Effect of Alumina Addition on the Tetragonal-to-Monoclinic Phase Transformation in Zirconia–3 mol% Yttria

The tetragonal-to-monoclinic martensitic phase transformation in ZrO–3 mol% Y₂O₃ (PSZ) containing 0 to 12 wt% Al₂O₃ was investigated by dilatometry, XRD, and SEM-EDS methods. The propagation of the transformation into the specimen interiors was suppressed by the addition of Al₂O₃. The grain size was independent of the addition of Al₂O₃. Both Y₂O₃ and Al₂O₃ segregated at grain boundaries. From this segregation behavior, it was suggested that a certain compound or phase of Y₂O₃–Al₂O₃ could be formed at grain boundaries, which would presumably prevent the propagation of the transformation into interiors of PSZ-containing Al₂O₃.     

Strengthening of Zirconia–Alumina During Cyclic Fatigue Testing

Recent fatigue results of advanced ceramics are reviewed. It is pointed out that current statements of fatigue properties often relate to specimens with long artificial cracks; in this study, a Y-ZrO₂+Al₂O₃ ceramic is tested under cyclic stresses using specimens with natural flaws. Cyclic fatigue is restricted to a narrow range of stresses near the ultimate strength. Survivor specimens reveal increased residual strength, possibly resulting from a higher ZrO₂ phase transformation encouraged by long-term cyclic stresses.     

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.     

Phase Transformation in EB-PVD Yttria Partially Stabilized Zirconia Thermal Barrier Coatings during Annealing

Electron-beam physical-vapor-deposited thermal barrier coatings consisting of ZrO₂ stabilized by 7 wt% Y₂O₃ were investigated in regard to phase transformation after annealing. Free-standing ceramic layers were heat-treated in air, for up to 200 h, in the temperature range 1200°—1400°C and then analyzed by X-ray diffractometry. Based on information obtained from the {111} and {400} peaks, the phase composition and the Y₂O₃ content in the phases were calculated. At the start of transformation, small grains of a low-Y₂O₃ t phase and a c phase formed. After >30 h at 1300°C and at 1400°C, a mixture of a t phase deficient in Y₂O₃, an m phase, and a c phase formed after cooling, with the Y₂O₃ contents in the phases roughly predicted by the phase diagrams. The results of the present study are discussed here in detail and compared with data for plasma-sprayed coatings.     

Increase in Phase Transition Temperature of Activated Alumina with Nano-Zirconia Synthesized by Pulsed Wire Discharge

Activated alumina powders have been synthesized by using a novel dry process of pulsed wire discharge. The temperature of phase transition from activated alumina to α-alumina and its variation caused by adding zirconia have been investigated. A mixture of activated alumina and zirconia was formed by mixing zirconium plasma with aluminum plasma and cooling together in an oxygen atmosphere. It was found that the transition temperature increased when the zirconia content ratio was increased. On the other hand, results of X-ray diffraction and X-ray photoelectron spectroscopy analysis indicated no substitution of zirconium in an alumina lattice. Thus, most of the zirconium atoms were located in zirconia particles on the surface and/or the grain boundary of alumina grains. Thus, it appears that the increase in the phase transition was caused by retardation of atomic diffusion at zirconia particles.     

Diffusionless Cubic-to-Tetragonal Phase Transition and Microstructural Evolution in Sintered Zirconia–Yttria Ceramics

