Oxidation Behavior of Silicon Yttrium Oxynitride

The oxidation behavior of the silicon yttrium oxynitride Y₁₀Si₇O₂₃N₄, so-called H-phase, in the temperature range 700–1400°C has been investigated. A nitrogen retention phenomenon in the oxidation product Y_4.67(SiO₄)₃O (O-apatite) is discussed. The H-phase is one of the four quaternary compounds identified in hot-pressed Si₃N₄ materials fabricated within the Si₃N₄–SiO₂–Y₂O₃ pseudoternary system.     

Processing, Mechanical Properties, and Oxidation Behavior of Silicon Oxynitride Ceramics

Silicon oxynitride ceramics were prepared by hot-pressing an equimolar Si₃N₄+ SiO₂ mixture with 3 mol% CeO₂. The Ce₂O₃/SiO₂ ratio of intergranular phase (liquid phase) increased as the formation of Si₂N₂O proceeded. The intergranular liquid remained as a glass on cooling until the Ce₂O₃/SiO₂ ratio exceeded a certain value, at which point the liquid crystallized. There were great differences in thermal and mechanical properties and oxideation behavior between the specimen containing intergranular glassy phase and the one containing intergranular crystalline phase (Ce₅(SiO₄)₃N–Ce_4.67(SiO₄)₃O). The specimen containing the intergranular glassy phase showed excellent hightemperature strength and oxidation resistance.     

Oxidation Behavior of Oxynitride Glasses

Oxynitride glasses begin to oxidize in air when they are heated above 800°C. The oxidation starts with bubble formation on the surface. Continued oxidation leads to a white oxide layer on the surface. Magnesia- and lithia-containing glasses formed crystalline layers, whereas soda- and baria-containing glasses formed bubbly glass layers. The lithia-, beryllia-, and magnesia-containing glasses have good oxidation resistance     

Silicon Nitride Oxidation Based on Oxynitride Interlayers with Graded Stoichiometry

The oxidation kinetics of Si₃N₄ were modeled by describing the simultaneous diffusion and reaction of interstitial oxygen that is believed to occur inside of the silicon oxynitride interlayer. The oxynitride was assumed to have a variable composition, and oxidation was described as a reaction where interstitial oxygen is incorporated into the network structure of the oxynitride and nitrogen is removed. It was assumed that both the diffusion coefficient and the solubility of interstitial oxygen decrease as the nitrogen content of the network structure increases. The results accurately describe both the formation of an oxynitride layer during oxidation, and the relatively slow oxidation kinetics of Si₃N₄ (compared to Si and SiC).     

Oxidation Behavior of Silicon Carbide

The oxidation of purified green silicon carbide in controlled atmospheres was studied by weight-gain measurement and by observation of the surface reaction products, including optical measurement of the thickness of the oxide surface film. The rate of oxidation was much greater for silicon carbide in contact with fluid silicate glasses than for silicon carbide alone. In a vacuum of 0.1 mm., oxidation proceeded with loss of weight, because of the formation of volatile SiO₂, and at a greater rate than at atmospheric pressure. It is postulated that the rate-controlling process in the normal oxidation of silicon carbide is the formation of solid SiO₂ on the surface.     

The Thermodynamic Properties of Silicon Oxynitride

A critical assessment of thermal and equilibrium data for silicon oxynitride (Si₂N₂O) is presented. Selected values for the heat of formation of Si₂N₂O from the elements and the absolute entropy of Si₂N₂O at 298.15 K are ΔH⁰_f,298=−947.7 ± 5.4 kJ/mol and S⁰₂₉₈= 45.35 ± 0.4 J/mol·K, respectively. A table of thermodynamic functions for Si₂N₂Ofrom 298 to 2500 K, which has been calculated from the analysis of the literature data, is also presented.     

渗硅碳化硅材料的高温氧化

研究了全碳粉反应渗硅碳化硅(PCRBSC)材料,在1300℃静态空气中的高温氧化行为.研究结果表明:PCRBSC材料的氧化过程遵循直线-抛物线规律,其结构对高温氧化有很大的影响,特别是游离硅fsi和游离碳fc的含量对氧化影响更大,fsi含量高的PCRBSC材料单位面积氧化增重(Δm/s)明显,fc含量高的PCRBSC材料氧化后表现为先减重后增重,氧化层断口经扫描电镜观察有明显的气孔存在.     

