Crystallite and Grain-Size-Dependent Phase Transformations in Yttria-Doped Zirconia

In pure zirconia, ultrafine powders are often observed to take on the high-temperature tetragonal phase instead of the "equilibrium" monoclinic phase. The present experiments and analysis show that this observation is one manifestation of a much more general phenomenon in which phase transformation temperatures shift with crystallite/grain size. In the present study, the effect of crystallite (for powders) and grain (for solids) size on the tetragonal → monoclinic phase transformation is examined more broadly across the yttria–zirconia system. Using dilatometry and high-temperature differential scanning calorimetry on zirconia samples with varying crystallite/grain sizes and yttria content, we are able to show that the tetragonal → monoclinic phase transformation temperature varies linearly with inverse crystallite/grain size. This experimental behavior is consistent with thermodynamic predictions that incorporate a surface energy difference term in the calculation of free-energy equilibrium between two phases.     

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.     

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.     

Hydrothermal Crystallization of Zirconia and Zirconia Solid Solutions

Zirconia as well as yttria-zirconia and calcia-zirconia solid-solution powders were crystallized under hydrothermal conditions from (co)precipitated hydroxides. The morphology of the powder particles is strongly dependent on the crystallization conditions. The powders crystallized in a water solution of Na, K, and Li hydroxides show elongated particles of much larger sizes than those which result from the process carried out in pure water or a water solution of Na, K, or Li chlorides. The shapes of the latter particles are isometric. The growth mechanism of the elongated particles is suggested.     

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.     

Influence of Fracture Toughness on the Wear Resistance of Yttria-Doped Zirconium Oxide

Yttria-doped zirconium oxide was prepared in the fully tetragonal, mixed tetragonal and cubic, and the fully cubic phases by varying the yttria conent. The fracture toughnesses of the materials were 11.6, 8.7, and 2.5 Mpa · m½, respectively. The wear resistance, measured in air at room temperature in slow sliding (1 mm/s speed and 9.8 N load), increases by a factor of 1200 from the brittle to the toughest material; it is proportional to the fourth power of toughness. Wear occurs predominantly by fracture in the brittle (cubic) material; plastic deformation is observed in the tougher zirconium oxide.     

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.     

Controlling the Diameter of Electrospun Yttria‐Stabilized Zirconia Nanofibers

This work reports the precise diameter control of electrospun yttria‐stabilized zirconia (YSZ) nanofibers from 200 to 900 nm after calcination. Fabricated YSZ nanofibers showed porous nanocrystalline structures with high aspect ratios of more than 500:1 and high surface‐to‐volume ratios with a specific surface area of 43.32 m²/g. The diameter of the YSZ nanofibers increased with the viscosity of the precursor solution, which was controlled by the concentrations of either polymers (polyacrylonitrile) or ceramic precursors (YSZ). We present a modified correlation between the diameter of a nanofiber and the synthetic conditions, as the observed behavior for calcined ceramic nanofibers deviated from the expected behavior. Our results demonstrate a modified but simple approach to fabricate ceramic nanofibers with desired diameters, providing a new design guideline for many electrochemical applications.     

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.     

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.     

陶瓷釉中锆的快速测定的研究

本文研究了对乙酰基偶氮胂与锆反应的最佳条件。实验表明：锆在稀硫酸介质中与对乙酰基偶氮胂显色反应灵敏，表观摩尔吸光系数ε（６４０）＝４．６４×１０４Ｌ·ｍｏｌ（－１）·ｃｍ（－１），锆在０～３５μｇ／２５ｍｌ范围内服从比耳定律。应用于陶瓷釉中锆的测定，结果准确，令人满意。     

Preparation of Fine, Spherical Yttria-Stabilized Zirconia by the Spray-Pyrolysis Method

Fine yttria-stabilized zirconia powders were prepared by the spray pyrolysis of aqueous solutions of ZrOCl₂·8H₂O and Y(NO₃)₃·5H₂O (3 mol%). An appropriate thermal treatment resulted in slightly porous spherical particles with a narrow size distribution. The sintering ability of these powders was evaluated.     

