Phase Relations and Reaction Sintering of Transparent Cubic Aluminum Oxynitride Spinel (ALON)

A new isobaric, condensed phase diagram in the region of stability of cubic aluminum oxynitride spinel (ALON) along the pseudobinary AI₂O₃-AIN composition join is presented, deduced primarily from various analytical measurements and microstructural observations. It is shown that cubic aluminum oxynitride spinel melts incongruently at ≊2050°C and is compositionally centered at ≊35.7 mol% AIN, which is equivalent to the following stoichiometric composition: AI₂₃O₂₇N₅ or 5AIN·9AI₂O₃. Single-phase ALON material sintered to nearly full density exhibits transparency in visible light.     

Reactions Between Aluminum Oxide and Carbon The Al2O3—Al4C3 Phase Diagram

A phase diagram of the system A1₂O₃-A1₄C₃ is proposed. Two intermediate oxycarbides, A1₄O₄C and A1₂OC, were established. Eutectic melting between alumina and A1₄O₄C occurred at 1840° C. No other low melting was observed. The alumina phase was not corundum but was similar to delta-alumina. Because of the high reactivity of aluminum carbide and all the intermediate compounds with moisture and oxygen, use of refractories based on the system A1₂O₃-A1₄C₃ must be limited to applications where these agents are excluded. The behavior of high-alumina refractories in the presence of carbon is explained.     

Elastic Properties of Polycrystalline Aluminum Oxynitride Spinel and Their Dependence on Pressure, Temperature, and Composition

The isotropic elastic moduli of four specimens of nitrogen-stabilized cubic aluminum oxide (ALON) were measured using pulse superposition interferometry. Experiments were carried out as a function of both pressure (ambient to 1 GPa) and temperature (0° to 25°C) for specimens of 30.0 and 35.7 mol% AlN. The second-order moduli results were corrected for porosity using the "self-consistent-scheme" approach. Pertinent ambient results for isotropic pore-free ALON are K = 226.3 GPa and G = 132.0 GPa for the 30.0 mol% AlN material, and K = 229.8 GPa and G = 135.5 GPa for 35.7 mol% ALON ( K and G denote the bulk and shear moduli, respectively). The estimated uncertainties in these values are about 2%. The second-order elastic properties of ALON, as well as their pressure and temperature derivatives, fall midway between spinel (MgAl₂O₄) and corundum (Al₂O₃), indicating the excellent potential of this material for structural engineering purposes.     

Growth of Large Optical-Quality Yttrium and Rare-Earth Aluminum Garnets

An improved flux consisting of PbO-PbF₂ and B₂O₃ was developed for the growth of garnets. Rare-earth aluminum garnet crystals weighing in excess of 100 g and modified yttrium aluminum garnet crystals weighing up to 60 g were obtained using this flux. Lead contamination was reduced to noncritical levels in these crystals by working with large excesses of A1₂O₃ in the melt. Excellent optical quality has been produced as indicated both by visual examination and by outstanding laser performance.     

Aluminum Nitride Prepared by Nitridation of Aluminum Oxide Precursors

Aluminum nitride (AlN) powders were prepared from the oxide precursors aluminum nitrate, aluminum hydroxide, aluminum 2-ethyl-hexanoate, and aluminum isopropoxide (i.e., Al(NO₃)₃, Al(OH)₃, Al(OH)(O₂CCH(C₂H₅)(C₄H₉))₂, and Al(OCH(CH₃)₂)₃). Pyrolyses were performed in flowing dry NH₃ and N₂ at 1000°–1500°C. For comparison, the nitride precursors aluminum dimethylamide (Al(N(CH₃)₂)₃) and aluminum trimethylamino alane (AlH₃·N(CH₃)₃) were exposed to the same nitridation conditions. Products were investigated using XRD, TEM, EDX, SEM, and elemental analysis. The results showed that nitridation was primarily controlled by the water:ammonia ratio in the atmosphere. Single-phase AlN powders were obtained from all oxide precursors. Complete nitridation was not obtained using pure N₂, even for the non-oxide precursors.     

