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.     

Effect of Seeding and Water Vapor on the Nucleation and Growth of α-Al2O3 from γ-Al2O3

Isothermal transformation kinetics and coarsening rates were studied in unseeded and alpha-Al₂O₃-seeded γ-Al₂O₃ powders heated in dry air and water vapor. Unseeded samples heated in dry air transformed to alpha-Al₂O₃ with an activation energy of 567 kJ/mol. Seeding with alpha-Al₂O₃ increased the transformation rates and reduced incubation times by providing low-energy sites for nucleation/growth of the alpha-Al₂O₃ transformation. The activation energy for the transformation was reduced to 350 kJ/mol in seeded samples heated in dry air. Seeded samples completely transformed to alpha-Al₂O₃ after 1 h at 1050°C when heated in dry air compared to 1 h at 925°C when heated in saturated water vapor. The combined effects of a lower nucleation barrier due to seeding and the increased diffusion due to water vapor reduced the activation energy for the transformation by 390 kJ/mol and the transformation temperature by ∼225°C compared to the unseeded samples heated in dry air. The accelerated kinetics is believed to be due to increased surface diffusion.     

Conversion of Diaspore to Corundum: A New α-Alumina Transformation Sequence

A new two-step transformation sequence has been identified for the conversion of diaspore (α-AlOOH) to corundum (alpha-Al₂O₃). The powder X-ray diffraction pattern of the intermediate phase, designated alpha'-Al₂O₃, has been indexed to a monoclinic (P2) cell, with a = 9.566(5) Å, b = 5.124(2) Å, c = 9.156(4) Å, and ß= 91.76(3)°. Nuclear magnetic resonance of alpha'-Al₂O₃ indicates that 15-20% of the aluminum is on tetrahedral sites, with the remainder in octahedral coordination. Controlled-atmosphere high-temperature X-ray diffraction shows that water accelerates the second transformation step, alpha'-Al₂O₃→> alpha-Al₂O₃, acting as a mineralizer for the conversion process.     

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.     

Effects of Processing Parameters on Alumina Coatings Deposited on Nickel Substrates by Reacting Aluminum Chloride and Hydrogen/Carbon Dioxide Gas Mixtures

Pure nickel coupons were used as substrates in the deposition of alumina (Al₂O₃) from the reaction of aluminum chloride (AlCl₃) with hydrogen/carbon dioxide gas mixtures in the temperature range of 954°–1100°C and system pressures of 2.7–13.3 kPa. The apparent activation energy estimated from the coating growth rate averaged 320 kJ/mol at 13.3 kPa. At temperatures <1000°C, transition theta, kappa, and delta modifications were codeposited with alpha-Al₂O₃, whereas single-phase alpha-Al₂O₃ was deposited at higher temperatures. At high AlCl₃ partial pressures, nickel aluminide phases were sometimes codeposited with Al₂O₃, which was attributed to the reaction of AlCl₃ with the nickel substrate in the presence of hydrogen gas.     

Variations in a Boehmite Gel and Oleic Acid Emulsion under Calcination

In this paper, we describe variations in a boehmite (AlOOH) and oleic acid emulsion during the process of forming superfine α-Al₂O₃ crystallites from the mixture of oleic acid and a boehmite gel precursor. We also propose that the oleic acid decomposes under calcination, generating carbon, which can effectively prevent agglomeration of Al₂O₃ particles. Calcination for the present study was conducted under a reduced oxygen atmosphere, in the temperature range 25°–1100°C. Phase variations of the mixture under calcination were identified by Fourier transform infrared spectrometry (FTIR), X-ray diffractometry (XRD), and transmission electron microscopy (TEM). The FTIR spectra were used when the mixed emulsion of oleic acid and boehmite gel was heated, to investigate the adsorption reaction of the aluminum oleate; the C—O—C cross-linking structure of oxygenation, which aided in carbon formation; and the ability of the carbon generated with α-Al₂O₃ during phase transformation to prevent agglomeration (vermicularity). The products were analyzed by XRD at different temperatures, and TEM was used to examine the individual diameters of the α-Al₂O₃ crystallites.     

