In Situ Formation of Hexaferrite Magnets within a 3Y-TZP Matrix: La2O3–ZnO–Fe2O3 and BaO–Fe2O3 Systems

The in situ formation of magnetoplumbite-type (M-type) hexaferrites within a 3Y-TZP matrix was examined for the La₂O₃–ZnO–Fe₂O₃ and BaO–Fe₂O₃ systems. The formation of barium hexaferrite (Ba-M) was rapid enough at a temperature of 1300°C for 2 h to result in a uniform dispersion of fine Ba-M particles in a tetragonal zirconia polycrystal (TZP) matrix. However, the formation of lanthanum-substituted hexaferrite (La-M) was rather sluggish, despite the existence of a charge-compensating divalent oxide. The 3Y-TZP/20-wt%-BaFe₁₂O₁₉ in situ composite possessed good magnetic properties, as well as moderately good mechanical properties.     

High-Strain-Rate Superplasticity in Y2O3-Stabilized Tetragonal ZrO2 Dispersed with 30 vol% MgAl2O4 Spinel

High-strain-rate superplasticity is attained in a 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystal (3Y-TZP) dispersed with 30 vol% MgAl₂O₄ spinel: tensile elongation at 1823 K reached >300% at strain rates of 1.7 × 10⁻²– 3.3 × 10⁻¹ s⁻¹. The flow behavior and the microstructure of this material indicate that the MgAl₂O₄ dispersion should enhance accommodation processes necessary for grain boundary sliding. Such an effect is assumed to arise from an enhancement of the cation diffusion by the dissolution of Al and Mg ions into the ZrO₂ matrix and from stress relaxation due to the dispersed MgAl₂O₄ grains.     

Room-Temperature Aging of Laminate Composites of Alumina/3-mol%-Yttria-Stablilized Tetragonal Zirconia Polycrystals

The stresses of laminate structures obtained by joining single layers of pure alumina (A), pure yttria-stabilized tetragonal zirconia, 3Y-TZP (Z), and an intimate mixture of alumina and zirconia (AZ) have been determined by fluorescence (in alumina) and Raman (in zirconia) piezospectroscopy. Three symmetrical stacking sequences were examined, namely, A/Z/A, A/AZ/A, and AZ/Z/AZ, with the aim of designing structures where the higher coefficient of thermal expansion (CTE) of zirconia could be used to induce compressive stress in the external layers (and ensuing tensile stress in the central layer). Two experimental sessions, 6 years apart, were conducted on the same samples, also taking care to record the spectra from the same locations; during the time elapsed between the two sessions, the samples were kept at room temperature and humidity. The stress values in alumina obtained during the more recent session were markedly different from those observed in the first session. Monoclinic zirconia ( m -zirconia) was absent in all samples in the first session, whereas up to 25 vol% zirconia could be observed during the second session. m -Zirconia could only be observed in AZ layers and not in Z layers, irrespective of the position in the stacking sequence. It was concluded that 3Y-TZP underwent spontaneous tetragonal-to-monoclinic ( t – m ) transformation, that is, "aging," when mixed with alumina at the grain-size level. Aging occurred only where pristine t -zirconia was subject to tensile stresses larger than ∼400 MPa.     

Effect of Carbon Reduction on the Properties of 13 mol% Tio2─3 mol% Y2O3─84 mol% ZrO2

Fully tetragonal and sintered 13 mol% TiO₂─3 mol% Y₂O₃─84 mol% ZrO₂ was thermally treated at 1300°C for 1 h in argon in the presence of carbon. No phase changes occurred on the as-received surface and in the bulk of the material, but t → m transformation occurred on polished surfaces under reducing conditions, and it resulted in increased fracture toughness, Young's modulus, and modulus of rigidity. Deoxidation of the system occurred and 0.174 wt% of carbon was found in the sample. This seemed to stabilize the tetragonal phase.     

Conversion from β-Ce2O3·11Al2O3 to α-Al2O3 in Tetragonal ZrO2 Matrix

Composites of β-Ce₂O₃·11Al₂O₃ and tetragonal ZrO₂ were fabricated by a reductive atmosphere sintering of mixed powders of CeO₂, ZrO₂ (2 mol% Y₂O₃), and Al₂O₃. The composites had microstructures composed of elongated grains of β-Ce₂O₃·11Al₂O₃ in a Y-TZP matrix. The β-Ce₂O₃·11Al₂O₃ decomposed to α-Al₂O₃ and CeO₂ by annealing at 1500°C for 1 h in oxygen. The elongated single grain of β-Ce₂O₃·11Al₂O₃ divided into several grains of α-Al₂O₃ and ZrO₂ doped with Y₂O₃ and CeO₂. High-temperature bending strength of the oxygen-annealed α-Al₂O₃ composite was comparable to the β-Ce₂O₃·11Al₂O₃ composite before annealing.     

