Transitions in Vapor-Deposited Alumina from 300° to 1200°C

The transition of amorphous alumina to α-alumina was studied by X-ray diffraction, electron diffraction, DTA, TGA, and microscopic observation. The amorphous alumina was prepared by condensing vapor from evaporating molten alumina in vacuo onto the glass envelope of the vacuum chamber. The amorphous alumina was transformed to a poorly crystalline material by heating for 16 hr between 570° and 670°C. Between 670° and 1200°C, the poorly crystalline alumina was converted to α-alumina via two parallel series of transition aluminas. The principal series was γ-alumina to δ-alumina to α-alumina. A minor amount of θ-alumina developed from the initial crystallization and persisted throughout the duration of the principal series as a parallel path. Some conversion of δ- to θ-alumina was detected above 900°C. DTA produced an unexplained exothermic peak at 320°C and a second exothermic peak at 860°C which corresponded to formation of metastable aluminas.     

Synthesis of Thermally Stable χ-Alumina by Thermal Decomposition of Aluminum Isopropoxide in Toluene

Thermal decomposition of aluminum isopropoxide in toluene at 315°C resulted in χ-alumina that had high thermal stability, whereas the reaction at lower temperatures resulted in formation of an amorphous product. The χ-alumina thus obtained directly transformed to α-alumina at ∼1150°C, bypassing the other transition alumina phases, whereas the amorphous product transformed to γ-alumina and then to θ-alumina before final transformation to α-alumina. When the χ-alumina, solvothermally synthesized at 315°C, was recovered by the removal of the solvent at the reaction temperature, thermal stability of the product was improved further. This procedure is convenient because it avoids bothersome work-up processes that yield large-surface-area and large-pore-volume alumina.     

Hydrothermal Synthesis of Submicrometer α-Alumina from Seeded Tetraethylammonium Hydroxide-Peptized Aluminum Hydroxide

Submicrometer α-alumina powder was successfully synthesized from seeded aluminum hydroxide peptized with tetraethylammonium hydroxide (TENOH) and hydrothermally treated at 200°C, using α-alumina particles as seeds. The powders were characterized by XRD, SEM, DTA-TG, and BET analyses. Results showed that seeding could greatly enhance the transition to α-alumina at 200°C without formation of other transient alumina phases. α-Alumina with some amount of boehmite formed in the seeded samples, whereas boehmite was the exclusive phase formed in the nonseeded sample. The morphology of α-alumina embedded in the boehmite matrix for the seeded samples suggests a direct transition from aluminum hydroxide to α-alumina without the formation of transient alumina phases. The formation of α-alumina in the seeded samples at temperatures as low as 200°C could be attributed to a favored nucleation in the TENOH-peptized aluminum hydroxide and to the subsequent hydrothermal treatment that supplies the necessary activation energy for crystal growth. Transition of boehmite to α-alumina in the hydrothermally treated samples with low-seed contents was significantly promoted by heat-treating the samples at 500°C.     

Thermal Transformation of X-Alumina Formed by Thermal Decomposition of Aluminum Alkoxide in Organic Media

Thermal decomposition of aluminum sec -alkoxide in inert organic solvents at 300°C yielded a product composed of agglomerates of 4- to 20-nm particles having the χ-alumina structure. The χ-alumina was stable and maintained a surface area above 100 m²/g until its transformation at 1150°C to α-alumina.     

Kaolinite–Mullite Reaction Series: The Development and Significance of a Binary Aluminosilicate Phase

The semiquantitative estimations of 980°C exothermic reaction products of kaolinite by quantitative X-ray diffraction (QXRD) and chemical leaching techniques show the formation of a significant amount of amorphous aluminosilicate phase (∼ 30 to 40 wt%). The theoretically expected AlO₄/AlO₆ ratio in the 980°C reaction is in close agreement with the value measured by the X-ray fluorescence (XRF) technique and the experimental radial electron distribution (RED) profile agrees with the suggested 980°C formation of Si-Al spinel with mullite-like composition. Mullitization of kaolinite has been compared with a synthetic Al₂O₃—SiO₂ mixture. In synthetic mixtures development of an intermediate amorphous aluminosilicate phase is an essential step prior to mullitization. Kaolinite forms mullite in two ways: (i) by polymorphic transformation of cubic mullite at 1150° to 1250°C and (ii) by nucleation of mullite in the amorphous aluminosilicate phase and its subsequent growth above 1250°C. Thus chemical continuity is maintained throughout the reaction series and the intermediate spinel phase is silicon bearing and its subsequent transformation to mullite confirms the topotactic concept in the kaolinite transformation.     

