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.     

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.     

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.     

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⁺.     

Some New Perspectives on Oxidation of Silicon Carbide and Silicon Nitride

This study provides new perspectives on why the oxidation rates of silicon carbide and silicon nitride are lower than those of silicon and on the conditions under which gas bubbles can form on them. The effects on oxidation of various rate-limiting steps are evaluated by considering the partial pressure gradients of various species, such as O₂, CO, and N₂. Also calculated are the parabolic rate constants for the situations when the rates are controlled by oxygen and/or carbon monoxide (or nitrogen) diffusion. These considerations indicate that the oxidation of silicon carbide and silicon nitride should be mixed controlled, influenced both by an interface reaction and diffusion.     

Developing Interfacial Carbon-Boron-Silicon Coatings for Silicon Nitride-Fiber-Reinforced Composites for Improved Oxidation Resistance

C-B-Si coatings were formed on a Si₃N₄ fiber using chemical vapor deposition and embedded in a Si-N-C matrix using polymer impregnation and pyrolysis. The boron-containing layer was anticipated to form borosilicate glass and seal oxygen-diffusion passes. Two types of C-B-Si coatings were tested on the fiber–matrix interface, and they improved the oxidation resistance of the composite. The first coating was multilayered: a crystalline sublayer composed of B-Si-C was sandwiched between two graphitelike carbon sublayers. The second coating was a graphitelike carbon layer containing a small amount of boron and silicon. The carbon (sub)layer of both coatings weakened the fiber–matrix bonding, giving the composites a high flexural strength (1.1 GPa). The composites retained 60%–70% of their initial strength, even after oxidation at 1523 K for 100 h. The mechanism for improved oxidation resistance was discussed through the microstructure of the interface, morphology of the fracture surface, and oxygen distribution on a cross section of the oxidized composite.     

Silicon Nitride/Molybdenum Disilicide Composite with Superior Long-Term Oxidation Resistance at 1500°C

The long-term high-temperature cyclic oxidation (100 cycles, 10⁴ h, 1500°C) of a Si₃N₄ material and a Si₃N₄/MoSi₂ composite, both fabricated with Y₂O₃ as a sintering additive, was studied. Both materials exhibited similar oxidation rates because of surface SiO₂ formation described by an almost parabolic law and a total weight gain of 3–4 mg/cm² after 10⁴ h. As a consequence of oxidation processes in the bulk, microstructural damage was found in the Si₃N₄ material. These effects were not observed in the composite. The remarkable microstructural stability observed offers the high potential of Si₃N₄/MoSi₂ composites for long-term structural applications at elevated temperatures up to 1500°C.     

Rising Crack-Growth-Resistance (R-Curve) Behavior of Toughened Alumina and Silicon Nitride

R -curves for a sinter/HIPed SiC(whisker)-reinforced alumina and a sintered silicon nitride were assessed by direct measurements of lengths of cracks associated with Vickers indentation flaws. The fracture toughness measurements based on (a) initial (as-indented) crack lengths, (b) equilibrium growth of cracks during increasing far-field loading, and (c) crack lengths corresponding to unstable fracture showed definitive trends of R -curves for both materials. The fracture mechanics analyses employed an indenter-material constant that was independently estimated using a physical model for the residual driving force and a free surface correction factor that accounted for the effects of size and shape of the cracks on stress intensity. It is shown that R -curve estimations based on crack length measurements have the intrinsic advantage that crack length dependence of fracture toughness is not assumed a priori as is done in conventional analysis based on strength. The measured fracture toughness of SiC(whisker)-reinforced alumina was in agreement with the prediction of a toughening model based on crack bridging by partially debonded whiskers.     

Paralinear Oxidation of Silicon Nitride in a Water-Vapor/Oxygen Environment

Three Si₃N₄ materials were exposed to dry oxygen flowing at 0.44 cm/s at temperatures between 1200° and 1400°C. Weight change was measured using a continuously recording microbalance. Parabolic kinetics were observed. When the same materials were exposed to a 50% H₂O–50% O₂ gas mixture flowing at 4.4 cm/s, all three types exhibited paralinear kinetics. The material was oxidized by water vapor to form solid SiO₂. The protective SiO₂ was in turn volatilized by water vapor to form primarily gaseous Si(OH)₄. Nonlinear least-squares analysis and a paralinear kinetic model were used to determine parabolic and linear rate constants from the kinetic data. Volatilization of the protective SiO₂ scale could result in accelerated consumption of Si₃N₄. Recession rates under conditions more representative of actual combustors were compared with the furnace data.     