Microstructural changes associated with the diffusionless cubic-to-tetragonal phase transition ( c–t ') in sintered ZrO₂–Y₂O₃ ceramics with 4 to 20 mol% Y₂O₃ are investigated. Ceramics containing 4 to 7 mol% Y₂O₃ that are quickly cooled from high temperatures experience cubic-to-tetragonal transformation by a diffusionless mechanism. The TEM diffraction pattern of the transformation product, t '-ZrO₂, reveals (112) reflections that are suppressed in the c -ZrO₂ phase. The microstructural features of the t '-ZrO₂ phase include antiphase boundaries and a twinned substructure in the (112) dark-field images. The (112) reflections result from the displacement of oxygen atoms in the lattice during phase transformation. With increasing Y₂O₃ content, the antiphase domain size, the tetragonality of the lattice, and the intensity of the (112) reflections decrease. When the Y₂O₃ content reaches 8 mol% or more, the (112) reflections appear, but the dark-field image shows no antiphase boundary, and the tetragonality decreases to 1. In ceramics with 14 to 20 mol% Y₂O₃, no suppressed reflection appears because the c–t transformation is fully suppressed. A model of the lattice structure is calculated and the intensity of diffraction determined experimentally; on this basis, the mechanism of diffusionless c–t 'transformation is discussed.     

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.     

Cation Interdiffusion and Phase Stability in Polycrystalline Tetragonal Ceria–Zirconia–Hafnia Solid Solution

Zr–Hf interdiffusions were carried out at 1350° to 1520°C for polycrystalline tetragonal solid solutions of 14CeO₂·86(Zr_{1- x} Hf _x )O₂ with X = 0.02 and 0.10. Lattice and grain-boundary interdiffusion parameters were calculated from the concentration distributions by using Oishi and Ichimura's equation. Lattice interdiffusion coefficients were described by D = 3.0 × 10³ exp[-623 (kJ/mol)/ RT ] cm²/s and grain-boundary interdiffusion parameters by δ D ' = 0.29 exp[-506 (kJ/mol)/ RT ] cm³/s. The cation diffusivity was lower than the anion diffusivity. The results were compared with diffusivities in the fluorite-cubic solid solution. The critical grain radii for stabilization of the tetragonal phase in CeO₂-doped ZrO₂ were 11 and 6 μm for the solutions with 2 and 10 mol% HfO₂ substitution, respectively, both of which are much greater than in the Y₂O₃-doped ZrO₂ solid solution.     

Development of Surface Compressive Stresses in Zirconia–Alumina Composites by an Ion-Exchange Process

A two-step ion-exchange technique was developed for introducing compressive stresses on the surface of ZrO₂–Al₂O₃ composites. In the first step, a thin layer (∼250 μm) of Na-β"-Al₂O₃ was formed on the surface of the composite by a vapor-phase process at ∼1400°C. In the second step, Na⁺ ions were replaced by K⁺ ions by a heat treatment at ∼385°C for 2 h in a molten KNO₃ bath. Replacement of sodium by potassium led to the creation of surface compressive stresses. The flexural strength and Weibull modulus of ZrO₂–Al₂O₃ composite were ∼915 MPa and 10, respectively, for the as-sintered samples. By contrast, the flexural strength and Weibull modulus were ∼1140 MPa and 26, respectively, for the ion-exchanged samples. A residual surface compressive stress of ∼480 MPa was measured by a strain-gauge technique in K⁺-ion-exchanged samples. The presence of surface compressive stresses also was confirmed using an indentation technique. The technique developed here can be used to introduce compressive stresses on components of virtually any shape.     

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.     

Phase development and pore stability of yttria- and ytterbia-stabilized zirconia aerogels

High-porosity yttria- and ytterbia-stabilized zirconia aerogels offer the potential of extremely low thermal conductivity materials for high-temperature applications. Yttria- and ytterbia-doped zirconia aerogels were synthesized using a sol-gel approach over the dopant range of 0-20 atomic percent. Surface area, pore volume, and morphology of the as-dried aerogels and materials thermally exposed for short periods of time to temperatures up to 1200°C were characterized by nitrogen physisorption, scanning and transmission electron microscopy, and X-ray diffraction. The aerogels as supercritically dried all were X-ray amorphous. At a 5% dopant level, a tetragonal structure with a smaller monoclinic phase developed on thermal exposure. Mixed tetragonal and cubic phases or predominantly cubic materials were observed at higher dopant levels, depending on the dopant level, temperature and exposure time. The formation of crystalline phases was accompanied by loss of surface area and pore volume, although some mesoporous structure was maintained on short-term exposure to 1000°C. Incorporation of the smaller Yb atom into the lattice structure resulted in smaller lattice dimensions on crystallization than was seen with Y doping and favored a more highly equiaxed structure. Aerogels synthesized with 15% Y maintained the smallest particle size without evidence of sintering at 1100°C. Largest shrinkage and loss of pore volume occurred on crystallization from the amorphous phase, with further loss of pores at temperatures above 1000°C attributable to changes in lattice parameters.     

