion prediction in the plastic response regime     

Synchrotron X-Ray Study of the Crystal Structure and Hydrothermal Degradation of Yttria-Stabilized Tetragonal Zirconia Polycrystal

Structural study with synchrotron X-ray diffractometry was made on phase separation phenomena in 2, 3, and 4 mol% Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (abbreviated as 2, 3, and 4Y-TZP, respectively). The sintered body of 3Y and 4Y-TZP underwent phase separation into high and low yttrium regions as sintering temperature increased, and the tetragonal phase was assigned to both regions. The sintering body is less separated, and a large monoclinic phase was detected in 2Y-TZP. Analysis of aging kinetics of tetragonal- to monoclinic-phase transition showed that the fraction of the transformable phase agreed with that of the low yttrium region.     

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.     

Isothermal Sintering Effects on Phase Separation and Grain Growth in Yttria-Stabilized Tetragonal Zirconia Polycrystal

The isothermal sintering behavior in 3 mol% yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) was investigated to clarify phase-separation and grain-growth mechanisms during sintering. In the Y-TZP sintered at 1300°C for 2 h, the Y³⁺ ion distribution of grain interiors in Y-TZP was nearly homogeneous, but Y³⁺ ions segregated along grain boundaries within a width of about 10 nm. When the holding time increased from 2 to 50 h, the cubic-phase regions with high Y³⁺ ion concentrations were clearly formed in the grain interiors adjacent to the grain boundaries, though the average grain size hardly increased. This result shows that the cubic-phase regions were formed without grain growth, which can be explained by the grain-boundary segregation-induced phase transformation mechanism. In the Y-TZP sintered at 1500°C for 2 h, the cubic-phase regions were already formed, and both of the cubic-phase region and average grain size increased with increasing holding time. This grain-growth behavior can be interpreted by the third-power growth low derived based on the solute drag theory, which indicates that the cubic-phase regions do not effectively act as the pinning points.     

Experimental Study of Stress-Induced Localized Transformation Plastic Zones in Tetragonal Zirconia Polycrystalline Ceramics

Stress-induced martensitic transformation plastic zones in ceria-stabilized tetragonal zirconia polycrystalline ceramics (Ce-TZP), under loading conditions of uniaxial tension, compression, and three-point bending, are studied by experiments. The transformed monoclinic phase volume fraction distribution and the corresponding plastic strain distribution and the surface morphology (surface uplift) are measured by means of moire interferometry, Raman microprobe spectroscopy, and the surface measurement system. The experimental results from the above three kinds of specimens and methods consistently show that the stress-induced transformation at room temperature of the above specimen is not uniform within the transformation zone and that the plastic deformation is concentrated in some narrow band; i.e., macroscopic plastic flow localization proceeds during the initial stage of plastic deformation. Flow localization phenomena are all observed in uniaxial tension, compression, and three-point bending specimens. Some implications of the flow localization to the constitutive modeling and toughening of transforming thermoelastic polycrystalline ceramics are explored.     

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.     

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.     

Sol–Gel Synthesis of Nanophase Yttria-Stabilized Tetragonal Zirconia and Densification Behavior below 1600 K

The hot-pressing behavior of nanophase, 3-mol%-yttria-stabilized, tetragonal zirconia (Y-TZP) was studied in the temperature range 1290 to 1570 K. Powder was sol-gel synthesized using zirconium tetrachloride and hydrated yttrium chloride precursors. After drying and calcination, the particle size was 40 nm, coarsening to 70 nm upon subsequent annealing at 1273 K. On compact heating at 23-MPa applied stress, densification initiated near the calcination/annealing temperature. Theoretical density was obtained at densification temperature above 1490 K with particle coarsening consistent with classical coarsening kinetics. Microstructural change accompanying densification involved formation of dense regions 2 to 4 μm in size separated by irregularly shaped porous regions. The observed densification behavior complements calculated densification maps for fine-particle Y-TZP.     

Microstructure and High-Temperature Mechanical Behavior of Alumina/Alumina–Yttria-Stabilized Tetragonal Zirconia Multilayer Composites

Layered composites of alternate layers of pure Al₂O₃(thickness of 125 μ m) and 85 vol% Al₂O₃-15 vol% ZrO₂ that was stabilized with 3 mol% Y₂O₃(thickness of 400 μ m) were obtained by sequential slip casting and then fired at either 1550° or 1700°C. Constant-strain-rate tests were conducted on these materials in air at 1400°C at an initial strain rate of 2 × 10^-5 s^-1. The load axis was applied both parallel and perpendicular to the layer interfaces. Catastrophic failure occurred for the composite that was fired at 1700°C, because of the coalescence of cavities that had developed in grain boundaries of the Al₂O₃ layers. In comparison, the composite that was fired at 1550°C demonstrated the ductility of the Al₂O₃+YTZP layer, but at a flow stress level that was determined by the Al₂O₃ layer.     

Influence of Porosity on Friction and Wear of Tetragonal Zirconia Polycrystal

Sliding wear properties of ultra-fine-grained (180 nm) yttria-doped tetragonal zirconia (Y-TZP) ceramics were examined with porosities from 1.5% to 7%. On a pin-on-plate tribometer under dry-N₂ conditions, e.g., wear rates of the material increase by a factor of 5 by increasing porosity with a factor of 5 (from 1.5 to 7.0 vol%). In all cases no (irreversible) phase transformation to monoclinic zirconia took place during wear tests. The results for the relatively dense nanostructured materials showed significant evidence of plastic deformation and less microcrack formation. The morphology of the wear tracks in these ceramics indicate that the degree and amount of microcracks on the contact surface increased with porosity. A change in wear mechanism is observed.     

