空气动力学学报2024，Vol.42Issue(4)：84-95,12.DOI:10.7638/kqdlxxb-2023.0195
压力影响硅基防热材料界面多相催化的微观机理研究
Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials
摘要
Abstract
Reactive molecular dynamics simulation provides an important approach to elucidate the microscale heating mechanisms involved in high-temperature wall effects and to deepen our understanding of non-equilibrium aerothermodynamics of high-speed aircraft.However,microscale simulations that enhance the computational efficiency by artificially increasing the gaseous pressure often lead to discrepancies in reaction pathways and rate coefficients,thereby affecting the aerothermodynamics and causing the misunderstanding of reaction mechanisms.Using a molecular dynamics approach based on the ReaxFF force field,this investigation addresses the catalytic recombination reaction system of dissociated oxygen atoms on the surface of silica-based thermal protective materials.The primary objectives involve the computation and analysis of elementary reaction rates,surface coverages,and recombination coefficients under various gaseous pressure conditions.The purpose is to establish a quantitative correlation between the rate constants of elementary reactions and pressure,thereby elucidating the upper bounds of computational efficiency enhancement through pressure augmentation.The results indicate that pressure augmentation leads to a transition in the dominant reaction pathway from adsorbate-adsorbate interactions to gas-adsorbate interactions.Furthermore,it causes a deviation in the relationship between the rate constants of elementary reactions and pressure from the patterns observed under experimental/flight conditions.At 1200 K,within the pressure range associated with single-atom collisions,a consistent decrease in the rate constants of individual elementary reaction steps is observed as the pressure decreases.Among them,the rate constants of ER1～ER3 recombination exhibit a linear relationship with pressure.Specifically,the rate constants can be expressed as a power law function of pressure,with exponents of 1.10179,1.01686 and 0.91654 respectively.The rate constants of LH1～LH3 recombination reactions display a logarithmic dependence on pressure,with significantly smaller pre-logarithmic factors compared to those observed in the non-single collision region.The rate constant of thermal desorption is exponentially related to pressure.Based on the microscale mechanism of catalytic reaction influenced by gaseous pressure,and with the stable relationship between elementary reaction rate constants and pressure,a constraint upper limit for artificially increasing pressure is proposed.The Knudsen number with the system height as the characteristic length should be greater than the magnitude of 102 to ensure the gas-solid single collision. This investigation provides support for molecular simulation methods of gas-solid interface reactions and the accumulation of microscale catalytic data for thermal protective materials.关键词
气固作用/多相催化/气相压力/主导路径/反应分子动力学Key words
gas-surface interaction/heterogeneous catalysis/gaseous pressure/dominant pathway/reactive molecular dynamics分类
航空航天引用本文复制引用
李芹,杨肖峰,董威,杜雁霞..压力影响硅基防热材料界面多相催化的微观机理研究[J].空气动力学学报,2024,42(4):84-95,12.基金项目
国家重点研发计划(2019YFA0405200) （2019YFA0405200）