Grain Size Control of Tetragonal Zirconia Polycrystals Using the Space Charge Concept

Grain growth kinetics and grain-boundary segregation of 12Ce-TZP and 2Y-TZP, containing divalent to pentavalent cationic dopants, were studied. In all cases, normal grain growth follwing the parabolic growth relation was observed at higher temperatures. The mobility of grain boundaries was suppressed by the addition of divalent and trivalent cations, unchanged or enhanced by the addition of tetravalent and pentavalent cations. Larger cations have a stronger effect in suppressing grain growth. From ESCA, AES, and STEM analysis of the near grain-boundary regions, it is further concluded that only divalent and trivalent cations segregate. These observations can be satisfactorily rationalized using the space charge concept and the model of impurity drag.     

Diffusion-Induced Grain-Boundary Migration in Ceria-Stabilized Tetragonal Zirconia Polycrystals

The microstructure and microchemistry of grain-boundary regions in (CeO₂+ La₂O₃)-stabilized tetragonal ZrO₂ polycrystals (Ce(La)-TZP) were studied by means of transmission electron microscopy (TEM). Evidence was found for the existence of crystalline and vitreous intergranular phases situated in small pockets at multiple grain junctions and in thin films along grain boundaries. In this ceramic system grain-boundary migration was observed in situ in the TEM in sample areas subjected to electron irradiation. Interfaces migrated away from their centers of curvature. Evidence was found for Ce de-alloying in the volume swept by the advancing boundaries. It is suggested that the coherency lattice strain brought about by a partial reduction of Ce, resulting in the diffusion of Ce³⁺ along grain boundaries to free surfaces, is the driving force for this phenomenon.     

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.     

Shape Memory-Like Effect Phenomena in a Ce-TZP/Al2O3 Composite

During an investigation of the role of alumina particles in ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP)¹ we observed that a group of samples (based on a Ce-TZP matrix (8.5 mol% Ceria) containing 15 vol% dispersed alumina particles), exhibited an extended plastic deformation after the first elastic response. This deformation could be retained upon a prompt unloading from a fourpoint bend jig. These deformed (bent) specimens recovered their original straight shape when heated above 200°C, exhibiting features like the shape memory effect (SME). A careful examination of the samples revealed the presence of wedgelike transformation zones intruding the bulk of the specimen inwards from the tensioned side.
In an attempt to increase the degree of bending, other samples of the same composition and microstructure have been placed under a static load and maintained under that condition for ≅15 min. The penetration depth of the transformation zone reached the opposite face of the samples and the monoclinic-phase concentration rose about 50% on both sides. Through this inwards movement, these samples, that were initially bent, showed an elongation of about 0.5% and became straightened. These samples returned to their original size after heating at ≅250°C. To get a deeper insight, samples have been examined by X-ray diffraction (XRD), differential thermal analysis (DTA), and thermodilatometry (TD).     

Deformation of Monoclinic ZrO2 Polycrystals and Y2O3-Stabilized Tetragonal ZrO2 Polycrystals below the Monoclinic–Tetragonal Transition Temperature

Ultrafine-grained monoclinic ZrO₂ polycrystals (MZP) and 3-mol%-Y₂O₃-stabilized tetragonal ZrO₂ polycrystals (3Y-TZP) were obtained by hot isostatic pressing (HIP). Both MZP and TZP were "high-purity" materials with impurities less than 0.1 wt%. The deformation behavior was studied at 1373 K, which was lower than the monoclinic ↔ tetragonal transition temperature. The stress exponent of 3Y-TZP with grain size of 63 nm was 3 in the higher stress region, and increased from 3 to 4 with decreasing stress. The deformation of MZP was characterized by a stress exponent of 2.5 over a wide stress range. The strain rate of 3Y-TZP was slower than that of MZP by 1 order of magnitude. It was suggested that either the doped yttrium or the difference in the crystal structure affected the diffusion coefficients of ZrO₂.     

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.     

Solid-Solution Effects of a Small Amount of Nickel Oxide Addition on Phase Stability and Mechanical Properties of Yttria-Stabilized Tetragonal Zirconia Polycrystals

Stability and mechanical properties of the tetragonal phase were investigated for NiO-doped yttria-stabilized tetragonal zirconia polycrystal (Y-TZP) systems. Only 0.3 mol% of NiO in solid solution could be added to the Y-TZP while maintaining the tetragonal phase. Fracture toughness improved remarkably on addition of a small amount of NiO. Raman spectroscopy analysis around cracks introduced by Vickers indentation revealed that the amount of monoclinic phase transformed from tetragonal phase was increased. It was confirmed that fracture toughness improvement was due not only to increased grain size, but also to Y-TZP destabilization by solid solution of NiO.     

Changes in Aging Behavior and Defect Structure of Yttria-Fully-Stabilized ZrO2 with Sc2O3 Doping

Methods of suppressing decreased conductivity in 8 mol% Y₂O₃-stabilized–92 mol% ZrO₂ (8YSZ) with aging were investigated. Different amounts of Sc₂O₃ were doped into 8YSZ. The electrochemical properties of Sc₂O₃-doped 8YSZ were measured, and the microstructural and local structural changes were characterized. The present results indicate that an appropriate amount of Sc₂O₃ doping, 3 or 4 mol%, effectively suppresses decreased conductivity with aging in 8YSZ.     

