Seeding with γ-Alumina for Transformation and Microstructure Control in Boehmite-Derived α-Alumina

The dehydration, transformation, and densification of boehmite (γ-AlOOH) are enhanced by addition of γ-Al₂O₃ seed particles. α-Al₂O₃ microstructures with uniform 1- to 2-μm grain size and sintered densities 98% of theoretical are achieved at 1300°C Thermal analysis shows that γ-Al₂O₃ seed particles transform to α-Al₂O₃ before the matrix, thus controllably nucleating the transformation of θ-AI₂O₃ to α-Al₂O₃.     

Transformation and Densification of Nanocrystalline θ-Alumina during Sinter Forging

The sinter forging behavior of α-Al₂O₃ seeded and unseeded nanocrystalline θ-Al₂O₃ was investigated as a function of temperature, stress, and strain rate. Seeded samples exhibited the highest degree of plastic deformation during the θ- to α-AI₂O₃ phase transformation. As a result, microstructure control, increased densification, and a higher degree of transformation were obtained. A uniform microstructure of 150 nm α-Al₂O₃ grains developed, reaching 57% relative density after sintering 1.5 wt%α-Al₂O₃ seeded samples for 30 min at 1060°C. When sinter forged at 0.25 mm/min to 63 MPa and 1060°C for 30 min large deformations during the phase transformation increased the relative density to 74%. When the stress was increased to 235 MPa (1060°C, 30 min), 99.7% dense α-Al₂O₃ with a grain size of 230 nm was obtained. By increasing the sinter forging temperature to 1150°C, 99.5% relative density was achieved at 190 MPa for 30 min.     

Preparation of Nanometer-Sized α-Alumina Powders by Calcining an Emulsion of Boehmite and Oleic Acid

This study proposes a method to form ultrafine α-Al₂O₃ powders. Oleic acid is mixed with Al(OH)₃ gel. The gel is the precursor of the Al₂O₃. After it is mixed and aged, the mixture is calcined in a depleted oxygen atmosphere between 25° and 1100°C. Oleic acid evaporates and decomposes into carbon during the thermal process. Residual carbon prevents the growth of agglomerates during the formation of α-Al₂O₃. The phase transformation in this process is as follows: emulsion →γ-Al₂O₃→δ-Al₂O₃→θ-Al₂O₃→α-Al₂O₃. This process has no clear θ phase. Aging the mixed sample lowers the formation temperature of α-Al₂O₃ from 1100° to 1000°C. The average crystallite diameter is 60 nm, measured using Scherrer's equation, which is consistent with TEM observations.     

Liquid-Phase-Assisted Transformation of Seeded γ-Alumina

α-Al₂O₃-seeded, boehmite-derived γ-Al₂O₃ was transformed in the presence of V₂O₅, resulting in a 205°C decrease in the α-Al₂O₃ transformation temperature and a 74% reduction in the apparent activation energy for the γ- to α-Al₂O₃ transformation at temperatures greater than 850°C. These changes are attributed to the lowered energy barrier for nucleation by seeding and the lowered activation energy for material transport through the liquid relative to the unseeded, solid-state transformation. Growth of the transforming alumina yielded fine-grained α-Al₂O₃ particles which exhibited a highly faceted morphology. It is proposed that the combined control of both nucleation and growth during liquid-phase-assisted transformation provides a potentially powerful technique for tailoring powder characteristics in many material systems which undergo nucleation and growth processes.     

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 of Larnthanum β-Alumina with High Surface Area by Coprecipitation

Mixtures of La₂O₃ and Al₂O₃ with various La contents were prepared by co-precipitation from La(NO₃)₃ and Al(NO₃)₃ solutions and calcined at 800° to 1400°C. The addition of small amounts of La₂O₃ (2 to 10 mol%) to Al₂O₃ gives rise to the formation of lanthanum β-alumina (La 2 O₃·11–14Al₂O₃) upon heating to above 1000°C and retards the transformation of γ-Al₂O₃ to α-Al₂O₃ and associated sintering.     

Synthesis of Magnesium Aluminate Spinel Platelets from α-Alumina Platelet and Magnesium Sulfate Precursors

Spinel platelets were formed from a powder mixture of 3–5 μm wide and 0.2–0.5 μm thick α-Al₂O₃ and 1–8 μm (average 3 μm) MgSO₄ heated 2 h at 1200°C. The hexagonal platelet shape of the original α-Al₂O₃ platelet was maintained in the spinel, although their size was slightly increased and their surface roughened. When a mixture of α-Al₂O₃ platelets and MgO powder was heated 3 h at 1400°C, the spinel formed lost the platelet morphology of the alumina.     