Sol-Gel Alumina Coating for Improved Cyclic Oxidation Resistance of Silicon Nitride

A 25 nm thick α-alumina layer was deposited on a turbine-grade silicon nitride by sol-gel dip coating and subsequent heat treatment in air at 1200°C. This layer had a nanometer grain structure. Silicon nitride protected by this thin layer showed a significant improvement in oxidation resistance over its uncoated counterpart after 200 cyclic exposures in air at 1250°C. The oxide layer grown on the coated silicon nitride also exhibited superior surface morphology, compared with the uncoated silicon nitride.     

Controlled Transformation and Sintering of a Boehmite Sol-Gel by α-Alumina Seeding

The transformation, microstructural development, and densification of an α-alumina-seeded boehmite sol-gel was studied. α-Alumina particles are shown to act as nuclei for the trans- formation of θ- to α-alumina and to result in an increase in the transformation kinetics and lowering of the transformation temperature by as much as 170°C. By increasing the seed concentration (i.e., nucleation frequency), a submicrometer aggregate-free microstructure develops, rather than the vermicular microstructure that usually characterizes the α-alumina transformation. As a result, the transformed α-alumina sinters to full density with a submicrometer grain size at 1200°C. It is believed that seeding may represent a unique method for microstructure control in the many ceramic systems that transform by nucleation and growth.     

Preparation Method of Submicrometer-Sized α-Alumina by Surface Modification of γ-Alumina with Alumina Sol

A method is introduced to prepare almost-spherical submicrometer-sized α-alumina via surface modification of γ-alumina with an alumina sol. Milled γ-alumina, in the presence of 3 wt% of α-alumina with a median particle size ( d ₅₀) of 0.32 μm (AKP-30), produced irregularly shaped α-alumina with d ₅₀∼0.3 μm after heat treatment at 1100°C for 1 h. γ-alumina that had been surface-modified by milling in the presence of 3 wt% of the alumina sol resulted in almost-monosized, spherical α-alumina ∼0.3 μm in size after heat treatment at 1100°C for 1 h. Furthermore, almost-spherical α-alumina 0.1—0.2 μm in size was obtained by milling γ-alumina with 3 wt% of AKP-30 alumina in the presence of 3 wt% of the alumina sol, followed by heat treatment at 1100°C for 1 h. The alumina sol that has been introduced in this work seems to act as a dispersant, in addition to helping to form a spherical shape.     

Kinetic Studies of Mullite Synthesis from Alumina Nanoparticles and a Preceramic Polymer

The crystallization kinetics of mullite formation in a diphasic precursor consisting of a silicone resin filled with commercial γ-alumina nanoparticles (15 nm mean particle size, specific surface area of 100 m²/g), heated in air from 1250° to 1350°C, was studied by X-ray diffraction. Transitional γ-alumina and amorphous silica from the pyrolysis of the preceramic polymer exhibited a remarkable reactivity, as demonstrated by a very low incubation time (from 500 s at 1250°C to 20 s at 1350°C), a high mullite yield (about 80 vol%, after 100 s at 1350°C), and a low activation energy for nucleation (677±60 kJ/mol). The activation energy values found were lower than those reported previously for other diphasic systems, including sol–gel precursors. Besides the high specific surface of nanosized γ-alumina particles, the low energy barrier could be attributed to the highly reactive silica deriving from the oxidation of Si–CH₃ bonds in the silicone and to the homogeneous dispersion of the nanosized filler inside the preceramic polymer. Furthermore, the possibility of applying plastic shaping processing methods to the mixture of a preceramic polymer and nanosized filler makes this approach particularly valuable, in comparison, for instance, with sol–gel based alternatives.     

