Improved Oxidation Resistance of Silicon Nitride by Aluminum Implantation: I, Kinetics and Oxide Characteristics

Hot-isostatically-pressed, additive-free Si₃N₄ ceramics were implanted with aluminum at multi-energies and multidoses to achieve uniform implant concentrations at 1, 5, and 10 at.% to a depth of about 200 nm. The oxidation behavior of unimplanted and aluminum-implanted Si₃N₄ samples was investigated in 1 atm flowing oxygen entrained with 100 and 220 ppm NaNO₃ vapor at 900–1100°C. Unimplanted Si₃N₄ exhibits a rapid, linear oxidation rate with an apparent activation energy of about 70 kJ/mol, independent of the sodium content in the gas phase. Oxides formed on the unimplanted samples are rough and are populated with cracks and pores. In contrast, aluminum-implanted Si₃N₄ shows a significantly reduced, parabolic oxidation rate with apparent activation energies in the range of 90–140 kJ/mol, depending on the sodium content as well as the implant concentration. The oxides formed on the implanted samples are glassy and mostly free from surface flaws. The alteration of the oxidation kinetics and mechanism of Si₃N₄ in a sodium-containing environment by aluminum implantation is a consequence of the effective modification of the properties of the sodium silicates through aluminum incorporation.     

Improved Oxidation Resistance of Silicon Nitride by Aluminum Implantation: II, Analysis and Optimization

In the preceding paper, it was shown that aluminum ion implantation significantly improves the oxidation resistance of Si₃N₄ ceramics under the influence of sodium. Not only is the oxidation rate reduced by up to an order of magnitude, the phase and morphological characteristics of the oxides grown on aluminum-implanted samples are improved as well. The role of aluminum in negating the detrimental effect of sodium on the oxidation resistance of Si₃N₄ ceramics can be interpreted on the basis of network modification of the oxide layers by sodium and aluminum cations. The degree of improvement in the oxidation resistance does not, however, necessarily increase with the aluminum concentration. A simple quantitative analysis is presented which correlates the optimum aluminum implant concentration and the sodium content in the gas phase for the optimization of the oxidation resistance of Si₃N₄ ceramics.     

刚玉氮化硅复合材料表面氧化膜的形成动力学

以刚玉粉和氮化硅粉为原料,借助微量热分析天平,结合X射线衍射和扫瞄电镜等检测手段,对刚玉氮化硅复合材料表面氧化膜的形成动力学机理进行了研究,并推导出了动力学方程.研究结果表明材料表面氧化膜的形成动力学可分为三个阶段:化学反应速度控制阶段,动力学方程为△W=Kc·t,其中Kc=52.21exp(-73806.3/RT);混合控制阶段,动力学方程为(△W)2+KO/Kc(△W)＝Km·t,其中Km=253.81exp(-85644.2/RT);扩散速度控制阶段,动力学方程为(△W)2=Kd·t,其中Kd=31.12exp(-66522.1/RT).     

Strengthening and Prevention of Oxidation of Aluminum Nitride by Formation of a Silica Layer on the Surface

A silica (SiO₂) layer was deposited on the surface of an AlN ceramic in order to increase the strength and to prevent the high-temperature oxidation of the material. The layer was formed on the surface by exposing coupons to the atmosphere downstream of a bed of SiC powder in a flowing H₂–0.1% H₂O atmosphere at 1450°C. A reaction between the SiC powder and H₂O in the H₂ gas resulted in the generation of SiO₂"smoke" in the product gas stream. Part of the SiO₂ smoke was subsequently deposited on the surface of the AlN specimen to form a dense and uniform SiO₂ layer. The strength of AlN was improved by about 20% apparently because of blunting of surface defects by SiO₂. More importantly, the layer was very effective in protecting the AlN from the oxidation at elevated temperatures, through the inhibition of transport of oxidants to the sample surface.     

