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.     

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.     

Fabrication of Fine YAG-Particulate-Dispersed Alumina Fiber

This paper involves novel fabrication processes for polycrystalline α-Al₂O₃-matrix composite fibers that contain nanosized yttrium aluminum garnet (YAG) particles. Dense α-Al₂O₃/YAG nanocomposite fibers with a fine and homogeneous microstructure can be successfully fabricated via a modified sol-gel process and α-Al₂O₃ seed-particle addition. YAG nanoparticles have been homogeneously dispersed within Al₂O₃-matrix grains as well as at grain boundaries. Effects of α-Al₂O₃ seed particles and YAG nanodispersions on crystallization and microstructure development of nanocomposite fibers are discussed.     

Size Control of α-Alumina Particles Synthesized in 1,4-Butanediol Solution by α-Alumina and α-Hematite Seeding

The effects of seed particles and shear rate on the size and shape of α-Al₂O₃ particles synthesized in glycothermal conditions are described. It is proposed that seed particles provide a low-energy, epitaxial surface in solution to lower the overall surface energy contribution to the nucleation barrier, thus increasing nucleation frequency and subsequently reducing the particle size of hexagonal α-Al₂O₃ platelets or polyhedra, depending on synthesis conditions, in 1,4-butanediol solution. Seeds have a significant effect on the size of hexagonal α-Al₂O₃ platelets in samples with high seed concentration. The particle size of α-Al₂O₃ platelets decreases from 3 to 4 µm to 100 to 200 nm by increasing the number concentration of seeds. In the case of α-Fe₂O₃ seeding, the effect of seeding on the size of α-Al₂O₃ particles closely resembles the effects obtained with α-Al₂O₃ seeding. Regardless of seed concentration, high stirring rate promotes the formation of hexagonal platelets with high aspect ratio, whereas medium and low stirring rates promote the formation of elongated platelets and polyhedra with 14 faces, respectively.     

Effects of Amorphous and Crystalline SiO2 Additives on γ-Al2O3-to-alpha-Al2O3 Phase Transitions

This paper focused on the effects of various phases of SiO₂ additives on the γ-Al₂O₃-to-α-Al₂O₃ phase transition. In the differential thermal analysis, the exothermic peak temperature that corresponded to the theta-to-α phase transition was elevated by adding amorphous SiO₂, such as fumed silica and silica gel obtained from the hydrolysis of tetraethyl orthosilicate. In contrast, the peak temperature was reduced by adding crystalline SiO₂, such as quartz and cristobalite. Amorphous SiO₂ was considered to retard the γ-to-α phase transition by preventing γ-Al₂O₃ particles from coming into contact and suppressing heterogeneous nucleation on the γ-Al₂O₃ surface. On the other hand, crystalline SiO₂ accelerated the α-Al₂O₃ transition; thus, this SiO₂ may be considered to act as heterogeneous nucleation sites. The structural difference among the various SiO₂ additives, especially amorphous and crystalline phases, largely influenced the temperature of γ-Al₂O₃-to-α-Al₂O₃ phase transition.     

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.     

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.     

Lowering Crystallization Temperatures by Seeding in Structurally Diphasic Al2O3-MgO Xerogels

Thermal reactions in 93% Al₂O₃-7% MgO and 95.8% Al₂O₃-4.2% MgO gels seeded with α-Al₂O₃, MgAl₂O₄, α-Fe₂O₃, and SiO₂, sols were investigated by differential thermal analysis to determine the extent of nucleation catalysis of solid-state reactions. Seeding with α-Al₂O₃ lowered the α-Al₂O₃ crystallization temperature in these xerogels by 100° to 150°C. Spinel seeds have much less effect on the γ-α transition, and α-Fe₂O₃ and SiO₂ seeds do not affect it significantly. Isostructural seeding of gels may therefore permit lower ceramic processing temperatures.     

