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.     

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.     

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.     

Grain-Boundary Grooving of Plasma-Sprayed Yttria-Stabilized Zirconia Thermal Barrier Coatings

The focus of this study was to determine the mechanisms responsible for the microstructural changes of plasma-sprayed 7 wt% Y₂O₃–ZrO₂ thermal barrier coatings with annealing from 800° to 1400°C. Mullins's thermal grooving theories have been applied to plasma-sprayed TBCs to determine the dominant mass transport mechanism at various temperatures. Grain-boundary groove widths were measured as a function of annealing time and temperature using atomic force microscopy (AFM). The same collection of grains was analyzed after progressive heat treatments. Surface diffusion was found to be the dominant diffusion mechanism at 1000°C, corresponding to the disappearance of intralamellar cracks at that temperature. At 1100°C, both surface and volume diffusion were active. Volume diffusion, found to be the dominant diffusion mechanism at 1200°C and above, was responsible for the sintering of interlamellar pores observed from AFM analysis of a single, progressively heat-treated interlamellar boundary. Surface roughening was observed to coarsen with increased annealing time and disappear with increased annealing temperature.     

Microstructure–Thermal Conductivity Relationships for Plasma-Sprayed Yttria-Stabilized Zirconia Coatings

The microstructures of plasma-sprayed yttria-stabilized zirconia (YSZ) coatings are complex, contributing to challenges in establishing microstructure–thermal conductivity relationships. Furthermore, the dynamic evolution of microstructure and properties during service offers a significant challenge in defining design strategies and extended coating performance. In this paper, the relationship between microstructure and thermal conductivity is investigated for three sets of plasma-sprayed YSZ coating systems prepared using different morphology powders, different particle size distributions, and controlled modification of particle states through plasma torch parameters. Both ambient and temperature-dependent thermal conductivity were conducted in the as-sprayed and thermally aged states. The results suggest that a range of thermal conductivities can be achieved from the coatings, offering potential for microstructural tailoring for desired performance. The results also demonstrate that different as-deposited microstructures display varying propensity for sintering and these attributes need to be considered in the design and manufacturing cycle. This expansive study of a range of coatings has also allowed synthesis of the results through thermal conductivity–porosity maps and has allowed elucidation of the contributing microstructural components for both the ambient and high-temperature thermal conductivity. Considering that the operating thermal transport mechanisms are different at these two temperature extremes, such mapping strategies are of value to both science and technology.     

Effect of NiO on the Phase Stability and Microstructure of Yttria-Stabilized Zirconia

Nickel oxide (NiO) was screen printed onto the surfaces of 3 and 8 mol% yttria-stabilized zirconia (YSZ) dense pre-fired substrates and then heat treated at temperatures from 1350° to 1550°C. The effect of NiO was dependent on the yttria content of the substrate. In 3 mol% YSZ, it was found to alter the phase composition from predominantly tetragonal with a small amount of cubic phase to one consisting of approximately equal amounts of cubic and monoclinic phase. The cubic grains were much larger than the monoclinic ones and contained more nickel. Furthermore, nickel was observed to migrate through the thickness of the tile, a distance of approximately 200 μm. In the 8 mol% YSZ substrates, the phase composition was unaltered, although large grains developed under the printed NiO layer and the nickel migration was confined to the extent of these large grains.     

Effects of Yttria-Stabilized Zirconia on Plasma-Sprayed Hydroxyapatite/Yttria-Stabilized Zirconia Composite Coatings

