Characterization of Interfacial Reactions Between β-Al2O3 and Y2O3-Partially-Stabilized ZrO2

The interfacial reaction between Y₂O₃-partially-stabilized ZrO₂ and α-Al₂O₃ was studied. It was noted that α-Al₂O₃ forms inside the periphery of the β-Al₂O₃ grains; its formation suggests the loss of Na₂O from the p-Al₂O₃, either by evaporation or by dissolution in the ZrO₂ matrix. The presence of Na₂ZrO₃ is suspected.     

Growth of α-Al2O3 Crystals by Na2O Evaporation

A technique for growing α-Al₂O₃ crystals is described in which Na₂O·11Al₂O₃ is dissolved in a liquid of composition Na₂O·4TiO₂·3Al₂O₃. Alpha Al₂O₃ is precipitated as Na₂O evaporates from the system; Na₂O·11Al₂O₃ serves as a source of Al₂O₃, and Na₂O in the liquid. The content of solids in the mixture is always such that it does not melt completely. The size of the α-Al₂O₃ crystals grown is related to the Na₂O content of the composition. Crystals as large as 4000 by 3000 μm in the α-axis direction and 500 μm in the c -axis direction have been grown.     

High-Temperature Strength and Fracture Toughness of Y2O3-Partially-Stabilized ZrO2/Al2O3 Composites

The temperature dependence of bending strength, fracture toughness, and Young's modulus of composite materials fabricated in the ZrO₂ (Y₂O₃)-Al₂O₃ system were examined. The addition of A1203 enhanced the high-temperature strength. Isostatically hot-pressed, 60 wt% ZrO₂ (2 mol% Y₂O₃)/40 wt% Al₂O₃ exhibited an extremely high strength, 1000 MPa, at 1000°C.     

Metastable Phase Formation in Plasma-Sprayed ZrO2 (Y2O3)–Al2O3

Rapidly solidified ZrO₂ (Y₂O₃)–Al₂O₃ powders were prepared by melting fine-particle aggregates in a high-enthalpy plasma flame and then rapidly quenching them in cold water or on a copper chill plate. To ensure complete melting and homogenization of all the particles before quenching, the water-quenching treatment was often repeated two or even three times. The resulting melt-quenched powders and splats displayed a variety of metastable structures, depending on composition and cooling rate. ZrO₂-rich material developed an extended solid solution phase, whereas eutectic material formed a nanofibrous or amorphous structure. Under high cooling rate conditions, the ZrO₂-rich material developed a nanocomposite structure ( t -ZrO₂+α-Al₂O) directly by melt-quenching, whereas, more typically, such a structure was developed only after postannealing of the as-quenched metastable material.     

Growth of Tabular α-Al2O3 Grains on Porous Alumina Substrate

Gradient, porous alumina ceramics were prepared with the characteristics of microsized tabular α-Al₂O₃ grains grown on a surface with a fine interlocking feature. The samples were formed by spin-coating diphasic aluminosilicate sol on porous alumina substrates. The sol consisted of nano-sized pseudo-boehmite (AlOOH) and hydrolyzed tetraethyl orthosilicate [Si(OC₂H₅)₄]. After drying and sintering at 1150°–1450°C, the crystallographic and chemical properties of the porous structures were investigated by analytical electron microscopy. The results show that the formation of tabular α-Al₂O₃ grains is controlled by the dissolution of fine Al₂O₃ in the diphasic material at the interface. The nucleation and growth of tabular α-Al₂O₃ grains proceeds heterogeneously at the Al₂O₃/glass interface by ripening nano-sized Al₂O₃ particles.     

Formation and Transformation of Cubic ZrO2 Solid Solutions in the System ZrO2—Al2O3

In the system ZrO₂-Al₂O₃, cubic ZrO₂ solid solutions containing up to 40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials prepared by the simultaneous hydrolysis of zirconium and aluminum alkoxides. The values of the lattice parameter, a, increase linearly from 0.5095 to 0.5129 nm with increasing Al₂O₃ content. At higher temperatures, the solid solutions transform into tetragonal ZrO₂ and α-Al₂O₃. Pure ZrO₂ crystallizes in the tetragonal form at 415° to 440°C.     

