CHINESE JOURNAL OF ENERGETIC MATERIALS
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基于溶剂/非溶剂法的微通道结晶制备CL-20/HMX共晶
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西南科技大学环境友好能源材料国家重点实验室, 四川 绵阳 621010

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国家自然科学基金资助(11572270和21905236)


Preparation of CL-20/HMX Co-crystal by Microchannel Crystallization Based on Solvent/non-solvent Method
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State Key Laboratory of Environment-friendly Energy Materials, Southwest University of Science and Technology, Mianyang 621010, China

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    摘要:

    为了发展易放大、可连续化的共晶制备方法,采用溶剂/非溶剂法的微通道结晶技术制备了六硝基六氮杂异伍兹烷/奥克托今(CL-20/HMX)共晶。采用场发射扫描电子显微镜(FE-SEM)、X射线粉末衍射(XRD)、拉曼光谱(Raman)、傅里叶红外光谱(FT-IR)、热分析和感度测试,对样品的形貌、结构、热性能和感度进行了表征分析。结果表明,该方法成功制备了CL-20/HMX共晶,其表观形貌部分呈花簇状,直径为20~30 μm,由厚度为200~600 nm的片状晶体组装而成,部分呈单独的片状结晶(厚度为200~600 nm);所制备的CL-20/HMX共晶在放热过程中仅有一个尖锐的放热分解峰,放热峰温位于243.4 ℃,低于原料CL-20(250.2 ℃)和HMX(284.7 ℃)。放热区间仅为242.7~246.0 ℃,比原料CL-20(230.0~254.6 ℃)和HMX(281.0~290.7 ℃)窄,具有较高的能量释放效率;表观活化能470.75 kJ·mol-1,介于CL-20(175.04 kJ·mol-1)和HMX(481.45 kJ·mol-1)之间,比CL-20提高了295.71 kJ·mol-1,具有较好的热稳定性;撞击感度为18 J,较原料CL-20(10 J)和HMX(14.4 J)分别提高8 J和3.6 J,摩擦感度比CL-20原料降低了20%,安全性有所提高。

    Abstract:

    In order to develop a scale-up and continuous preparation method, the microchannel crystallization technology based on solvent/non-solvent method has been used to prepare hexanitrohexaazaisowurtzitane/octogen (CL-20/HMX) co-crystal. The field emission scanning electron microanalyzer (FE-SEM), X-ray powder diffraction (XRD), Raman spectroscopy, Fourier infrared spectroscopy (FT-IR), thermal analysis and sensitivity test were applied to characterize and analyze the morphology, structure, thermal performance and sensitivity of samples. Results show that this method has successfully prepared CL-20/HMX co-crystal. Its apparent morphology is the flower clusters with a diameter of 20-30 μm, assembled by platelet crystals with thickness of 200-600 nm, accompanying individual flaky crystals (thickness of 200-600 nm). The CL-20/HMX co-crystal prepared by microchannal crystallization has only one sharp exothermic decomposition peak during the exothermic process. Its exothermic peak temperature is at 243.4 ℃, which is lower than that of the raw materials CL-20 (250.2 ℃) and HMX (284.7 ℃). Its temperature range of thermal decomposition is only from 242.7 to 246.0 ℃, much narrower than those of raw CL-20 (230.0-254.6 ℃) and HMX (281.0-290.7 ℃), which means a higher energy release efficiency. Its apparent active energy is 470.75 kJ·mol-1,falling between CL-20 (175.04 kJ·mol-1) and HMX (481.45 kJ·mol-1), which is 297.29 kJ·mol-1 hagher than that of raw CL-20,indicating a good thermal stability. Its impact sensitivity is 18 J, which is 8 J and 3.6 J higher than those of raw CL-20 (10 J) and HMX (14.4 J) respectively, and the friction sensitivity is 20% lower than that of raw CL-20. The sensitivity results show the safety of the CL-20/HMX co-crystal has been improved compared with the raw materials.

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李丽,尹婷,伍波,等.基于溶剂/非溶剂法的微通道结晶制备CL-20/HMX共晶[J].含能材料, 2021, 29(1):62-69. DOI:10.11943/CJEM2020214.
LI Li, YIN Ting, WU Bo, et al. Preparation of CL-20/HMX Co-crystal by Microchannel Crystallization Based on Solvent/non-solvent Method[J]. Chinese Journal of Energetic Materials, 2021, 29(1):62-69. DOI:10.11943/CJEM2020214.

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  • 收稿日期: 2020-08-06
  • 最后修改日期: 2020-12-02
  • 录用日期: 2020-11-27
  • 在线发布日期: 2020-12-02
  • 出版日期: 2021-01-25