Synthesis of α-Alumina Hexagonal Platelets Using a Mixture of Boehmite and Potassium Sulfate

Single-crystal α-alumina (Al₂O₃) hexagonal platelets with a diameter of about 200 nm and 25 nm in thickness were synthesized by heating a mixture of boehmite and potassium sulfate at 1000°C for 2 h and washing with water. The potassium sulfate addition effects on the Al₂O₃ phase and morphology were investigated using differential thermal analysis (DTA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). It was found that potassium sulfate addition helps in the formation of single-crystal α-Al₂O₃ hexagonal platelets and promotes phase transformation from intermediate γ-Al₂O₃ to α-Al₂O₃.     

Method for Production of α-Alumina Whiskers via Vapor-Liquid-Solid Deposition

α-alumina (α-Al₂O₃, corundum) fibers exhibit high thermal and chemical stability, as well as good mechanical properties, even at high temperatures. Such characteristics make them good candidates for use in composites. Nevertheless, very few methods of producing α-Al₂O₃ fibers are available. In the present work, we describe a method that uses aluminum pieces deposited on SiO₂ powder, in an argon atmosphere, at temperatures in the range 1300°–1600°C. The α-Al₂O₃ fibers are obtained via vapor-liquid-solid deposition. The novel addition of nickel and cobalt (or their oxides) allows the use of temperatures >1500°C, resulting in improved fiber production. We demonstrate that the metals do not contaminate the fibers produced in this way. Finally, we also estimate the tensile strength of the Al₂O₃ fibers produced through this method.     

Controlled Gelation and Sintering of Monolithic Gels Prepared from γ-Alumina Fume Powder

The gelation, phase transformation, and densification of a colloidal monolithic gel made from γ-Al₂O₃ fume powder are investigated. Among the six gelation agents that we use, formamide and urea are quick in causing gelation and easy to burn off. The densification rate of this gel decreases rapidly after the γ-to-α phase transformation. TiO₂ is an effective sintering aid to overcome this bottleneck of densification because (1) it enhances the phase transformation rate so that the sintering of α-alumina occurs at a lower temperature, and (2) it promotes sintering rates at the initial and intermediate stages after phase transformation. On the other hand, MgO has an inappreciable effect on gel sintering. The effect of MgO at the final sintering stage is obstructed by this densification barrier after transformation. The titania-doped gel monoliths can be sintered to high density and fine microstructure at 1400°C.     

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.     

Seeding of the Reaction-Bonded Aluminum Oxide Process

The effect of the initial α-Al₂O₃ particle size in the reaction-bonded aluminum oxide (RBAO) process on the phase transformation of aluminum-derived γ-Al₂O₃ to α-Al₂O₃, and subsequently densification, was investigated. It has been demonstrated that if the initial α-Al₂O₃ particles are fine (∼0.2 μm, i.e., 2.9 × 10¹⁴γ-Al₂O₃ particles/cm³), then they seed the phase transformation. The fine α-Al₂O₃ decreases the transformation temperature to ∼962°C and results in a finer microstructure. The smaller particle size of the seeded RBAO decreases the sintering temperature to as low as ∼1135°C. The results confirm that seeding can be utilized to improve phase transformations and densification and subsequently to tailor final microstructures in RBAO-derived ceramics.     

Reaction Hot Pressing of α'- and β'- SiAlON Ceramics

Hot pressing kinetics of α-Si₃N₄, AIN, Al₂O₃, and Y₂O₃ powder mixtures forming α'- and β'-SiAlONs have been studied. Densification proceeds in two steps, first by a small shrinkage upon ternary eutectic oxide melting (SiO₂–Al₂O₃–Y₂O₃) at 1340°C, followed by a massive particle rearrangement and further shrinkage at higher temperature when nitride dissolution begins. With better wettability, AIN initially traps the oxide melt and delays densification. In addition, the preferential dissolution of AIN at 1450°C enriches the melt composition in AI, triggering transient precipitation of supersaturated β'-SiAlON. Full densification is readily achieved at 1550°C without complete α-Si₃N₄ conversion.     

Fabrication of Nano-Scaled α-Al2O3 Crystallites Through Heterogeneous Precipitation of Boehmite in a Well-Dispersed θ-Al2O3-Suspension

The possibility of eliminating finger or vermicular growth of α-Al₂O₃ particles obtained by calcination of boehmite was examined. Heterogeneous precipitation of boehmite in a well-dispersed θ-Al₂O₃ suspension was first prepared, in which the mass ratio of boehmite to θ-crystallite was evaluated to form agglomerates of similar sizes that will form α-Al₂O₃ crystallites of <100 nm in diameter. θ- to α-phase transformation of alumina experiences a nucleation and growth mechanism, with the critical size of nucleation being ∼25 nm for θ-Al₂O₃ and the size for accomplishment of transformation followed by finger growth being ∼100 nm. Hence, fabricating agglomerates that would form α-Al₂O₃ crystallites with sizes <100 nm accompanied with appropriate thermal treatments can be a method for obtaining α-Al₂O₃ crystallites free of finger growth. It is found that proper preparation of the agglomerate with appropriate size may initiate a simultaneous and lower temperature θ- to α-Al₂O₃ phase transformation for such powder systems, substantially limiting the mass transfer among the newly formed α-Al₂O₃ particles. Moreover, α-Al₂O₃ crystallites free of finger growth can be obtained.     