Precipitation of Magnesium Aluminum Spinel from Alumina-Matrix Solid Solution: I, Fundamental Concept and Precipitation Behavior

Al₂O₃ ceramics with magnesium aluminum spinel dispersion particulates were produced by a precipitation treatment of Al₂O₃-matrix solid solution, (Al_1—2x,Ti _x ,Mg _x )₂O₃. We successfully constructed the precipitation process for synthesizing the nanocomposite, using the solubility dependence of titanium and magnesium in Al₂O₃ on the valence of titanium. Changing of the valence of titanium from 4+ to 3+ was accomplished by controlling the heating atmosphere, and, thereby, magnesium precipitation was promoted. The precipitation behavior was characterized using X-ray diffractometry, and the microstructure was observed using transmission electron microscopy. We confirmed that magnesium aluminum spinel nanosized particulate were precipitated in the Al₂O₃ grain.     

Microstructure and Mechanical Properties of Porous Alumina Ceramics Fabricated by the Decomposition of Aluminum Hydroxide

The mechanical properties of Al₂O₃-based porous ceramics fabricated from pure Al₂O₃ powder and the mixtures with Al(OH)₃ were investigated. The fracture strength of the porous Al₂O₃ specimens sintered from the mixture was substantially higher than that of the pure Al₂O₃ sintered specimens because of strong grain bonding that resulted from the fine Al₂O₃ grains produced by the decomposition of Al(OH)₃. However, the elastic modulus of the porous Al₂O₃ specimens did not increase with the incorporation of Al(OH)₃, so that the strain to failure of the porous Al₂O₃ ceramics increased considerably, especially in the specimens with high porosity, because of the unique pore structures related to the large original Al(OH)₃ particles. Fracture toughness also increased with the addition of Al(OH)₃ in the specimens with higher porosity. However, fracture toughness did not improve in the specimens with lower porosity because of the fracture-mode transition from intergranular, at higher porosity, to transgranular, at lower porosity.     

Carbothermal Synthesis of Aluminum Nitride Using Sucrose

Several aluminum oxides (α-Al₂O₃, θ-Al₂O₃, and AIOOH) were examined to study the differences in reaction behavior and powder characteristics during carbothermal nitrida-tion to AIN using sucrose and carbon black. The reaction conditions investigated were carbon-to-alumina ratio, reaction temperature, and time. Carburized sucrose resulted in Full conversion to AIN and produced a uniform powder morphology using a near-istoichiometric ratio of C:Al₂O₃ while carbon black required higher C:Al₂O₃ ratios (i.e., >4:1) for full conversion and led to agglomeration of the AIN powder. The most favorable reaction temperature was 1600°C, with the reaction time to full conversion being dependent on the type of Al₂O₃. The particle and agglomerate size of the AIN powders did not change significantly with reaction time. However, the particle size and morphology were strongly dependent on that of the initial AI₂O₃ with sucrose, whereas agglomeration of the AIN occurs when using carbon black. A solid–solid reaction mechanism is proposed.     

Low-Temperature Synthesis of Calcium Hexa-Aluminate

Calcium hexa-aluminate (CaO·6Al₂O₃) has been prepared from calcium nitrate and aluminum sulfate solutions in the temperature range of 1000°–1400°C. A 0.3 mol/L solution of aluminum sulfate was prepared, and calcium nitrate was dissolved in it in a ratio that produced 6 mol of Al₂(SO₄)₃·16H₂O for each mole of Ca(NO₃)₂·4H₂O. It was dried over a hot magnetic stirrer at ∼70°C and fired at 1000°–1400°C for 30–360 min. The phases formed were determined by XRD. It was observed that CaO·Al₂O₃ and CaO·2Al₂O₃ were also formed as reaction intermediates in the reaction mix of CaO·6Al₂O₃. The kinetics of the formation of CaO·6Al₂O₃ have been studied using the phase-boundary-controlled equation 1 − (1 − x )^1/3= K log t and the Arrhenius plot. The activation energy for the low-temperature synthesis of CaO·6Al₂O₃ was 40 kJ/mol.     