Effect of Preparation Conditions on Phase Formation, Densification, and Microstructure Evolution in La-β-Al2O3/Al2O3 Composites

In situ development of La-ß-Al₂O₃(LBA) platelets in alpha-Al₂O₃was studied as a function of the preparation method: a conventional solid-state reaction of commercial Al₂O₃powder and La(NO₃)₃as well as a sol-gel method starting with boehmite and the same La₂O₃precursor. In both cases, homogeneous distribution of the reinforcing phase was achieved, and a noteworthy inhibition of Al₂O₃grain growth resulted. However, samples prepared by solid-state reaction densified more easily than those prepared via sol-gel, but the formation of the LBA phase occurred at a lower temperature in samples prepared by the sol-gel approach. Results on the correlation of the onset of LBA grain growth and densification to microstructure are discussed.     

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.     

Effect of Hydrothermal Conditions on the Morphology of Colloidal Boehmite Particles: Implications for Fibril Formation and Monodispersity

The synthesis of colloidal boehmite (AlOOH) is studied by heating basic aluminum chloride solutions under constant stirring. The temperature and Al₂O₃: Cl molar ratio influence the product morphology. Synthesis at 140°C generates highly fibrous polycrystalline particles that are on average 360 nm long, 30 nm broad, and 8 nm thick. They contain 0.11 mol of excess H₂O per 1 mol of AlOOH. Synthesis at temperatures between 140° and 190°C produces broader fibrils and less excess H₂O. Preparation at 220°C eventually produces fully crystalline platelike boehmite particles about 260 nm long, 95 nm broad, and 14 nm thick, without excess H₂O. Fibril synthesis requires an Al₂O₃:Cl molar ratio exceeding 1.0 to yield noncoagulated particles. The fibrils are fairly monodisperse with 20% standard deviation in their length for an Al₂O₃: Cl molar ratio about 1.0.     

Novel Low-Temperature Processing Route of Dense Mullite Ceramics by Reaction Sintering of Amorphous SiO2-Coated γ-Al2O3 Particle Nanocomposites

Dense mullite ceramics were successfully produced at temperatures below 1300°C from amorphous SiO₂-coated gamma-Al₂O₃ particle nanocomposites (AS-gammaA). This method reduces processing temperatures by similar/congruent300°C or more with respect to amorphous SiO₂-coated alpha-Al₂O₃ particle microcomposites (AS-alphaA) and to other Al₂O₃-SiO₂ reaction couples. The good densification behavior and the relatively low mullite formation temperature make AS-gammaA nanocomposites an excellent matrix raw material for polycrystalline aluminosilicate fiber-reinforced mullite composites.     

Synthesis and Characterization of MgAl2O4 Spinel Precursor from a Heterogeneous Alkoxide Solution Containing Fine MgO Powder

A precursor was synthesized from a heterogeneous alkoxide solution that contained fine MgO powder, which allowed the preparation of MgAl₂O₄ spinel powder with high sinterability characteristics. The precursor consisted of a mixture of boehmite (AlO(OH)) and a mixed hydroxide (Mg₄Al₂(OH)₁₄· 3H₂O). The spinel phase formed through two steps: (i) decomposition of the mixed hydroxide at low temperature and (ii) solid-state reaction between MgO and γ-Al₂O₃ at higher temperatures. Dense polycrystalline spinel could be obtained from the calcined powders at sintering temperatures as low as 1400°C.     

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.     

