Synthesis of AlN Nanopowder from γ-Al2O3 by Reduction–Nitridation in a Mixture of NH3–C3H8

Aluminum nitride (AlN) powders were synthesized by gas reduction–nitridation of γ-Al₂O₃ using NH₃ and C₃H₈ as the reactant gases. AlN was identified in the products synthesized at 1100°–1400°C for 120 min in the NH₃–C₃H₈ gas flow confirming that AlN can be formed by the gas reduction–nitridation of γ-Al₂O₃. The products synthesized at 1100°C for 120 min contained unreacted γ-Al₂O₃. The ²⁷A1 MAS NMR spectra show that Al–N bonding in the product increases with increasing reaction temperature, the tetrahedral AlO₄ resonance decreasing prior to the disappearance of the octahedral AlO₆ resonance. This suggests that the tetrahedral AlO₄ sites of the γ-Al₂O₃ are preferentially nitrided than the AlO₆ sites. AlN nanoparticles were directly formed from γ-Al₂O₃ at low temperature because of this preferred nitridation of AlO₄ sites in the reactant. AlN nanoparticles are formed by gas reduction–nitridation of γ-Al₂O₃ not only because the reaction temperature is sufficiently low to restrict grain growth, but also because γ-Al₂O₃ contains both AlO₄ and AlO₆ sites, by contrast with α-Al₂O₃ which contains only AlO₆.     

Effect of B2O3 and hBN Crystallinity on cBN Synthesis

Four kinds of BN powders—amorphous BN with B₂O₃, partially crystallized BN without B₂O₃, well-crystallized hBN with B₂O₃, and well-crystallized hBN without B₂O₃—were prepared to determine the effect of B₂O₃ on the crystallization of amorphous BN and the effect of BN crystallinity on the formation of cBN under high pressure (4–5 GPa) and at high temperature (1350–1450°C). The amorphous BN with B₂O₃ easily crystallized and transformed to cBN in the presence of A1N catalyst, while the partially crystallized BN without B₂O₃ did not. The well-crystallized hBN transformed very slowly to cBN without B₂O₃, in contrast to fast transformation with B₂O₃. It is thus found that the transformation from hBN to cBN in the presence of AIN catalyst is determined by the degree of BN crystallinity as well as the presence of B₂O₃. Cubic BN can be synthesized only from crystallized hBN under the experimental conditions used. The formation of cBN from amorphous BN is possible through its prior crystallization, which can occur in the presence of B₂O₃.     

Reaction Synthesis of Aluminum Nitride–Boron Nitride Composites Based on the Nitridation of Aluminum Boride

Aluminum nitride–boron nitride (AlN–BN) composites were prepared based on the nitridation of aluminum boride (AlB₂). AlN powder was added to change the BN volume fraction in the obtained composites. Thermogravimetry–differential thermal analysis (TG-DTA), X-ray diffractometry, and the nitridation ratio were used to investigate the nitridation process of AlB₂. At ∼1000°C, a sharp exothermic peak occurred in the DTA curve, corresponding to the rapid nitridation of aluminum in AlB₂. On the other hand, the nitridation of the transient phase, Al_1.67B₂₂, was very slow when the temperature was <1400°C. However, the nitridation speed obviously accelerated at temperatures >1600°C. The pressure of the nitrogen atmosphere was also an important factor; high nitrogen pressure remarkably promoted nitridation. Treatment at 2000°C was disadvantageous for nitridation, because of the rapid formation of a dense surface layer that inhibited nitrogen diffusion into the specimen interior. Three specimens, with 5 wt% Y₂O₃ additive and different BN contents, were prepared by pressureless reactive sintering, according to the determined sintering schedule. Electron microscopy (scanning and transmission) observations revealed that the in-situ -formed BN flakes were homogeneously and isotropically distributed in the AlN matrix. A schematic mechanism for microstructural formation was developed, based on the results of nitridation and the microstructural features of the obtained composites. The obtained composites, with a low BN content, exhibited a high bending strength, comparable to that of reported hot-pressed AlN–BN composites.     

