Textured Magnetoplumbite Fiber-Matrix Interphase Derived from Sol-Gel Fiber Coatings

A calcium hexaluminate (CaAl₁₂O₁₉, magnetoplumbite structure) sol was used to coat alumina and yttrium-aluminum-garnet (YAG) single-crystal fibers and single-crystal alumina plates. When the coated substrates were either annealed or hot-pressed in polycrystalline alumina and YAG matrices, the calcium hexaluminate basal cleavage planes were aligned parallel with the fiber-matrix interface. A complex series of reactions and phase transformations contributed to texture formation on alumina substrates. The alumina fibers and plates seeded the phase transformation of sol-derived transition aluminas to α-Al₂O₃. CaAl₁₂O_l9 and CaAl₄O₇ formed between the seeded α-Al₂O₃, and CaAl₄O₇ later reacted with the seeded α-Al₂O₃ to form CaAl₁₂O₁₉, resulting in a single-phase coating. Several different mechanisms may be responsible for the texture. The microstructure, phase evolution, and possible mechanisms for texture formation of CaAl₁₂O₁₉ powders, sol-derived thin films, and coated plates and fibers, with and without hot-pressed matrices, were studied and are discussed. Deflection and propagation of cracks within the fiber-matrix interphase in thin foils suggests that such an inter-phase may protect fibers from matrix cracks.     

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.     

Thermal Expansions and Chemical Durabilities of Yttria–Aluminosilicate Glasses Containing Na2O and ZrO2

Properties of glasses in the system Y₂O₃–Al₂O₃–SiO₂ containing Na₂O and ZrO₂ were investigated. The difference between the thermal expansion coefficients (Δα) at temperatures above T _g and those below T _g, microhardness, density, and chemical durability were measured in relation to the Al₂O₃/Y₂O₃ molar ratio. These glasses were found to have a smaller value of Δα than that of a commercial coating glass.     

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.     

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.     

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.     

Effect of Divalent Cation Additives on the γ-Al2O3-to-α-Al2O3 Phase Transition

The effect on the γ-Al₂O₃-to-α-Al₂O₃ phase transition of adding divalent cations was investigated by differential thermal analysis, X-ray diffractometry, and surface-area measurements. The cations, Cu²⁺, Mn²⁺, Co²⁺, Ni²⁺, Mg²⁺, Ca²⁺, Sr²⁺, and Ba²⁺, were added by impregnation, using the appropriate nitrate solution. These additives were classified into three groups, according to their effect: (1) those with an accelerating effect (Cu²⁺ and Mn²⁺), (2) those with little or no effect (Co²⁺, Ni²⁺, and Mg²⁺), and (3) those with a retarding effect (Ca²⁺, Sr²⁺, and Ba²⁺). The crystalline phase formed by reaction of the additive with γ-Al₂O₃ at high temperature was a spinel-type structure in groups (1) and (2) and a magnetoplumbite-type structure in group (3). In groups (2) and (3), a clear relationship was found between the transition temperature and the difference in ionic radius of Al³⁺ and the additive (Δ r ): The transition temperature increased as Δ r increased. This result indicates that additives with larger ionic radii are more effective in suppressing the diffusion of Al³⁺ and O²⁻ in γ-Al₂O₃, suppressing the grain growth of γ-Al₂O₃, and retarding the transformation into α-Al₂O₃.     

Influence of Diaspore Seeding and Chloride Concentration on the Transformation of "Diasporic" Precursors to Corundum

"Diasporic" precursors derived from sols formed by the controlled hydrolysis of aluminum sec-butoxide in the presence of HCl yielded mixtures of corundum and amorphous alumina when calcined between 500° and 800°C. The fraction of corundum in the calcined products depended on the HCl/alkoxide ratio used during hydrolysis and was maximized at 64 wt% when the molar ratio was 1. Precursors formed from sols hydrolyzed in the presence of HNO₃ rather than HCl yielded only amorphous products or transition aluminas when treated below 900°C. The corundum yield of the precursors was enhanced when they were seeded with diaspore (α-AlOOH) crystals. Precursors synthesized with an HCl/alkoxide ratio of 1 and seeded with 7.6 × 10¹⁶ diaspore seeds/(mol of Al₂O₃) were transformed to phase-pure corundum within 12 h at 700°C. Based on studies of the phase evolution of the precursors during calcining, it was concluded that the diaspore seeds promoted conversion by acting as corundum nuclei once they decomposed at ∼450°C.     

