梯恩梯-吉纳、地恩梯-太安装药体系自旋爆轰特性的研究

本文研究了梯恩梯-吉纳(TNT-DINA)和地恩梯-太安(DNT-PETN)体系的自旋爆轰现象,爆轰波是以低频脉冲方式传播.这些体系具有的爆速、爆热分别为DJ=7.3～7.4km/s和Qv=(5.40±0.01)MJ/kg.不同组成的爆速和爆压PJ通过SW程序计算.用扩散区的爆压P3和爆温T3来评估爆轰波的衰减和重新点火.敏化剂含量相同,梯恩梯-黑索金(TNT-RDX)体系的爆压PJ大于TNT-DINA的爆压,TNT-RDX体系的温度T3比TNT-DINA高60～100K.计算值与实验结果吻合较好.     

Condensed combustion products of aluminized propellants. IV. Effect of the nature of nitramines on aluminum agglomeration and combustion efficiency

The condensed combustion products of two model propellants consisting of ammonium perchlorate, aluminum, nitramine, and an energetic binder were studied by a sampling method. One of the propellants contained HMX with a particle size D ₁₀ ≈ 490 μm, and the other RDX with a particle size _{D 10} ≈ 380 μm. The particle-size distribution and the content of metallic aluminum in particles of condensed combustion products with a particle size of 1.2 μm to the maximum particle size in the pressure range of 0.1–6.5 MPa were determined with variation in the particle quenching distance from the burning surface to 100 mm. For agglomerates, dependences of the incompleteness of aluminum combustion on the residence time in the propellant flame were obtained. The RDX-based propellant is characterized by more severe agglomeration than the HMX-based propellant — the agglomerate size and mass are larger and the aluminum burnout proceeds more slowly. The ratio of the mass of the oxide accumulated on the agglomerates to the total mass of the oxide formed is determined. The agglomerate size is shown to be the main physical factor that governs the accumulation of the oxide on the burning agglomerate. __________ Translated from Fizika Goreniya i Vzryva, Vol. 42, No. 4, pp. 78–92, July–August, 2006.     

超临界CO2GAS沉析HMX制细过程的影响因素

研究了超临界CO2GAS沉析丙酮溶液中HMX的过程压力、温度、溶液初始浓度和溶液的膨胀速度及影响晶体粒度的因素。结果表明，压力增加，沉析颗粒的平均粒度减小；温度控制沉析晶体的晶型，对颗粒度的影响相对较小，温度增加，沉析平均粒度略有增加；溶液初始浓度对平均粒度的影响相对较大，膨胀速度亦是影响粒度及其分布的一个因素。快速膨胀溶液．并使过饱和度足够大，使过饱和度主要消耗在成核上，可得到颗粒小、分布窄的HMX颗粒。     

基于分子模拟方法选择推进剂键合剂的研究

为从界面吸附以探讨含有奥克托金(HMX)和铝粉的固体推进剂的键合剂,采用Material Studio软件Discover模块和COMPASS力场,在不同温度条件下,分别模拟常用的三(-2甲基氮丙啶-1)氧化磷(MAPO)和三乙醇胺(TEA)键合剂在HMX晶体表面和铝粉(Al2O3)表面的吸附后发现:(1)MAPO和TEA在Al2O3表面的吸附能远大于在HMX晶体表面的吸附能;(2)TEA对HMX晶体表面的吸附能高于MAPO,可以判定在该体系下TEA作为HMX键合剂效果优于MAPO,数值模拟结果同实验摹本吻合;(3)数值模拟结果表明,随着温度升高,界面吸附能力先增后减.     

N_2O_5/HNO_3/有机溶剂混合体系硝解DPT制备HMX

为了提高以N_2O_5为硝化剂的硝化体系硝解3,7-二硝基-1,3,5,7-四氮杂双环[3,3,1]壬烷(DPT)制备HMX的收率,考察了在N_2O_5/HNO_3/有机溶剂混合体系中,乙酸酐、乙腈、硝基甲烷、二氯甲烷4种有机溶剂与HNO_3在不同体积比下对DPT的硝解,测定了体系的H+浓度和N_2O_5的电导率,并分析了其对HMX收率的影响。结果表明,与4种N_2O_5/有机溶剂体系相比,N_2O_5/HNO_3/有机溶剂混合体系中产品收率明显提高;体系的酸度和硝化能力是影响HMX收率的两个重要因素,低酸度且硝化能力介于乙酰硝酸酯和NO2+之间时,有利于HMX生成;N_2O_5/HNO_3/乙酸酐混合体系为最适宜的硝解体系,当HNO_3与乙酸酐的体积比为3∶2时制备的HMX收率最高,为87.9%。     