Preparation of ZnGa2O4 Spinel Fine Particles by the Hydrothermal Method

ZnGa₂O₄ fine particles with a single phase of spinel were synthesized from a mixed solution of gallium sulfate and zinc sulfate in the presence of aqueous ammonia under hydrothermal conditions above 180°C. The effects of treatment temperature and ZnO/Ga₂O₃ molar ratio in the starting solution on the crystallite size, morphology, lattice parameter, and chemical composition of the ZnGa₂O₄ spinel particles were examined. Spinel with different morphologies, cubic nanoparticles, and elongated rodlike particles were thought to be formed based on the structure of amorphous gallium hydroxide and needlelike GaO(OH) particles, respectively. By treatment at a higher temperature, these particles with nonstoichiometric composition grew large and thick, and their composition approached ZnO/Ga₂O₃= 1. With an increase in the starting ZnO/Ga₂O₃ molar ratio, the lattice parameter of the synthesized ZnGa₂O₄ spinel approached the reported value for the stoichiometric composition and reached a = 0.8335 nm at ZnO/Ga₂O₃= 1.95 by treatment at 240°C for 50 h.     

Preparation of Strontium Ferrite Particles by Spray Pyrolysis

Crystalline, submicrometer strontium ferrite powders, including SrFeO_2.97, SrFe₂O₄, Sr₂FeO₄, Sr₃Fe₂O_6.16, and SrFe₁₂O₁₉, were prepared by spray pyrolysis of an aqueous solution of mixed metal nitrates. The Sr:Fe mole ratio in the precursor solution was retained in the final products. Phase-pure materials were typically obtained only at the highest temperatures investigated (>1100°C) and powders prepared at lower temperatures frequently contained crystalline Fe₂O₃. The as-prepared particles were unagglomerated, polycrystalline, and hollow at lower temperatures, but densified in the gas phase at higher temperatures to give solid particles. The strontium ferrite (SrFe₁₂O₁₉) system was studied in detail as a representative example of the Sr-Fe-O system. At temperatures of 1200°C, dense, phase-pure magnetoplumbite-structure material, SrFe₁₂O₁₉, was obtained, while at lower temperatures, small amounts of Fe₂O₃ were observed. The particles prepared at 800° and 1100°C were 0.1-1.0 μm in diameter, and consisted of crystallites <100 nm, and were nearly solid. The difficulty in forming phase-pure SrFe₁₂O₁₉ was the different thermal decomposition temperatures of Sr(NO₃)₂ (725°C) and Fe(NO₃)₃9H₂O (125°C) as demonstrated by thermogravimetric analysis in the SrFe₁₂O₁₉ system.     

Possible Role of the Oxygen Potential Gradient in Enhancing Diffusion of Foreign Ions on α-Al2O3 Grain Boundaries

Thermally grown, alpha-Al₂O₃ external scales formed on alloys after oxidation in pure oxygen at temperatures between 1000° and 1500°C were analyzed using FEG-STEM/XEDS. Alloy dopants such as Y, Zr, La, Hf, and Ti were found to segregate to the alpha-Al₂O₃ grain boundaries and to the alloy-scale interface. With increasing oxidation time and temperature, the amount of segregant on the oxide grain boundaries near the gas interface increases until a critical level is reached and precipitates begin to nucleate and grow. These observations are a result of the outward transport of dopants from the alloy, through the external alumina scale, to the gas interface. The apparent driving force for the dopant diffusion is the oxygen potential gradient in the growing oxide scale.     

Hydrothermal Synthesis of Petal-Like Alumina Flakes

Petal-like alumina flakes were prepared by hydrothermal reaction at 170°C for 6 h with aqua-based precursor materials. The gel particles were calcined at 550°–1200°C. The gel and calcined particles were characterized by differential thermal analysis (DTA), thermogravimetry (TG), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), multipoint Brunauer–Emmett–Teller (BET) surface area, and field emission scanning electron microscopy (FESEM). Crystallization of alumina was confirmed by DTA and XRD studies. XRD results showed that boehmite particles were formed in as-prepared sample while γ-alumina (γ-Al₂O₃) persisted up to 800°C followed by the appearance of θ-alumina (θ-Al₂O₃) at 1000°–1200°C. The characteristics Al–O vibrations in alumina polymorphs were examined by FTIR study. FESEM confirmed the formation of petal-like alumina flakes with the assembly of alumina nanorods.     

