悬浮床氮化硅合成热过程的实验研究与数值模拟

针对基于流态化技术利用硅粉直接氮化合成氮化硅粉的新工艺,建立了悬浮床内热过程的二维数学模型,并借助CFD商业软件FLUENT对悬浮床内热过程进行了数值模拟,分析了氮气速度、粉气比和氮化温度等因素对温度场和硅转化率的影响. 结果表明,模拟计算值与实验值误差小于5%,该模型可以用来预测悬浮床内的热过程. 在本文条件下,当以平均粒径2.7μm的硅粉为原料、氮化温度为1380℃、氮化时间为54.5s时,硅的转化率为22.5%. 模型预测表明,如果将氮化温度升至1450℃、氮化时间延长至7.1min,那么硅转化率可达98.6%,氮化硅纯度达98%以上.     

叠氮化钠联合卤化铵燃烧合成氮化硅粉体

采用叠氮化钠作为固态氮化剂,同时以卤化铵作为活性稀释剂,通过对燃烧温度特征曲线和燃烧产物相组成的分析,研究了两者的协同作用对于燃烧合成氮化硅粉体的影响. 研究结果表明:叠氮化钠和卤化铵的热分解可增加硅粉内部孔隙率和氮气渗透性,也能为Si-N反应提供内部氮源. 叠氮化钠和卤化铵均可作为Si-N反应的催化剂,可促进硅粉向氮化硅的氮化转变. 叠氮化钠联合卤化铵的使用能够有效地降低燃烧温度,使燃烧反应以低温模式进行,有利于α-Si3N4的生成. 随着反应物中叠氮化钠含量的增多,燃烧产物中α相氮化硅含量也相应地有所提高.     

硅粉常压直接氮化过程的非催化气固反应模型

以平均粒径2.2μm、纯度99.99%的硅粉为原料,采用纯度99.993%的高纯氮气作为反应气体,在1350和1400℃下进行了氮化时间为10～30 min 的氮化实验,得出了不同温度下硅粉转化率随反应时间的变化关系.将硅氮反应看成非催化气固反应,建立了硅颗粒氮化动力学模型.通过对实验数据的拟合,得出两个模型参数：硅氮反应速率常数和氮气在产物层中的扩散系数.假定反应速率常数和扩散系数均满足阿伦尼乌斯公式,求得化学反应激活能和指前因子分别为2.71×104 J·mol?1和3.07×10?5 m·s?1,扩散激活能和指前因子分别为1.06×105 J·mol?1和1.12×10?9 m2·s?1.利用本文得出的氮化动力学模型对各温度下不同粒径硅粉的转化曲线进行了预测,预测曲线与文献中的实验数据在趋势上吻合较好.     

硅粉常压直接氮化过程的非催化气固反应模型

以平均粒径2.2μm、纯度99.99%的硅粉为原料,采用纯度99.993%的高纯氮气作为反应气体,在1350和1400℃下进行了氮化时间为10～30 min的氮化实验,得出了不同温度下硅粉转化率随反应时间的变化关系.将硅氮反应看成非催化气固反应,建立了硅颗粒氮化动力学模型.通过对实验数据的拟合,得出两个模型参数:硅氮反应速率常数和氮气在产物层中的扩散系数.假定反应速率常数和扩散系数均满足阿伦尼乌斯公式,求得化学反应激活能和指前因子分别为2.71×104J·mol-1和3.07×10-5m·s-1,扩散激活能和指前因子分别为1.06×105J·mol-1和1.12×10-9m2·s-1.利用本文得出的氮化动力学模型对各温度下不同粒径硅粉的转化曲线进行了预测,预测曲线与文献中的实验数据在趋势上吻合较好.     