Synthesis of Nanocrystalline Aluminum Nitride by Nitridation of δ-Al2O3 Nanoparticles in Flowing Ammonia

Nanocrystalline aluminum nitride (AlN) with surface area more than 30 m²/g was synthesized by nitridation of nanosized δ-Al₂O₃ particles using NH₃ as a reacting gas. The resulting powders were characterized by CHN elemental analysis, X-ray diffraction (XRD), Fourier transform infrared spectra, X-ray photoelectron spectra, field-emission scanning electron microscopy, transmission electron microscopy, and Brunauer–Emmett–Teller surface area techniques. It was found that nanocrystalline δ-Al₂O₃ was converted into AlN completely (by XRD) at 1350°–1400°C within 5.0 h in a single-step synthesis process. The complete nitridation of nanosized alumina at relatively lower temperatures was attributed to the lack of coarsening of the initial δ-Al₂O₃ powder. The effect of precursor powder types on the conversion was also investigated, and it was found that α-Al₂O₃ was hard to convert to AlN under the same conditions.     

Reactions and Microstructure Development in Mullite Fibers

Microstructural and compositional changes during heat treatment of sol–gel-derived mullite fibers with additions of 2 wt% B₂O₃, 2 wt% P₂O₅, 2 wt% Cr₂O₃, and (1 wt% P₂O₅+ 1 wt% Cr₂O₃) were compared with those of undoped mullite fibers. For all compositions the sequence of phase development was the crystallization of a spinel phase (†-Al₂O₃ or Al–Si spinel) from amorphous material, followed by the formation of mullite at higher temperatures. Differential thermal analysis showed that additions of B₂O₃ and P₂O₅ increased the temperature of spinel formation and that B₂O₃ significantly decreased the temperature of mullite formation. After 1 h at 1200°C, the size of mullite grains in fibers that contained B₂O₃ was less than 1000 Å the grains in fibers of other compositions were 6000 to 12000 Å. After 60 h at 1400°C, fibers modified with B₂O₃ had a grain size less than 2000 to 3000 Å the grains in fibers of other compositions were 6000 to 12000 Å. B₂O₃ was the most volatile additive.     

Influence of Additives on Slag Resistance of Al2O3-SiO2-SiC-C Refractory Bond Phases under Reducing Atmosphere

The microstructures of Al₂O₃–SiO₂–SiC–C refractory matrices with aluminum, silicon, Si₃N₄, BN, B₂O₃, and B₄C additives are characterized before and after a crucible slag test, and the phases present are compared to those expected at thermodynamic equilibrium. The carbon content dominates the resistance to CaO–MgO–Al₂O₃–SiO₂ slag penetration, while the viscosity of liquid phases present has a significant influence when the matrix carbon contents are similar. Silicon and Si₃N₄ additives reduce slag penetration resistance because of indirect oxidation of carbon to form SiC. B₄C, in particular, and B₂O₃ also reduce slag penetration resistance because of formation of a more fluid boron-containing liquid, while aluminum and BN addition have no significant effect. Carbon and BN hardly react with the slag, while SiC partially reacts with it, leading to deposition of carbon as a dense layer. Corundum present in the refractories also readily dissolves in the slag. Microstructurally, slag penetration resistance is associated with the dense carbon layer located at the slag-refractory interface.     

Reactive Hot-Pressed Alumina–Boron Nitride Composites with Y2O3 Sintering Additive

The effect of Y₂O₃ addition (0–5 wt%) on the densification and properties of reactive hot-pressed alumina (Al₂O₃)–boron nitride composites based on the reaction between aluminum borate (2Al₂O₃·B₂O₃) and aluminum nitride (AlN) was investigated. The densification process was very sensitive to the amount of Y₂O₃. Compared with a low relative density of 79.3 theoretical density (TD)% for material with no Y₂O₃ addition, the material density reached 98.6 TD% with 0.25% Y₂O₃ addition. High Y₂O₃ additions resulted in the formation of a new phase Al₅Y₃O₁₂. The grain growth of the Al₂O₃ matrix was promoted by the Y₂O₃ addition. Owing to the high density and the small Al₂O₃ particle size the sample with 0.25% Y₂O₃ addition demonstrated the highest bending strength of 540 MPa.     

