催化氮化制备氮化硅粉体

氮化硅陶瓷由于具有优良的机械性能、化学性能和物理性能而被广泛应用于化工、冶金及航天等领域.催化氮化法制备氮化硅可以有效避免“硅芯”及“流硅”等不完全氮化形为的发生;并促进氮化硅晶须的原位反应合成,改善氮化硅基材料界面的显微结构,提高最终制品的力学性能.本文综述了金属及金属氧化物催化剂催化氮化反应生成氮化硅的最新进展及一维氮化硅的原位生成机理,并在此基础上展望了催化氮化制备氮化硅工艺今后的发展方向.     

硅粉直接氮化反应合成氮化硅研究

研究了硅粉直接氮化反应合成氮化硅粉末的工艺因素(包括硅粉粒度、氮化温度、成型压力、稀释剂含量等),借助XRD,SEM等测试手段测定和观察了氮化产物的物相组成和断口形貌.研究结果表明:硅粉在流动氮气氛下,高于1200℃氮化产物中氮含量明显增加;在氮化反应同时还伴随着硅粉的熔结过程,它阻碍硅粉的进一步氮化,其影响程度与氮化温度、氮化速度,素坯成型压力及硅粉粒度等工艺因素有关.在硅粉素坯中引入氮化硅作为稀释剂,提高了硅粉的氮化率,使产物中残留硅量降低;同样在实际生产中可以通过控制适当热处理制度(如分段保温、慢速升温),达到硅粉的完全氮化.在生产中批量合成了含氮量为32.5%,残留硅量为0.05%,主要为α相,含少量β相的针状、柱状的氮化硅.     

Nitridation Kinetics and Thermodynamics of Silicon Powder Compacts

The nitridation kinetics of Si powder compacts were studied by measuring the flow rate dependence of N₂ and N₂–H₂ gas mixtures during slow heating of Si compacts while simultaneously monitoring the oxygen partial pressure of the egress gas. The reaction was found to occur in two distinct stages. In pure nitrogen the initial stage was interpreted in terms of devitrification of the native silica layer, catalyzed by Fe impurities, and the exposure of the underlying Si. The reaction sequence at that point has been unequivocally shown to be followed by the formation of oxynitride according to as evidenced by a large increase in the oxygen partial pressure simultaneously with the onset of the initial stage. In the absence of hydrogen, both reactions are rapidly suppressed as the oxygen liberated competes with the nitrogen for the exposed silicon surface and reoxidizes it. However, in the presence of hydrogen, the oxygen liberated reacts with the hydrogen and prevents the reoxidation of the Si. The net reaction in this case is and/or with the second reaction being thermodynamically favored. The main nitridation reaction occurring between 1300° and 1400°C appears to be diffusion controlled and depends on the nature of the passivating layer that forms during the initial stage.     

Catalytic Activity of Noble Metals for Metal-Assisted Chemical Etching of Silicon

ABSTRACT: Metal-assisted chemical etching of silicon is an electroless method that can produce porous silicon by immersing metal-modified silicon in a hydrofluoric acid solution without electrical bias. We have been studying the metal-assisted hydrofluoric acid etching of silicon using dissolved oxygen as an oxidizing agent. Three major factors control the etching reaction and the porous silicon structure: photoillumination during etching, oxidizing agents, and metal particles. In this study, the influence of noble metal particles, silver, gold, platinum, and rhodium, on this etching is investigated under dark conditions: the absence of photogenerated charges in the silicon. The silicon dissolution is localized under the particles, and nanopores are formed whose diameters resemble the size of the metal nanoparticles. The etching rate of the silicon and the catalytic activity of the metals for the cathodic reduction of oxygen in the hydrofluoric acid solution increase in the order of silver, gold, platinum and rhodium.     

Preparation of α-Si3N4 by direct nitridation using polysilicon waste by diamond wire cutting

With the rapid development of the semiconductor industry and solar photovoltaic industry, a large number of polysilicon wastes from diamond wire cutting are accumulated, which not only pollute the environment, but also cause safety problems due to the ultrafine particle size and high reactivity. The diamond wire cutting polysilicon waste was used to prepare α-Si₃N₄ by direct nitridation method. This method could not only fully recycle the waste and reduce environmental pollution, but also could reduce the production cost of α-Si₃N₄. Furthermore, the effects of FeCl₃, NaCl, and metal Cu on the nitridation of polysilicon waste are investigated in detail, respectively. It is found that FeCl₃ and NaCl are not ideal additives for the preparation of α-Si₃N₄. However, α-Si₃N₄-dominated Si₃N₄ can be obtained via adding 5 wt% Cu after nitridation at 1250°C for 8 hours, and the relative content of α-Si₃N₄ reaches 92.37%.     