Oxidation Studies of Aluminum-Implanted NBD 200 Silicon Nitride

The effects of aluminum-ion-implantation on the oxidation behavior of NBD 200 Si₃N₄ were investigated over an implant concentration range of 0–30 at.%, at 800°–1100°C, in 1 atm dry O₂. Oxidation of both unimplanted and implanted samples follows a parabolic rate law. The parabolic rate constant decreases and the activation energy increases with aluminum concentration. Smooth and crack-free oxides are formed under the combination of high implant concentrations and low oxidation temperatures. Outward diffusion of Mg²⁺ from the bulk of NBD 200 to the oxide layer remains the rate-limiting step for aluminum-implanted samples. The enhancement of the oxidation resistance of NBD 200 by aluminum implantation is attributed to the retardation of the outward diffusion of Mg²⁺.     

Intrinsic Disorder in Aluminum Nitride

An interatomic potential model is developed for aluminum nitride and is used in conjunction with atomistic computer simulation methods to obtain the energies of intrinsic point defects. These energies are found to be very high, indicating no significant intrinsic disorder, even close to the melting point. Interstitial formation is particularly unfavorable, suggesting that these species will play no part in defect-controlled processes in AlN.     

Degradation of Aluminum Nitride Powder in an Aqueous Environmet

The degradation of A1N powder in excess H₂O at room temperature for up to 24 h was investigated. Samples were characterized by various techniques (IR; XRD; SEM; XPS; C, H, N analysis; surface area, particle size, and weight change measurements). The reaction rate was found to be significant, with 80% of the A1N being consumed in 24 h. The initial reaction product was found to be a porous, amorphous, hydrated alumina with stoichiometry near AlOOH. After ∽16 h a crystalline phase, bayerite Al(OH)₃, was detected which became the predominant phase after 24-h contact. The kinetics of the A1N consumption were found to be first order and the reaction rate linear. The kinetic data fitted an unreacted core model with a porous product layer where the surface chemical reaction controlled the overall kinetics.     

Composition and Microstructure of Chemically Vapor-Deposited Boron Nitride, Aluminum Nitride, and Boron Nitride + Aluminum Nitride Composites

The composition and microstructure of dispersed-phase ceramic composites containing BN and AIN as well as BN and AIN single-phase ceramics prepared by chemical vapor deposition have been characterized using X-ray diffraction, scanning electron microscopy, electron microprobe, and transmission electron microscopy techniques. Under certain processing conditions, the codeposited coating microstructure consists of small single-crystal AIN fibers (whiskers) surrounded by a turbostratic BN matrix. Other processing conditions resulted in single-phase films of AIN with a fibrous structure. The compositions of the codeposits range from 2 to 50 mol% BN, 50 to 80 mol% AIN with 7% to 25% oxygen impurity as determined by electron microprobe analysis.     

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.     

Oxidation of Chemically-Vapor-Deposited Silicon Nitride and Slnglem-Crystal Silicon

Oxidation of {111} single-crystal silicon and dense, chemically-vapor-deposited silicon nitride was done in clean silica tubes at temperatures of 1000° to woo°C. The oxidation rates of silicon nitride under various atmospheres (dry O₂, wet O₂, wet inert gas, and steam) were several orders of magnitude slower than those of silicon under the identical conditions. The activation energy for the oxidation of silicon nitride decreased from 330 to 259 kJ/mol in going from dry O₂ to steam while that for Si decreased from 120 to 94 kJ/mol. The parabolic rate constant for Si increased linearly as the water vapor pressure increased. However, the parabolic rate constant for silicon nitride showed nonlinear dependency on the water vapor pressure in the presence of oxygen. The oxidation kinetics of silicon nitride is explained by the formation of nitrogen compounds (NO and NH₃) at the reaction interface and the counterpermeation of these reaction products.     

Simultaneous Chemical Vapor Deposition of Boron Nitride and Aluminum Nitride

Two chemically different phases, hexagonal BN and AIN, were simultaneously produced by chemical vapor deposition (CVD) using an impinging jet reactor and the BCl₃─AlCl₃─NH₃─Ar reagent system. The microstructure of the BN + AIN composite coatings was strongly dependent on temperature, pressure, and BCl₃ and AlCl₃ concentrations. The growth characteristics of BN and AIN in the codeposition system were similar to those expected from the single-phase deposition processes (i.e., BN-CVD and AIN-CVD), except the growth of AIN whiskers was accentuated, and competition between BN and AIN deposition in the composites was suspected to be the cause of less-crystalline deposits. In both BN + AIN-CVD and AIN-CVD, the growth of AIN whiskers became more apparent with increasing pressure or temperature. The codeposition behavior observed experimentally was compared with thermodynamic predictions.     