Microwave-Hydrothermal Synthesis of Monodispersed Nanophase α-Fe2O3

Synthesis of monodispersed nanophase α-Fe₂O₃ (hematite) powder to be used as a red pigment in porcelains was investigated using microwave-hydrothermal and conventional-hydrothermal reactions using 0.018 M FeCl₃·6H₂O and 0.01 M HCl solutions at 100°–160°C. Acicular and yellow β-FeOOH (akaganite) particles 300 nm in length and 40 nm in thickness were dominantly formed at 100°C after 2–3 h, while spherical α-Fe₂O₃ particles 100–180 nm in diameter were preferentially formed after 13 h using a conventional-hydrothermal reaction. However, a microwave-hydrothermal reaction at 100°C led to monodispersed and red α-Fe₂O₃ particles 30–66 nm in diameter after 2 h without the formation of β-FeOOH particles. In this paper, the effect of microwave radiation during hydrothermal treatment at 100°–160°C on the formation yield, kinetics, morphology, phase type, and color of α-Fe₂O₃ was investigated.     

Formation of Zirconia Solid Solutions Containing Alumina Prepared by New Preparation Method

In the system ZrO₂–Al₂O₃, a new method for preparing ZrO₂ solid solutions from ZrCl₄ and AlCl₃ using hydrazine monohydrate is investigated. c -ZrO₂ solid solutions containing up to ∼40 mol% Al₂O₃ crystallize at low temperatures from amorphous materials. The formation mechanism is discussed from IR spectral data. The values of the lattice parameter α increase linearly from 0.5072 to 0.5105 nm with increasing Al₂O₃ content. At higher temperatures, transformation of the solid solutions proceeds as follows: c ( SS ) → t ( ss ) → t ( ss ) +α-Al₂O₃→ m +α-Al₂O₃. m -ZrO₂–α-Al₂O₃ composite ceramics are fabricated by hot isostatic pressing for 2 h at 1250°C and 196 MPa. Microstructures and mechanical properties are examined, in connection with increasing Al₂O₃ content.     

Mechanochemical Synthesis of Lanthanum Aluminate by Grinding Lanthanum Oxide with Transition Alumina

Grinding lanthanum oxide (La₂O₃) with Al₂O₃ was conducted to investigate their mechanochemical reactions to form lanthanum aluminate (LaAlO₃) powder using a planetary ball mill. Grinding for 120 min allowed us to obtain single-phase LaAlO₃ with a large surface area when transition alumina was used, whereas no formation of LaAlO₃ was achieved when α-Al₂O₃ was used. The mechanochemical process can be applied to synthesize other rare-earth (RE) aluminates (REAlO₃) from mixtures of a rare-earth oxide and transition alumina.     

Defect Clustering and Color in Fe,Ti: α-Al2O3

A comprehensive theory is presented which successfully explains the polarization, isothermal, and isochronal behavior of the optical absorption bands responsible for the color in blue and blue-green sapphire (Fe,Ti: α-Al₂O₃). The experimental study on which this theory is based has conclusively shown that (Fe,Ti) and (Fe,Fe) vacancy-containing defect clusters are responsible for the optical properties of Fe,Ti: α-Al₂O₃ and H,Fe,Ti: α-Al₂O₃. The experimental results also prove that V‴ is the charge-compensating defect for Ti˙_Al in Fe, Ti and Ti: α-Al₂O₃ with an [Ti˙_Al] = 3[V‴] electroneutrality condition and that V¨_o provides the charge balance for Fe'_Al in Fe: α-Al₂O₃ with an [Fe'_Al] = 2[V¨_o]electroneutrality condition. Defect clusters were found to form via diffusion-limited solid-state reactions where the relative concentration of charged and neutral point defects depends on both the association energy and the diffusivity of the defects participating in the clustering reactions. In this paper, a model is presented which attempts to explain both the origin and the thermal behavior of the optical bands responsible for the color of Fe,Ti: α-Al₂O₃.     

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.     

Mixed Protonic–Electronic Conduction in "α-Al2O3": An Alternative Hypothesis

As an alternative, the voltage data of Kurita et al . recently published on galvanic cells with commercial α-Al₂O₃ as a solid electrolyte and with O₂, H₂O/α-Al₂O₃ as well as H₂, H₂O/α-Al₂O₃ as electrodes can be quantitatively described by assuming that α-Al₂O₃ represents a mixed sodium ionic–electronic conductor rather than a protonic–electronic conductor. From the evaluation of the experimental data, numerical values for the p -type electronic conduction parameter are obtained that agree sufficiently well with the data known to date for the sodium ion conductor Na-beta-Al₂O₃.     

