Rui-min Tang , Chen Wang , Mao-guo Zhu , Liang-liang Sun , Jian-xing Yang , Su-hang Chen , Feng-qi Zhao , Kang-zhen Xu
{"title":"高氮化合物4,4 ',6,6 ' -四(叠氮)-肼-1,3,5-三嗪的热解行为及机理","authors":"Rui-min Tang , Chen Wang , Mao-guo Zhu , Liang-liang Sun , Jian-xing Yang , Su-hang Chen , Feng-qi Zhao , Kang-zhen Xu","doi":"10.1016/j.enmf.2025.04.001","DOIUrl":null,"url":null,"abstract":"<div><div>The pyrolysis behavior and mechanism of energetic materials are crucial for assessing their safety and application. In this study, the pyrolysis behavior, gas-phase decomposition products, condensate phase products and pyrolysis mechanism of high nitrogen compound 4,4′,6,6′-tetri(azide)-hydrazine-1,3,5-triazine (TAHT) were fully studied through differential scanning calorimetry (DSC), thermogravimetric analysis (TG), thermogravimetric-infrared-mass spectrometry (TG-IR-MS) and in-situ infrared spectroscopy. The results indicate that the thermal behavior of TAHT exhibits a big exothermic decomposition process and an endothermic decomposition process accompanied by the mass loss of 42.5 % and 52.1 %, respectively. At the heating rate of 10 °C·min<sup>−1</sup>, the peak temperature (<em>T</em><sub>p</sub>) and decomposition enthalpy of exothermic decomposition process are 230.4 °C and −2021.0 J g<sup>−1</sup>, respectively. The peak temperature (<em>T</em><sub>p</sub>) of endothermic decomposition process is 703.5 °C. In the exothermic decomposition stage, the main gas-phase decomposition products of TAHT are N<sub>2,</sub> and contain small amounts of NH<sub>3</sub> and HCN, the hydrazine bond and azide groups in the condensed-phase almost completely disappear during the pyrolysis process, and the residues form a network structure of triazine ring. Based on the analysis of gas-phase and condensed-phase products, a possible pyrolysis mechanism for TAHT is proposed. This work provides valuable theoretical insights for the application of TAHT as a new green energetic material.</div></div>","PeriodicalId":34595,"journal":{"name":"Energetic Materials Frontiers","volume":"6 2","pages":"Pages 195-201"},"PeriodicalIF":3.3000,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Pyrolysis behavior and mechanism of high nitrogen compound 4,4′,6,6′-tetra(azido)-hydrazine-1,3,5-triazine\",\"authors\":\"Rui-min Tang , Chen Wang , Mao-guo Zhu , Liang-liang Sun , Jian-xing Yang , Su-hang Chen , Feng-qi Zhao , Kang-zhen Xu\",\"doi\":\"10.1016/j.enmf.2025.04.001\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The pyrolysis behavior and mechanism of energetic materials are crucial for assessing their safety and application. In this study, the pyrolysis behavior, gas-phase decomposition products, condensate phase products and pyrolysis mechanism of high nitrogen compound 4,4′,6,6′-tetri(azide)-hydrazine-1,3,5-triazine (TAHT) were fully studied through differential scanning calorimetry (DSC), thermogravimetric analysis (TG), thermogravimetric-infrared-mass spectrometry (TG-IR-MS) and in-situ infrared spectroscopy. The results indicate that the thermal behavior of TAHT exhibits a big exothermic decomposition process and an endothermic decomposition process accompanied by the mass loss of 42.5 % and 52.1 %, respectively. At the heating rate of 10 °C·min<sup>−1</sup>, the peak temperature (<em>T</em><sub>p</sub>) and decomposition enthalpy of exothermic decomposition process are 230.4 °C and −2021.0 J g<sup>−1</sup>, respectively. The peak temperature (<em>T</em><sub>p</sub>) of endothermic decomposition process is 703.5 °C. In the exothermic decomposition stage, the main gas-phase decomposition products of TAHT are N<sub>2,</sub> and contain small amounts of NH<sub>3</sub> and HCN, the hydrazine bond and azide groups in the condensed-phase almost completely disappear during the pyrolysis process, and the residues form a network structure of triazine ring. Based on the analysis of gas-phase and condensed-phase products, a possible pyrolysis mechanism for TAHT is proposed. 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引用次数: 0
摘要
含能材料的热解行为和热解机理是评价含能材料安全性和应用前景的关键。本研究通过差示扫描量热法(DSC)、热重分析(TG)、热重-红外-质谱法(TG- ir - ms)和原位红外光谱技术,对高氮化合物4,4′,6,6′-四叠氮-肼-1,3,5-三嗪(TAHT)的热解行为、气相分解产物、凝析相产物和热解机理进行了全面研究。结果表明:TAHT的热行为表现为大的放热分解过程和吸热分解过程,质量损失分别为42.5%和52.1%。在升温速率为10℃·min−1时,放热分解过程的峰值温度(Tp)为230.4℃,分解焓为- 2021.0 J g−1。吸热分解过程的峰值温度Tp为703.5℃。在放热分解阶段,TAHT的主要气相分解产物为N2,并含有少量的NH3和HCN,在热解过程中缩合相的联氨键和叠氮基团几乎完全消失,残基形成三嗪环网状结构。通过对TAHT气相和冷凝产物的分析,提出了TAHT可能的热解机理。这项工作为TAHT作为一种新型绿色能材料的应用提供了有价值的理论见解。
Pyrolysis behavior and mechanism of high nitrogen compound 4,4′,6,6′-tetra(azido)-hydrazine-1,3,5-triazine
The pyrolysis behavior and mechanism of energetic materials are crucial for assessing their safety and application. In this study, the pyrolysis behavior, gas-phase decomposition products, condensate phase products and pyrolysis mechanism of high nitrogen compound 4,4′,6,6′-tetri(azide)-hydrazine-1,3,5-triazine (TAHT) were fully studied through differential scanning calorimetry (DSC), thermogravimetric analysis (TG), thermogravimetric-infrared-mass spectrometry (TG-IR-MS) and in-situ infrared spectroscopy. The results indicate that the thermal behavior of TAHT exhibits a big exothermic decomposition process and an endothermic decomposition process accompanied by the mass loss of 42.5 % and 52.1 %, respectively. At the heating rate of 10 °C·min−1, the peak temperature (Tp) and decomposition enthalpy of exothermic decomposition process are 230.4 °C and −2021.0 J g−1, respectively. The peak temperature (Tp) of endothermic decomposition process is 703.5 °C. In the exothermic decomposition stage, the main gas-phase decomposition products of TAHT are N2, and contain small amounts of NH3 and HCN, the hydrazine bond and azide groups in the condensed-phase almost completely disappear during the pyrolysis process, and the residues form a network structure of triazine ring. Based on the analysis of gas-phase and condensed-phase products, a possible pyrolysis mechanism for TAHT is proposed. This work provides valuable theoretical insights for the application of TAHT as a new green energetic material.