Effects of Transition-Metal Substitution on the Catalytic Properties of Barium Hexaaluminogallate

The effects of the substitution of transition-metal ions and/or reductant gases on the catalytic properties of barium hexaaluminogallate were investigated. Transition-metal-substituted hexaaluminogallates (BaM(Al,Ga)₁₁O₁₉, M = transition metal, Al/Ga = 9/3) were synthesized from aqueous metal nitrates and ammonium carbonate by the coprecipitation followed by crystallization at 1100°C. The direct NO _x reduction was observed over BaM(Al,Ga)₁₁O₁₉ to be around 10%. The NO _x removal activity of BaM(Al,Ga)₁₁O₁₉ powders was improved by addition of C₃H₆ as a reductant gas. Co-, Ni- and Cu-substituted BaM(Al,Ga)₁₁O₁₉ catalysts exhibited about 40% NO _x reduction with C₃H₆ in excess oxygen at a high space velocity of 10 000 h⁻¹. The NO _x reduction on Mn- and Fe-substituted BaM(Al,Ga)₁₁O₁₉ catalysts was less than 10% even in the presence of C₃H₆. The temperature of the effective NO _x reduction on BaM(Al,Ga)₁₁O₁₉ catalysts could be adjusted from 350° to 500°C by the selection of the transition-metal substitution in the catalysts. The catalysts hold high activities for NO _x reduction even at 500°C in water vapor produced in the combustion system of reductant gases.     

结合体系对氮化后碳化硅基浇注料冷/热态强度的影响

本工作研究了二氧化硅微粉+铝酸钙水泥(MS+ CAC),二氧化硅微粉+水合氧化铝(MS+ HA),二氧化硅溶胶三种不同结合体系对添加9％硅粉的碳化硅基浇注料1420℃氮化后的冷态耐压强度,冷态和800～1400℃热态抗折强度的影响,应用SEM,XRD和EDAX,分析了不同试样中的物相及显微结构.结果表明,无水泥的结合体系结合的试样氮化后由于基质不含玻璃相,因而高温下更稳定,原位形成的氮化物呈网络状,使1200℃以上强度保持率高;含水泥的结合体系结合的试样基质中有CAS2相,形成的氮化物为粒状或柱状,使热态强度降低显著.     

Nitridation behavior of silicon powder compacts of various thicknesses with Y2O3 and MgO as sintering additives

The effects of the nitriding temperature (1300 and 1350°C), holding time (0‐4 hours), and thickness of Si powder compacts on the nitridation behavior of silicon were investigated by examining the nitridation rates, analyzing phase compositions, and observing the microstructures of nitrided compacts. Si powder compacts doped with Y₂O₃ and MgO as sintering additives were prepared with thicknesses of 3, 6, and 9 mm. The phases of nitrided compacts were transformed from Si to α‐Si₃N₄ and β‐Si₃N₄ with an increase in the nitriding temperature and holding time. The degree of nitridation increased with the nitriding temperature and holding time. The β/(α+β) ratio increased with the nitriding temperature and holding time, and with a decrease in the thickness of the Si powder compacts. However, all compacts exhibited the same tendency for a higher β/(α+β) ratio at the compact surface than in the bulk of the compact. The variation in the β/(α+β) ratio for each compact decreased with an increase in the nitriding temperature and holding time.     

氮化制度对Si-Al-Al2O3体系合成Sialon的影响

以SiC、α-Al2O3微粉、Si粉、Al粉为原料,在1450℃流动氮气中制备Sialon/SiC材料。研究了不同温度保温氮化对Sialon合成的影响。研究结果表明:有部分硅粉残余没有氮化;在1100℃保温氮化的氮化率高于在1150℃、1200℃保温氮化;1100℃保温氮化,残余Si量少、分布均匀,残余硅熔聚现象较轻,利于Sialon的合成。     

氮化硅结合碳化硅复合材料性能优化的研究进展

氮化硅结合碳化硅具有优异的力学性能、抗蠕变性能、抗热冲击性能、热学性能和抗化学侵蚀性能,被广泛应用于冶金、化工、机械和国防军工等领域.氮化硅结合碳化硅的服役环境恶劣,材料的力学性能、抗热震性能、抗侵蚀性能和抗氧化性能是影响其服役寿命的关键.本文针对如何提升氮化硅结合碳化硅材料的服役性能,对氮化硅结合碳化硅力学性能、抗热...     