Particle Interactions in Zirconia-Toughened Alumina

In order to determine the effect of the coarse tail of the ZrO₂ size distribution of the monoclinic ZrO₂ content of zirconia-toughened alumina, quantitative hot-stage X-ray measurements were made on (1) A1₂O₃-10% Zr0₂ (submicrometer with a coarse tail >1 μm), (2) A1₂O₃-10% ZrO₂ with the coarse tail of the ZrO₂ carefully removed by centrifugation, and (3) Al₂O₃-10% ZrO₂ in which 10% of Zr0₂(1) and 90% of Zr0₂(2) were used. The monoclinic content of (3) was compared with the weighted average of(1) and (2). A disproportionate amount of monoclinic ZrO₂ was found in (3) and it was concluded that transformation of the coarse particles promotes transformation in finer particles. Microstructural examination supports this conclusion. Results were interpreted as being due both to autocatalytic transformation and to constraint relief from microcracking.     

Imaging Secondary-Ion Mass Spectroscopy Observation of the Scavenging of Siliceous Film from 8-mol%-Yttria-Stabilized Zirconia by the Addition of Alumina

The scavenging of a resistive siliceous phase via the addition of Al₂O₃ was studied, using imaging secondary-ion mass spectroscopy (SIMS), given the improved grain-boundary conductivity in 8-mol%-yttria-stabilized zirconia (8YSZ). The grain-boundary resistivity in 8YSZ decreased noticeably with the addition of 1 mol% of Al₂O₃. Strong SiO₂ segregation at the grain boundaries was observed in a SIMS map of pure 8YSZ that contained 120 ppm of SiO₂ (by weight). The addition of 1 mol% of Al₂O₃ caused the SiO₂ to gather around the Al₂O₃ particles. The present observations provided direct and visual evidence of SiO₂ segregation at the grain boundaries (which had a deleterious effect on grain-boundary conductivity) and the scavenging of SiO₂ via Al₂O₃ addition.     

Effect of Alumina Addition on the Distribution of Intergranular-Liquid Phase during Sintering of 15-mol%-Calcia-Stabilized Zirconia

In a 15-mol%-CaO-stabilized zirconia (CSZ) specimen, the grain boundaries at the surface region exhibited a lower electrical resistance than those at the inner region. However, when up to 1.5 mol% Al₂O₃ was added, the grain boundaries at the surface showed a higher resistance. These results were explained in terms of redistribution of the intergranular-liquid phase during CSZ sintering.     

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.     

Femtosecond laser microstructuring of monolithic zirconia: Effects of laser parameters on resin bond strength

