Effect of a Liquid Phase on the Morphology of Grain Growth in Alumina

In this investigation we have studied how the presence of a liquid phase affects the grain morphology and grain growth kinetics in Al₂O₃ at 1800°C using the growth of both matrix grains and large spherical single-crystal seeds growing into the matrix. The growth rates of the matrix grains were found to decrease in the following order: undoped Al₂O₃, AI₂O₃ with anorthite, AI₂O₃ with anorthite and MgO, and Al₂O₃ with MgO. Except for the samples doped with MgO alone, the matrix grains were faceted and appeared tabular in polished sections. In samples containing anorthite both with and without MgO, the single-crystal seeds exhibit basal facets with continuous liquid films and slow growth in the 〈0001〉 relative to all other crystallographic directions. When only MgO is added, the growth of the single-crystal seeds was not isotropic; however, no faceting was observed. We discuss how anisotropic growth rates caused by the anorthite additions can stimulate discontinuous grain growth in Al₂O₃.     

Growth of Single-Crystal and Polycrystalline Thin Films of MgAl2O4 and MgFe2O4

Single-crystal and polycrystalline films of Mg-Al₂O₄ and MgFe₂O₄ were formed by two methods on cleavage surfaces of MgO single crystals. In one procedure, aluminum was deposited on MgO by vacuum evaporation. Subsequent heating in air at about 510°C formed a polycrystalline γ-Al₂O₈ film. Above 540°C, the γ-Al₂O, and MgO reacted to form a single-crystal MgAl₂O₄ film with {001} MgAl₂O₄‖{001} MgO. Above 590°C, an additional layer of MgAl₂O₄, which is polycrystalline, formed between the γ-Al₂O₃ and the single-crystal spinel. Polycrystalline Mg-Al₂O₄ formed only when diffusion of Mg²⁺ ions proceeded into the polycrystalline γ-Al₂O₃ region. Corresponding results were obtained for Mg-Fe₂O₄. MgAl₂O₄ films were also formed on cleaved MgO single-crystal substrates by direct evaporation, using an Al₂O₃ crucible as a source. Very slow deposition rates were used with source temperatures of ∼1350°C and substrate temperatures of ∼800°C. Departures from single-crystal character in the films may arise through temperature gradients in the substrate.     

New Sol–Gel Route for the Preparation of Pure α-Alumina at 950°C

An anhydrous alumina (Al₂O₃) sol was prepared from aluminum isopropoxide and an organic solvent, using an acetic acid stabilizer. The complete conversion of the dried sol to α-Al₂O₃ was accomplished at a temperature of 950°C by a single transition via γ-Al₂O₃. Al₂O₃ that was deposited via dip coating resulted in amorphous films, even after annealing at 1100°C, because of the silicon diffusion from the substrate. This phenomenon was avoided using a rapid thermal treatment in a flame after dip coating, which resulted in uniform thin films that are converted to α-Al₂O₃ via heat treatment.     

Preparation and Analysis of a Silicon Carbide Composite Membrane

Silicon carbide (SiC) porous substrates, containing alumina (Al₂O₃) dopant levels of 3, 5, and 8 wt%, are prepared by slip casting and sintering in the temperature range of 1450°–1800°C. The linear shrinkage, bulk density, and pore size of the sintered substrate increase as the sintering temperature and the amount of dopant increase. A large amount of β-phase SiC is transformed to α-phase SiC if the dopant concentration is 5 or 8 wt%. The flexural strength of the substrate doped with 8 wt% Al₂O₃ is higher than that of the substrate doped with 3 wt% Al₂O₃; however, the Weibull modulus of the former is lower. SiC composite membranes of improved selectivity and strength are fabricated by coating the porous substrate with layers of lower Al₂O₃ contents at lower sintering temperatures.     