Synthesis and Mechanism of Nanosized AlN from an Aluminum Oleic Emulsion Using Carbothermal Reduction at Low Temperatures

Nanosized Al₂O₃ particles homogeneously dispersed in a matrix of amorphous carbon (a-C) were prepared by decomposition of an aluminum oleic emulsion at 600°C in Ar. Nanosized aluminum nitride (AlN) grains were prepared by carbothermal reduction and nitridation (CRN) of this Al₂O₃–a-C mixture in NH₃ using graphite, BN, and alumina crucibles or boats. The phases formed by CRN were identified by X-ray diffraction analysis. The morphology and grain size of the AlN were determined by transmission electron microscopy. The formation of single-phase AlN was achieved at temperatures as low as 1150°–1200°C in NH₃ using a cylindrical graphite crucible with holes in its two flat faces. Mass spectroscopy (MS) showed that a significant amount of HCN and a minor amount of C₂H₂ are formed at 500°C by reaction of NH₃ with carbon at the decomposition temperature of NH₃. A most probable formation mechanism of the AlN from nanosized Al₂O₃ and a-C in NH₃ is discussed on the basis of MS results and thermodynamic considerations.     

Al-System Non-Oxide Spherical Powder Synthesis by Liquefied Petroleum Gas Firing

Synthesis of non-oxide materials includes solid-phase grinding, liquid building-up, plasma, and CVD. The raw powder of the sintered body is commercialized by solid-state synthesis; however, it is non-spherical in shape and its size is below the submicron range. We considered the changes in free energy of Al, O₂, N₂, NH₃, liquefied petroleum gas (LPG) and focused on the reaction accelerator effect of LPG for Al nitridation or Al₂O₃ reduction. As a result, we found that, conceptually, some Al nitridation syntheses via LPG firing could occur. The LPG firing method can provide a gas diffusion nitridation mechanism, and can therefore produce Al-oxynitride (AlON) directly (Al powder did not convert to AlON completely), and AlN spherical powders with diameters above the submicron range.     

Effects of Additives on the Pressure-Assisted Densification and Properties of Silicon Carbide

The densification of silicon carbide (SiC) was studied using a variety of additives (Al, AlN, Al₂O₃, B₄C, C, Si₃N₄, and Y₂O₃). The onset of densification of SiC with small amounts of additives occurred at temperatures between 1500° and 1900°C with 28 MPa applied pressure. Al, B₄C, and C promoted densification, while N (added as AlN or Si₃N₄) retarded sintering. A 96.75 wt% SiC–2 wt% Al–1 wt% C–0.25 wt% B₄C starting composition yielded the same percent of theoretical density (in the range of 70%–90% theoretical density) 400°C lower than a 95 wt% SiC–5 wt% AlN material. Yttria additions promoted intergranular fracture, which increased the single-edged precracked beam fracture toughness. The appropriate selection and amount of additives allowed for the tailoring of grain size and intergranular fracture, thus controlling the mechanical properties. While oxygen was present in all materials containing aluminum, the incorporation of additional oxygen as alumina resulted in reduced sintering activity compared with Al metal. Corrosion resistance decreased in both HF and NaOH solutions at 80°C for materials containing a grain boundary phase.     

Machinable α-SiAlON/BN Composites

Dense machinable α-SiAlON/BN composites were fabricated by hot-pressing using turbostratic boron nitride (tBN) obtained from nitridation of melamine diborate. The tBN was added to the starting powders, or introduced as a coating that formed in situ on α-Si₃N₄ carrier powders during nitridation, and was subsequently converted to hexagonal boron nitride (hBN) during hot pressing by solution reprecipitation. These composites maintain high strength at 1000°C and their strength/hardness are much higher than similar composites prepared using commercial hBN powder, which yielded a coarser microstructure. Good machinability was achieved despite a flat R curve.     