自蔓延法制备Si3N4粉时的氮气压力

探讨了硅粉在普通氮气和高纯氮气中的高温自蔓延合成反应过程,分析了稀释剂、氮气纯度与压力、成型坯体的气孔率等工艺参数对硅粉自蔓延过程的点火、最高燃烧温度及产物特征的影响.从热力学、动力学及Si3N4热分解过程几个方面分析了低氮气压力下燃烧合成Si3N4的可行性.研究结果表明:只要最高燃烧温度不高于相应氮气压力下Si3N4的热分解温度,就可以用SHS方法合成Si3N4;并在氮气压力为0.6～2.6 MPa时.以纯硅粉为起始原料燃烧合成出游离硅含量小于O.5％,β与α相混合,粒度为1～2 μm的Si3N4粉末;低氮气压力下硅粉的自蔓延合成反应,必须要引入Si3N4稀释荆,压坯气孔率控制在0～70％,否则反应不能进行;体系最高燃烧温度随着氮气压力和压坯气孔率的增加而升高;所需的最低氮气压力随硅粉粒度增大而提高;产物形态沿圆柱样径向有差异,由外到里β—Si3N4相明显增加.     

原位反应制备Mg-α-Sialon结合镁质耐火材料研究

采用Si粉，Al粉和电熔镁砂为原料，研究在流动氮气中制备Mg-α-Sialon结合镁质耐火材料，借助XRD，SEM等手段分析和观察材料的物相组成和显微结构。结果表明，通过原位氮化反应可以在1450～1500℃范围内制备含Mg-α-Sialon镁质耐火材料；其产物的组成和显微结构取决于初始组成和氮化处理温度；在高温下尤其在高于1550℃时，试样内部大量气相物质Al（g），Si（g），Si2（g），Si3（g）等逸出试样表面，偏离初始组成，形成21R，O＇-Sialon等杂质相，造成试样质量损失和结构疏松。     

氮气中C-Si系材料的高温变化过程

以9组不同配料比的炭黑和单质硅为原料压制成试样, 在氮气气氛下,分别于1350,1400,1450,1500,1550℃下烧结,获得5个不同温度点合成样品: 采用XRD分析技术研究试样的物相演变过程, 研究C-Si系原料在氮气气氛合成过程中的物相变化和反应动力学机制.试验结果表明:试样在氮气气氛下合成,最终物相为SiC,α-Si3N4和β-Si3N4,硅含量高时还存在Si2N2O相,石英相和方石英相作为中间产物出现:氮化硅不仅可由单质硅氮化生成,还可由SiO2,Si2N2O与C还原氮化生成,α-Si3N4先于β-Si3N4生成,且温度升高会向β相转化,温度高于1500℃时,Si3N4会与残余的C反应生成SiC:合成温度和配料比是影响C-Si系原料合成产物的重要动力学因素.     

反应气氛对铝热还原氧化钛合成氮化钛的影响

研究在流动氮气和埋炭条件下铝热还原氮化TiO2的反应过程,借助于X射线衍射(XRD)和扫描电子显微镜(SEM)分别测试和观察两种气氛中不同温度下处理后产物的物相组成和显微结构。结果显示,与流动氮气氛下一样,在埋炭气氛下采用铝热还原氮化法可以制备氮化钛复相材料,但处理气氛明显影响着铝热反应的程度及产物的形貌,在埋炭条件下处理后的产物中氮化钛含量、晶粒大小、晶格常数明显低于流动氮气氛下处理产物中上述各项值;热力学计算发现埋炭条件下铝除参与铝热还原反应外,还与炭粉床中氧发生反应,使参与铝热反应的金属铝不足,造成产物中有剩余的金红石存在。     

V_2O_5还原氮化一步法合成氮化钒

在热力学计算的基础上,以五氧化二钒和碳黑为原料并通入氮气一步法合成氮化钒,研究了不同配碳比(即碳黑中的碳质量与V2O5中的氧质量之比)和反应温度对氮化产物的相组成和化学成分的影响。实验结果表明,原料配碳比直接影响氮化产物氮含量,当配碳比增加时氮化产物氮含量会减少;按理论配碳比添加碳黑,可以获得成分合适的氮化产物;随着反应温度的升高,氮化产物碳含量迅速降低,氮含量逐渐增加,反应温度在1300~1500℃范围内时氮化产物的物相组成均为VN.     

