Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials

LI Qin; YANG Xiaofeng; DONG Wei; DU Yanxia

doi:10.7638/kqdlxxb-2023.0195

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Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials

更新时间：2026-05-28

- Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials
- Vol. 42, Issue 4, Pages: 84-95(2024)
- 作者机构：
  
  1. 上海交通大学机械与动力工程学院,上海,200240
  2. 空天飞行空气动力科学与技术全国重点实验室,绵阳,621000
- 作者简介：
- 基金信息：
- DOI：10.7638/kqdlxxb-2023.0195
  CLC： V411
- Published：2024
- 稿件说明：
移动端阅览
李芹, 杨肖峰, 董威, 等. 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.

LI Qin, YANG Xiaofeng, DONG Wei, et al. Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials[J]. 2024, 42(4): 84-95.
李芹, 杨肖峰, 董威, 等. 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. DOI： 10.7638/kqdlxxb-2023.0195

LI Qin, YANG Xiaofeng, DONG Wei, et al. Microscale mechanism study of pressure effects on interfacial heterogeneous catalysis of silica-based thermal protective materials[J]. 2024, 42(4): 84-95. DOI： 10.7638/kqdlxxb-2023.0195.

摘要

反应分子动力学模拟是阐明高温壁面效应微观致热机理、深化高速飞行器非平衡气动热认知的重要途径之一，然而通过人为增加压力实现计算效率提升的微观模拟，往往会导致反应路径和速率系数差异，进而影响气动热，造成机理认知偏差。采用基于ReaxFF力场的分子动力学方法，以离解氧原子在硅基防热材料表面的催化复合反应体系为对象，计算分析了不同气相压力条件下的基元反应速率、表面覆盖率和复合系数，用于获得基元反应速率常数与压力的量化关系，明确通过增压提高计算效率的上限范围。结果表明，增压可导致主导反应路径从吸附相间作用至气相-吸附相作用的转变，且使基元反应速率常数-压力的关系偏离实验/飞行条件下的规律。在

1200

K条件下、单原子碰撞的压力范围内，各基元反应步骤的速率常数均随压力的降低而下降。其中，ER1～ER3复合反应的速率常数随压力呈近似线性变化，速率常数分别与压力的

1.10179

、

1.01686

和

0.91654

次方呈线性关系；LH1～LH3复合反应的速率常数与压力呈对数关系，且对数前因子显著小于非单原子碰撞区；热解附反应的速率常数与压力呈指数关系。根据气相压力影响催化反应机制的微观机理，以基元反应速率常数-压力关系可以稳定解析为判据，提出了人为增加压力的约束上限条件：以体系高度为特征长度的努森数应大于10

量级，以保证气固单原子碰撞。相关研究为气固界面反应的分子模拟方法和防热材料微观催化数据的累积提供了支撑。

Abstract

Reactive molecular dynamics simulation provides an important approach to elucidate the microscale heating mechanisms involved in high-temperatu

re 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

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

espectively. 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

$ {10^2} $

img text_id='M2' class='formula-img' style='display:none;' src='2023-195_M2.jpg'>

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

Keywords

references

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