Oxidation Behavior of NBD 200 Silicon Nitride Ceramics

The oxidation behavior of NBD 200 Si₃N₄ containing 1 wt% MgO sintering aid was investigated in oxygen at 900°-1300°C. The oxide growth followed a parabolic rate law with an apparent activation energy of 260 kJ/mol. The oxide layers were enriched with sodium and magnesium because of outward diffusion of intergranular Na⁺ and Mg²⁺ cations in the ceramics. The 2-4 orders of magnitude higher oxidation rate for NBD 200 Si₃N₄ than for other Si₃N₄ ceramics with a similar amount of MgO could be attributed to the presence of sodium. The oxidation process was most likely rate limited by grain-boundary diffusion of Mg²⁺.     

熔融渗硅对石墨氧化行为的影响

分别在500 ℃、700 ℃、900 ℃及1 100 ℃空气条件下,对石墨及渗硅石墨进行氧化实验,以分析熔融渗硅对等静压石墨氧化行为的影响。采用扫描电镜(SEM)分析了样品表面及内部形貌,通过压汞法表征了样品的孔隙结构,并对材料的力学性能进行了测试分析。结果表明:500 ℃条件下,石墨和渗硅石墨均未发生明显的氧化失重现象;温度为700 ℃时,石墨的氧化失重率随时间延长明显增加,而该温度下渗硅石墨的氧化失重率变化较小。而且,渗硅石墨在700 ℃时仍能保持较好的强度,而此温度下,石墨随氧化时间的延长,强度明显降低,甚至被氧化成粉末状。因此,熔融渗硅在提高材料抗氧化性能的同时能够显著提升材料的强度。     

Oxidation Behavior of Rare-Earth Disilicate–Silicon Nitride Ceramics

The oxidation behavior and microstructure of the oxidized surfaces of RE₂Si₂O₇–Si₃N₄ ceramics were investigated. The high oxidation resistance of these materials at 1400°C is attributed to the minimization of amorphous phases via devitrification to disilicates that are in equilibrium with SiO₂, the oxidation product of Si₃N₄. Crystals of RE₂Si₂O₇ grew out of the surface silicate in prefered orientations that were dictated by crystal structure. The morphology of the microstructure of the oxidized surfaces was shown to be partially dependent on the concentration of impurities; the presence of Ca was found to coincide with the growth of Gd₂Si₂O₇ and Dy₂Si₂O₇ crystals with high aspect ratios.     

Microstructure and Oxidation Behavior of Silicon Carbide Fibers Derived from Polycarbosilane

Polycarbosilane-derived SiC fibers (CG Nicalon, Hi-Nicalon, and Hi-Nicalon type S) were exposed for 1–100 h at 1273–1673 K in air. Oxide layer growth and changes in tensile strength for these fibers were examined after exposure. The three types of SiC fibers decreased in strength as the oxide layer thickness increased. Fracture origins were located near the oxide layer–fiber interface. The Hi-Nicalon type S showed better oxidation resistance than the other polycarbosilane-derived SiC fibers after exposure in air at 1673 K for 10 h. This result was attributed to the nature of the silicon oxide layer on the surface of the SiC fibers.     

Processing and Microstructural Development of In Situ TiN-Reinforced Silicon Nitride/Silicon Oxynitride Composites

The development of a novel TiN-reinforced silicon nitride/silicon oxynitride composite using an innovative in situ TiN-forming technique was investigated. Silicon powder compacts containing various amounts of TiO₂ (anatase structure) and sintering additives were nitrided under N₂ atmosphere and then further densified by hot pressing. The microstructure of the resultant composite was analyzed by X-ray diffraction, scanning electron microscopy, and solid-state nuclear magnetic resonance spectroscopy. The results of this study show that TiO₂ can be successfully converted to TiN during the nitridation of Si + TiO₂ mixture. The TiO₂ content affects not only the microstructure of the matrix but also the composition of the intergranular phase. The type and amount of sintering additives also show a significant effect on the microstructural development of the composite.     