Volatility Diagrams for Silica, Silicon Nitride, and Silicon Carbide and Their Application to High-Temperature Decomposition and Oxidation

Volatility diagrams—isothermal plots showing the partial pressures of two gaseous species in equilibrium with the several condensed phases possible in a system—are discussed for the Si-O and Si-N systems, and extended to the Si-N-O and Si-C-O systems, in which the important ceramic constituents SiO₂, Si₃N₄, Si₂N₂O, and SiC appear as stable phases. Their use in understanding the passiveactive oxidation transitions for Si, Si₃N₄, and SiC are demonstrated.     

Preparation of Mesoporous Silicon Nitride via a Nonaqueous Sol–Gel Route

A silicon diimide gel Si(NH) _x (NH₂) _y (NMe₂) _z was prepared by an acid-catalyzed ammonolysis of tris(dimethylamino)silylamine. Pyrolysis of the gel at 1000°C under NH₃ flow led to the formation of an amorphous silicon nitride material without carbon contamination. All of the gel and pyrolyzed products exhibited a mesoporous structure with a high surface area and narrow pore-size distribution. The effective surface area of the pyrolyzed silicon nitride residues decreases with increasing temperature, but the heating rate during pyrolysis has little influence on the surface area and pore-size distribution of the final mesoporous ceramic Si₃N₄ products because of the highly cross-linked structures of the precursor silicon diimide gel.     

冷冻注凝制备氮化硅陶瓷基耐高温复合材料

采用硅溶胶冷冻胶凝陶瓷成型技术制备Si3N4/BAS陶瓷复合材料,分析了硅溶胶冷冻胶凝技术原理和特点,并对Si3N4/BAS陶瓷复合材料性能及微观形貌进行了研究。结果表明:该成型方法所获得的坯体干燥无变形无开裂,收缩率小于1%;陶瓷烧结体密度为2.9 g/cm3时,烧结体抗弯强度、弯曲弹性模量、断裂韧性以及洛氏硬度分别为350 MPa、193GPa、6.2 MPa·m1/2和58。该成型技术实现了陶瓷界多年来对先进陶瓷高效、低成本、原位近净尺寸成型的追求。     

Oxidation Behavior of Silver- and Copper-Based Brazing Filler Metals for Silicon Nitride/Metal Joints

The oxidation behavior of reactive-element-containing brazing filler metals at 600°C was studied. Weight-gain measurements coupled with scanning electron microscopy and energy dispersive X-ray analysis indicated the formation of a nonprotective oxide on the following three ternary alloys: (i) Cu-80%, Sn-10%, Ti-10%; (ii) Ag–Cu eutectic + 5% Ti; and (iii) Ag–Cu eutectic + 5% Zr. Additions of Ni and Si to these alloys failed to reduce spallation. However, a protective oxide was formed by adding Al. The resultant quaternary alloys possessed excellent flow properties on silicon nitride.     

Bond Energetics at Intergranular Interfaces in Alumina-Doped Silicon Nitride

In Si₃N₄ ceramics sintered with Al₂O₃, the interfacial strength between the intergranular glass and the reinforcing grains has been observed to increase with increases in the aluminum and oxygen content of the epitaxial β-Si_{6- z} Al _z O _z N_{8– z} layer that forms on the Si₃N₄ grains. This has been attributed to the formation of a network of strong bonds (cross bonds) that span the glass-crystalline interface. This proposed mechanism is considered further in light of first-principles atomic cluster calculations of the relative stabilities of bridge and threefold-bonded atomic fragments chosen to represent compositional changes at the glass/Si₃N₄ grain interface. Calculated binding energies indicate Al-N binding is favorable at the Si₃N₄ grain surface, where aluminum occupancy can promote the growth of SiAlON, further enhancing the cross-bonding mechanism of interfacial strengthening.     

Foreign Object Damage Resistance of Silicon Nitride and Silicon Carbide

To clarify the foreign object damage (FOD) resistance of ceramics, chipping fracture mode and flexural fracture mode were investigated using several types of Si₃N₄ and Sic. The critical velocity which is the threshold impact velocity of the projectile for chipping fracture and flexural fracture was determined. The critical velocity of the chipping fracture mode is explained as a function of K ^5/2_IC a ^–5/4, and depends on the hardness and the shape of the projectile. The critical velocity of the flexural fracture mode is explained as a function of σ^5/6_C t ^5/3. The mechanisms of impact damage are discussed.     