The low bonding strength between hydroxyapatite (HA) and the metal substrate interface of plasma-sprayed HA coating has been a point of potential weakness in its application as a biomedical prosthesis. In the present study, yttria-stabilized (8 wt%) zirconia (YSZ) has been used to enhance the mechanical properties of HA coatings. The effects of YSZ additions (in the range 10–50 wt%) on the phase composition, microstructure, bond strength, elastic modulus, and fracture toughness of plasma-sprayed HA/YSZ composite coatings have been studied. The results indicated that decomposition of HA during plasma spraying was reduced significantly with the addition of zirconia. The higher the zirconia content, the lower the amount of calcium oxide, tricalcium phosphate, and tetracalcium phosphate formed in the coatings. In addition, there was a trace of calcium zirconate formed when less than 30 wt% zirconia was present. A solid solution of HA mixed with YSZ formed during plasma spraying; however, the amount of unmelted particles increased as the zirconia increased. The mechanical properties of the HA/YSZ composite coatings, such as bond strength, elastic modulus, and fracture toughness, increased significantly as the contents of zirconia increased.     

EXAFS Study of Yttria-Stabilized Zirconia

The local structural environments of Y³⁺ and Zr⁴⁺ in 18 wt% Y₂O₃-stabilized zirconia were studied using extended X-ray absorption fine structure spectroscopy over the temperature range –120° to 770°C. The measured cation-oxygen distances reflect those of the parent oxides, with the mean Zr-O distance 0.017 nm shorter than the mean Y-O distance. The spread in the Zr–nearest-neighbor and Zr–next-nearest-neighbor distances is considerably larger than observed for Y³⁺. This result is attributed to the anion vacancies being preferentially sited adjacent to the smaller Zr⁴⁺ cation which, with ensuing relaxations, permits a closer contact between Zr⁴⁺ and its oxygen neighbors. Thus, the structural environment of these Zr⁴⁺ ions resembles that of the 7-coordinated Zr⁴⁺ in monoclinic zirconia. Increasing the temperature of the sample results in the local structural environments of the two cations becoming more alike, suggesting that increased anionic mobility leads to an increasingly random distribution of anion vacancies.     

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.     

Piezo-Spectroscopic Coefficients of Tetragonal-Prime Yttria-Stabilized Zirconia

The Raman piezo-spectroscopic constants of tetragonal prime yttria-stabilized zirconia under uniaxial compression have been determined. Although the Raman band at 461 cm⁻¹ is not the most intense, it is the most appropriate peak for stress measurement because of its large stress-induced peak shift and the minimum overlap with the other Raman peaks. The peak separation between bands at 258 and 461 cm⁻¹ or 258 and 638 cm⁻¹ can also be used to measure stress.     

Transformation of Electron-Beam Physical Vapor-Deposited 8 wt% Yttria-Stabilized Zirconia Thermal Barrier Coatings

Yttria-stabilized (8.6 mol% YO_1.5) zirconia thermal barrier coatings evolve at high temperatures from the "non-transformable," metastable tetragonal-prime phase in their as-deposited condition to a mixture of the tetragonal and cubic phases. The kinetics of the transformation at 1200° and 1425°C are reported based on X-ray diffraction measurements. Complementary Raman spectroscopy measurements indicate a sharpening of the tetragonal bands at 263 and 465 cm⁻¹ that is attributed to a systematic decrease in disorder of the Y³⁺ and oxygen vacancies with annealing. No transformation to the monoclinic form of zirconia is observed immediately after high-temperature treatment. However, partial transformation to monoclinic occurs after a prolonged time (months) at room temperature in those samples treated at 1425°C, indicating the development of isothermal martensite.     

Determination of Scattering and Absorption Coefficients for Plasma-Sprayed Yttria-Stabilized Zirconia Thermal Barrier Coatings

