CHINESE JOURNAL OF ENERGETIC MATERIALS
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铁负载碳纳米管的制备及对固体推进剂中高能组分的催化
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中北大学环境与安全工程学院, 山西 太原 030051

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国家自然科学基金(22275169)


Preparation of Iron-loaded Carbon Nanotubes and Catalysis of Energetic Components in Solid Propellants
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School of Environmental and Safety Engineering, North University of China, Taiyuan 030051, China

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Grant support: National Natural Science Foundation of China (No. 22275169)

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    摘要:

    为发展固体推进剂用高性能燃速催化剂,采用前体笼装高温热解方法合成了一种铁负载碳纳米管材料(Fe@CNTs),并通过扫描电镜-能谱仪联用(SEM-EDS)、透射电镜(TEM)、X-射线衍射(XRD)、X-射线光电子能谱(XPS)、傅里叶变换红外光谱(FTIR)、氮气等温吸附(BET)、差示扫描量热法(DSC)和热重-质谱联用技术(TG-MS)等测试方法详细探究了Fe@CNTs的元素组成、微观形貌、物相结构、比表面积和催化分解性能。结果表明,Fe@CNTs是一种具有高比表面积的铁负载碳纳米管材料,当添加量为6%时,奥克托今(HMX)、1,1''-二羟基-5,5''-联四唑二羟铵盐(TKX-50)、1,1-二氨基-2,2-二硝基乙烯(FOX-7)、黑索今(RDX)和六硝基六氮杂异伍兹烷(CL-20)这5种高能组分的热分解放热峰温分别提前了1.8,40.4,4.9,6 ℃和8.8 ℃。基于Kissinger-Ozawa模型的热分解动力学计算显示,6%Fe@CNTs/HMX和6%Fe@CNTs/TKX-50的表观活化能各自降低了96.9~97.1 kJ·mol-1和11.2~11.9 kJ·mol-1;热力学和热安全性参数的理论计算表明,添加Fe@CNTs后,HMX和TKX-50仍处于热力学稳定状态;基于TG-MS结果进一步提出了Fe@CNTs对HMX和TKX-50两类高能物质可能的催化机理。

    Abstract:

    To develop a high-performance burning rate catalyst for solid propellant, an iron-loaded carbon nanotube material (Fe@CNTs) was synthesized by high-temperature pyrolysis of the caged precursor. The elemental composition, microscopic morphology, phase structure, specific surface area, and catalytic decomposition performance of Fe@CNTs were investigated by scanning electron microscope-energy dispersive spectrometer (SEM-EDS), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), nitrogen sorption isotherm measurement (BET), differential scanning calorimeter (DSC), and thermogravimetry-mass spectrometry (TG-MS). The results show that, Fe@CNTs is an iron-loaded carbon nanotube material with a high specific surface area, which can reduce the exothermic peak temperatures of octogen (HMX), dihydroxylammonium 5,5′-bistetrazole-1,1′-diolate (TKX-50), 1,1-diamino-2,2-dinitroethylene (FOX-7), hexogeon (RDX), and hexanitrohexaazaisowurtzitane (CL-20) by 1.8 ℃, 40.4 ℃, 4.9 ℃, 6 ℃, and 8.8 ℃, respectively, when the addition amount of this material is 6%. The calculations of thermal decomposition kinetics based on the Kissinger-Ozawa model show that the apparent activation energies of 6%Fe@CNTs/HMX and 6%Fe@CNTs/TKX-50 decrease by 96.9-97.1 kJ·mol-1 and 11.2-11.9 kJ·mol-1, respectively. Theoretical calculations of thermodynamic and thermal safety parameters indicate that HMX and TKX-50 are still in a thermodynamically stable state after adding Fe@CNTs. Based on the results of TG-MS, the possible catalytic mechanism of Fe@CNTs on HMX and TKX-50 is further proposed.

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引用本文

杜熙凤,要雅靖,张鑫慧,等.铁负载碳纳米管的制备及对固体推进剂中高能组分的催化[J].含能材料, 2024, 32(12):1321-1333. DOI:10.11943/CJEM2024156.
DU Xi-feng, YAO Ya-jing, ZHANG Xin-hui, et al. Preparation of Iron-loaded Carbon Nanotubes and Catalysis of Energetic Components in Solid Propellants[J]. Chinese Journal of Energetic Materials, 2024, 32(12):1321-1333. DOI:10.11943/CJEM2024156.

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  • 收稿日期: 2024-06-15
  • 最后修改日期: 2024-09-14
  • 录用日期: 2024-08-20
  • 在线发布日期: 2024-08-21
  • 出版日期: 2024-12-25