纳米碳颗粒/碳化硅陶瓷基复合材料的氧化行为

以微米硅(Si)和纳米碳黑(Cp)粉体为主要原料,采用经机械化学法合成的碳化硅(SiC)和15%和25%的纳米碳颗粒与碳化硅(Cp-SiC)的复合粉体,并经无压烧结得到了Cp/SiC陶瓷基复合材料,分析了在不同温度条件下Cp/SiC烧结体的氧化行为。结果表明:当温度小于700℃时,Cp/SiC复合陶瓷在空气中的氧化受C—O2反应控制,致使其为均匀氧化;700℃时,氧化后的复合材料显气孔率最大,弯曲强度达极小值;大于700℃,氧化过程受O2的气相扩散控制,呈非均匀氧化;700~900℃之间,O2通过微裂纹的扩散控制着Cp/SiC的氧化过程;900~1 100℃之间,O2通过SiC缺陷的扩散控制着Cp/SiC的氧化过程,并在1 000℃时的最初的2 h内,复合材料弯曲强度增大,且达到了极大值。同时表明,纳米碳含量是影响复合材料强度及氧化行为的关键因素,添加纳米碳质量分数为15%的Cp/SiC复合陶瓷可以作为一种抗氧化性能优良的玻璃夹具材料。     

Mullite Coating on Recrytallized Silicon Carbide and Its Cycling Oxidation Behavior

1IntroductionThere are strong interests in identifying approa-ches to protect silicon carbide ceramics from high tem-perature oxidative environments and prolong their serv-ice lives.One method is to apply a refractory coating.The advantage of coating tech…     

Characterization of Surface-Oxidized Phase in Silicon Nitride and Silicon Oxynitride Powders by X-ray Photoelectron Spectroscopy

Surface-oxidized phases on α-silicon nitride, β-silicon nitride, and silicon oxynitride powders were investigated by X-ray photoelectron spectroscopy (XPS) and X-ray Auger electron spectroscopy (XAES). The spectra of Si2 p XPS and Si( KLL ) XAES were measured precisely and were deconvoluted into some separate peaks, which correspond to each parent phase, a SiO x N y , oxidized phase, a nonstoichiometric SiN x . nitride phase, and a satellite peak of the parent phase, by the least-squares method. The Auger parameter (AP) was calculated for each phase using the Si2 p XPS and Si( KLL ) XAES data, and the average chemical compositions of the oxidized phases in each sample were evaluated from the AP data. The chemical compositions of these phases were between those of silica and silicon oxynitride and varied among the samples, but were usually close to SiO₂. Average thicknesses of the surface-oxidized phases were estimated to be 0.1–0.8 nm from the peak area ratio of the oxidized phase against the parent phase of the XAES spectra, assuming a continuous surface layer model.     

Oxidation Behavior of a Fully Dense Polymer-Derived Amorphous Silicon Carbonitride Ceramic

The oxidation behavior of a polymer-derived amorphous silicon carbonitride (SiCN) ceramic was studied at temperature range of 900°–1200°C using fully dense samples, which were obtained using a novel pressure-assisted pyrolysis technique. The oxidation kinetics was investigated by measuring the thickness of oxide layers. The data were found to fit a typical parabolic kinetics. The measured oxidation rate constant and activation energy of the SiCN are close to those of CVD and single-crystal SiC. The results suggest that the oxidation mechanism of the SiCN is the same as that of SiC: oxygen diffusion through a silica layer.     

Suppression of Frothing by Silicon Addition During Oxynitride Glass Synthesis

Several oxynitride glasses were synthesized with and without the addition of a few weight percent of free silicon. For Mg-Si-0-N and Si-Al-0-N glass compositions, the severe frothing (or "bubbling") which was observed during melting could be eliminated completely by the addition of silicon. In a Y-Si-Al-0-N composition, frothing was not observed, even when no silicon was added. The results are used to explain why A1N is superior to Si₃N₄ for synthesizing transparent oxynitride glasses.