This study aimed to investigate the effects of different femtosecond (fs) laser treatment protocols on the surface roughness (Ra) and shear bond strength (SBS) of resin cement to zirconia. A total of 110 zirconia specimens were divided into 11 subgroups according to the surface treatment: Control (C), airborne-particle abrasion (APA), laser irradiation applying 400 mW, 600 mW, and 800 mW of 90 fs laser pulses with 1, 5, and 10 repetitions (Fs_(400/1), Fs_(400/5), Fs_(400/10), Fs_(600/1), Fs_(600/5), Fs_(600/10), Fs_(800/1), Fs_(800/5), and Fs_{(800/10) )}, respectively). Ra values were measured using a profilometer, and topographical changes were evaluated under a scanning electron microscope. X-ray diffraction analyses were performed to determine the crystallographic changes. Self-adhesive resin cement was bonded to zirconia specimens, and SBS tests were conducted. C and Fs_(800/10) groups exhibited the lowest and the highest Ra and SBS values, respectively. Regardless of the fs laser power, application of five and 10 repetitions resulted in higher Ra values than air-abrasion. Fs_(400/10), Fs_(600/5), Fs_(600/10), Fs_(800/5), and Fs_(800/10) groups showed higher SBS values than the APA group (p < .05), while SBS of other laser groups did not differ from the APA group (p > .05). Fs laser treatment protocols used in this study may be promising for zirconia-resin bonding. However, the effects of these treatments on the mechanical properties of zirconia need evaluation.     

Influence of Tetragonality on Tetragonal-to-Monoclinic Phase Transformation during Hydrothermal Aging in Plasma-Sprayed Yttria-Stabilized Zirconia Coatings

The influence of tetragonality, which is defined as the lattice parameter ratio c / a , on the tetragonal-to-monoclinic phase transformation during hydrothermal aging was investigated in yttria-stabilized zirconia coatings. The yttria content was adjusted in the range of 4–8 mass% (denoted as x YZ, where x = 4–8 and YZ represents the yttria-stabilized zirconia). The tetragonality of the zirconia in the as-sprayed coatings was less than that in the powders. To change the tetragonality for each yttria content, the coatings were annealed at 1273 K before aging. Without annealing, the phase transformation was prevented only in 8YZ. When annealing was applied, an increase of the tetragonality (i.e., recovery of the tetragonality) was observed, and transformation during hydrothermal aging was also suppressed in 6YZ. It was concluded that the increase in tetragonality that occurred without a change in the yttria content was suggested to be caused by the lattice relaxation of the tetragonal phase, and this relaxation is believed to cause a reduction of the critical yttria concentration, thus preventing the phase transformation.     

Effect of Yttria and Yttrium-Aluminum Garnet on Densification and Grain Growth of Alumina At 1200°–1300°C

Densification and grain growth of alumina were studied with yttria or yttrium-aluminum garnet (YAG) additives at the relatively low temperatures of 1200°–1300°C. Yttria doping was found to inhibit densification and grain growth of alumina at 1200°C and, depending on dopant level, had a lesser effect at 1300°C. At 1200°C, yttria inhibits densification more than it hinders grain growth. The rate of grain growth increases faster with temperature than the rate of densification. Alumina-YAG particulate composites were difficult to sinter, yielding relative densities of only 65% and 72% after 100 h at 1200° and 1300°C, respectively. Pure YAG compacts exhibited essentially no densification for times up to 100 h at 1300°C.     

Neutron Diffraction Studies of Phase Transformations between Tetragonal and Orthorhombic Zirconia in Magnesia-Partially-Stabilized Zirconia

Neutron powder diffraction and conventional dilatometry have been used to investigate the tetragonal-to-orthorhombic phase transformation and the orthorhombic-to-tetragonal reversion in a high-toughness magnesia-partially-stabilized zirconia. For this material, the onset temperature on cooling for the tetragonal-to-orthorhombic transformation (determined by dilatometry) was 192 K, and the reversion on subsequent heating occurred between 500 and 620 K. Neutron diffraction patterns were recorded at temperatures down to 19 K then up to 664 K, and analyzed by the multiphase Rietveld method to determine the amounts of different phases as well as their lattice parameters and unit-cell volumes. It is notable that, at its maximum, the orthorhombic phase amounted to 45% of the sample by weight. Length changes were measured, using pushrod dilatometers, in the temperature range 80 to 700 K. Length changes calculated from the neutron diffraction determinations of the proportions and unit-cell volumes of the different phases are in very good agreement with the directly measured values.