Investigation of the thermal decomposition reactions of HMX using online photoionization mass spectrometry

IF 5.2 2区工程技术 Q2 ENERGY & FUELS

Proceedings of the Combustion Institute Pub Date : 2025-01-01 DOI:10.1016/j.proci.2025.105849

Hairong Ren , Guangda Luo , Xintong Xiao , Yuzhou Huang , Feng Zhang , Long Zhao , Zhongyue Zhou , Xinghui Liu , Xiang Guo , Fei Qi

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引用次数: 0

Abstract

1,3,5,7-Tetranitro-1,3,5,7-tetrazoctane (HMX) is a high-performance energetic material widely used in solid propellants. Understanding its thermal decomposition process is crucial for improving the combustion efficiency of these propellants. However, the rapid pyrolysis process and the complexity of the resulting products pose significant challenges to elucidating its decomposition mechanism. To investigate the pyrolysis process of HMX, online photoionization time-of-flight mass spectrometry (PI-TOFMS) and atmospheric photoionization ultra-high resolution mass spectrometry (APPI-HRMS) were employed to characterize the thermal decomposition products at atmospheric pressure (10⁵ Pa) and low pressure (10⁻³ Pa), respectively. Leveraging the soft ionization capability of photoionization, several key pyrolysis products of HMX were identified, such as HONO-elimination products, NO₂-elimination products, fragments from ring opening, and products from ring contraction and growth. The experimental results reveal that the thermal decomposition process of HMX involves several possible channels: (i) HONO-elimination & NNO₂ bond cleavage; (ii) cleavage of HMX along the symmetry axis into two INT148; (iii) ring contraction; (iv) ring scission; (v)growth of nitrogen-containing polycyclic aromatic hydrocarbons (NPAHs).

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在线光电离质谱法研究HMX的热分解反应

1,3,5,7-四硝基-1,3,5,7-四氮辛烷（HMX）是一种高性能含能材料，广泛应用于固体推进剂中。了解其热分解过程对提高推进剂的燃烧效率至关重要。然而，其快速的热解过程和产物的复杂性给其分解机理的阐明带来了巨大的挑战。为了研究HMX的热解过程，采用在线光电离飞行时间质谱法（PI-TOFMS）和大气光电离超高分辨率质谱法（api - hrms）分别对常压（105 Pa）和低压（10−3 Pa）下的热分解产物进行了表征。利用光电离的软电离能力，确定了HMX的几个关键热解产物，如hono -消除产物、no2 -消除产物、开环碎片、环收缩和生长产物。实验结果表明，HMX的热分解过程包括几个可能的通道：(i) hono消除和NNO2键解理；（ii） HMX沿对称轴裂解成两个INT148；（iii）环收缩；（iv）环断裂；(v)含氮多环芳烃（NPAHs）的生长。

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来源期刊

Proceedings of the Combustion Institute 工程技术-工程：化工

CiteScore

7.00

自引率

0.00%

发文量

420

审稿时长

3.0 months

期刊介绍： The Proceedings of the Combustion Institute contains forefront contributions in fundamentals and applications of combustion science. For more than 50 years, the Combustion Institute has served as the peak international society for dissemination of scientific and technical research in the combustion field. In addition to author submissions, the Proceedings of the Combustion Institute includes the Institute''s prestigious invited strategic and topical reviews that represent indispensable resources for emergent research in the field. All papers are subjected to rigorous peer review. Research papers and invited topical reviews; Reaction Kinetics; Soot, PAH, and other large molecules; Diagnostics; Laminar Flames; Turbulent Flames; Heterogeneous Combustion; Spray and Droplet Combustion; Detonations, Explosions & Supersonic Combustion; Fire Research; Stationary Combustion Systems; IC Engine and Gas Turbine Combustion; New Technology Concepts The electronic version of Proceedings of the Combustion Institute contains supplemental material such as reaction mechanisms, illustrating movies, and other data.