CHINESE JOURNAL OF ENERGETIC MATERIALS
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2,4-MDNI/DNTF二元低共熔物的制备与性能
作者:
作者单位:

1.中北大学环境与安全工程学院, 山西 太原 030051;2.四川华川工业有限公司, 四川 成都 510100

作者简介:

朱俊伍(1997-),男,硕士研究生,主要从事含能材料的应用研究。e-mail:junwuzhu@126.com

通讯作者:

刘玉存(1961-),男,教授,主要从事含能化合物研究。e-mail:lyc2ct@vip.sina.com

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Preparation and Properties of 2,4-MDNI / DNTF Binary Eutectic
Author:
Affiliation:

1.School of Environmental and Safety Engineering, North University of China,Taiyuan 030051, China;2.Sichuan Huachuan Industries Co., Ltd,Chengdu 510100, China

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    摘要:

    为了改善熔铸炸药载体3,4-二硝基呋咱基氧化呋咱(DNTF)感度高、熔点高的问题,使用高能钝感炸药1-甲基-2,4-二硝基咪唑(2,4-MDNI)制备了2,4-MDNI/DNTF低共熔物体系。通过差示扫描量热法(DSC)研究了不同比例2,4-MDNI/DNTF的熔融及液化过程,建立了T-x相图;研究了不同升温速率下2,4-MDNI、DNTF及2,4-MDNI/DNTF低共熔物的熔融和分解过程,分别使用Flynn-wall-ozawa方法、Doyle方法和Kissinger方法计算了2,4-MDNI、DNTF及其低共熔物的热反应动力学参数;对三种物质进行了XRD和SEM分析;通过感度测试研究了2,4-MDNI对DNTF的降感作用;使用EXPLO-5软件,计算了2,4-MDNI/DNTF低共熔物的爆轰性能。结果表明:2,4-MDNI/DNTF最低共熔物的物质的量组成为51:49,平均熔点为92.7 ℃;随着升温速率的升高,熔融及分解反应都将延迟,低共熔物热分解反应的活化能Ea、指前因子A分别为 146.0 kJ·mol-1和4.09×1013;XRD测试中,2,4-MDNI/PETN低共熔物在2θ=18.60°处产生新的衍射峰;且其凝固表面微观形貌比DNTF明显改善。2,4-MDNI的撞击和摩擦感度均为0%,低共熔物的撞击和摩擦感度分别为64%和52%;2,4-MDNI/DNTF低共熔物的理论密度1.844 g·cm-3,计算爆速为8705 m·s-1。2,4-MDNI与DNTF制备成低共熔物后熔点理想,热稳定性良好,同时可以显著降低DNTF的感度而又保持其较高能量水平。

    Abstract:

    2,4-MDNI/DNTF eutectic system was prepared by using 1-methyl-2,4-dinitroimidazole (2,4-MDNI), a high energy insensitive explosive, to improve the high sensitivity and high melting point of the dynamite carrier 3,4-dinitrofuroxan (DNTF). The melting and liquefaction processes of 2,4-MDNI/DNTF with different ratios were studied by differential scanning calorimetry (DSC), and the T-x phase diagram was established. The melting and decomposition processes of 2,4-MDNI, DNTF and 2,4-MDNI/DNTF eutectic at different heating rates were studied. The kinetic parameters of 2,4-MDNi, DNTF and their eutectic were calculated by flynn-wall-Ozawa method, Doyle method and Kissinger method respectively. XRD and SEM analysis were carried out for the three substances. The hyposensitivity of 2,4-MDNI to DNTF was studied by sensitivity test.The detonation properties of 2,4-MDNI/DNTF eutectic were calculated by using EXPLO5. The results show that the molar composition of 2,4-MDNI/DNTF eutectic is 51∶49, and the average melting point is 92.7 ℃. As the heating rate increases, both melting and decomposition reactions are delayed. The activation energy Ea and pre-exponential factor A of thermal decomposition of eutectic are 146.0 kJ·mol-1 and 4.09×1013, respectively. In XRD test, the low eutectic of 2,4-MDNI/PETN generates a new diffraction peak at 2θ=18.60°. The microstructure of the solidified surface is obviously better than that of DNTF. The impact and friction sensitivities of 2,4-MDNI are both 0%.The impact sensitivity and friction sensitivity of eutectic are 64% and 52%, respectively. The theoretical density of 2,4-MDNI/DNTF eutectic is 1.844 g·cm-3, and the calculated detonation velocity is 8705 m·s-1. The eutectic of 2,4-MDNI and DNTF was prepared with ideal melting point and good thermal stability. At the same time, the sensitivity of DNTF can be significantly reduced while maintaining its high energy level.

    表 2 2,4-MDNI、DNTF及其低共熔物与其他常见熔铸炸药载体爆轰性能比较[1,11,17,19-22]Table 2 Comparison of detonation properties of 2,4-MDNI/DNTF eutectic and other melt cast explosive carrier
    表 1 2,4-MDNI、及2,4-MDNI/DNTF低共熔物热反应动力学参数Table 1 Kinetic parameters of thermal reaction of 2,4-MDNI and 2,4-MDNI/ DNTF eutectic
    图1 2,4-MDNI的HPLC谱图Fig.1 HPLC chromatogram of 2,4-MDNI
    图2 二元混合体系的熔融过程DSC曲线示意图[12]Fig.2 DSC diagram of binary mixture system[12]
    图3 不同比例2,4-MDNI/DNTF二元混合体系DSC曲线Fig.3 DSC curves of 2,4-MDNI/DNTF mixtures with different proportions
    图4 2,4-MDNI/DNTF二元混合体系T-x相图Fig.4 T-x phase diagram of 2,4-MDNI/DNTF binary mixture system
    图7 2,4-MDNI、DNTF及其低共熔物的XRD图谱Fig.7 XRD patterns of 2,4-MDNI, DNTF and their eutectic
    表 3 2,4-MDNI、DNTF及2,4-MDNI/DNTF低共熔物的撞击和摩擦感度测试结果Table 3 Impact and friction sensitivity test results of MDNI、DNTF and their eutectic
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引用本文

朱俊伍,王林剑,刘玉存,等.2,4-MDNI/DNTF二元低共熔物的制备与性能[J].含能材料, 2022, 30(3):228-235. DOI:10.11943/CJEM2021166.
ZHU Jun-wu, WANG Lin-jian, LIU Yu-cun, et al. Preparation and Properties of 2,4-MDNI / DNTF Binary Eutectic[J]. Chinese Journal of Energetic Materials, 2022, 30(3):228-235. DOI:10.11943/CJEM2021166.

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  • 收稿日期: 2021-06-23
  • 最后修改日期: 2021-07-25
  • 录用日期: 2021-10-21
  • 在线发布日期: 2022-03-17
  • 出版日期: 2022-03-25