Effect of Polynuclear Complex Content on the Synthesis of Aluminum Nitride from Aluminum Polynuclear Complex

Aluminum nitride powders were synthesized from an aluminum polynuclear complex and glucose. Basic aluminum chloride (BAC) was used as the aluminum polynuclear complex. The effect of the polynuclear complex content on the nitridation reaction and particle size of the AIN powder synthesized was investigated. BAC solutions with various polynuclear complex contents were synthesized using an aqueous solution prepared from AlCl₃ and Al metal with various compositions. In this system, AlN was synthesized through γ-Al₂O₃ as an intermediate regardless of the polynuclear complex content. Polynuclear complex content affects the reactivity of nitridation and the particle size of the synthesized AIN powder. The reactivity of nitridation and specific surface area of the products increased with the polynuclear complex content. When the precursor with a polynuclear complex content of 94% was calcined at 1400°C, the AlN content reached 95%. Crystallite size by X-ray diffraction measurement and particle size calculated from the specific surface area for the products were in good agreement, indicating that AlN particles formed in the synthesis process are in the form of single crystals. AlN powder synthesized from the precursor with a polynuclear complex content above 80% had a fine particle size and narrow size distribution.     

Auger Electron Spectroscopy of Aluminum Nitride Powder Surfaces

The chemical states of powder surfaces depend on the manufacturing processes of the powders. The surface chemistry of three different commercial AIN powders, which are processed by carbothermal nitridation of Al₂O₃, chemical vapor deposition (CVD), and direct nitridation of aluminum, were evaluated by using Auger electron spectroscopy (AES). In order to obtain reference AES spectra of aluminum compounds, α-, γ-, θ-Al₂O₃, γ-AIOOH, γ-AION, and sintered AIN were also examined. Line shapes of aluminum LVV ; Al( LVV ), nitrogen KLL ; N( KLL ) and oxygen KLL ; O( KLL ) are discussed for the AIN powders and all the other aluminum compounds. The differential Auger electron spectra, i.e., E dn /AE were obtained directly, where n is the number of Auger electrons, and E is the kinetic energy of the electron. Their integrated spectra, i.e., n ( E ) are also employed for analysis. The results confirm the conclusions of our previous temperature-programmed desorption work. The AES line shape analysis implies the presence of an oxide-like θ -Al₂O₃ containing AION phase on the carbothermal nitride AIN powder surfaces. The surfaces of CVD and direct-nitrided AIN powders are covered by an oxide–like γ-Al₂O₃ with an oxygen diffusion layer and does not have AION phase.     

Microwave Plasma Synthesis of Nanostructured γ-Al2O3 Powders

Nanostructured Al₂O₃ powders have been synthesized by combustion of aluminum powder in a microwave oxygen plasma, and characterized by X-ray diffraction and electron microscopy. The main phase is γ-Al₂O₃, with a small amount of δ-Al₂O₃. The particles are truncated octahedral in shape, with mean particle sizes of 21–24 nm. The effect of reaction chamber pressure on the phase composition and the particle size was studied. The γ-alumina content increases and the mean particle size decreases with decreasing pressure. No α-Al₂O₃ appears in the final particles. Electron microscopy studies find that a particle may contain more than one phase.     

Mullite–Boron Nitride Composite with High Strength and Low Elasticity

Mullite–boron nitride (BN) composite with high strength, low Young's modulus, and highly improved strain tolerance was prepared by reactive hot pressing (RHP) using aluminum borates (9Al₂O₃·2B₂O₃ and 2Al₂O₃·B₂O₃) and silicon nitride as starting materials. Compared with the monolithic mullite, the composite RHPed at 1800°C showed 1.64 times (540 MPa) the strength, 70% (153 GPa) the Young's modulus, and 2.34 times (3.53 × 10⁻³) the strain tolerance. Transmission electron microscopy observation revealed that the composite had an isotropic microstructure with a fine mullite matrix grain size of less than 1 μm and nanosized hexagonal BN (h-BN) platelets of about 200 nm in length and 60–80 nm in thickness. The high strength was suggested to be from the reduced matrix grain size and the small toughening effect by the h-BN platelets.     