Accelerated Aging in 3-mol%-Yttria-Stabilized Tetragonal Zirconia Ceramics Sintered in Reducing Conditions

The aging behavior of 3-mol%-yttria-stabilized tetragonal zirconia (3Y-TZP) ceramics sintered in air and in reducing conditions was investigated at 140°C in water vapor. It was observed by X-ray diffraction (XRD) that 3Y-TZP samples sintered in reducing conditions exhibited significantly higher tetragonal-to-monoclinic transformation than samples with similar density and average grain size values but obtained by sintering in air. This fact is explained by the increase of the oxygen vacancy concentration and by the presence at the grain boundary region of a new aggregate phase formed because of the exolution of Fe²⁺ ions observed by X-ray photoelectron spectroscopy.     

Oxygen Diffusion in Yttria-Stabilized Zirconia: A New Simulation Model

We present a multiscale modeling approach to study oxygen diffusion in cubic yttria-stabilized zirconia. In this approach, we employ density functional theory methods to calculate activation energies for oxygen migration in different cation environments. These are used in a kinetic Monte Carlo framework to calculate long-time oxygen diffusivities. Simulation results show that the oxygen diffusivity attains a maximum value at around 0.1 mole fraction yttria. This variation in the oxygen diffusivity with yttria mole fraction and the calculated values for the diffusivity agree well with experiment. The competing effects of increased oxygen vacancy concentration and increasing activation energy and correlation effects for oxygen diffusion with increasing yttria mole fraction are responsible for the observed dopant content dependence of the oxygen diffusivity. We provide a detailed analysis of cation-dopant-induced correlation effects in support of the above explanation.     

Measurement of the Crystallographically Transformed Zone Produced by Fracture in Ceramics Containing Tetragonal Zirconia

During fracture of ceramics containing tetragonal zirconia particles, a volume of zirconia material on either side of the crack irreversibly transforms to the monoclinic crystal structure. Transformation zone sizes, measured using Raman microprobe spectroscopy, are presented for three sintered ceramics. In a single-phase ZrO₂−3.5 mol% Y₂O₃ material, an upper bound measurement of 5 μm is obtained for the zone size. In the Al₂O₃/ZrO₂ composites studied, the zone size is deduced to correspond to ∼1 grain in diameter. On the basis of the monoclinic concentrations derived from the Raman spectra it is further concluded that only a fraction of the ZrO₂ grains within the transformation zone transform, providing indirect evidence for the effect of particle size on the propensity for transformation.     

Stress Relief Mechanisms in Magnesia- and Yttria-Stabilized Zirconia

Stabilized zirconias exhibit pronounced photoelastic effects when viewed with transmitted polarized light. Thin sections reveal stress concentrations around pores and inclusions and at grain boundaries. The yield point of these materials, at some high temperature, is exceeded and plastic deformation tends to relieve these stress concentrations. The microhardness measurements of magnesia-stabilized zirconia indicate both solution hardening and solute segregation and help to explain the physical behavior of this system as the amount of MgO is varied.     

Diffusional Creep and Kinetic Demixing in Yttria-Stabilized Zirconia

The creep behavior of fine-grained yttria-stabilized zirconia with 25 mol% Y₂O₃ has been characterized as part of an investigation of kinetic demixing in solid-solution oxides which are subjected to a nonhydrostatic state of stress. At temperatures between 1400° and 1600°C, the steady-state strain rate of (Zr_0.6Y_0.4)O_1.8 samples with average grain sizes between 2.5 and 14.5 μm can be summarized by the flow law ɛ= 6.5 × 10⁻⁷σ^1.2 exp[−550 (kJ/mol)/ RT ] d ^−2.2 (s⁻¹) for stresses in the range 8 to 60 MPa, where σ is in pascals and d is in meters. This flow law indicates that deformation occurs by a Nabarro-Herring creep mechanism in which the creep rate is limited by cation lattice diffusion. Kinetic demixing was not observed in deformed polycrystalline samples even though diffusional creep was rate limited by cation lattice diffusion. This result can be explained if the cation diffusivities are approximately equal or if extensive grain rotation occurs during diffusional creep.     

Mechanical and Magnetic Properties of Novel Yttria-Stabilized Tetragonal Zirconia/Ni Nanocomposite Prepared by the Modified Internal Reduction Method

Dense ceramic/metal nanocomposite has been fabricated by internal reduction method, which includes a two-step process: sintering of ceramic–metal oxide solid solution and subsequent heat treatment in a reducing atmosphere to precipitate metal nanoparticles. This novel technique has been applied to yttria-stabilized tetragonal zirconia (Y-TZP) and nickel oxide (NiO) system to fabricate Y-TZP/Ni nanocomposite. Dense Y-TZP and 0.3 mol% NiO solid solution ceramic was successively prepared by the pressureless sintering, and Y-TZP/Ni was fabricated by the internal reduction treatment. The obtained Y-TZP/Ni nanocomposite possessed characteristic intragranular nanostructure with nano-sized metallic Ni particles of around 20 nm. Fracture toughness of both the solid solution and nanocomposite was remarkably improved because of the solid solution of NiO into Y-TZP and resultant destabilization of the tetragonal phase, and the Y-TZP/Ni nanocomposite was still destabilized by the remaining nickel solution after the reduction. The nanocomposite exhibited ferromagnetism, while the Y-TZP–NiO solid solution had diamagnetic nature. Comparison of saturation magnetization values revealed that 39.5 at.% of introduced nickel was reduced to metallic nanoparticle, proving the existence of residual NiO solute in zirconia that contributed to higher toughness value than the monolithic Y-TZP. It is concluded that the introduced internal reduction method is a suitable process to achieve multifunctional ZrO₂/Ni nanocomposite with high toughness and coexistent magnetic characteristic.     

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.