Synthesis of Nanocrystalline Chromium Nitride Powders by Direct Nitridation of Chromium Oxide

Nanocrystalline CrN powder was synthesized by the direct nitridation of nanosized Cr₂O₃ powder. Powder X-ray diffractometry patterns indicated that pure cubic-phase CrN powder could be obtained by nitridation at 800°C for 8 h. Transmission electron microscopy images showed that the particle sizes were 40–80 nm. The effect of the nitridation temperature and holding time on the powder properties was studied.     

Experimental strategy to determine nitrogen catalytic behavior of high-temperature woven ceramics

New vehicle deceleration strategies have led to the development of deployable thermal protection systems with woven fabric outer layers that can withstand the harsh aerothermal environment of planetary entry. In this work, we present an experimental strategy for testing fabric samples and a method to determine nitrogen catalytic efficiency, γ_N, from two-photon laser-induced fluorescence measurements of recombining nitrogen atoms near the sample surface. Measurements were made on other silicon carbide materials to better understand the influence of the fabric structure and porosity on catalytic recombination. The three test materials studied were a monolithic α-SiC, a CVD β-SiC, and a single-ply, Hi-Nicalon β-SiC fabric layup. Extracted catalytic efficiencies for atomic nitrogen recombination for monolithic α-SiC, CVD β-SiC, and single-ply β-SiC fabric are (6.18 ± 1.55) × 10⁻⁴ (at 1460 K), (3.59 ± 0.90) × 10⁻³ (at 1500 K), and (8.34 ± 2.19) × 10⁻⁴ (at 1675 K), respectively. This would categorize these materials as low-catalytic materials for nitrogen atom recombination in this temperature range.     

Formation Mechanism of AlN–SiC Solid Solution by Combustion Nitridation in Si3N4–Si-Al-C System

The synthesis of solid solutions of AlN–SiC was investigated through the combustion reaction between Si₃N₄, aluminum, and carbon powders and nitrogen gas at pressures ranging from 0.1 to 6.0 MPa. The combustion reaction was initiated locally and then the wave front propagated spontaneously, passing through the cylindrical bed containing the loose powder. In the presence of Si₃N₄ as a reactant, it was feasible to synthesize solid solutions at an ambient pressure (0.1 MPa). The relationship between nitrogen pressure and full-width at half-maximum of the (110) peak of the product showed that lower pressures produced more-homogeneous solid solutions. Some aspects of formation of the AlN–SiC solid solutions were discussed with special emphasis on the influence of nitrogen pressure and reactant stoichiometry.     

Nitridation of silicon powder studied by XRD, Si MAS NMR and surface analysis techniques

The nitridation of elemental silicon powder at 900–1475 °C was studied by X-ray photoelectron spectroscopy (XPS), X-ray excited Auger electron spectroscopy (XAES), XRD, thermal analysis and ²⁹Si MAS NMR. An initial mass gain of about 12% at 1250–1300 °C corresponds to the formation of a product layer about 0·2 μm thick (assuming spherical particles). XPS and XAES show that in this temperature range, the surface atomic ratio of N/Si increases and the ratio O/Si decreases as the surface layer is converted to Si₂N₂O. XRD shows that above 1300 °C the Si is rapidly converted to a mixture of - and β-Si₃N₄, the latter predominating >1400 °C. In this temperature range there are only slight changes in the composition of the surface material, which at the higher temperatures regains a small amount of an oxidised surface layer. By contrast, in the interval 1400–1475 °C, the ²⁹Si MAS NMR chemical shift of the elemental Si changes progressively from about −80 ppm to −70 ppm, in tandem with the growth of the Si₃N₄ resonance at about −48 ppm. Possible reasons for this previously unreported change in the Si chemical shift are discussed. ©     

Nitridation of Silicon Containing MgO and CeO2 Powders and SiC Whiskers

Processing and nitridation of MgO/CeO₂-doped silicon containing SiC whiskers was studied. The reaction time was dramatically reduced by incorporating MgO/CeO₂ dopants and SiC whiskers in silicon powders prior to nitridation. The decomposition of SiC whiskers depends on the nitriding temperature, sintering aids, and whisker surface composition.     

