利用电磁法研究HMX与TATB混合钝感炸药的冲击起爆特性

为研究含有少量奥克托金(HMX)且以三氨基三硝基苯(TATB)为基的高能钝感炸药PBX-3的冲击起爆反应增长规律,采用火炮驱动蓝宝石飞片的方法和铝基组合式电磁粒子速度计技术进行了一维平面冲击实验。通过实验测量撞击表面及内部不同深度处的冲击波后粒子速度,得到PBX-3炸药的Hugoniot关系。根据冲击波示踪器所测数据绘制了炸药到爆轰的时间-距离(x-t)图,获得了反映炸药冲击起爆性能的Pop关系。将入射压力为12.964 GPa时达到爆轰的6条速度曲线修整成相同零点,通过读取6条曲线的分离点即反应区末端的C-J点,计算出化学反应区时间和宽度。     

运用三维离散元技术模拟落锤撞击下奥克托今颗粒的点火燃烧过程

炸药颗粒的点火燃烧过程一直是人们关注的热点问题。近年来，三维离散元技术在中尺度观测颗粒材料的动力学过程中拥有显著优势。炸药燃烧属于颗粒材料的反应动力学，运用三维离散元技术(DM3)可以有效地观测炸药燃烧传播的过程。以奥克托今(HMX)颗粒为例，本文成功模拟并观测到了HMX颗粒的燃烧反应程度，确定了颗粒开始燃烧反应的时间，以及燃烧反应传播的时间。同时，结合落锤冲击颗粒的三维图像以及其表观压强和放热功率，得到了HMX颗粒燃烧反应、燃烧传播的整个反应动力学过程，包括颗粒在冲击加载下碎化塑性变形的过程，颗粒燃烧反应放热的过程，落锤回弹颗粒喷射的过程等。同时，进一步说明了尖顶颗粒更利于颗粒点火，平顶颗粒有抑制颗粒点火的能力。     

Establishing TA-Pb/Cu and SA-Pb/Cu interface catalyst shells on HMX surfaces via in situ coprecipitation to ameliorate the performances of HMX

Lead/copper tannate (TA-Pb/Cu) and lead/copper salicylate (SA-Pb/Cu) interface catalyst shells are established on the surface of 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) via in situ coprecipitation to prepare HMX@TA-Pb/Cu and HMX@SA-Pb/Cu composites. The structures and properties of the obtained HMX@TA-Pb/Cu and HMX@SA-Pb/Cu composites are characterized in detail. Molecular dynamics simulations are performed to study the adsorption mechanism of TA-Pb/Cu and SA-Pb/Cu on HMX surface. The residues after HMX@TA-Pb/Cu and HMX@SA-Pb/Cu combusted in air are collected and characterized to study the catalytic effect of TA-Pb/Cu and SA-Pb/Cu on combustion. The study results show that TA-Pb/Cu shells are coated on HMX surface due to the excellent membrane-forming properties of TA, while SA-Pb/Cu shells are embedded in the gullies and holes of HMX surface. TA-Pb/Cu and SA-Pb/Cu shells can decrease the mechanical sensitivities and catalyze the decomposition and combustion of HMX, and the catalytic effects of in situ coprecipitation are better than that of physical mixing. In addition, the phase transition temperature of HMX in HMX@TA-Pb/Cu is increased while that of HMX@SA-Pb/Cu is decreased, illustrating that TA-Pb/Cu can enhance the thermal stability of HMX while SA-Pb/Cu can catalyze the phase transition of HMX.     

Decomposition in HTPB bonded HMX followed by heat generation rate and chemiluminescence

The decomposition in HTPB bonded HMX was characterized with two highly sensitive methods: heat flow microcalorimetry (HFMC) and Chemiluminescence (CL). The material is stabilized with a phenolic antioxidant. The heat generation (HFMC) rate was determined from 120 to 150 °C using a TAM™ microcalorimeter and the oxidation of the substance was followed by the CL emission between 100 and 140 °C directly from the solid state sample. The end of antioxidant activity results in both measurements sets in characteristic changes in the curves. Kinetic parameters were calculated applying Arrhenius parameterization for the times to the end of antioxidant activity and by applying modelling with an autocatalytic model extended by a side reaction, which is assigned to the antioxidant consumption. The evaluation with the characteristic times gives good agreement between the two methods; the modelling represents the different but supplementing probing of the two measurement methods. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

热损伤奥克托金(HMX) 缺陷的X射线小角散射研究

奥克托金(HMX) 在温度作用下, 会发生热膨胀、 相转变、 热分解等物理、 化学变化, 导致在材料内部产生大量缺陷, 进而会对其宏观性能造成明显影响. 为了深入了解热损伤HMX内部的缺陷演化, 本文采用X射线小角散射和原子力显微技术研究了热损伤HMX的内部缺陷. 结果发现HMX在180 °C相变过程中散射曲线有明显的变化, 颗粒内部生成了大量10nm左右的孔洞, 随着加载时间延长, 其尺寸增大到25nm, 数量明显降低. 当HMX在190 °C、 200 °C保温5h时, 由于HMX热分解内部有新缺陷生成, 小角散射发现其尺寸约为5至8nm, 随着加载温度升高, 其数量增加.     