Effect of α to β (β') Phase Transition on the Sintering of Silicon Nitride Ceramics

By using α-Si₃N₄ and β-Si₃N₄ starting powders with similar particle size and distribution, the effect of α-β (β') phase transition on densification and microstructure is investigated during the liquid-phase sintering of 82Si₃N₄·9Al₂O₃·9Y₂O₃ (wt%) and 80Si₃N₄·13Al₂O₃·5AIN·5AIN·2Y₂O₃. When α-Si₃N₄ powder is used, the grains become elongated, apparently hindering the densification process. Hence, the phase transition does not enhance the densification.     

Influence of the Y2O3 Content and Temperature on the Mechanical Properties of Melt-Grown Al2O3–ZrO2 Eutectics

The effect of Y₂O₃ content on the flexure strength of melt-grown Al₂O₃–ZrO₂ eutectics was studied in a temperature range of 25°–1427°C. The processing conditions were carefully controlled to obtain a constant microstructure independent of Y₂O₃ content. The rod microstructure was made up of alternating bands of fine and coarse dispersions of irregular ZrO₂ platelets oriented along the growth axis and embedded in the continuous Al₂O₃ matrix. The highest flexure strength at ambient temperature was found in the material with 3 mol% Y₂O₃ in relation to ZrO₂(Y₂O₃). Higher Y₂O₃ content did not substantially modify the mechanical response; however, materials with 0.5 mol% presented a significant degradation in the flexure strength because of the presence of large defects. They were nucleated at the Al₂O₃–ZrO₂ interface during the martensitic transformation of ZrO₂ on cooling and propagated into the Al₂O₃ matrix driven by the tensile residual stresses generated by the transformation. The material with 3 mol% Y₂O₃ retained 80% of the flexure strength at 1427°C, whereas the mechanical properties of the eutectic with 0.5 mol% Y₂O₃ dropped rapidly with temperature as a result of extensive microcracking.     

Microstructures of Y2O3-Stabilized ZrO2 Electron Beam-Physical Vapor Deposition Coatings on Ni-Base Superalloys

The microstructures of ZrO₂–20 wt% Y₂O₃ thermal barrier coatings formed by electron beam-physical vapor deposition on a Nibase superalloy have been studied by transmission electron microscopy. The coating systems consist of several layers, including a superalloy substrate, a bond coat, an Al₂O₃ scale, and the PVD coating. The overall ceramic thermal barrier coatings were characterized, with special emphasis being given to the α-Al₂O₃ scale which forms between the bond coat and the ZrO₂₋Y₂O₃ coating. The oxide scale exhibited various morphologies in different coating systems; the majority of the porosity formed in this region for all coatings.     

Influence of Cr and Fe on Formation of α-Al2O3 from γ-Al2O3

The effect of Cr and Fe in solid solution in γ-Al₂O₃ on its rate of conversion to α-Al₂O₃ at 1100°C was studied by X-ray diffraction. The δ form of Al₂O₃ was the principal intermediate phase produced from both pure γ-Al₂O₃ and that containing Fe³⁺ in solid solution, although addition of Fe greatly reduced crystallinity. Reflectance spectra and magnetic susceptibilities showed that Cr exists as Cr⁶⁺ in γ-Al₂O₃ and as Cr³⁺ in α-Al₂O₃, with θ-Al₂O₃ as the intermediate phase. The intermediates formed rapidly, and the rates of their conversion to α-Al₂O₃ were increased by 2 and 5 wt% additions of Fe and decreased by 2 and 4 wt% additions of Cr. An approximately linear relation observed between α-Al₂O₃ formation and decrease in specific surface area was only slightly affected by the added ions. This relation can be explained by a mechanism in which the sintering of δ- or θ-Al₂O₃, within the aggregates of their crystallites, is closely coupled with conversion of cubic to hexagonal close packing of O^2- ions by synchro-shear.     

Modification of αAI2O3 Platelet/ZrO2 Matrix Interface by Epitaxial Growth of β-AI2O3 on the α-AI2O3

An epitaxial β-alumina crystal growth method was used to modify α-AI₂O₃ platelet surfaces before inclusion as a reinforcing phase in partially stabilized zirconia (3Y-TZP). The as-grown surface phase was Na-β"-AI₂O₃. This was converted to Ca-β"-AI₂O₃ by ion exchange, as the latter is more temperature-stable at composite sintering temperatures. The conditions of formation, thermal stability, and chemical compatibility of these interfacial phases were examined. α-AI₂O₃ platelets with Ca-β"-AI₂O₃ film were incorporated into 3Y-TZP. The β"-AI₂O₃/ZrO₂ interface was found to promote platelet debonding and pullout, thus enhancing the α-AI₂O₃ platelet/crack interactions during the fracture process.     