Molecular Dynamic Simulation for HMX/NTO Supramolecular Explosive

Based on the crystal engineering, six models of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine(HMX)/3-nitro-1,2,4-triazol-5-one(NTO) supramolecular explosive were designed. The probable formation of HMX/NTO supramolecular explosive was investigated by the molecular dynamic (MD) method. Interaction between oxygen atoms in HMX and hydrogen atoms in NTO or between hydrogen atoms in HMX and oxygen atoms in NTO were studied by the radial distribution function (RDF). It shows that there are strong hydrogen bonds and Van Der Waals forces between HMX and NTO, in which the hydrogen bonds between oxygen atoms in the NTO and hydrogen atoms in HMX are the main host-guest interactions. The distributions of bond length, bond angle and dihedral angle were simulated by MD. It shows that the structure of HMX is seriously distorted. The binding energies and X-ray powder diffraction (XRD) patterns were calculated on the basis of the final HMX/NTO supramolecular structures. The results show that the binding energies of six supramolecular models are E binding (1 1 1-) >E binding (1 0 0)>E binding (0 2 0)>E binding (random)>E binding (1 0 2-)>Ebinding (0 1 1), and the XRD patterns of six supramolecular models are quite different from pure HMX or NTO. Based on the investigation for growth morphology, binding energies and RDF, the model of HMX supercell substituted by NTO along the (1 1 1-) surface of HMX is easier to form.     

The Nitrolysis Mechanism of 3,7‐Dinitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane

Two intermediates, 1,5‐dinitroso‐3,7‐dinitro‐1,3,5,7‐tetraazacyclooctane (DNDS) and 1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane (MNX), were isolated and characterized in the synthesis of 1,3,5,7‐tetranitro‐1,3,5,7‐tetraazacyclooctane (HMX) from the nitrolysis of 3,7‐dinitro‐1,3,5,7‐tetraazabicyclo[3,3,1]nonane (DPT) for the first time. When the nitrolysis of DPT was slowed down, two intermediates were detected with HPLC. It was proposed that electrophilic NO₂⁺ and NO⁺ from HNO₃ and N₂O₄ might attack nitrogen atoms at positions 3 and 7 of DPT to form the cations of the intermediates, then nucleophilic H₂O attacked the bridge carbon atoms of DPT to produce the intermediates, which were oxidized to form HMX.     

回收HMX基炸药制备民用耐热炸药性能研究

利用回收HMX基炸药制备民用炸药H781A,对该炸药药粉在产品组成、热安定性、机械感度等性能和装药的高温安全性、使用性能以及穿深性能进行试验。药粉试验结果表明,该产品符合民用炸药产品验收规范;装药试验结果表明,H781A与民用炸药H781性能相当。因此,由废旧HMX基炸药回收制备的耐热炸药H781A,可安全、有效地装填射孔弹进行高温射孔作业。     

Particle Size Effects on Thermal Decomposition of Energetic Material

This work refers to a study of the thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) by differential scanning calorimetry (DSC) under nonisothermal conditions, with heating rates from 5 to 20°C min^?1. The influence of the particle size in the thermal decomposition of HMX was verified. The activation energy for the decomposition of each sample was calculated using the peak temperature shift methods, proposed by Kissinger and Ozawa. A significant variation in the results was observed according to the range of the particle size used. The results showed that, as the particle size of HMX increased, the thermal decomposition temperature of HMX and the decompositional activation energies ranges enhanced. At the same time, at a constant heating rate, the decomposition temperatures of the smaller particles were lower than those of larger ones. The critical temperature for thermal explosion of each sample was calculated. Also, the values of ΔS^#, ΔH^#, and ΔG^# of reaction for each particle size were computed.     

HMX热膨胀系数的分子动力学模拟研究

首先通过分子动力学(MD)模拟考察了COMPASS力场对HMX的适用性。然后通过对β-HMX(4×2×3)超晶胞在常压205～385K温度范围七个不同温度的NPT系综MD模拟,计算出β-HMX晶体晶胞参数的变化,并通过线性拟合求得β-HMX晶体沿不同棱边a、b、c方向的线膨胀系数和它的体膨胀系数,结果与先前的实验和理论工作相符。