Multicomponent Glasses of GeO2 and Sb2O3 with Bi2O3, T12O, andlor PbO

Previous studies on glass formation involving GeO₂ with Bi₂O₃, TI₂O, and PbO were extended by the use of Sb₂O₃. Wide areas of glass formation occur in the systems GeO₂-PbO-Sb₂O₃ and GeO₂-Bi₂O₃-Sb₂O₃ at all but the lowest GeO₂ contents; the region of single-phase glasses in the system GeO₂-Tl₂O-Sb₂O₃ is severely restricted. Glasses were examined by powder X-ray diffraction, differential thermal analysis, thermomechanical analysis, and Archimedes'technique to obtain glass transition and crystallization exotherm temperatures, thermal expansion coefficients, and densities; these properties are presented in diagrams for the GeO₂-Sb₂O₃ binary and for two ternary systems. Based on calculated values of Δ_o,the waveleneth for zero material dispersion. and dM/dΔ . the material disiersion slope at Δ_o, compositions in these systems may be useful for the construction of ultralow-loss optical waveguides in the 3 to 4 μm region.     

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.     

Effect of α to β (β') Phase Transition on the Sintering of Silicon Nitride Ceramics

By using α-Si₃N₄ and β-Si₃N₄ starting powders with similar particle size and distribution, the effect of α-β (β') phase transition on densification and microstructure is investigated during the liquid-phase sintering of 82Si₃N₄·9Al₂O₃·9Y₂O₃ (wt%) and 80Si₃N₄·13Al₂O₃·5AIN·5AIN·2Y₂O₃. When α-Si₃N₄ powder is used, the grains become elongated, apparently hindering the densification process. Hence, the phase transition does not enhance the densification.     

Effect of Monovalent Cation Additives on the γ-Al2O3-to-α-Al2O3 Phase Transition

The effect of monovalent cation addition on the γ-Al₂O₃-to-α-Al₂O₃ phase transition was investigated by differential thermal analysis, powder X-ray diffractometry, and specific-surface-area measurements. The cations Li⁺, Na⁺, Ag⁺, K⁺, Rb⁺, and Cs⁺ were added by an impregnation method, using the appropriate nitrate solution. β-Al₂O₃ was the crystalline aluminate phase that formed by reaction between these additives and Al₂O₃ in the vicinity of the γ-to-α-Al₂O₃ transition temperature, with the exception of Li⁺. The transition temperature increased as the ionic radii of the additive increased. The change in specific surface area of these samples after heat treatment showed a trend similar to that of the phase-transition temperature. Thus, Cs⁺ was concluded to be the most effective of the present monovalent additives for enhancing the thermal stability of γ-Al₂O₃. Because the order of the phase-transition temperature coincided with that of the formation temperature of β-Al₂O₃ in these samples, suppression of ionic diffusion in γ-Al₂O₃ by the amorphous phase containing the added cations must have played an important role in retarding the transition to α-Al₂O₃. Larger cations suppressed the diffusion reaction more effectively.     

Effect of Yttria on Interfacial Reactions Between Titanium Melt and Hot-Pressed Yttria/Zirconia Composites at 1700°C

Various Y₂O₃/ZrO₂ samples were fabricated by hot pressing, whereby Y₂O₃ was mutually dissolved or reacted with ZrO₂ as a solid solution or Zr₃Y₄O₁₂. Hot-pressed samples were allowed to react with Ti melt at 1700°C for 10 min in argon. Microstructural characterization was conducted using X-ray diffraction and analytical electron microscopy. The Y₂O₃/ZrO₂ samples became more stable with increasing Y₂O₃ because Y₂O₃ was hardly reacted and dissolved with Ti melt. The incorporation of more than 30 vol% Y₂O₃ could effectively suppress the reactions in the Ti side, where only a very small amount of α-Ti and β'-Ti was found. When ZrO₂ was dissolved into Ti on the zirconia side near the original interfaces, Y₂O₃ reprecipitated in the samples containing 30%–70 vol% Y₂O₃, because the solubility of Y₂O₃ in Ti was very low. In the region far from the original interface, α-Zr, Y₂O₃, and/or residual Zr₃Y₄O₁₂ were found in the samples containing more than 50 vol% Y₂O₃ and the amount of α-Zr decreased with increasing Y₂O₃.     

High-Pressure-High-Temperature Polymorphism of the Oxides of Lead

The common oxides of lead, PbO, PbO₂, and Pb₃O₄, were examined at pressures of 0 to 60,000 atmospheres and temperatures of 100° to 600° C. The pressure-temperature curve for the litharge-massicot transition was measured, giving a ΔH of transition of 57 cal. per mole. Unusual meta-stability and inversion characteristics of the massicot phase were examined in detail. PbO₂ (rutile) transformed at pressures in excess of 13,000 atmospheres at 300°C. to an ortho-rhombic form. The univariant equilibrium curve for the transition gave a Δ H of 11 cal. per mole. Pb₃O₄ underwent a disproportionation reaction yielding PbO and "Pb₂O₃." The equilibrium curve for this reaction was measured, and Δ H was determined to be 4500 cal. per mole.