反应烧结法制备BN/Si_3N_4复相陶瓷的结构和性能

采用在硅(Si)粉中添加硼(B)粉,利用反应烧结法制备氮化硼/氮化硅(BN/Si_3N_4)复相陶瓷,分别采用X射线衍射、傅里叶变换红外光谱、扫描电子显微镜对其相组成和断面形貌进行表征,并采用同轴法分析其介电性能.结果表明:成型压强的增加会导致样品氮化率下降;随着氮化温度的升高,样品氮化率增大;随着B添加量的增加,样品的氮化率先升高后降低.采用12 MPa成型且B添加量为10%(质量分数)时,经1 450℃氮化处理制得的陶瓷以β-Si_3N_4相为主,孔隙率为40.12%,在2~18GHz频率下,其介电常数为3.27~3.58,介电损耗角正切值为1.10×10~(-3)~1.12×10~(-2).B的加入有效地改善了Si_3N_4陶瓷的介电性能,有望应用于透波材料领域.     

Kinetic study on the direct nitridation of silicon powders diluted with α-Si3N4 at normal pressure

Silicon nitride (Si₃N₄) powders were prepared by the direct nitridation of silicon powders diluted with α-Si₃N₄ at normal pressure. Silicon powders of 2.2 μm in average diameter were used as the raw materials. The nitriding temperature was from 1623 to 1823 K, and the reaction time ranged from 0 to 20 min. The phase compositions and morphologies of the products were analyzed by X-ray diffraction and scanning electron microscopy, respectively. The effects of nitriding temperature and reaction time on the conversion rate of silicon were determined. Based on the shrinking core model as well as the relationship between the conversion rate of silicon and the reaction time at different temperatures, a simple model was derived to describe the reaction between silicon and nitrogen. The model revealed an asymptotic exponential trend of the silicon conversion rate with time. Three kinetic parameters of silicon nitridation at atmospheric pressure were calculated, including the pre-exponential factor (2.27 cm·s^?1) in the Arrhenius equation, activation energy (114 kJ·mol^?1), and effective diffusion coefficient (6.2×10^?8 cm²·s^?1). A formula was also derived to calculate the reaction rate constant.     

机械化学法制备纳米锰酸镧粉体

本文将La2O3和Mn3O4的混合粉体作为原料,通过高温(1223K)固相反应方法和机械混合(球磨)法合成出锰酸镧粉体,并利用XRD、SEM和BET对各种粉体进行了相组成、微观结构和比表面积的分析和测试。结果表明,机械化学法可以制成超细的无定形混合粉体,将这种粉体在973K下煅烧5h可以获得纳米锰酸镧粉体。     

微波加热与常规加热硅锰粉固相脱硅动力学比较

采用微波加热和常规加热对硅锰粉和巴西粉锰的脱硅反应进行了动力学行为研究,以巴西粉锰为脱硅剂,与硅锰粉中的硅发生氧化还原反应.微波加热和常规加热分别加热到不同温度并保温一定时间,测定产物中硅含量并计算固相脱硅反应的表观活化能.实验表明:单一和混合料均可在微波场中快速升温.随着温度的升高和保温时间的延长,两种加热方式脱硅率均随之提高,在相同实验条件下,微波加热的脱硅率和反应速率均高于常规加热,微波加热可以提高固相脱硅率;微波加热固相脱硅反应的限制性环节为扩散环节,其表观活化能为102.93 kJ·mol-1,常规加热脱硅反应的表观活化能为180 kJ·mol-1,说明微波加热能改善固相脱硅的动力学条件,提高固相脱硅反应速率,降低脱硅反应的活化能.     

Synthesis of Ultrafine AlN Powders in an Al-O-C-N System

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Nitridation of chromium powder in ammonia atmosphere

CrN powder was synthesized by nitriding Cr metal in ammonia gas flow, and its chemical reaction mechanism and nitridation process were studied. Through thermodynamic calculations, the Cr-N-O predominance diagrams were constructed for different temperatures. Chromium nitride formed at 7002-1200℃ under relatively higher nitrogen and lower oxygen partial pressures. Phases in the products were then investigated using X-ray diffraction (XRD), and the Cr₂N content varied with reaction temperature and holding time. The results indicate that the Cr metal powder nitridation process can be explained by a diffusion model. Further, Cr₂N formed as an intermediate product because of an incomplete reaction, which was observed by high-resolution transmission electron microscopy (HRTEM). After nitriding at 1000℃ for 20 h, CrN powder with an average grain size of 63 nm was obtained, and the obtained sample was analyzed by using a scanning electron microscope (SEM).     