Effects of Brazing Time and Temperature on the Microstructure and Mechanical Properties of Aluminum Air Brazed Joints

High-purity aluminum foil was used to join alumina substrates directly in air at temperatures ranging from 800° to 1200°C and soak times of 1–100 h. It was found that the bend strengths of the resulting Al₂O₃/Al/Al₂O₃ joints generally increase with increasing brazing temperature and time, with a maximum bend strength of 135 MPa on average achieved in samples joined at 1200°C for 100 h. Additionally it was determined that measurable ductility is retained in the joint even after exposure under extended high-temperature conditions. During joining, an Al₂O₃ scale forms along the interface between the aluminum and adjacent substrates. An increase in brazing temperature and/or time leads to intergrowth and sintering between this thermally grown oxide layer and the substrate surface, which appears to be the primary source of improved joint strength. Fracture analysis indicates that the Al₂O₃/Al/Al₂O₃ joints generally fail via one of three mechanisms, (1) by de-bonding along the foil/substrate interface in specimens that were joined at low temperature or held at temperature for an insufficient period of time; (2) by ductile rupture in specimens that were joined at conditions that promoted sintering between the oxidized foil and adjacent alumina faying surfaces, but left behind a continuous residual aluminum layer within the joint; or (3) by mixed-mode fracture in specimens joined at high temperature and long exposure times, in which the thermally grown alumina that forms between the two substrates is interrupted by dispersed pockets of residual aluminum metal.     

The System Al2O3-Cr2O3-Sio2

Liquidus phase equilibrium data are presented for the system Al₂O₃-Cr₂O₃-SiO₂. The liquidus diagram is dominated by a large, high-temperature, two-liquid region overlying the primary phase field of corundum solid solution. Other important features are a narrow field for mullite solid solution, a very small cristobalite field, and a ternary eutectic at 1580°C. The eutectic liquid (6Al₂O₃-ICr₂O₃-93SiO₂) coexists with a mullite solid solution (61Al₂O₃-10Cr₂O₃-29SiO₂), a corundum solid solution (19Al₂O₃-81Cr₂O₃), and cristobalite (SO₂). Diagrams are presented to show courses of fractional crystallization, courses of equilibrium crystallization, and phase relations on isothermal planes at 1800°, 1700°, and 1575°C. Tie lines were sketched to indicate the composition of coexisting mullite and corundum solid solution phases.     

Coarsening of Lamellar Microstructures in Directionally Solidified Yttrium Aluminate/Alumina Eutectic Fiber

Coarsening of the fine lamellar structure of a directionally solidified Y₃Al₅O₁₂ (yttrium aluminum garnet, YAG)/Al₂O₃ eutectic fiber at elevated temperatures was investigated. The fibers were grown continuously by an edge-defined film-fed growth (EFG) technique. To study the thermal stability of the lamellar structure, the fibers were heat-treated in air at 1360°–1460°C for up to 200 h. X-ray diffractometry and scanning electron microscopy were used to characterize the microstructures of the fibers. Image analysis was used to measure the length of the interface line between Y₃Al₅O₁₂ and Al₂O₃ phases. The kinetics of coarsening and the rate-controlling mechanisms were investigated. Also, the Graham and Kraft model for describing the coarsening behavior of the lamellar Al-CuAl₂ eutectic alloy was used to explain the coarsening behavior of Y₃Al₅O₁₂/Al₂O₃ eutectic fiber.     

Rapid Crystallization of SiO2-Al2O3 Glasses

The crystallization of Al₂O₃-rich glasses in the system SiO₂-Al₂O₃ which were prepared by flame-spraying and/or splat-cooling was studied by DTA, electron microscopy, and X-ray diffraction. Over a wide range of compositions, the crystallization temperature ( T_x ) remained near 1000°C, changing smoothly with composition. In all cases crystallization of mullite was detected by X-ray diffraction. In the low-Al₂O₃ region, coarsening of the microstructure during crystallization was observed by electron microscopy. In the high-Al₂O₃ region mullite and γ-Al₂O₃ cocrystallized; this behavior may be interpreted as evidence of a cooperative process of crystallization at the respective T_x 's. The crystallite size of the mullite immediately after rapid crystallization increased continuously with increasing Al₂O₃ content. In light of the T_x data, the adequacy of the evidence for the proposed metastable miscibility gap in the SiO₂-Al₂O₃ system is questioned.     

Chemical Vapor Deposition of Polycrystalline Al2O3

Polycrystalline Al₂O₃ was chemically vapor-deposited onto sintered Al₂O₃ substrates by reaction of AlCl₃ with (1) H₂O, (2) CO:H₂, and (3) O₂ at 1000° and 1500°C and 0.5 and 5.0 torr. Although the thermodynamics of all these reactions predict the formation of solid Al₂O₃, the deposition rate of the first reaction was considerably greater than that of the second. The third reaction was so slow that no measurable deposit was formed in 6 h at 1500°C. Formation of dense deposits of α-Al₂O₃ was favored by increasing temperature and decreasing pressure. Microstructural examination of the dense deposits showed long columnar grains, the largest of which extended through the deposit from the substrate to the surface.     