Oxidation Resistance of Alumina–Titanium Nitride and Alumina–Titanium Carbide Composites

The presence of TiC or TiN paritcles in an Al₂O₃ matrix affects the thermal stability of the composites in oxidizing environments. In isothermic oxidation tests at 700°, 800°, 900°, 1000°, and 1100°C for up to 20 h, two different oxidation regimes have been observed at T < 900°C and at 900°C ≤ T ≤ 1100°C. At low temperatures ( T < 900°C), the oxidation follows a phase-boundary reaction; the reaction product initially consists of aggregates of submicrometer needlelike TiO₂ rutile crystals that subsequently grow and coalesce. When a continuous TiO₂ rutile layer is formed ( T ≥ 900°C), the oxidation kinetics change to parabolic, and the diffusion of O₂ through a thick TiO₂ layer is proposed as the governing step.     

Active-to-Passive Transition in the Oxidation of Silicon Carbide and Silicon Nitride in Air

The active-to-passive transition in the oxidation of SiC and Si₃N₄ was determined in a flowing air environment as a function of temperature and total pressure. The experimentally observed transition temperatures ranged from a low of 1347°C to a high of 1543°C for partial pressures of oxygen of 2.5 and 123.2 Pa, respectively. The SiC and Si₃N₄ samples had approximately the same transition point for a given pressure. In general, the higher the flow rate, the higher the transition temperature for a given pressure. The transitions for SiC measured in this study agree with previous data for the transition of SiC measured in pure oxygen at reduced pressures and in oxygen inert gas mixtures.     

High-Temperature Oxidation Behavior of High-Purity α-, β-, and Mixed Silicon Nitride Ceramics

High-temperature oxidation behavior, microstructural evolution, and oxidation kinetics of additive-free α-, β-, and mixed silicon nitride ceramics is investigated. The oxidation rate of the ceramics depends on the allotropic ratio; best oxidation resistance is achieved for ceramics rich in α-phase. Variations in the oxidation kinetics are directly related to average grain size and glass distribution in the oxidation scale. The oxygen contents incorporated into the Si₃N₄ phase before its dissolution at the oxidation front affects the local glass composition and thereby yields nucleation and growth rates of SiO₂ crystallites within the glass phase and a final oxidation scale microstructure, which depend on the incorporated oxygen contents. For the α-polymorph, the dynamic oxygen solubility is found to remain negligible; therefore, a nitrogen-rich glass forms at the oxidation front, which promotes devitrification and yields a scale with small grain size and thin intergranular glass films. β-Si₃N₄ is observed to form oxygen-rich solid solutions on oxidation, which are in contact with silicon oxynitride or oxygen-rich glass. Nucleation of cristobalite in the latter is sluggish, yielding coarse-grained oxidation scales with thick intergranular glass film.     

Densification and Sintering Kinetics in Sintered Silicon Nitride

The sintering sequence of Y₂O₃-Al₂O₃-doped Si₃N₄ was investigated with respect to the relationship between densification, α→β transformation, and microstructural development. Quenching studies were performed to reveal these interactions during a complete sintering cycle. Isothermal studies were conducted to examine the sintering kinetics and compared to Kingery's liquid-phase sintering model. The bulk density increased to ≥90% of theoretical density with only minor transformation taking place. Major transformation occurred in a late sintering stage and was accompanied by the development of elongated grains. The kinetic order of the densification process, taking into account an appropriate correction, was larger than any of the rate exponents predicted by the Kingery model, indicating that other single or mixed mechanisms were active.     

Burner Rig Hot Corrosion of Silicon Carbide and Silicon Nitride

A number of commercially available SiC and Si₃N₄ materials were exposed to 1000°C for 40 h in a high-velocity, pressurized burner rig as a simulation of an aircraft turbine environment. Na impurities (2 ppm) added to the burner flame resulted in molten Na₂SO₄ deposition, attack of the SiC and Si₃N₄, and formation of substantial Na₂O. x (SiO₂) corrosion product. Room-temperature strength of the materials decreased as a result of the formation of corrosion pits in SiC and grain-boundary dissolution and pitting in Si₃N₄.