Microscopic kinetics of scission and reformation in the pyrolysis of nitrocellulose

IF 3.5 3区工程技术 Q2 ENGINEERING, CHEMICAL

AIChE Journal Pub Date : 2025-04-01 DOI:10.1002/aic.18844

Changwei Liu, Haojie Qian, Qing Wang, Jinkai Qiu, Yajun Ding, Cheng Lian, Honglai Liu

引用次数: 0

Abstract

Nitrocellulose (NC) is essential in high-energy propellants, with nitrogen content affecting its pyrolysis rate and thermal stability. This study creates all-atom models of NC with varying nitrogen levels to explore pyrolysis mechanisms and validate them against experimental thermal response data. Results show that RO − NO₂ bond cleavage initiates NC decomposition. Lower nitration levels convert nitrogen oxides into carbon-nitrogen compounds, primarily HCN. Additionally, HCHO production is linked to CH₂ONO₂ group transformation, with low-nitration, high-hydrogen NC reducing HCHO yield. Kinetic parameters for cellulose thermal decomposition indicate that pyrolysis activation energies decrease with nitration levels, demonstrating that nitration significantly lowers the energy barrier for ring-opening. Molecular dynamics simulations reveal pathways for HCHO, NO₂, and NO generation during combustion, enhancing understanding of NC combustion mechanisms and safety in explosive applications.

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硝化纤维素热解裂解和重整的微观动力学

硝化纤维在高能推进剂中是必不可少的，氮含量影响其热解速率和热稳定性。本研究建立了不同氮水平NC的全原子模型，探索热解机理，并通过实验热响应数据进行验证。结果表明：RO - NO2键解理引发NC分解；较低的硝化水平将氮氧化物转化为碳-氮化合物，主要是HCN。此外，HCHO的生成与CH2ONO2基团转化有关，低硝化、高氢NC降低了HCHO的产率。纤维素热分解动力学参数表明，热解活化能随硝化水平的增加而降低，说明硝化作用显著降低了纤维素开环能垒。分子动力学模拟揭示了燃烧过程中HCHO、NO2和NO生成的途径，增强了对NC燃烧机制和炸药应用安全性的理解。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

AIChE Journal 工程技术-工程：化工

CiteScore

7.10

自引率

10.80%

发文量

411

审稿时长

3.6 months

期刊介绍： The AIChE Journal is the premier research monthly in chemical engineering and related fields. This peer-reviewed and broad-based journal reports on the most important and latest technological advances in core areas of chemical engineering as well as in other relevant engineering disciplines. To keep abreast with the progressive outlook of the profession, the Journal has been expanding the scope of its editorial contents to include such fast developing areas as biotechnology, electrochemical engineering, and environmental engineering. The AIChE Journal is indeed the global communications vehicle for the world-renowned researchers to exchange top-notch research findings with one another. Subscribing to the AIChE Journal is like having immediate access to nine topical journals in the field. Articles are categorized according to the following topical areas: Biomolecular Engineering, Bioengineering, Biochemicals, Biofuels, and Food Inorganic Materials: Synthesis and Processing Particle Technology and Fluidization Process Systems Engineering Reaction Engineering, Kinetics and Catalysis Separations: Materials, Devices and Processes Soft Materials: Synthesis, Processing and Products Thermodynamics and Molecular-Scale Phenomena Transport Phenomena and Fluid Mechanics.