斜波压缩下HMX晶体的弹塑性行为

开展了（010）、（011）晶向HMX晶体的斜波压缩实验,获得了约15 GPa压力下的速度响应剖面。实验结果表明,HMX单晶存在明显弹塑性转变行为,且速度波形有下降趋势,这是材料的黏性效应导致,材料的弹性极限随着样品厚度增加而变化,不同晶向的材料动力学特性存在差异。结合Hobenemser-Prager黏弹塑性本构关系和三阶Birch-Murnaghan物态方程开展了HMX晶体斜波压缩物理过程的数值模拟,计算结果可以很好地描述HMX晶体的弹塑性转变这一物理过程。     

The pressure-induced phase transition of the solid β–HMX

The structural, vibrational and thermodynamic properties of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (β–HMX) crystal have been studied using the isothermal-isobaric molecular dynamics (NPT-MD) simulations. The variations of cell volume, lattice constants and molecular geometry of solid β–HMX are presented and discussed at different pressure and temperature. It was found that the N–N bond is significantly lengthened with increasing temperature, which suggests that it is relevant to the initial decomposition. An abrupt change at 27 Gpa for the volume and internal geometrical parameters was observed. This is in good accord with the experimental observation that there is a phase transition at 27 GPa, which is clearly due to conformational change, not chemical reaction. The vibrational frequencies at ambient conditions agree well with experimental results, and the pressure/temperature-induced frequency shifts of these modes are discussed. Frequency discontinuity was also observed at pressure when the phase transition occurred. The Grüneisen parameter was obtained using the vibrational frequency.     

RDX/HMX颗粒炸药落锤撞击点火-燃烧机理

对单质炸药受低速撞击的力学和化学响应研究,是进行炸药敏感性评价的基础。利用配备了光学观测的落锤撞击装置,实现了频率为1.5×105 s-1的实时观测,不但可以区分样品的“爆”或“不爆”,而且可以获取RDX和HMX颗粒炸药受落锤低速撞击变形、破碎、溅射、点火和燃烧随时间演化的特征。结果表明:RDX颗粒是在液相中点火,而HMX颗粒在固相中点火; 燃烧反应前常常发生剧烈的溅射现象,溅射是由气相反应产物释放能量推动破碎的颗粒所致。对比了单个和单层颗粒炸药响应的特点,多个颗粒由于热点密集和破碎后相互作用,其燃烧反应比单个颗粒燃烧反应更剧烈。根据图像处理估算燃烧波传播速度,很好地表征了样品宏观燃烧反应的剧烈程度。     

Experimental investigations of mechanical and reaction responses for drop-weight impacted energetic particles

Low-velocity drop-weight impact experiments on individual and multiple Cyclotetramethylene tetranitramine (HMX) energetic particles were performed using a modified drop-weight machine equipped with high-speed photogra-phy components. Multiple particles experienced more severe burning reactions than an individual particle. Comparisons between impacted salt and HMX particle show that jetting in HMX is mainly due to the motion of fragmented parti-cles driven by gaseous reaction products. Velocity of jetting, flame propagation, and area expansion were measured via image processing, making it possible to quantify the chemi-cal reaction or mechanical deformation violence at different stages.     

Structure and detonation performance of a novel HMX/LLM‐105 cocrystal explosive

Intermolecular interactions and properties of octahydro‐1,3,5,7‐tetranitro‐1,3,5,7‐ tetrazocine (HMX) / 2,6‐diamino‐3,5‐dinitropyrazine‐1‐oxide (LLM‐105) cocrystal were studied by using the dispersion‐corrected density functionals (ωB97XD, B97D) and meta‐hybrid functional (M062x) methods. Binding energies, heats of formation, thermodynamic properties, atoms in molecules, and natural bond orbital analysis were performed to investigate HMX/LLM‐105 complexes. Results show that the main intermolecular interactions between HMX and LLM‐105 are CH…O, NH…O, N…O, and O…O interactions. In addition, Monte Carlo simulation was employed to predict the crystal structure of HMX/LLM‐105 cocrystal. The HMX/LLM‐105 cocrystal is most likely to crystallize in C2/c space group, and its corresponding cell parameters are Z = 8, a = 41.63 Å, b = 6.77 Å, c = 45.63 Å, ß = 164.55°, and ρ = 1.99 g/cm³. Detonation velocity and pressure of HMX/LLM‐105 cocrystal are 8.95 km/s, 37.69GPa, a little lower than those of HMX (9.10 km/s, 37.76GPa). However, according to the net charges of nitro group, HMX/LLM‐105 cocrystal exhibits less sensitive than HMX. Finally, bond dissociation energy calculation shows that HMX/LLM‐105 complexes are thermally stable. Considering thermal stability, sensitivity, and detonation performance, HMX/LLM‐105 cocrystal meets the requirements of insensitive high energy density materials. Copyright © 2013 John Wiley & Sons, Ltd.