Reactivity of Aluminum Nitride Powder in Aqueous Silicon Nitride and Silicon Carbide Slurries

The reactivity of AlN powder with water in supernatants obtained from centrifuged Si₃N₄ and SiC slurries was studied by monitoring the pH versus time. Various Si₃N₄ and SiC powders were used, which were fabricated by different production routes and had surfaces oxidized to different degrees. The reactivity of the AlN powder in the supernatants was found to depend strongly on the concentration of dissolved silica in these slurries relative to the surface area of the AlN powder in the slurry. The hydrolysis of AlN did not occur if the concentration of dissolved silica, with respect to the AlN powder surface, was high enough (1 mg SiO₂/(m² AlN powder)) to form a layer of aluminosilicates on the AlN powder surface. This assumption was verified by measuring the pH of more concentrated (31 vol%) Si₃N₄ and SiC suspensions also including 5 wt% of AlN powder (with respect to the solids).     

Microstructural Characterization of High-Thermal-Conductivity Aluminum Nitride Ceramic

An aluminum nitride (AlN) ceramic with a thermal conductivity value of 272 W·(m·K)⁻¹, which is as high as the experimentally measured thermal conductivity of an AlN single crystal, was successfully fabricated by firing at 1900°C with a sintering aid of 1 mol% Y₂O₃ under a reducing N₂ atmosphere for 100 h. Oxygen concentrations were determined to be 0.02 and 0.03 mass% in the grains and in the grain-boundary phases, respectively. Neither stacking fault in the grains nor crystalline phase in the grain-boundary regions was found by transmission electron microscopy. An amorphous phase possessing yttrium and oxygen elements was detected between the grains as thin films with a thickness of <1 nm. Because the amount of grain-boundary phase was small, the high-thermal conductivity of the ceramic was attributable to the low oxygen concentration in the AlN grains.     

Oxidation Behavior of Liquid-Phase Sintered Silicon Carbide with Aluminum Nitride and Rare-Earth Oxides (Re2O3, where Re = Y, Er, Yb)

Silicon carbide (SiC) ceramics have been fabricated by hot-pressing and subsequent annealing under pressure with aluminum nitride (AlN) and rare-earth oxides (Y₂O₃, Er₂O₃, and Yb₂O₃) as sintering additives. The oxidation behavior of the SiC ceramics in air was characterized and compared with that of the SiC ceramics with yttrium–aluminum–garnet (YAG) and Al₂O₃–Y₂O₃–CaO (AYC). All SiC ceramics investigated herein showed a parabolic weight gain with oxidation time at 1400°C. The SiC ceramics sintered with AlN and rare-earth oxides showed superior oxidation resistance to those with YAG and Al₂O₃–Y₂O₃–CaO. SiC ceramics with AlN and Yb₂O₃ showed the best oxidation resistance of 0.4748 mg/cm² after oxidation at 1400°C for 192 h. The minimization of aluminum in the sintering additives was postulated as the prime factor contributing to the superior oxidation resistance of the resulting ceramics. A small cationic radius of rare-earth oxides, dissolution of nitrogen to the intergranular glassy film, and formation of disilicate crystalline phase as an oxidation product could also contribute to the superior oxidation resistance.     

