Xiao Lei, Guo Shuangfeng, Su Hongping, Gou Bingwang, Liu Qiaoe, Hao Gazi, Hu Yubing, Wang Xiaohong, Jiang Wei
National Special Superfine Powder Engineering Research Center of China, School of Chemical Engineering, Nanjing University of Science and Technology Nanjing 210094 China
Xi'an Modern Chemistry Research Institute Xi'an 710065 China.
RSC Adv. 2019 Mar 21;9(16):9204-9210. doi: 10.1039/c8ra10512j. eCollection 2019 Mar 15.
In order to decrease the sensitivity and broaden the application of pentaerythritol tetranitrate (PETN), a novel energetic co-crystal composed of PETN and dihydroxylammonium 5,5'-bistetrazole-1,1'-diolate (TKX-50) with high energy and low sensitivity was successfully prepared through the solvent/non-solvent method. The morphology and structure of the as-prepared co-crystal were characterized by scanning electron microscopy (SEM), X-ray diffraction spectroscopy (XRD), X-ray photoelectron spectrometry (XPS), fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy and high performance liquid chromatography (HPLC). The thermal decomposition properties were also analyzed by simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC). The safety performance was judged by mechanical sensitivity tests. The SEM results revealed that the prepared new material was homogeneous with a mean granularity of 1 μm and the morphology was distinct from raw PETN and TKX-50. The XRD analysis indicated that a new crystalline formation appeared in the co-crystal which was quite different from the raw materials and their mixture. The XPS analysis showed peak shifts of C, N, O elements in the co-crystal. The FTIR spectra and Raman spectra suggested that hydrogen bond interactions existed between PETN and TKX-50 molecules. The molar ratio of PETN and TKX-50 was 1 : 1 determined by HPLC. There were two thermal decomposition peaks (194.1 °C and 261.3 °C) for the co-crystal at 20 °C min, while the raw materials and mixture had only one. Besides, the activation energy of the co-crystal increased compared to the raw materials, indicating better thermal stability of the co-crystal. The impact sensitivity and friction sensitivity of the PETN/TKX-50 co-crystal were reduced compared to raw PETN, and were even better than for 1,3,5-trimethylene trinitramine (RDX). The results showed a prospective application of the prepared PETN/TKX-50 co-crystal in the future.
为了降低季戊四醇四硝酸酯（PETN）的感度并拓宽其应用范围，通过溶剂/非溶剂法成功制备了一种由PETN和5,5'-双四唑-1,1'-二醇二羟铵盐（TKX-50）组成的新型高能低感度含能共晶。采用扫描电子显微镜（SEM）、X射线衍射光谱（XRD）、X射线光电子能谱（XPS）、傅里叶变换红外光谱（FT-IR）、拉曼光谱和高效液相色谱（HPLC）对所制备共晶的形貌和结构进行了表征。同时通过热重-差示扫描量热联用仪（TG-DSC）分析了其热分解性能。通过机械感度测试判断其安全性能。SEM结果表明，所制备的新材料均匀，平均粒度为1μm，其形貌与原料PETN和TKX-50不同。XRD分析表明，共晶中出现了一种与原料及其混合物截然不同的新晶型。XPS分析显示共晶中C、N、O元素存在峰位偏移。FTIR光谱和拉曼光谱表明PETN与TKX-50分子之间存在氢键相互作用。通过HPLC测定PETN与TKX-50的摩尔比为1∶1。共晶在20℃/min时有两个热分解峰（194.1℃和261.3℃），而原料和混合物只有一个热分解峰。此外，与原料相比，共晶的活化能增加，表明共晶具有更好的热稳定性。PETN/TKX-50共晶的撞击感度和摩擦感度比原料PETN降低，甚至优于1,3,5-三硝基-1,3,5-三氮杂环己烷（RDX）。结果表明所制备的PETN/TKX-50共晶具有良好的应用前景。