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.     

Stabilization of Tetragonal ZrO2 in ZrO2–SiO2 Binary Oxides

Gel-glasses of various compositions in the x ZrO₂^.(10 – x )SiO₂system were fabricated by the sol–gel process. Precipitation due to the different reactivities between tetraethyl orthosilicate (TEOS) and zirconium(IV) n -propoxide has been eliminated through the use of 2-methoxyethanol as a chelating agent. Thermal treatment of these gels produced crystalline ZrO₂particles. While monoclinic is the stable crystalline phase of zirconia at low temperatures, the metastable tetragonal phase is usually the first crystalline phase formed on heat treatment. However, stability of the tetragonal phase is low, and it transforms to the monoclinic phase on further heat treatment. In this study, it has been found that the transformation temperature increases as the SiO₂content in the ZrO₂–SiO₂ binary oxide increases. The most significant results were from samples containing only 2 mol% SiO₂, where the metastable tetragonal phase formed at low temperatures and remained stable over a broad temperature range. X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy were used to elucidate the structure of these binary oxides as a function of temperature.     

Microstructure and Short-Term Oxidation of Hot-Pressed Si3N4/ZrO2(+Y2O3) Ceramics

Composite ceramic materials based on Si₃N₄ and ZrO₂ stabilized by 3 mol% Y₂O₃ have been formed using aluminum isopropoxide as a precursor for the Al₂O₃ sintering aid. Densification was carred out by hot-pressing at temperatures in the range 1650° to 1800°C, and the resulting micro-structures were related to mechanical properties as well as to oxidation behavior at 1200°C. Densification at the higher temperatures resulted in a fibrous morphology of the Si₃N₄ matrix with consequent high room-temperature toughness and strength. Decomposition of the ZrO₂ grains below the oxidized surface during oxidation introduced radial stresses in the subscalar region, and from the oxidation experiments it is suggested that the ZrO₂ incorporated some N during densification.     

Creep Deformation and the Grain-Boundary Resistivity of Tetragonal Zirconia Polycrystalline Materials

The grain-boundary resistivity of tetragonal zirconia polycrystals, which had undergone creep with different applied compressive loads and at different temperatures, has been measured with impedance spectroscopy. A stress exponent of unity was determined from strain rate versus stress data. The grain-boundary resistivity decreased significantly with increasing stress at a constant creep temperature indicating squeezing out of the glassy phase from interfaces between grains. This, however, had no effect on the activation energy for the grain-boundary resistivity.     

Crack Resistance and Fatigue of Transforming Ceramics: II, CeO2-Stabilized Tetragonal ZrO2

Crack resistance characteristics and fatigue properties have been investigated in Ce-TZP ceramics with different grain sizes. The relatively low critical transformation stress allows the development of larger transformation zones (≦200 μm), leading to flaw-tolerant behavior. However, autocatalytic transformation processes are found to be bound to grain sizes beyond a critical value; transformation is then very limited in finer microstructures. Fatigue as a specific cyclic effect is more pronounced in microstructures with larger grains. Thus, damaging processes in the course of extensive t–m transformation are suspected to be intensified during cyclic loading.     

Phase Relationships in the Si3N4–SiO2–Lu2O3 System

Phase relationships in the Si₃N₄–SiO₂–Lu₂O₃ system were investigated at 1850°C in 1 MPa N₂. Only J-phase, Lu₄Si₂O₇N₂ (monoclinic, space group P 2₁/ c , a = 0.74235(8) nm, b = 1.02649(10) nm, c = 1.06595(12) nm, and β= 109.793(6)°) exists as a lutetium silicon oxynitride phase in the Si₃N₄–SiO₂–Lu₂O₃ system. The Si₃N₄/Lu₂O₃ ratio is 1, corresponding to the M-phase composition, resulted in a mixture of Lu–J-phase, β-Si₃N₄, and a new phase of Lu₃Si₅ON₉, having orthorhombic symmetry, space group Pbcm (No. 57), with a = 0.49361(5) nm, b = 1.60622(16) nm, and c = 1.05143(11) nm. The new phase is best represented in the new Si₃N₄–LuN–Lu₂O₃ system. The phase diagram suggests that Lu₄Si₂O₇N₂ is an excellent grain-boundary phase of silicon nitride ceramics for high-temperature applications.     

Compatibility Relations of A1203 in the System Zr02-Al203-Si02-CaO

Compatibility relations of Al₂0₃ in the quaternary system Zr02-Al₂0₃-Si0₂-CaO were studied by firing and quenching followed by microscopy and energy-dispersive X-ray examination. A projection of the boundary surface of the primary crystallization volume of Al₂0₃ was constructed in terms of the CaO, Si0₂, and Zr0₂ contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, are defined, and the positions of the isotherms were established.