Low-Temperature Sintering of Seeded Sol—Gel-Derived, ZrO2-Toughened Al2O3 Composites

Seeding a mixture of boehmite (AIOOH) and colloidal ZrO₂ with α-alumina particles and sintering at 1400°C for 100 min results in 98% density. The low sintering temperature, relative to conventional powder processing, is a result of the small alumina particle size (∼0.3 μm) obtained during the θ-to α-alumina transformation, homogeneous mixing, and the uniform structure of the sol-gel system. Complete retention of pure ZrO₂ in the tetragonal phase was obtained to 14 vol% ZTA because of the low-temperature sintering. The critical grain size for tetragonal ZrO₂ was determined to be ∼0.4 μm for the 14 vol% ZrO₂—Al₂O₃ composite. From these results it is proposed that seeded boehmite gels offer significant advantages for process control and alumina matrix composite fabrication.     

Synthesis and Properties of CaAl2O4-Coated AI2O3 Microcomposite Powders

Novel microcomposite powders, consisting of inert cores (αAL-Al₂O₃) surrounded by reactive cement-based coatings (CaAl₂O₄), were synthesized by a modified Pechini process. The evolution of the crystalline CaAl₂O₄ phase during calcination was studied using multiple analytical techniques, including DRIFTS,¹³C and ²⁷AlMAS FT-NMR, and XRD, for both pure CaAl₂O₄ and CaAl₂O₄-coated Al₂O₃ precursor powders. In both powders, decomposition proceeded via hydrocarbon chain scission and removal of ester groups at low temperatures ( T < 450°C), followed by the formation of inorganic carbonates at higher temperatures ( T > 450°C). These decomposition processes were accelerated by the underlying Al₂O₃ cores. Transmission electron microscopy (TEM) of the fully calcined powders showed that the inert αAL-Al₂O₃ particles were surrounded by relatively uniform CaAl₂O₄ coatings ranging in thickness from approximately 10 to 100 nm.     

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.     

Single-Calcination Synthesis of Pyrochlore-Free 0.9Pb(Mg1/3Nb2/3)O3–0.1PbTiO3 and Pb(Mg1/3Nb2/3)O3 Ceramics Using a Coating Method

A coating approach for synthesizing 0.9Pb(Mg_1/3Nb_2/3)O₃–0.1PbTiO₃ (0.9PMN–0.1PT) and PMN using a single calcination step was demonstrated. The pyrochlore phase was prevented by coating Mg(OH)₂ on Nb₂O₅ particles. Coating of Mg(OH)₂ on Nb₂O₅ was done by precipitating Mg(OH)₂ in an aqueous Nb₂O₅ suspension at pH 10. The coating was confirmed using optical micrographs and zeta-potential measurements. A single calcination treatment of the Mg(OH)₂-coated Nb₂O₅ particles mixed with appropriate amounts of PbO and PbTiO₃ powders at 900°C for 2 h produced pyrochlore-free perovskite 0.9PMN–0.1PT and PMN powders. The elimination of the pyrochlore phase was attributed to the separation of PbO and Nb₂O₅ by the Mg(OH)₂ coating. The Mg(OH)₂ coating on the Nb₂O₅ improved the mixing of Mg(OH)₂ and Nb₂O₅ and decreased the temperature for complete columbite conversion to ∼850°C. The pyrochlore-free perovskite 0.9PMN–0.1PT powders were sintered to 97% density at 1150°C. The sintered 0.9PMN–0.1PT ceramics exhibited a dielectric constant maximum of ∼24 660 at 45°C at a frequency of 1 kHz.