CHINESE JOURNAL OF ENERGETIC MATERIALS
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α-HMX对RDX热安全性的影响研究
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1北京理工大学材料学院, 北京 100081;2甘肃银光化学工业集团有限公司, 甘肃 白银 730900

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火炸药基础创新项目


Study on the Effect of α-Octogen on the Thermal Stability of Hexogen
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1School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China;2Gansu Yinguang Chemical Industry Group Co., Ltd., Baiyin 730900, China

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    摘要:

    为探讨工业制备黑索今(RDX)的过程中生成的副产物α-奥克托今(α-HMX)对RDX的热安全性影响,以醋酐法制备了不同HMX含量(0、9.50%、12.41%、17.00%和21.68%)的RDX样品。通过红外光谱和扫描电镜分析,确认样品中HMX晶型均为α型。采用差示扫描量热(DSC)技术获得了样品的热分解参数,并利用Ozawa法和Kissinger法计算样品的活化能,最终得出样品的相容性等级。研究结果显示,α-HMX显著降低了RDX的活化能和热分解峰温。当α-HMX的含量为21.68%时,相容性评价为1级,表明二者具有良好的相容性。当α-HMX含量为21.68%时,根据Ozawa法和Kissinger法计算的表观活化能从213.81 kJ·mol-1降至137.29 kJ·mol-1,相容性评价降至4级,显示出二者相容性较差。利用TSS软件对DSC结果进行拟合分析,评估了样品的储存与运输安全性。结果表明:RDX及其与α-HMX的复合体系遵循“自催化→N级→自催化”的三步连续反应模型,在α-HMX为21.68%时,自加速分解温度(SADT)由138 ℃降至108 ℃,自加速分解温度提前,热失控风险提高。在10,20 kg和50 kg的装载量条件下,SADT并未表现出显著差异。

    Abstract:

    To investigate the effect of α-HMX content on the thermal safety of RDX produced via the acetic anhydride method, and thus addressing a gap in the existing research, five RDX samples (R1-R5) were prepared with α-HMX contents of 0, 9.50%, 12.41%, 17.00%, and 21.68%, respectively. The crystal form of HMX was identified using infrared spectroscopy and scanning electron microscopy. By employing differential scanning calorimetry (DSC) combined with the Ozawa method, Kissinger method, and modelling techniques, we systematically analyzed the thermal decomposition characteristics, kinetic patterns, and storage/transport safety parameters of the samples. Findings indicate that α-HMX reduces the activation energy and decomposition peak temperature of RDX. When the α-HMX content is ≤17.00%, compatibility remains satisfactory and thermal stability is maintained. However, when the α-HMX content reaches 21.68%, the apparent activation energy drastically decreases to 137.29 kJ·mol-1, compatibility deteriorates, and the self-accelerating decomposition temperature (SADT) drops to approximately 108 ℃, which markedly increases the risk of thermal detonation. Both the RDX and RDX/α-HMX systems follow a three-step sequential reaction model: ‘autocatalysis → N-stage → autocatalysis’. The Ozawa and Kissinger methods can provide initial parameter values for kinetic model fitting. For storage and transportation, there were no significant differences in the SADT among the groups at load capacities of 10, 20 kg and 50 kg. The kinetic model and critical safety parameters established herein provide essential technical support for production control and storage/transport safety in acetic anhydride-based RDX manufacturing, and confirm that the α-HMX content in the product must be maintained below 17.00%.

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陈鑫雅,李丽洁,陶玉婷,等. α-HMX对RDX热安全性的影响研究[J]. 含能材料,DOI:10.11943/CJEM2026006.

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  • 收稿日期: 2025-12-22
  • 最后修改日期: 2026-04-14
  • 录用日期: 2026-04-03
  • 在线发布日期: 2026-04-26
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