Mullite Crystallization from SiO2-Al2O3 Melts

SiO₂-Al₂O₃ melts containing 42 and 60 wt% A1₂O₃ were homogenized at 2090°C (∼10°) and crystallized by various heat treatment schedules in sealed molybdenum crucibles. Mullite containing ∼78 wt% A1₂O₃ precipitated from the 60 wt% A1₂O₃ melts at ∼1325°± 20°C, which is the boundary of a previously calculated liquid miscibility gap. When the homogenized melts were heat-treated within this gap, the A1₂O₃ in the mullite decreased with a corresponding increase in the Al₂O₃ content of the glass. A similar decrease of Al₂O₃ in mullite was observed when crystallized melts were reheated at 1725°± 10°C; the lowest A1₂O₃ content (∼73.5 wt%) was in melts that were reheated for 110 h. All melts indicated that the composition of the precipitating mullite was sensitive to the heat treatment of the melts.     

Development of Nano-Composite Microstructures in ZrO2-Al2O3 via the Solution Precursor Method

Aqueous mixtures of zirconium acetate and aluminum nitrate were pyrolyzed and crystallized to form a metastable solid solution, Zr_{1- x} Al _x O_{2− x /2} ( x < 0.57). The initial, metastable phase partitions at higher temperatures to form two metastable phases, viz., t −ZrO₂+γ-Al₂O₃ with a nano-scale microstructure. The microstructural observations associated with the γ- →α-Al₂O₃ phase transformation in the t -ZrO₂ matrix are reported for compositions containing 10, 20, and 40 mol% A1₂O₃. During this phase transformation, the α-Al₂O₃ grains take the form of a colony of irregular, platelike grains, all with a common crystallographic orientation. The plates contain ZrO₂ inclusions and are separated by ZrO₂ grains. The volume fraction of A1₂O₃ and the heat treatment conditions influence the final microstructure. At lower volume fractions of A1₂O₃, the colonies coarsen to single, irregular plates, surrounded by polycrystalline ZrO₂. Interpenetrating microstructures produced at high volume fractions of A1₂O₃ exhibit very little grain growth for periods up to 24 h at 1400°C.     

Electrical Conductivity of A12O3: Fe + Y

High-temperature dc electrical conductivity and emf of oxygen concentration cells with A1₂O₃ as the electrolyte were studied. The defect structure of α-Al₂O₃ doped with Fe and Y was investigated to test an explanation proposed for the favorable effect of Y addition to super alloys (Fe, Cr, Ni, Al) which leads to well-adherent and nonconvoluted A1₂O₃ oxide scales. Results indicate that Y is a singly ionizable donor in Al₂O₃ and Y additions are effective in compensating Fe acceptors in A1₂O₃ at iron concentrations up to the solubility limit of Y. At higher acceptor concentrations leading to a decrease in [ V "'_Al] and an increase in [Al^…_i], incorporation of Y leads to a small increase in the concentration of V'" _Al. This suggests that the mechanism proposed for the prevention of oxide scale spallation based on the Y donor action to suppress the bulk diffusion of aluminum interstitials created by the Fe acceptors cannot explain the effect. Energy level positions of Fe and Y in A1₂O₃ are estimated, and values for electron and hole mobility at 1500°C are derived.     