Growth of α-AI2O3 Platelets in the HF-γy-AI2O3 System

In the presence of a fluorine mineralizer, highly aggregated, <5 μm α-Al₂O₃ platelet particles form by vapor transport during the thermal transformation of γ-alumina. Platelet aggregation was determined to occur by platelet inter-growth and by edge nucleation on primary α-Al₂0₃ platelets. The addition of 10¹⁰α-alumina seed particles/cm³γ–Al₂O₃ resulted in the development of discrete particles during the initial stage of transformation. Impingement of the growing platelets during the latter stage of transformation, however, resulted in intergrowth, a process which was not changed by seeding. Particle size distribution broadening was observed to increase with increasing HF and H₂O concentrations because vapor reactant supersaturation increases the degree of edge nucleation. When initially low HF and H₂O concentrations were used in seeded systems, however, essentially aggregate-free α-Al₂O₃ platelets of 10–15 μm were obtained.     

Transformation, Microstructure Development, and Densification in α-Fe2O3-Seeded Boehmite-Derived Alumina

Addition of α-Fe₂O₃ seed particles to alkoxide-derived boehmite sols resulted in a 10-fold increase in isothermal rate constants for the transformation of γ- to α-Al₂O₃. Changes in porosity and surface area with sintering temperature showed no effect of seeding on coarsening of the transition alumina gels, but the 200-fold decrease in surface area associated with transformation to α-Al₂O₃ occurred ∼ 100°C lower in seeded gels compared with unseeded materials. As a result of high nucleation frequency and reduced microstructure coarsening, fully transformed seeded alumina retained specific surface areas >22 m²/g and exhibited narrow pore size distributions, permitting development of fully dense, submicrometer α-Al₂O₃ at ∼ 1200°C.     

Mechanical Properties of Hot Isostatically Pressed Zirconia-Toughened Alumina Ceramics Prepared from Coprecipitated Powders

Amorphous Al₂O₃–ZrO₂ composite powders with 5–30 mol% ZrO₂ have been prepared by adding aqueous ammonia to the mixed solution of aqueous aluminum sulfate and zirconium alkoxide containing 2-propanol. Simultaneous crystallization of γ-Al₂O₃ and t -ZrO₂ occurs at 870°–980°C. The γ-Al₂O₃ transforms to α-Al₂O₃ at 1160°–1220°C. Hot isostatic pressing has been performed for 1 h at 1400°C under 196 MPa using α-Al₂O₃– t -ZrO₂ composite powders. Dense ZrO₂-toughened Al₂O₃ (ZTA) ceramics with homogeneous-dispersed ZrO₂ particles show excellent mechanical properties. The toughening mechanism is discussed. The microstructures and t / m ratios of ZTA are examined, with emphasis on the relation between strength and fracture toughness.     

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.     

Growth of α-Al2O3 Within a Transition Alumina Matrix

The growth of α-Al₂O₃ from a planar specimen of thermally grown γ-alumina on a molybdenum transmission electron microscope grid was studied. The α-Al₂O₃ grows into the transition alumina matrix and then thickens via a ledge growth mechanism. Faceted Mo crystallites cause pinning of α-Al₂O₃ ledges and are larger on α-Al₂O₃ than on the transition alumina matrix.     

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.     

Mechanical-Activation-Triggered Gibbsite-to-Boehmite Transition and Activation-Derived Alumina Powders

Mechanical activation of monoclinic gibbsite (Al(OH)₃) in nitrogen led to the formation of nanocrystalline orthorhombic boehmite (AlOOH) at room temperature. The boehmite phase formed after merely 3 h of mechanical activation and developed steadily as the mechanical-activation time increased. Forty hours of mechanical activation resulted in essentially single-phase boehmite, together with α-alumina (α-Al₂O₃) nanocrystallites 2–3 nm in size. The sequence of phase transitions in the activation-derived boehmite was as follows: boehmite to γ-Al₂O₃ and then to α-Al₂O₃ when flash-calcined at a heating rate of 10°C/min in air. γ-Al₂O₃ formed at 520°C, and flash calcination to 1100°C led to the formation of an α-Al₂O₃ phase, which exhibited a refined particle size in the range of 100–200 nm. In contrast, the gibbsite-to-boehmite transition in the unactivated gibbsite occurred over the temperature range of 220°–330°C. A flash-calcination temperature of 1400°C was required to complete the conversion to α-Al₂O₃ phase, with both δ-Al₂O₃ and θ-Al₂O₃ as the transitional phases. The resulting alumina powder consisted of irregularly shaped particles 0.4–0.8 μm in size, together with an extensive degree of particle agglomeration.     