Thermodynamic and Kinetic Effects of Oxygen Removal on the Thermal Conductivity of Aluminum Nitride

High thermal conductivity, low dielectric constant, high electrical resistivity, low density, and a thermal expansion coefficient that matches well with that of silicon are the principal attributes of AIN that have attracted much attention over the past decade. It is also now well established that oxygen as an impurity lowers the thermal conductivity of AIN. Processing techniques have been developed which not only facilitate pressureless densification of AIN but also enhance its thermal conductivity. The present work explores the thermodynamics and the kinetics of oxygen removal and the resultant enhancement of thermal conductivity. Polycrystalline AIN ceramics were fabricated with Y₂O₃, Dy₂O₃, Yb₂O₃, CaO, BaO, or MgO as additives. Samples were sinter/annealed at 1850°C for up to 1000 min. The AIN grain size of sintered samples ranged between 2 and 9 μm. The samples typically contained two or three phases with the predominant phase being AIN. Secondary phases in Y₂O₃-doped AIN consisted of yttrium aluminates which were along three grain junctions and along grain facets. The presence of Y₃Al₅O₁₂, YAIO₃, and Y₄Al₂O₉, as well as Y₂O₃, depending upon the Y₂O₃/Al₂O₃ ratio, was revealed by X-ray diffraction. Thermal conductivity increased with the amount of additive and annealing time. Thermal conductivity also depended on the type of additive. Samples with thermal conductivity up to 200 W/(m · K) were fabricated. The variation in thermal conductivity with the type and the amount of the additive is explained on the basis of the thermodynamics of oxygen removal. In particular, the higher thermal conductivity of CaO-doped, in comparison with MgO-doped, samples is rationalized on the basis that the free energy of formation, ΔG°, of CaAl₂O₄ is less than that of MgAl₂O₄. It is proposed that the higher the |ΔG°|, with ΔG° < 0, the higher is the resultant thermal conductivity. An increase in the thermal conductivity with annealing time is attributed to the kinetics of oxygen removal from AIN grains.     

氮化铝陶瓷材料制备工艺与应用

概述了氮化铝材料的结构性质，粉末的合成方法，A1N陶恣的帛备方法及其应用。     

Aluminum Nitride Whisker Formation during Combustion Synthesis

In this study, the microstructural development of AlN during combustion synthesis (CS) in a nitrogen atmosphere was investigated. CS using an aluminum–50 wt% AlN–3 wt% MgCl₂ powder compact yielded a mixture of AlN whiskers and powder. The microstructural development during the combustion reaction was studied by heating the compact to various temperatures. Based on the experimental results, the formation mechanisms of the AlN with a whisker morphology were discussed.     

氮化铝陶瓷的研制及应用

氮化铝 (AlN)因具有高热导率、低介电常数、与硅相匹配的热膨胀系数及其他优良的物理特性 ,在新材料领域越来越引起人们的关注。此文主要介绍并分析了AlN粉体合成、烧结、性能结构、AlN陶瓷的应用与前景     

Preparation of Aluminum Nitride Powder from Aluminum Polynuclear Complexes

AIN powder was synthesized from aluminum polynuclear complexes. Basic aluminum chloride and basic aluminum lactate were used as the aluminum polynuclear complexes. These starting materials and glucose were dissolved in water and mixed homogeneously. AIN powder was obtained by calcining after drying and precalcining at 800°C under nitrogen gas flow. Then excess carbon was removed by firing in air. Nitridation in the system was investigated and compared with that in the alumina–carbon black system. It was found that in our reaction system nitridation began and proceeded at lower calcination temperatures above 1200°C than in the alumina–carbon black system. Using aluminum polynuclear complexes, AIN was synthesized through the nitridation of γ-alumina and produced in a very fine and sharp particle size distribution.     

Pyrolysis of Poly(isopropyliminoalane) to Aluminum Nitride

The pyrolysis processes of poly(isopropyliminoalane) ((HAlN ⁱ Pr) _n ) were investigated, using mass spectrometry to analyze the gases and infrared spectroscopy to analyze the residual solids. The major mass loss (in the temperature range of 240°–540°C) consisted of two different pyrolysis stages. At the first stage (240°–320°C), (HAlN ⁱ Pr)₆ was detected continuously as a gas, and the precursor was converted to a cross-linked structure. A polymerization mechanism without a release of organic compounds has been proposed, and the formation of (HAlN ⁱ Pr)₆ during polymerization (besides its evaporation) has been suggested. The second stage (320°–560°C) involved the formation of various organic compounds, and radical processes for their formation were proposed.