Sintering of Mixtures of Seeded Boehmite and Ultrafine α-Alumina

α-Alumina was fabricated by dry pressing mixtures of seeded boehmite and fine α-alumina (i.e., 0.2 and 0.3 μm diameter) to reduce the large shrinkage of boehmite-derived α-alumina. The maximum green density was obtained with mixtures containing ∼70%α-alumina for both alumina powders. The ∼15% linear shrinkage and microstructures of these samples were comparable to 100% alumina powder samples. Samples with 0.2 μm alumina sintered to densities >95% at 1300°C whereas 1400°C was needed for samples with 0.3 μm alumina. These results indicate that boehmite can be used as a substitute for relatively expensive ultrafine α-alumina powders.     

Topotactic Growth of β-Alumina on α-Alumina

Thin foils of polycrystalline α-alumina were reacted with a potassium-rich vapor at ≤900°C. Potassium β-alumina formed along α-alumina grain boundaries and protruded from holes in the foils. Conventional transmission electron microscopy was used to analyze the α-alumina/β-alumina phase boundary for possible orientation relations.     

Morphological Forms of α-Alumina Particles Synthesized in 1,4-Butanediol Solution

Phase-pure, monodispersed, hexagonal plates of single-crystal α-alumina (∼ 2 μm wide and ∼0.5 μm thick) have been prepared via precipitation by treating an aluminum hydrous oxide precursor in 1,4-butanediol at 300°C under autogenous vapor pressure. Present work shows that KOH is the only reagent that precipitates an aluminum hydrous oxide precursor suitable to synthesize α-alumina in 1,4-butanediol solution. In contrast, the use of NaOH or NH₄OH as the precipitating reagent for the precursor material does not yield the alpha phase. The solution pH at which the precursor materials are precipitated is also a critical factor for the formation of α-Al₂O₃. Phase-pure α-alumina powders were also only synthesized from the aluminum hydrous oxide precursors precipitated in the pH range from 10 to 10.5. The results of X-ray diffraction and scanning electron microscopy indicate that longer reaction times promote the phase transformation from the intermediate boehmite phase to α-alumina. The complete transformation from boehmite to α-alumina requires reaction times of about 12 h.     

Enhanced Densification of Boehrmte Sol-Gels by α-Alumina Seeding

Boehmite sol-gels were seeded by adding <2.0 wt%α-alumina powder to a 20% boehmite hydrosol at pH =3. The seeded gel sintered to 98% of theoretical density after 100 min at 1200°C, whereas the unseeded gel had to be sintered at 1600°C to reach 94% of theoretical density. This difference results primarily from nucleation by the α-alumina seeds and enhanced transformation of the boehmite to α-alumina, such that a uniform, well-ordered, fine-grained α-alumina micro-structure forms prior to densification.     

Synthesis of Aluminum Oxide Platelets

Aqueous solutions of boehmite and hydrofluoric acid (HF) were used to prepare homogeneous mixtures of alumina and aluminum fluoride. Calcination at temperatures as low as 1000°C resulted in the formation of well-defined hexagonal-shaped α-alumina platelets. Containment of the aluminum fluoride by covering the calcination crucible promoted crystal growth presumably by a reaction of continuous evaporation–condensation of aluminum fluoride. Hexagonal-shaped platelet α-alumina was observed with average diameters ranging from 7 to 33 μm. Large platelets with a narrow size distribution and average diameter of over 25 μm were prepared by controlling the initial concentration of HF and the calcination time, temperature, and atmosphere.     

Microstructural Evolution in Clay-Based Ceramics I: Single Components and Binary Mixtures of Clay, Flux, and Quartz Filler

Microstructural evolution on heating kaolinite clay, quartz, nepheline syenite, and soda–lime–silica (SLS) glass to various temperatures to 1300°C was investigated in quenched and slowly cooled samples by XRD, thermal analysis and SEM, and by in situ XRD. In the individual components, the expected behavior was observed and in SLS glass, devitrification led to crystallization of cristobalite, quartz, devitrite, and wollastonite, which dissolved at 900°–1000°C. Significant effects of each component on microstructural evolution in the others were often observed in binary mixtures. For example, in SLS glass and quartz mixtures, devitrification of SLS glass to form cristobalite was delayed and two forms of cristobalite with different morphologies were identified. Albite and plagioclase crystallized on heating kaolin clay and SLS glass mixtures, decreasing the alumina content available for mullite formation. Melting of nepheline syenite promoted reaction with the clay, including accelerated phase dissolution. SLS glass accelerated dissolution of nepheline syenite and prevented leucite formation.     