Imaging and Diffraction Study of Continuous α-Fe2O3 Films on (0001)Al2O3

Continuous α-Fe₂O₃ films grown on bulk (0001)Al₂O₂ substrates by low-pressure chemical vapor deposition have been studied by transmission electron microscopy and the observations compared to those obtained from discontinuous films at an earlier stage of the growth process. Plan-view specimens revealed significant thermal stress in the continuous films, while cross-sectional specimens showed that cracking occurs in thicker films. The free surface of the film and the film/substrate interface appeared sharp and flat, apart from growth ledges and steps. Weak-beam imaging revealed a hexagonal misfit dislocation network consisting of perfect edge dislocations. Fine structure in the selected-area diffraction patterns which corroborates these observations is also discussed. The misfit network of partial dislocations previously observed in the discontinuous films was not observed for the continuous films, indicating an effect of film thickness, growth rate, or surface preparation on the Fe₂O₃/(0001)Al₂O₃ interface structure.     

Indentation of Silicate-Glass Films on Al2O3 Substrates

The deformation of thin layers of glass on crystalline materials has been examined using newly developed experimental methods for nanomechanical testing. Continuous films of anorthite (CaAl₂Si₂O₈) were deposited onto Al₂O₃ surfaces by pulsed-laser deposition. Mechanical properties such as Young's modulus and hardness were probed with a high-resolution depth-sensing indentation instrument. Nanomechanical testing, combined with AFM in situ imaging of the deformed regions, allowed force-displacement measurements and imaging of the same regions of the specimen before and immediately after indentation. This new technique eliminates any uncertainty in locating the indentation after unloading. Emphasis has been placed on examining how the Al₂O₃ substrate crystallographic orientation will affect mechanical composite response of silicate-glass film/Al₂O₃ system.     

Crack-Healing Behavior of Al2O3 Toughened by SiC Whiskers

Al₂O₃ reinforced by SiC whiskers (Al₂O₃/SiC-W) was hot-pressed to investigate the crack-healing behavior. Semielliptical surface cracks of 100 μm in surface length were introduced using a Vickers indenter. The specimens containing precracks were crack-healed at temperatures between 1000° and 1300°C for 1 h in air, and their strengths were measured by three-point bending tests at room temperature and elevated temperatures between 400° and 1300°C. The results show that Al₂O₃/SiC-W possesses considerable crack-healing ability. The surface cracks with length of 2 c = 100 μm could be healed by crack-healing at 1200° or 1300°C for 1 h in air. Fracture toughness of the material was also determined. As expected, the SiC whiskers made their Al₂O₃ tougher.     

Phase Diagram of the Alumina–Zirconia–Samaria System

The phase diagram of the Al₂O₃–ZrO₂–Sm₂O₃ system was constructed in the temperature range 1250°–2800°C. The phase transformations in the system are completed in eutectic reactions. No ternary compounds or regions of appreciable solid solution were found in the components or binaries in this ternary system. Two new ternary and one new binary eutectics were found. The minimum melting temperature is 1680°C and it corresponds to the ternary eutectic Al₂O₃+F-ZrO₂+SmAlO₃. The solidus surface projection, the schematic of the alloy crystallization path, and the vertical sections present the complete phase diagram of the Al₂O₃–ZrO₂–Sm₂O₃ system.     

Characterization and Crystallization of Y-Si-Al-O-N Glass

Glasses were prepared from sintered powders ofSi₃N₄, Al₂O₃, Y₂O₃ AlN, andSiO₂ to study their crystallization on subsequent heat treatment. Appreciable crystallization was efected only after the glasses were doped with up to 5 wt% ZrO₂. Electron microscopy and microanalysis showed that the crystalline phase was Y₂O₃·2SiO₂ without detectable Zr. The sofening temperature is in the range 850° to 1020°C. In-situ heating in a high-voltage electron microscope at ∼12OO°C produced renucleation and growth of the crystalline phase; at higher temperatures, however, the glass phase volatilized.     