Purity of SiC powders fabricated by coat-mix

Silicon carbide powders were synthesized by the coat-mix process, with phenolic resin and silicon powders as starting materials. The effects of synthetic conditions, including sintering temperature and the molar ratio of resin-derived carbon to silicon on the composition and the purity of the resultant powders were investigated. The results show that a higher sintering temperature and an appropriate molar ratio of resin-derived carbon to silicon are favorable for producing high purity silicon carbide powders. It is found that the silicon carbide content increases slightly with increasing the sintering temperature during the solid-solid reaction. The temperature gradient plays an important role on this trend. When the sintering temperature is raised up to 1500℃, the formation of silicon earbide is based on the liquid-solid reaction, and high purity (99.8wt%) silicon carbide powders can easily be obtained. It can also be found that the optimum molar ratio of resin-derived carbon to silicon is 1:1.     

Investigation on preparing boron nitride by nitriding pure boron at 1200–1550 1C

Boron nitride (BN) was prepared by nitriding pure boron (B) deposited on carbon substrates by chemical vapor deposition (CVD). Thermodynamic analysis of preparing BN by nitriding CVD B at 1200–1550 1C was firstly performed. And then, the effects of nitridation conditions, including temperature, nitridation atmosphere and CVD B microstructure, on the conversion of B to BN were analyzed by scanning electron microscopy (SEM), energy dispersion spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). Results show that the conversion degree of B to BN firstly increased and then slightly decreased with rising temperature. The nitridation degree was controlled by mutual actions between the nitridation of B and consumption of the effective nitrogen source (NH3). The morphology of products and the reaction mechanism between B and N were influenced by nitridation temperature. At high temperatures (1400–1500 1C), BN with highly ordered microstructure was produced. On using N2–H2 as nitridation atmosphere instead of NH3–H2– N2, no BN was obtained in the studied temperature range. The microstructure and component of BN obtained in nitridation process were little affected by the microstructure of CVD B.     

由氨解法制备的Si_3N_4粉末的表面元素状态

用XPS表面分析,研究了由氨解法在不同温度下热解所得的Si_3N_4粉末,并与由硅粉氮化所得的商用Si_3N_4粉末作了比较。由氨解法制备的Si_3N_4粉末其表面存在两种状态的氧:结合状态的氧和吸附态的氧,其表面组成为Si_(2.2-2.7)N_(2.9-3.7)O。由硅粉氮化所制得Si_3N_4其表面也存在两种状态的氧,其表面组成则为Si_(0.8)N_(0.8)O。     

硅溶胶粒径和分散性的影响因素

采用硅粉催化水解工艺,以硅粉为原料,无机碱做催化剂,制备出粒径分布均匀的单分散二氧化硅胶体.通过考察催化剂种类、用量,硅粉投料方式及温度等对二氧化硅胶体的粒径和性质的影响,探索制备此类硅溶胶的最佳条件.结果表明:用硅粉催化水解法制得的二氧化硅胶体呈现出很好的稳定性;在一次性投料、投料温度为85℃,碱性pH值,制备的二氧化硅胶体性能最好.     

二元无硫黑火药研究

运用最小自由能原理计算了不同配比C/KNO3体系燃烧产物的平衡气相组成和热力学参数,从反应动力学的角度对模拟结果进行定性分析,并以平衡态气相组成、火药力、爆温为目标函数,设计出低腐蚀、无污染的无硫黑火药配方,改善了体系的热力学性能,并就优化后配方的理化、感度性能及输出特性与制式黑火药进行了对比分析.结果表明,无硫黑火药火焰感度提高;机械感度与静电感度降低;输出感度有所增加.