Anomalous Temperature Dependence of the Growth Rate of the Reaction Layer between Silica and Molten Aluminum

An aluminum/Al₂O₃ composite body is produced by a displacement reaction between SiO₂ and molten aluminum. The growth rate of the reaction layer possesses negative (anomalous) temperature dependence at 1000–1300 K. This study compared reported reaction-kinetic data and investigated causes for this temperature dependence. The reaction product, Al₂O₃, changed from the γ-/θ-Al₂O₃ phase to the α-Al₂O₃ phase in this temperature range and α-Al₂O₃ became the dominant phase at >1273 K. Isothermal transformation of the γ-/θ-Al₂O₃ product phases to the α-Al₂O₃ phase was also observed. Morphologies and scales of the Al₂O₃ phases change drastically at 1173 K; this transition occurred in a spatially discontinuous manner. Reaction-rate retardation was interpreted in terms of occurrence of the competitive and simultaneous reactions to produce different Al₂O₃ phases in this temperature range. It was also found that the hydrogen release from the raw SiO₂ and the SiO₂ phase transformation were not related to the negative temperature dependence.     

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.     

Formation and Sintering of Yttria-Doped Tetragonal Zirconia with 50 mol% Alumina Prepared by the Hydrazine Method

Al₂O₃/Y₂O₃-doped ZrO₂ composite powders with 50 mol% Al₂O₃ are prepared by the hydrazine method. As-prepared powders are mixtures of AlO(OH) gel and amorphous ZrO₂ solid solutions containing Y₂O₃ and Al₂O₃. The formation process leading to α-Al₂O₃- t -ZrO₂ composite powders is examined. Hot isostatic pressing is performed for 2 h at 1400°C under 196 MPa using θ-Al₂O₃- t -ZrO₂ composite powders. The resulting dense, sintered α-Al₂O₃- t -ZrO₂ composites show excellent mechanical strength.     

Abnormal Grain Growth During Rapid Annealing of Sol–Gel Alumina Thin Film Deposited on Ni-Based Superalloy

A ∼50 nm thick alumina layer was deposited on an Ni-based superalloy substrate by a sol–gel method. α-AlOOH particles presented in the layer after drying at 140°C transformed mostly to α-Al₂O₃ grains within ∼1 min at 1100°C under a low oxygen partial pressure annealing environment. During the same time period, the α-Al₂O₃ grains grew significantly in the lateral direction, resulting in the aspect ratio of grain diameter to thickness of ∼20. The presence of a preferred orientation in the α-Al₂O₃ layer suggested that the mechanism for the lateral growth was abnormal. The lateral growth mechanism appeared to become very slow when a critical thickness (∼100 nm) was reached.     

Effects of an Electroplated Platinum Interlayer on the Morphology and Phases of Chemically-Vapor-Deposited Alumina on Single-Crystal, Nickel-Based Superalloy

The feasibility of preparing a thin layer of α-Al₂O₃ on the surface of a single-crystal, Ni-based superalloy was examined using a chloride-based chemical vapor deposition (CVD) process previously developed for cutting tool applications. A coating directly deposited by this method on the alloy surface consisted of ∼1 μm α-Al₂O₃ crystals in a matrix of amorphous Al₂O₃. When the alloy surface was predeposited with an electroplated Pt layer, the coating was mostly α-Al₂O₃, but with the presence of fine microcracks on the coating surface. In comparison to the results observed for pure Pt substrate, the role of the Pt interlayer was apparently to promote the rapid formation of κ-Al₂O₃ nuclei, which subsequently transformed to α-Al₂O₃ during the CVD growth process.