Formation of MgO-B4C Composite via aThermite-Based Combustion Reaction

The combustion synthesis of MgO-B₄C composites was investigated by coupling a highly exothermic Mg-B₂O₃ thermite reaction with a weakly exothermic B₄C formation reaction. Unlike the case of using Al as the reducing agent, the interaction between Mg and B₂O₃ depends on the surrounding inert gas pressure due to the high vapor pressure of Mg. The interaction changes from one involving predominantly gaseous Mg and liquid B₂O₃ to one involving liquid Mg and liquid B₂O₃ as the pressure increases. At low inert gas pressure, the initiation temperature is found to be just below the melting point of Mg (650°C). As the inert gas pressure increases, the vaporization loss of reactants is reduced, and this in turn increases the combustion temperature, which promotes greater grain growth of the product phases, MgO and B₄C. The particle size of B₄C increased from about 0.2 to 5 μm as the pressure changed from 1 to 30 atm.     

Growth of Quasi-Aligned AlN Nanofibers by Nitriding Combustion Synthesis

Quasi-aligned AlN nanofibers were formed by the nitriding combustion synthesis according to a unique micro-reactor model. A charge composed of aluminum and aluminum nitride diluent powders (40/60 mol%) with a mixture of yttria and ammonium chloride as additives (5 wt% each) was combusted at low nitrogen gas pressures of 0.25 MPa. The FE-SEM images of as-synthesized AlN product showed the formation of ball-like grains (same shape and size as the original Al reactant) that consisted of a thin surface nitride layer or crust cover quasi-aligned AlN nanofibers grown in the interior. The cross-sectional view is sea anemone like. Formation of this novel morphology is believed to occur through a two-stage process. The first one occurs at the preliminary stage of the combustion outside Al particles. After the ignition, the heat generated causes the sublimation and dissociation of ammonium chloride into various gaseous species. This effectively interrupts the combustion and slows down the increase of reaction temperature. In addition, yttria interacts with the native oxide layer present on the surface of Al particles and forms a stable Al–N–Y–O crust. The second stage begins by the infiltration of various gaseous species such as HCl_(g), NH_3(g), and N_2(g) through the crust into the molten Al cores. The "crust–core" systems function as "micro-reactors" where both the nitridation and growth processes occur inside. The molten Al cores are spontaneously halogenated to AlCl₃ vapors and the nitridation proceeds by the gas–gas reaction of AlCl₃ and NH₃/N₂ vapors. The AlN nanofibers are then grown from the vapor phase quasi-aligned inside the micro-reactors by VLS and VS mechanisms.     

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.     

Convection Patterns in Liquid Oxide Films on ZrB2–SiC Composites Oxidized at a High Temperature

During the high-temperature oxidation of ZrB₂–SiC composites, liquid boron oxide (B₂O₃) is formed at the zirconium diboride–zirconium oxide interface and transported through the overlying layer of silica liquid by convection, forming distinct convection cells arranged like the petals of a flower. The convection cells are localized by a viscous fingering phenomenon, as the fluid B₂O₃ rich liquid solution rises through the viscous silica layer. The upwelling B₂O₃ rich liquid contains dissolved zirconium dioxide, which deposits in the center of the flower-like structure as the B₂O₃ evaporates. The driving force for the B₂O₃ liquid flow is the volume increase upon oxidation of ZrB₂. Convective transport of B₂O₃ liquids suggests a novel mechanism for the high-temperature oxidation of these materials.     

High-Temperature Oxidation of Boron Nitride: I, Monolithic Boron Nitride

High-temperature oxidation of monolithic boron nitride (BN) is examined at 900–1200°C. Hot-pressed BN and both low- and high-density chemically vapor-deposited BN are studied. The oxidation product is B₂O₃( l ) and the oxidation kinetics are sensitive to crystallographic orientation, porosity, and impurity levels. The B₂O₃ product also reacts readily with ambient water vapor in the test furnace (ppm levels) to form the volatile species HBO₂( g ), leading to overall paralinear kinetics. The linear rate constant extracted from these experiments agreed with that predicted from diffusion of HBO₂( g ) across a static boundary layer.