{"title":"Microscopic kinetics of scission and reformation in the pyrolysis of nitrocellulose","authors":"Changwei Liu, Haojie Qian, Qing Wang, Jinkai Qiu, Yajun Ding, Cheng Lian, Honglai Liu","doi":"10.1002/aic.18844","DOIUrl":null,"url":null,"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 − NO<sub>2</sub> bond cleavage initiates NC decomposition. Lower nitration levels convert nitrogen oxides into carbon-nitrogen compounds, primarily HCN. Additionally, HCHO production is linked to CH<sub>2</sub>ONO<sub>2</sub> 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, NO<sub>2</sub>, and NO generation during combustion, enhancing understanding of NC combustion mechanisms and safety in explosive applications.","PeriodicalId":120,"journal":{"name":"AIChE Journal","volume":"58 1","pages":""},"PeriodicalIF":3.5000,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"AIChE Journal","FirstCategoryId":"5","ListUrlMain":"https://doi.org/10.1002/aic.18844","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
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.
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.
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Articles are categorized according to the following topical areas:
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Inorganic Materials: Synthesis and Processing
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Separations: Materials, Devices and Processes
Soft Materials: Synthesis, Processing and Products
Thermodynamics and Molecular-Scale Phenomena
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