Particle Size Comparison of Hydrothermally Synthesized Cobalt and Zinc Aluminate Spinels

Nanosized CoAl₂O₄ and ZnAl₂O₄ powders with particle sizes of 67 and 6.5 nm are synthesized under hydrothermal conditions at 245°C for 20 h. The precursors are reacted at different temperatures to provide intermediate phase transformations using X-ray diffraction (XRD), infrared (IR) spectra, and thermal gravity and differential thermal analysis (TG-DTA). XRD patterns and IR spectra demonstrate that the CoAl layered double hydroxide structure (CoAl-LDHs) is more stable than ZnAl layered double hydroxide structure (ZnAl-LDHs) when they are hydrothermally treated. The different thermal stability of the CoAl- and ZnAl-LDHs results in the different aluminum source, e.g., β-Al(OH)₃ for ZnAl₂O₄ vs γ-AlO(OH) for CoAl₂O₄, when the aluminate spinels are formed. The different aluminum sources lead to the particle size difference. The phenomenon is reasonably expounded based on the nucleation theory from the microscopic scale.     

Phase Relations and Microstructural Development of Aluminum Nitride–Aluminum Nitride Polytypoid Composites in the Aluminum Nitride–Alumina–Yttria System

AlN–AlN polytypoid composite materials were prepared in situ using pressureless sintering of AlN–Al₂O₃ mixtures (3.7–16.6 mol% Al₂O₃) using Y₂O₃ (1.4–1.5 wt%) as a sintering additive. Materials fired at 1950°C consisted of elongated grains of AlN polytypoids embedded in equiaxed AlN grains. The Al₂O₃ content in the polytypoids varied systematically with the overall Al₂O₃ content, but equilibrium phase composition was not established because of slow nucleation rate and rapid grain growth of the polytypoid grains. The polytypoids, 24 H and 39 R , previously not reported, were identified using HRTEM. Solid solution of Y₂O₃ in the polytypoids was demonstrated, and Y₂O₃ was shown to influence the stability of the AlN polytypoids. The present phase observations were summarized in a phase diagram for a binary section in the ternary system AlN–Al₂O₃–Y₂O₃ parallel to the AlN–Al₂O₃ join. Fracture toughness estimated from indentation measurements gave no evidence for a strengthening mechanism due to the elongated polytypoids.     

Microstructure and Properties of Co2+: ZnAl2O4/SiO2 Nanocomposite Glasses Prepared by Sol–Gel Method

Transparent bulk Co²⁺: ZnAl₂O₄/SiO₂ nanocomposites containing nanocrystalline Co²⁺: ZnAl₂O₄ dispersed in silica glass matrix were obtained by the sol–gel method. The gels of composition 89SiO₂–6Al₂O₃–5ZnO− x CoO ( x =0.2, 0.4, 0.6, 0.8, 1.0) (mol%) were prepared at room temperature by using two different aluminum salts, aluminum nitrate and aluminum alkoxide (aluminum-iso-propoxide, Al(OPrⁱ)₃), as starting materials. The transparent gels were converted to the crystalline phase of gahnite by heating above 900°C. The microstructural evolution of gels was characterized. The effect of Co²⁺ concentration on spectroscopic properties was also discussed. Co²⁺: ZnAl₂O₄ nanocrystals dispersed in the SiO₂-based glass are formed at lower heat-treatment temperature and shorter heating time by using Al(OPrⁱ)₃ as raw material.     

Formation of Titanium Carbide/Aluminum Oxide Nanocomposite Powder by High-Energy Ball Milling and Subsequent Heat Treatment

The preparation of titanium carbide/aluminum oxide (TiC/Al₂O₃) nanocomposite powders from a mixture of titanium, carbon, and Al₂O₃ powders via a high-energy ball milling process and subsequent heat treatment was investigated. The microstructure development of the powder mixtures was monitored by X-ray diffraction and transmission electron microscopy. The ball milling of an elemental carbon, titanium, and Al₂O₃ powder mixture at ambient temperature resulted in the formation of TiC within 15 h of milling. With further milling of up to 25 h, the resulting powder mixture was composed of nanosized TiC particles and nanocrystalline carbon, titanium, and Al₂O₃. The nanocrystalline titanium and carbon were transformed into nanosized TiC particles after subsequent heat treatment. The final product was composed of nanosized TiC and microcrystalline Al₂O_3. Most of the nanosized TiC particles were located within Al₂O₃ grains.     