Prevention of Low-Temperature Surface Transformation by Surface Recrystallization in Yttria-Doped Tetragonal Zirconia

The low-temperature (100° to 400°C) tetragonal to monoclinic transformation in yttria-doped tetragonal zirconia (Y-TZP) can be inhibited by a postsintering grinding and annealing treatment. The surface region so treated contains fine tetragonal grains which have recrystallized from the severely damaged ground surface. The various features of the recrystallized surface that may affect the lowtemperature transformation are analyzed.     

Martensitic Relief Observation by Atomic Force Microscopy in Yttria-Stabilized Zirconia

The tetragonal to monoclinic (t–m) phase transformation of zirconia has been the object of extensive investigations of the past 20 years and is now recognized as being of martensitic nature. However, martensitic transformation has only been observed by transmission electron microscopy or indirect methods. Though the benefit on the fracture toughness and crack resistance was the main interest, the transformation is now considered for its consequences on the degradation of the material. The use of atomic force microscopy reported here allowed the observation of the first stages of martensite relief growth and of new martensitic features.     

Strength and Phase Stability of Yttria-Ceria-Doped Tetragonal Zirconia/Alumina Composites Sintered and Hot Isostatically Pressed in Argon–Oxygen Gas Atmosphere

Yttria-ceria-doped tetragonal zirconia (Y,Ce)-TZP)/alumina (Al₂O₃) composites were fabricated by hot isostatic pressing at 1400° to 1450°C and 196 MPa in an Ar–O₂ atmosphere using the fine powders prepared by hydrolysis of ZrOCl₂ solution. The composites consisting of 25 wt% Al₂O₃ and tetragonal zirconia with compositions 4 mol% YO_1.5–4 mol% CeO₂–ZrO₂ and 2.5 mol% YO_1.5–5.5 mol% CeO₂–ZrO₂ exhibited mean fracture strength as high as 2000 MPa and were resistant to phase transformation under saturated water vapor pressure at 180°C (1 MPa). Postsintering hot isostatic pressing of (4Y, 4Ce)-TZP/Al₂O₃ and (2.5Y, 5.5Ce)-TZP/Al₂O₃ composites was useful to enhance the phase stability under hydrothermal conditions and strength.     

Thermodynamic Model of the Cubic → Tetragonal Transition in Nonstoichiometric Zirconia

Nonstoichiometric zirconia is described with a model recently developed for ZrO₂—Y₂O₃ alloys. It is thus possible to rationalize the experimental information on the cubic/tetragonal phase boundaries in zirconia.     

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.     

Fundamental Optical Absorption Edge of Sputter-Deposited Zirconia and Yttria

Zirconia and yttria films were sputter deposited onto unheated fused silica substrates using a metal target and rare gas-oxygen discharges. Double-beam spectrophotometry was used to measure the transmission and reflection as a function of incident photon energy, E , from which the absorption coefficient, α( E ), was calculated. An indirect interband transition at E _i= 4.70 eV and two direct interband transitions at E _g1= 5.17 eV and E _g2= 5.93 eV occur in monoclinic zirconia. Two direct interband transitions at E _g1= 5.07 eV and E _g2= 5.73 eV occur in cubic yttria. The absorption edge structure is modified when unusual phases, such as tetragonal zirconia, and zirconia and yttria with no longrange crystallographic order, are present.     

氧化钇稳定氧化锆的制备及电性能测试

氧化钇稳定氧化锆(yttria-stabilized zirconia,YSZ)是目前使用最多的电解质材料,探索了以YSZ纳米粉体为原料,采用固相法制备YSZ电解质薄片。采用X射线衍射(XRD)测试了它的微结构;采用交流四端子法测瓷体的电导率。实验表明,最佳烧结温度在1300℃,气孔含量少、晶粒均匀,电导率高,800℃时为0.08 S.m-1,是理想的高温电解质材料。     

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.