基于玻璃毛细管坩埚DSC的高能化学品含能量分析

doi:10.16265/j.cnki.issn1003-3033.2026.07.0230

中国安全科学学报 ›› 2026, Vol. 36 ›› Issue (7): 164-170.doi: 10.16265/j.cnki.issn1003-3033.2026.07.0230

基于玻璃毛细管坩埚DSC的高能化学品含能量分析

李玮晔¹(), 吕小宝², 沈雯怡³, 赵晓雷², 田均均⁴, 盛敏⁵^,^**()

¹ 华东理工大学反应安全中心, 上海 200237
² 上海市公安局物证鉴定中心, 上海 200083
³ 上海市公安局涉火案件现场物证重点实验室, 上海 200083
⁴ 中国工程物理研究院化工材料研究所, 四川绵阳 621900
⁵ 上海市应急管理局化工反应安全重点实验室, 上海 200237

收稿日期:2026-02-26 修回日期:2026-05-14 出版日期:2026-07-28
通信作者:
^**盛敏(1980—),男,江西九江人,博士,教授,博士生导师,主要从事反应安全风险评估、反应动力学和锂电池热安全研究。E-mail:minsheng@ecust.edu.cn。
作者简介:
李玮晔 (2001—),男,江苏盐城人,博士研究生,主要研究方向为反应安全风险评估。E-mail: weiyeli@mail.ecust.edu.cn。

Anslysis of energy content of high-energy chemicals using DSC with glass capillary crucible

Li Weiye¹(), Lyu Xiaobao², Shen Wenyi³, Zhao Xiaolei², Tian Junjun⁴, Sheng Min⁵^,^**()

¹ Reactive Chemical Safety Center, East China University of Science and Technology, Shanghai 200237, China
² Physical Evidence Identification Center, Shanghai Municipal Public Security Bureau, Shanghai 200083, China
³ Key Laboratory for Fire-related Case Scene Material Evidence, Shanghai Municipal Public Security Bureau, Shanghai 200083, China
⁴ Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang Sichuan 621900, China
⁵ Key Laboratory of Chemical Reaction Safety, Shanghai Emergency Management Bureau, Shanghai 200237, China

Received:2026-02-26 Revised:2026-05-14 Published:2026-07-28

摘要/Abstract

摘要：

为解决常规量热测试高能化学品含能量误差较大的问题,在玻璃毛细管坩埚内微量填充样品,并使用差示扫描量热仪(DSC)测试样品的热分解特性,分析三硝基甲苯(2,4,6-TNT、2,3,6-TNT)、硝基甲烷及特屈儿(Tetryl)4种高能化学品的含能量,获取其热分解特征图谱与吸放热数据,深入解析复杂多硝基化合物的分解反应机制,并结合Yoshida关系式评估其爆炸属性区间。研究结果表明:相较于目前常用的高压镀金坩埚,采用在玻璃毛细管坩埚内填充样品在可靠性与经济性上更具优势;2,4,6-TNT与硝基甲烷在玻璃毛细管坩埚中测得的含能量分别为-4 545.9、-5 436.5 J/g,在高压镀金坩埚中测得的含能量分别为-2 907.6、-2 997.5 J/g,相比之下,玻璃毛细管坩埚中测得的含能量更贴合理论值(-4 184、-5 246 J/g)。同时,采用玻璃毛细管坩埚方法的测量误差均控制在10%以内,展现出良好的重现性与测试精度。

关键词: 玻璃毛细管坩埚, 差示扫描量热仪(DSC), 高能化学品, 含能量, 高压镀金坩埚

Abstract:

To address the issue of significant errors in measuring the energy content of high-energy chemicals using conventional calorimetry, trace amounts of samples were loaded into glass capillary crucibles, and their thermal decomposition characteristics were tested using differential scanning calorimetry (DSC). The energy contents of four high-energy chemicals—trinitrotoluene (2,4,6-TNT and 2,3,6-TNT), nitromethane, and tetryl—were analyzed to obtain their thermal decomposition profiles and endothermic/exothermic data. Furthermore, the decomposition reaction mechanisms of these complex polynitro compounds were thoroughly investigated, and their explosive property ranges were evaluated using the Yoshida correlation. The results indicate that, compared to the commonly used high-pressure gold-plated crucibles, filling samples in glass capillary crucibles offers greater advantages in reliability and cost-effectiveness. The energy contents of 2,4,6-TNT and nitromethane measured in glass capillary crucibles were -4 545.9 and -5 436.5 J/g, respectively, while those measured in high-pressure gold-plated crucibles were -2 907.6 and -2 997.5 J/g; in comparison, the energy contents measured in the glass capillary crucibles are much closer to the theoretical values (-4 184 and -5 246 J/g). Meanwhile, the measurement errors of the glass capillary crucible method are maintained within 10%, demonstrating good reproducibility and high measurement accuracy.

Key words: glass capillary crucible, differential scanning calorimetry(DSC), high-energy chemicals, energy content, high-pressure gold-plated crucible

中图分类号:

X937

李玮晔, 吕小宝, 沈雯怡, 赵晓雷, 田均均, 盛敏. 基于玻璃毛细管坩埚DSC的高能化学品含能量分析[J]. 中国安全科学学报, 2026, 36(7): 164-170.

Li Weiye, Lyu Xiaobao, Shen Wenyi, Zhao Xiaolei, Tian Junjun, Sheng Min. Anslysis of energy content of high-energy chemicals using DSC with glass capillary crucible[J]. China Safety Science Journal, 2026, 36(7): 164-170.

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样品容器	最大温度/℃	最大压力/kPa	容器质量/mg	支架质量/mg	容器体积/μL	样品质量/mg
玻璃毛细管坩埚	500	40 000	25	~200	5	0.2 ~ 1.5
高压镀金坩埚	400	20 000	850	—	25	1

样品名	峰	试验1总能量/(J/g)	试验2总能量/(J/g)	试验3总能量/(J/g)	试验4总能量/(J/g)	均值/ (J/g)	标准差/ (J/g)	方差/ %
2,4,6-TNT	吸热	100.7	100.5	98.8	99.0	99.7	1.0	1.0
2,4,6-TNT	放热	-4 104.8	-4 058.5	-4 528.4	-4 016.9	-4 177.2	236.9	5.7

样品名	峰	试验1总能量/(J/g)	试验2总能量/(J/g)	试验3总能量/(J/g)	均值/ (J/g)	标准差/ (J/g)	误差/ %
2,3,6-TNT	吸热	106.2	108.1	105.1	106.5	1.5	1.4
2,3,6-TNT	放热	-4 458.2	-4 595.5	-4 522.0	-4 525.2	68.7	1.5
硝基甲烷	放热	-5 436.5	-5 497.2	-5 360.6	-5 431.4	68.4	1.3
Tetryl	吸热	88.1	81.5	83.5	84.4	3.4	4.0
Tetryl	放热	-5 151.4	-4 903.5	-4 635.1	-4 896.6	258.2	5.3

基于玻璃毛细管坩埚DSC的高能化学品含能量分析

Anslysis of energy content of high-energy chemicals using DSC with glass capillary crucible

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