Prediction of radiative transport through translucent thermal barrier coatings (TBCs) can only be performed if the scattering and absorption coefficients and index of refraction of the TBC are known. To date, very limited information on these coefficients, which depend on both the coating composition and the microstructure, has been available for the very commonly utilized plasma-sprayed 8 wt% yttria-stabilized zirconia (8YSZ) TBCs. In this work, the scattering and absorption coefficients of freestanding plasma-sprayed 8YSZ coatings were determined from room-temperature normal-incidence directional-hemispherical reflectance and transmittance spectra over the wavelength range from 0.8 to 7.5 μm. Spectra were collected over a wide range of coating thickness from 60 to almost 900 μm. From the reflectance and transmittance spectra, the scattering and absorption coefficients as a function of wavelength were obtained by fitting the reflectance and transmittance values predicted by a four flux model to the experimentally measured values at all measured 8YSZ thicknesses. While the combined effects of absorption and scattering were shown in general to exhibit a nonexponential dependence of transmittance on specimen thickness, it was shown that for sufficiently high absorption and optical thickness, an exponential dependence becomes a good approximation. In addition, the implications of the wavelength dependence of the plasma-sprayed 8YSZ scattering and absorption coefficients on (1) obtaining accurate surface-temperature pyrometer measurements and on (2) applying mid-infrared reflectance to monitor TBC delamination are discussed.     

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.     

Hot Isostatic Pressing of a Presintered Yttria-Stabilized Zirconia Ceramic

The effect of hot isostatic pressing on the bend strength of ZrO₂–3 mol% Y₂O₃ was critically dependent on the presintering process. Optimally sintered bodies contained no open porosity and exhibited large increases in strength following hot isostatic pressing. When open porosity of as little as 0.3% persisted after sintering, hot isostatic pressing increased the bulk density, but little or no increase in strength was realized. Two-parameter Weibull analysis of the strength data was used to quantify the strength improvement obtained following hot isostatic pressing. Typical fracture-initiating flaws were identified through optical and electron microscopy.     

Thermal Conductivity of Plasma-Sprayed Monolithic and Multilayer Coatings of Alumina and Yttria-Stabilized Zirconia

The temperature dependence of the thermal conductivity of plasma-spray-deposited monolithic coatings, as well as multilayer coatings that consisted of Al₂O₃ and ZrO₂ that was stabilized by 8% Y₂O₃ (YSZ), was investigated. The coatings exhibited a large reduction in thermal conductivity at all temperatures, when compared to the bulk monolithic Al₂O₃ and YSZ. This reduction was due to porosity as well as thermal resistance that was caused by interfaces in the coatings. The largest decrease in the thermal conductivity of the coatings, relative to monolithic fully dense materials, was due to splat interfaces within each layer, as well as the coating/substrate interface. On the other hand, the multilayer coatings showed little variation in the thermal conductivity, relative to the number of layers, which suggests that the influence of interlayer interfaces on heat transfer is relatively small. A one-dimensional analysis of steady-state heat transfer has been presented to illustrate the significance of porosity, splat interfaces, and interlayer interfaces, with respect to the overall thermal conductivity of multilayer coatings.     

Formation of a Zinc Oxide/Yttria-Stabilized Zirconia Interface

Zinc oxide was deposited on the (111) face of an yttria-stabilized zirconia single crystal using the chemical vapor phase method. Zinc vapor was obtained by reducing polycrystalline ZnO in hydrogen at 1200°C. The deposition of the ZnO was accomplished by the reoxidation of zinc vapor at temperatures of 1300° to 1345°C.     

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.     

Temperature-Dependent Optical Reflectivity of Tetragonal-Prime Yttria-Stabilized Zirconia

The optical reflectance of dense, metastable, tetragonal-prime zirconia plates, made by densifying electron beam physical vapor-deposited powder, is reported as a function of temperature up to 1673 K (1400°C) over the range of 400–1500 cm⁻¹ (6.67–25 μm). Curve fitting of the reflectance as a function of temperature was performed using two different damped oscillator models, each with three infrared (IR)-active modes. Oscillator parameters were then used to calculate the values of the indices of refraction and absorption as a function of temperature using the classical dispersion theory. The reflectance data of tetragonal-prime yttria-stabilized zirconia at room temperature are qualitatively similar to that reported for the equilibrium tetragonal phase in that it can be fit with three IR-active modes.     

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.