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.     

Effect of Calcination on the Sintering of Gel-Derived, Zirconia-Toughened Alumina

The densification behavior of ZrO₂ (+ 3 mol% Y₂O₃)/85 wt% Al₂O₃ powder compacts, prepared by the hydrolysis of metal chlorides, can be characterized by a transition- and an α-alumina densification stage. The sintering behavior is strongly determined by the densification of the transition alumina aggregates. Intra-aggregate porosity, resulting from calcination at 800°C, partly persists during sintering and alumina phase transformation and negatively influences further macroscopic densification. Calcination at 1200°C, however, densifies the transition alumina aggregates prior to sintering and enables densification to almost full density (96%) within 2 h at 1450°C, thus obtaining a microstructure with an alumina and a zirconia grain size of 1 μm and 0.3–0.4 μm, respectively.     

Synthesis of Nanocrystalline α-Alumina Powder Using Triethanolamine

Nanocrystalline α-Al₂O₃ powders have been prepared by pyrolysis of a complex compound of aluminum with triethanolamine (TEA). The soluble metal-ion–TEA complex forms the precursor material on complete dehydration of the complex of aluminum-TEA. The single-phase α-Al₂O₃ powder has resulted after heat treatment at 1025°C. The precursors and the heat-treated final powders have been characterized by X-ray diffractometry, thermogravimetric and differential thermal analysis, and transmission electron microscopy (TEM). The average particle sizes as measured from X-ray line broadening and TEM are ∼25 nm. The powder has crystallite sizes of the same order indicates the poor agglomeration of crystallites.     

Effect of Tween-80 on the Control of Particle Size and Shrinkage Properties of Nanoscale α-Alumina Synthesized by Sol–Gel Processing

The concept of tailored interfaces has been applied to the synthesis of nanoscale α-Al₂O₃. Tween-80 (poly-oxyethylene(20) sorbitan monooleate, T-80) was used as a surface modifier in the sol–gel process for this purpose. High-resolution transmission electron microscopy study of the powder obtained with T-80 confirmed the particle size of α-Al₂O₃ (∼55 nm) and morphology (spherical). The exothermic peak temperature in the differential thermal analysis was shifted to a lower temperature (∼917°C) when the powder was derived from a T-80 modifier content of 10 wt%. X-ray diffraction showed that the α-Al₂O₃ phase was the major phase that existed in modifier-derived powder that was sintered at 1000°C. The experiments, based on linear shrinkage, indicated that the powder with T-80 (10 wt%) could be densified at a low temperature.     

The α–β Transformation in Silicon Nitride Single Crystals

Single crystals of α-Si₃N₄ were annealed at 2000°–2150°C. The β phase was detected after annealing at 2150°C only when the crystals were surrounded by MgO·3Al₂O₃ or Y₂O₃ powders. On the other hand, no evidence of the α–β transformation was found when the crystals were annealed without additives. The solution–precipitation mechanism was concluded to be the dominant factor in the α–β transformation of Si₃N₄.     

Preparation and Properties of Hydrothermally Stable γ-Alumina Membranes

Supported mesoporous γ-Al₂O₃ membranes deteriorate and blister in steam-containing environments at high temperatures. This deterioration led us to the development of a new type of supported γ-Al₂O₃ membrane with significantly improved stability under hostile conditions. Two measures were taken to achieve this result. First, the γ-Al₂O₃ itself was stabilized by an addition of 6 mol% La₂O₃ to suppress pore growth of the mesoporous structure. Second, the adherence of the γ-Al₂O₃ membrane to the α-Al₂O₃ support was significantly improved by application of phosphate bonding between the membrane layer and the support, using an Al(H₂PO₄)₃ precursor solution. Membranes applied without phosphate bonding were separated from the α-Al₂O₃ support during high-temperature steam treatment, resulting in complete loss of separative properties. The newly developed membranes could be operated for 100 h at 600°C in H₂O/CH₄= 3/1 (by volume) at 2.5 MPa total pressure with no delamination or cracking in the membrane–support interface and with no significant pore growth in the γ-Al₂O₃ membrane.