Effect of Monovalent Cation Additives on the γ-Al2O3-to-α-Al2O3 Phase Transition

The effect of monovalent cation addition on the γ-Al₂O₃-to-α-Al₂O₃ phase transition was investigated by differential thermal analysis, powder X-ray diffractometry, and specific-surface-area measurements. The cations Li⁺, Na⁺, Ag⁺, K⁺, Rb⁺, and Cs⁺ were added by an impregnation method, using the appropriate nitrate solution. β-Al₂O₃ was the crystalline aluminate phase that formed by reaction between these additives and Al₂O₃ in the vicinity of the γ-to-α-Al₂O₃ transition temperature, with the exception of Li⁺. The transition temperature increased as the ionic radii of the additive increased. The change in specific surface area of these samples after heat treatment showed a trend similar to that of the phase-transition temperature. Thus, Cs⁺ was concluded to be the most effective of the present monovalent additives for enhancing the thermal stability of γ-Al₂O₃. Because the order of the phase-transition temperature coincided with that of the formation temperature of β-Al₂O₃ in these samples, suppression of ionic diffusion in γ-Al₂O₃ by the amorphous phase containing the added cations must have played an important role in retarding the transition to α-Al₂O₃. Larger cations suppressed the diffusion reaction more effectively.     

High-Toughness Ce-TZP/Al2O3 Ceramics with Improved Hardness and Strength

Simulataneous additions of SrO and Al₂O₃ to ZrO₂ (12 mol% CeO₂) lead to the in situ formation of strontium aluminate (SrO · 6Al₂O₃) platelets (∼0.5 μm in width and 5 to 10 μm in length) within the Ce-TZP matrix. These platelet-containing Ce-TZP ceramics have the strength (500 to 700 MPa) and hardness (13 to 14 GPa) of Ce-TZP/Al₂O₃ while maintaining the high toughness (14 to 15 MPa ± m^1/2) of Ce-TZP. Optimum room-temperature properties are obtained at SrO/Al₂O₃ molar ratios between 0.025 and 0.1 for ZrO₂ (12 mol% CeO₂) with starting Al₂O₃ contents ranging between 15 and 60 vol%. The role of various toughening mechanisms is discussed for these composite ceramics.     

Strength and Fracture Toughness of Isostatically Hot-Pressed Composites of Al2O3 and Y2O3-Partially-Stabilized ZrO2

Composites of Al₂O₃ and Y₂O₃ partially-stabilized ZrO₂ were isostatically hot-pressed using submicrometer powders as the starting material. The addition of Al₂O₃ resulted in a large increase in bending strength. The average bending strength for a composite containing 20 wt% Al₂O₃ was 2400 MPa, and its fracture toughness was 17 MN·w^−3/2     

Microstructure, Conductivity, and NO2 Sensing Characteristics of α-Al2O3-Doped (8 mol% Sc2O3)ZrO2 Composite Solid Electrolyte

α-Al₂O₃-doped (8 mol % Sc₂O₃)ZrO₂ composite solid electrolyte has been investigated in the fabrication of solid-state ceramic gas sensors. The microstructure and electrical conductivity of the composite solid electrolyte have been measured over a range of temperature from 240°C to 596°C. The composite solid electrolyte has been found to exhibit a higher conductivity compared with the commonly used (8 mol% Y₂O₃)ZrO₂ at temperatures above ∼448°C. The sensing characteristics for NO₂ detection have been studied in the temperature range of 500–650°C at the low concentration from 10 to 30 ppm and at high concentration from 100 to 500 ppm of NO₂. The NO₂ sensor was found to respond reproducibly and rapidly to the variations of NO₂, concentration, indicating that the composite solid electrolyte has promising application as a solid electrolyte for on-board exhaust gas monitoring.     

Neutron Diffraction Measurements of the Residual Stresses in Al2O3-ZrO2 (CeO2) Ceramic Composites

High-resolution neutron powder diffraction was used to study the residual stresses in Al₂O₃-ZrO₂ (12 mol% CeO₂) ceramic composites containing 10, 20, and 40 vol% ZrO₂ (CeO₂). The diffraction data were analyzed using the Rietveld structure refinement technique. The analysis shows that for all samples, the CeO₂-stabilized tetragonal ZrO₂ particles are in tension and the Al₂O₃ matrix is in compression. For both the ZrO₂ particles and the Al₂O₃ matrix, the average lattice strains are anisotropic and increase approximately linearly with a decrease in the corresponding phase content. It is shown that these features can be qualitatively understood by taking into consideration the thermal expansion mismatch between the ZrO₂ and Al₂O₃ grains. Also, for all composite samples, the diffraction peaks are broader than the instrumental resolution, indicating that the strains in these samples are inhomogeneous. From an analysis of the refined peak shape parameters, the average root-meansquare strain, which describes the distribution of the inhomogeneous strain field, was determined. Finally, the average residual stresses were evaluated from the experimentally determined average lattice strains and compared with recent results of X-ray measurements on similar composites.     