Mullite Joining by the Oxidation of Malleable, Alkaline-Earth-Metal-Bearing Bonding Agents

Metallic Ba-Al-Si bonding agents have been used to produce all-ceramic, BaO-Al₂O₃-SiO₂ bonds between plates of mullite (Al₆Si₂O₁₃). Ba-Al-Si tapes (200 (μm thick) were fabricated by compaction and rolling of mechanically alloyed powder. The Ba-Al-Si tapes were placed between mullite plates and then oxidized by heating to a peak temperature of 1230°C in air. The oxidized tapes strongly adhered to the mullite plates at 25° and 1000°C, as indicated by the fracture morphologies obtained from compressive shear tests. Electron microscopy (EPMA, TEM) revealed that the bulk of the oxidized Ba-Al-Si tapes (away from the interfaces with mullite) consisted largely of the compound BaAl₂Si₂O₈, along with some BaSiO₃ and an amorphous, barium-rich aluminosilicate. The interface between the oxidized bonding agent and bulk mullite consisted of a mixture of BaAl₂Si₂O₈, Al₆Si₂O₁₃, A1₂O₃, BaAl₂O₄, and an amorphous, barium-bearing aluminosilicate.     

Sol–Gel Synthesis of λ–Na2O·xAl2O3 Films

Na₂O· x Al₂O₃ ( x = 9, 11)films have been obtained by sol–gel method. Crystallization processes during heat treatments have been investigated by X–ray diffraction analysis. A metastable phase with the mullite structure, λ–Na₂O· x Al₂O₃, has been observed starting from 800°C. Films remained stable after a heat treatment at 1000°C for 250 h. Impedance spectroscopy measurements showed that the films of λ-Na₂O· x Al₂O₃ possess a large three–dimensional ionic conductivity at 400°C.     

Fabrication and Microstructure Characterization of Continuous Porous TiO2/Al2O3 Composite Membrane

Using a multipass extrusion process, continuous porous Al₂O₃ body (∼41% porosity) was produced and used as a substrate to fabricate continuous porous TiO₂/Al₂O₃ composite membrane. The diameter of the continuous pores of the porous Al₂O₃ body was about 150 μm. The TiO₂ nanopowders dip coated on the continuous pore-surface Al₂O₃ body existed as rutile and anatase phases after calcination at 520°C in air. However, after aging of the fabricated continuous porous TiO₂/Al₂O₃ composite membrane in 20% NaOH at 60°C for 24 h, a large number of TiO₂ fibers frequently observed on the pore surface. The diameter of the TiO₂ fibers was about 150 nm having a high specific surface area. However, after 48-h aging period, the diameter of the TiO₂ fibers increased, which was about 3 μm. Most of the TiO₂ fibers had polycrystalline structure having nanosized rutile and anatase crystals of about 20 nm.     

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.     

Thermal Analysis of a SiO2─Al2O3─CaO─CaF2 Glass

A SiO₂─Al₂O₃─CaO─CaF₂ ionomer glass was investigated using thermal analysis, X-ray diffraction, and scanning electron microscopy. The purpose of this investigation was to control the susceptibility of the glass to acid attack. The differential thermal analysis trace exhibited a sharp glass transition at about 645°C and two exotherms. The first exotherm corresponded to liquid–liquid phase separation followed by crystallization of fluorite. The second, much larger, exotherm was the result of crystallization of the remaining glass phase to form anorthite. Prolonged heat treatment below the glass-transition temperature demonstrated that crystallization of fluorite can occur without prior liquid–liquid phase separation.     

Microstructure and High-Temperature Mechanical Behavior of Alumina/Alumina–Yttria-Stabilized Tetragonal Zirconia Multilayer Composites

Layered composites of alternate layers of pure Al₂O₃(thickness of 125 μ m) and 85 vol% Al₂O₃-15 vol% ZrO₂ that was stabilized with 3 mol% Y₂O₃(thickness of 400 μ m) were obtained by sequential slip casting and then fired at either 1550° or 1700°C. Constant-strain-rate tests were conducted on these materials in air at 1400°C at an initial strain rate of 2 × 10^-5 s^-1. The load axis was applied both parallel and perpendicular to the layer interfaces. Catastrophic failure occurred for the composite that was fired at 1700°C, because of the coalescence of cavities that had developed in grain boundaries of the Al₂O₃ layers. In comparison, the composite that was fired at 1550°C demonstrated the ductility of the Al₂O₃+YTZP layer, but at a flow stress level that was determined by the Al₂O₃ layer.