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.     

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.     

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.     

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.     

In Situ Raman Spectroscopic Study of Yttria-Stabilized Zirconia Attack by Molten Sodium Vanadate

Raman spectroscopy has been used to study the molten salt attack of ceramics used as thermal barrier coatings. Zirconia stabilized with 8 wt% yttria was immersed in sodium metavanadate melts and in sodium metavanadate/sodium sulfate melts. In situ Raman measurements allowed simultaneous observation of the ceramic phases and salt chemistry during the attack process. The ceramic was seen to transform from the cubic/tetragonal to the monoclinic phase, concurrent with chemical changes in the molten salt layer in contact with the ceramic. These in situ measurements were complemented by conventional postexposure examination and by postexposure Raman measurements. The rate of attack was found to be quite sensitive to the mole fraction of vanadate in the molten salt solution.     

Microstructure and Fracture Toughness of Yttria-Daped Tetragonal Zirconia Polycrystal/Mullite Composites Prepared by an in Situ Method

Yttria-daped tetragonal zirconia polycrystal (Y-TZP)/ mullite composites were prepared by three methods: in situ whisker growth (IS), physical mixing (PM) of zirconia powder and mullite whiskers, and reaction sintering (RS). Microstructures and fracture toughness values were compared. All the composites with 15 vol% of mullite could be densified to more than 95% relative density by firing at 1500° to 1500°C for 10 h. The fracture toughness of the composites as measured by the indentation method showed a clear enhancement compared with that of pure Y-TZP; the ranking was Y-TZP ≦ RS composite < PM composite < IS composite. Enhancement of the fracture toughness in composites was found to relte strongly to the aspect ratio of mullite particles.     

Raman Investigation of the Nitridation of Yttria-Stabilized Tetragonal Zirconia

Raman spectroscopy has been used to obtain Raman spectra of yttria-stabilized tetragonal zirconia subject to surface nitridation induced by contact with zirconium nitride. Raman spectra recorded from regions at increasing distance from the source of nitridation have been used to obtain diffusion profiles from samples treated at different times and temperatures. The coupling of X-ray diffraction data previously taken and of the Raman spectra shows that in the samples there is a two-phase region (tetragonal + cubic) near the nitrided surface and that, at larger distance inside the samples, there is only one phase (tetragonal). Fitting of the diffusive profiles in the single-phase tetragonal region with an appropriate diffusion function allows the determination of the diffusion coefficient of nitrogen in tetragonal zirconia which is expressed in terms of the preexponential factor, D ₀= (3.98 ± 0.5) × 10⁻³ cm²/s, and the activation energy, Q = 170 ± 10 kJ/mol.     

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.     

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.     

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.     

In Vitro Aging of Yttria-Stabilized Zirconia

Yttria-stabilized zirconia was aged in distilled water, saline, and Ringer's solution for 140, 304, and 453 d. The significant decreases in strength (13% to 22%) is attributed to the phase transformation of zirconia from tetragonal to monoclinic. The effect of aging stabilized zirconia in physiological media is still unresolved.     

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.     

Microstructure and Mechanical Properties of Fine-Grained Magnesia-Partially-Stabilized Zirconia Containing Titanium Carbide Particles

Fine-grained Mg-PSZ has been fabricated by adding TiC particles. The average cubic grain size was smaller by more than an order of magnitude than without TiC when the TiC content was over 2.5 vol%. Pressurelessly sintered specimens contained numbers of relatively large pores while hot-pressed ones were fully dense. For hot-pressed specimens, addition of TiC particles did not affect the growth behavior of tetragonal precipitates during annealing. With increasing TiC content, the bend strength of hot-pressed specimens increased while the fracture toughness decreased. The bend strength and the fracture toughness of fine-grained Mg-PSZ containing 5 vol% TiC were 980 MPa and 8.2 MPa·m^1/2, respectively.     

In Situ Polysilane-Derived Silicon Carbide Particulates Dispersed in Silicon Nitride Composite

A dense (97% of theoretical density) Si₃N₄—SiC composite containing 10 wt%β-SiC was prepared by introducing a SiC phase by the pyrolysis of a polymeric SiC precursor. The composite material was produced by mixing an alkyl/aryl-substituted polysilane with Si₃N₄ powder and, by subsequently forming green compacts, pyrolyzing the polymeric species, and finally sintering the sample. Synthesis and characterization of the polymeric compound was described. Its transformation reactions to SiC and the characterization of the ceramic residue were also studied. High ceramic yields were obtained by curing the as-synthesized polysilane at 500°C in an Ar atmosphere. The heat treatment had no effect on the good solubility of the polymeric precursor in organic solvents. This was important for processes such as infiltration, sealing, and coating and for the mixing of the polymer with powders for the preparation of homogeneous composite ceramics. The dense microstructure of the pyrolyzed and sintered Si₃N₄ powder–polysilane mixture exhibited reduced grain growth of the Si₃N₄ particles and a very homogeneous distribution of the in situ-formed β-SiC phase.     

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.     

Synthesis of Highly Porous Yttria-Stabilized Zirconia by Tape-Casting Methods

Porous ceramics of Y₂O₃-stabilized ZrO₂ (YSZ) were prepared by tape-casting methods using both pyrolyzable pore formers and NiO followed by acid leaching. The porosity of YSZ wafers increased in a regular manner with the mass of graphite or polymethyl methacrylate (PMMA) to between 60% and 75% porosity. SEM indicated that the shape of the pores in the final ceramic was related to the shape of the pore formers, so that the pore size and microstructure of YSZ wafers could be controlled by the choice of pore former. Dilatometry measurements showed that measurable shrinkage started at 1300 K, and a total shrinkage of 26% was observed, independent of the amount or type of pore former used. Temperature-programmed oxidation (TPO) measurements on the green tapes demonstrated that the binders and dispersants were combusted between 550 and 750 K, that PMMA decomposed to methyl methacrylate between 500 and 700 K, and that graphite combusted above 900 K. The porosity of YSZ ceramics prepared by acid leaching of nickel from NiO–YSZ, with 50 wt% NiO, was studied as a function of NiO and YSZ particle size. Significant changes in pore dimension were found when NiO particle size was changed.     

Evaluation of Fracture Toughness Determination Methods as Applied to Ceria-Stabilized Tetragonal Zirconia Polycrystal

A comparison of several fracture toughness determination methods based upon the use of cracks emanating from a Vickers hardness indent to the bulk techniques of double cantilever beam and single edge notch beam is made in a tough zirconia material which shows little evidence of transformation toughening based on the amount of monoclinic phase detected by XRD on ground surfaces. Results indicate that some indentation methods yield values close to those obtained by bulk methods, in contrast to results obtained on zirconia materials which show large effects of transformation toughening.     

Role of Grain-Boundary Glass Phase on the Superplastic Deformation of Tetragonal Zirconia Polycrystal

Superplastic deformation of tetragonal zirconia polycrystal (TZP) was investigated by compression test in the temperature range of 1000° to 1500°C. Special attention was paid to the role of the grain-boundary glass phase on hightemperature deformation behavior. A small addition of glass phase markedly improved the high-temperature deformability of TZP. Lithium silicate glass was much superior to aluminosilicate or lithium aluminum silicate glasses for lowering the high-temperature flow stress. The deformation mechanism was discussed on the basis of mechanical testing data and microstructural examinations.