Residual α–Si3N4 in O' Crystals in CeO2-Doped O'+β' SiAlON Ceramics

The microstructure of a pressureless sintered (1605°C, 90 min) O'+β' SiAlON ceramic with CeO₂ doping has been investigated. It is duplex in nature, consisting of very large, slablike elongated O' grains (20–30 μm long), and a continuous matrix of small rodlike β' grains (< 1.0 μm in length). Many α-Si₃N₄ inclusions (0.1–0.5 μm in size) were found in the large O' grains. CeO₂-doping and its high doping level as well as the high Al₂O₃ concentration were thought to be the main reasons for accelerating the reaction between the α-Si₃N₄ and the Si-Al-O-N liquid to precipitate O'–SiAlON. This caused the supergrowth of O' grains. The rapid growth of O' crystals isolated the remnant α–Si₃N₄ from the reacting liquid, resulting in a delay in the α→β-Si₃N₄ transformation. The large O' grains and the α-Si₃N₄ inclusions have a pronounced effect on the strength degradation of O'+β' ceramics.     

Size Control of α-Al2O3 Platelets Synthesized in Molten Na2SO4 Flux

α-Al₂O₃ platelet powders were synthesized in molten Na₂SO₄ flux. The size of α-Al₂O₃ platelets was significantly reduced when partially decomposed rather than pure Al₂(SO₄)₃ was used as the source of Al₂O₃; a further reduction in the platelet size was realized through additional seeding with nanosized α-Al₂O₃ seeds. The addition of microsized α-Al₂O₃ platelet seeds significantly influenced the platelet morphology of the final powder, as well. The platelet size of the final powder was in direct proportion to the size of the platelet seeds, and was in reverse proportion to the cube root of the platelet seed content.     

Development of Nano-Composite Microstructures in ZrO2-Al2O3 via the Solution Precursor Method

Aqueous mixtures of zirconium acetate and aluminum nitrate were pyrolyzed and crystallized to form a metastable solid solution, Zr_{1- x} Al _x O_{2− x /2} ( x < 0.57). The initial, metastable phase partitions at higher temperatures to form two metastable phases, viz., t −ZrO₂+γ-Al₂O₃ with a nano-scale microstructure. The microstructural observations associated with the γ- →α-Al₂O₃ phase transformation in the t -ZrO₂ matrix are reported for compositions containing 10, 20, and 40 mol% A1₂O₃. During this phase transformation, the α-Al₂O₃ grains take the form of a colony of irregular, platelike grains, all with a common crystallographic orientation. The plates contain ZrO₂ inclusions and are separated by ZrO₂ grains. The volume fraction of A1₂O₃ and the heat treatment conditions influence the final microstructure. At lower volume fractions of A1₂O₃, the colonies coarsen to single, irregular plates, surrounded by polycrystalline ZrO₂. Interpenetrating microstructures produced at high volume fractions of A1₂O₃ exhibit very little grain growth for periods up to 24 h at 1400°C.     

Refractory α-SiAlON Containing La2O3

Refractory Y-α-SiAlON with elongated grain morphology was obtained by utilizing La₂O₃ as a densification aid, which resulted in excellent room-temperature and high-temperature strength. Room-temperature strength of 1000 MPa was achieved when La₂O₃ was augmented by adding Y₂O₃ or removing AlN. With only La₂O₃, a temperature-independent strength of 800–950 MPa was maintained up to 1100°C, then gradually decreasing by 25% when reaching 1300°C. The R-curve measurements of fracture toughness showed relatively little dependence on microstructure, consistent with a strong interface that suppresses grain boundary decohesion. Compared with other densification aids such as SiO₂, Al₂O₃, Sc₂O₃, Y₂O₃, and Lu₂O₃, a finer microstructure was obtained by using La₂O₃. High nitrogen content in the residual La–Si–Al–O–N glass in equilibrium with the nitrogen-rich α-SiAlON is suggested to be the cause of these findings.