Preparation of Aluminum Nitride–Silicon Carbide Nanocomposite Powder by the Nitridation of Aluminum Silicon Carbide

Aluminum nitride (AlN)–silicon carbide (SiC) nanocomposite powders were prepared by the nitridation of aluminum-silicon carbide (Al₄SiC₄) with the specific surface area of 15.5 m²·g⁻¹. The powders nitrided at and above 1400°C for 3 h contained the 2H-phases which consisted of AlN-rich and SiC-rich phases. The formation of homogeneous solid solution proceeded with increasing nitridation temperature from 1400° up to 1500°C. The specific surface area of the AlN–SiC powder nitrided at 1500°C for 3 h was 19.5 m²·g⁻¹, whereas the primary particle size (assuming spherical particles) was estimated to be ∼100 nm.     

微波掺氮改性纳米二氧化钛的研究

以水合肼为掺杂氮源,采用微波辐照对锐钛矿型纳米二氧化钛（TiO2）进行改性,考察了掺氮纳米二氧化钛的光催化性能,并用XPS、Uv-Vis、XRD．TEM等方法对其进行了表征。结果表明,在nc：nno2：n水合阱=0.5：1：11、微波辐照功率为500W、微波辐照时间为20min的条件下所得粉体的光催化性能最佳,在可见光下具有较高的反应活性,表明微波掺氮改性纳米二氧化钛大幅提高了其光催化性能;微波辐照后,氮原子取代了二氧化钛粉体表面少量氧原子,TiO：的粒径和晶型均保持不变,但吸收边明显向可见光方向偏移。     

Effects of Technological Parameters on Carbothermal Reduction and Nitridation of Zircon

Carbothermal reduction and nitridation(CRN)of zircon(ZrSiO4)permits obtaining different composites of oxides and nitrides such as ZrO2-Si2N2O and ZrN-Si3N4.The effects of technological parameters(carbon source,reaction temperature,and carbon content)on the reaction rate and product phase composition of CRN of zircon were investigated by TGA and XRD.The results show that:(1)carbon source is an important factor for a rapid reaction,and activated carbon is chosen as the carbon source considering the expect pro...     

Synthesis of Aluminum Nitride–Silicon Carbide Solid Solutions by Combustion Nitridation

AlN–SiC solid solutions were synthesized via a combustion nitridation process. Reactions between powder mixtures of aluminum, silicon, and carbon or aluminum with β-SiC and gaseous nitrogen under pressures of 0.1–8.0 MPa are self-sustaining once they have been initiated. Investigations were made with reactant ratios of Al:Si:C = 7:3:3, 6:4:4, and 5:5:5 and Al:SiC = 7:3, 6:4, and 5:5. For the Al-Si-C system (molar ratio of 6:4:4), the maximum combustion temperature was dependent on the nitrogen pressure, increasing from 2300°C to 2480°C with an increase in pressure, from 0.1 MPa to 6.0 MPa. In all cases, the product contained the solid solution as the primary phase, with minor amounts of silicon. The amount of unreacted silicon decreased as the nitrogen pressure increased; the presence and dependence of unreacted silicon on pressure has been explained in terms of the volatilization of aluminum. The full width at half maximum for the (110) peak of the AlN–SiC solid solution decreased as the nitrogen pressure increased, which indicated the formation of a more homogeneous product.     

Aluminum Reduction and Nitridation of Bauxite

The application of bauxite with low Al2O3 content has been studied in this paper and β-SiAlON has been obtained from two kinds of bauxites (Al2O3 content 68.08 mass% and 46.30 mass% respectively) by aluminum reduction and nitridation method. The sequence of reactions has been studied using thermal analysis (TG-DTA), X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) with EDS. Compared with carbon thermal reduction and nitridation of aluminosilicates employed presently, the reaction in the system of bauxite-Al-N2 occurs at lower temperature. β-SiAlON appears as one of the main products from 1573K and exists stably in the range of the present experimental temperature. The microstructure of β-SiAlON obtained at 1773 K is short column with 5-10μm observed by SEM.