Preparation of Aluminum Oxynitride by Nitridation of a Precursor Derived from Aluminum–Glycine Gel and the Effects of the Presence of Europium

Spinel-type AlON, Al_2.75□_0.25O_3.74N_0.26, was obtained by ammonia nitridation of an oxide precursor prepared by peptizing a glycine gel with aluminum nitrate. To achieve crystallization, the nitrided product had to be annealed at 1500°C for 10 min in flowing nitrogen. The use of glycine instead of citric acid was important for obtaining a white product without residual carbon. A similar preparation method was used for adding small amounts of europium below 10 mol%. A strong blue emission was observed for products ranging from 0.5 to 3.0 mol% Eu doping. The product with 0.5 mol% doping had a maximum emission intensity at 400 nm for an excitation of 254 nm. The products with 1 and 3 mol% doping showed double maxima at 475 and 520 nm. These three emissions were due to the presence of divalent europium in the EuAl₁₂O₁₉ magnetoplumbite-like aluminum oxynitride impurity mixed with the AlON spinel major phase. The 1 mol% Eu-doped product exhibited expanded hexagonal lattice parameters ( a =0.5591 and c =2.236 nm) compared with the values for EuAl₁₂O₁₉ magnetoplumbite itself, observed in the 7.7 mol%-doped product without any strong emission. The above spectrum change was discussed in relation to the coordination around Eu²⁺.     

Effect of Trace A12O3 on Transformation of Quartz to Cristobalite

The effect of additions of 0.22, 0.44, 0.88, and 1.76% A1₂O₃ (Si⁴⁺/A1³⁺ ratio of 200:1, 100:1, 50:1, and 25:1) on the transformation of Brazilian quartz to cristobalite was studied at 1500°, 1530°, and 1570°C. The smaller percentages of A1₂O₃ (0.22 and 0.44%) catalyzed the transformation of quartz and the formation of cristobalite considerably. The rates of transformation of quartz with 0.88 and 1.76% A1₂O₃ were slower than with 0.22 or 0.44%, indicating a critical A1³⁺/Si⁴⁺ ratio where the catalytic effect was found to be maximum. This appeared to occur at about 0.5% A1₂O₃. The transformation rate of quartz indicated that the reaction was first order. Cristobalite, however, showed two different rates; the initial rapid growth was followed by a slower rate. The point of changeover was found to be at about 30 ± 5% cristobalite. The critical nature of the A1³⁻/Si⁴⁺ ratio at about 0.01 (or A1₂O₃/SiO₂± 0.005) may have some bearing on the properties of silica refractories with more or less than 0.5% A1₂O₃.     

Reactions in Silica-Alumina Mixtures

Examination of mixtures of extremely pure silica and alumina shows that the greatest reactivity is not encountered with stoichiometric ratios to form mullite with the formula 3Al₂O₃. 2SiO₂ but rather with the formula 2A1₂O₃-SiO₂, and that reactivity also depends on the crystalline modification of alumina. A sharp exothermic differential thermal peak at 980°C. is attributed to three simultaneous reactions dependent on the silica-alumina ratio of the mixture: (1) the crystallization of gamma alumina, (2) the crystallization of a hydrogen aluminum spinel (HAl₅O₅), and (3) the reaction of silica with the hydrogen aluminum spinel to form mullite.     

Lubricated Rolling Wear of SiC-Whisker-Reinforced Al2O3 Composites against M2 Tool Steel

Lubricated rolling wear studies of SiC-whisker (SiC_w) reinforced A1₂O₃ composites and monolithic A1₂O₃ against M2 tool steel were conducted using a cylinder-on-cylinder apparatus. The composites wore considerably less than A1₂O₃. The wear of the tool steel against the composites was also considerably less than against A1₂O₃. Microfracture occurred on a smaller scale in the composites than in the Al₂O₃. This was attributed to the differences in microstruc-ture and fracture toughness. The worn surfaces of the steel and the composites were polished, possibly due to fine, hard wear debris circulating with the lubricant to the contact area.