Preparation and Characterization of High-Temperature Thermally Stable Alumina Composite Membrane

A crack- and pinhole-free composite membrane consisting of an α-alumina support and a modified γ-alumina top layer which is thermally stable up to 1100°C was prepared by the sol–gel method. The supported thermally stable top layer was made by dipcoating the support with a boehmite sol doped with lanthanum nitrate. The temperature effects on the microstructure of the (supported and unsupported) La-doped top layers were compared with those of a common γ-alumina membrane (without doping with lanthanum), using the gas permeability and nitrogen adsorption porosimetry data. After sintering at 1100°C for 30 h, the average pore diameter of the La-doped alumina top layer was 17 nm, compared to 109 nm for the common alumina top layer. Addition of poly(vinyl alcohol) to the colloid boehmite precursor solution prevented formation of defects in the γ-alumina top layer. After sintering at temperatures higher than 900°C, the common alumina top layer with addition of poly(vinyl alcohol) exhibits a bimodal pore distribution. The La-doped alumina top layer (also with addition of poly(vinyl alcohol)) retains a monopore distribution after sintering at 1200°C.     

High-Temperature Reactions of Clay Mineral Mixtures and Their Ceramic Properties: I, Kaolinite-Mica-Quartz Mixtures with 25 Weight % Quartz

The mineralogy and ceramic properties (linear shrinkage and porosity) of fired compacts of quartz, kaolinite, and mica containing 25% of quartz and variable proportions of kaolinite and mica were studied systematically in relation to composition and firing temperature. A procedure for the quantitative determination of components by X-ray diffraction measurements is outlined and applied to the determination of quartz and mullite in the fired samples. For a mixture containing 25%, quartz, 75% kaolinite, the amount of mullite developed at 1300°C. is 41% and this contains 85% of the total Alsoa available. In micarich mixtures, mullite develops at lower temperatures and in smaller proportions. The shrinkage and porosity vary systematically with the percentage of mica in the samples and with firing temperature. The formation of cristobalite depends on the kaolinite content and is not related to the quartz content. Mullite and cristobalite develop at about 1100°C. from the transitory Si-Al spinel-type phase derived from kaolinite.     

Effect of Milling Treatment on the Particle Size in the Preparation of AIN Powder from Aluminum Polynuclear Complexes

Aluminum nitride powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride (BAC) provided the aluminum polynuclear complexes. The effect of the milling treatment for the precursor made from basic aluminum chloride and glucose on the particle size was investigated. BAC and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining under a nitrogen gas flow after drying, milling by vibration mill, and precalcining at 800°C. Then excess carbon was removed by firing in air. It was found that the milling treatment affected the particle size of AIN powder and nitridation mechanism. Without the milling treatment, AIN powder was synthesized directly from the γ-alumina of an intermediate product. In using a milled precursor, however, α-alumina was formed during the calcining, and the particle size of the AIN powder obtained was about five times larger than that of AIN powder synthesized from a raw precursor. The formation of α-alumina phase began at the rather low temperature of 800°C. These results suggest that the mechanochemical effects added by the milling promotes the formation of α-alumina during calcining, and the α-alumina phase formed accelerates the particle growth. AIN powders obtained were very uniform. The oxygen content and the surface area of AIN powders synthesized from the raw and milled precursors were 2.9 wt% and 17.5 m²/g, and 1.1 wt% and 3.6 m²/g, respectively.     

Mullite Development from Fibrous Kaolin Mineral

The development of mullite from kaolin minerals was studied using transmission electron microscopy and X-ray powder diffraction methods on the unusual long-fibered kaolin from Piedade, Sao Paulo, Brazil. The mullite crystals observed at ≥ 1200°C initially exhibited an elliptical shape and were randomly oriented inside the tubes; at 1250°C their shape changed to laths oriented either parallel to the tube length or at 120° to the adjacent lath. At 1300°C, the shape changed to a bipointed lath and the crystals developed a hexagonal configuration with preferred orientation at 120°, similar to mullite developed from kaolinite plates. Thus, the temperature at which mullite begins to develop from this tubular kaolin is ∼200°C above that normally observed in well-crystallized kaolinites and is 100°C above b axis disordered kaolinite. Cristobalite was not observed in the electron microscope in the range 1000° to 1300°C.