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. 

Noncatalytic gas-solid reaction model for directly nitridizing silicon powder under atmospheric pressure

In order to study the nitridation kinetics of silicon powder under atmospheric pressure, a set of nitrida- tion experiments were performed at 1350 and 1400 ℃ for 10 to 30 rain. Silicon powder of 2.2 ~m in average diameter and 99.99% in purity was adopted as the experimental materials, and nitrogen of 99.993% in purity was used as the reaction gas. At different temperatures, the conversion rate of silicon is obtained as a function of reaction time. Based on the noncatalytic gas-solid reaction model, a dynamic model of silicon nitridation under atmospheric pressure is introduced, which includes two key model parameters: reaction rate constant of silicon nitridation and diffusion coefficient of nitro- gen in silicon nitride, These model parameters are obtained by fitting the experimental data under different conditions. Assuming that reaction rate constant and the diffusion coefficient can both be expressed as the Arrhenius style, the activation energy and pre-exponential factor of the reaction are calculated as 2.71× 104 J·mol-1 and 3.07× 10-5 m·s-1, and the activation energy and pre-exponential factor of diffusion are calculated as 1.06×105 J·mol-1 and 1.12×10-9 m2·s-1, respectively. Then a series of conversion curves are predicted at different temperatures and powder sizes. On the trend, the predicted curves are in good agreement with experimental data in literatures.