降感HMX的制备及性能测试

为了改善奥克托今(HMX)结晶形态并降低感度,以二甲基亚砜为溶剂,以水为非溶剂,以糊精为晶体控制剂,对普通HMX采用溶剂/非溶剂重结晶法处理,制备降感HMX。使用电子偏光显微镜、液相色谱仪分析测试了HMX重结晶前、后的晶体形貌和质量,表明重结晶后HMX的晶体颗粒更加规整圆滑,近似球形,并且纯度达到99.15%。撞击感度实验表明,重结晶后HMX的撞击感度比普通HMX降低32%。     

硝胺类反式十氢萘含能材料的爆炸性质和稳定性的理论研究

本文以量子化学作为指导,通过对现有的硝铵类含能材料分子结构的特点进行分析讨论,选取了反式十氢萘作为分子主体,在此基础上引入硝铵取代基,设计了一系列新型的含能材料。通过使用高斯09软件包,结合密度泛函理论B3LYP/6-31G的水平下对这一系列材料的分子进行几何结构优化,并通过基团加和法等方法对目标化合物的密度、爆速、爆压、生成热、撞击感度、键解离能等性质、性能进行计算,最终筛选出具有应用前途的高能密度化合物,为进一步实验研究潜在的高能密度材料提供理论线索。     

重结晶降低RDX感度研究

采用N-甲基吡咯烷酮、二甲基甲酰胺、二甲基亚砜作溶剂,对普通RDX进行重结晶.研究了不同溶剂对RDX晶体形貌、晶体内空穴、位错、残存溶剂的影响,通过扫描电镜和光学显微镜,分析了重结晶RDX晶体的结晶形貌和内部质量,用密度瓶法测试了晶体密度,用10kg落锤测定了撞击感度.结果表明,用二甲基亚砜重结晶制备的RDX有较好的晶体质量,撞击感度最低(54%),晶体密度达1.823g/cm3.     

硝酸-水重结晶HMX工艺研究

硝酸-水（溶剂非溶剂法）重结晶β-HMX,通过优化工艺条件,制备出高能低感的球形化HMX晶体颗粒。实验结果表明,撞击感度与重结晶工艺密切相关。温度为5℃、搅拌速度为100r／min、稀释速率为0.375mL／min、静置时间为0min的条件下,重结晶出的HMX颗粒孔隙率较小,球形化程度较高,撞击感度较低。     

高能推进剂钝感含能材料研究现状

钝感高能推进剂是当前固体推进剂的重要发展方向,降低高能固体推进剂感度主要技术途径是要采用低感度高能量的原材料,一方面是应用新型低感度含能原材料,另一方面是对现有含能原材料改性使之降低感度。高能推进剂所用钝感含能原材料主要分为3部分:能量高而感度低的氧化剂,低感度的含能黏合剂,低感度的含能增塑剂。在推进剂配方研制过程中通过选择应用这3类原材料来降低高能固体推进剂的感度,满足高能固体推进剂的钝感安全性能。论述了国内外上述3类钝感含能原材料的研究进展。     

降感RDX的制备及晶形控制

采用溶剂-非溶剂重结晶方法制备了降感RDX,研究了温度、溶剂、非溶剂、搅拌强度、表面活性剂和加料方式等工艺条件对双重结晶的影响.采用光学显微镜和扫描电镜分析了所得晶体的形貌,测定了其撞击感度.结果表明,采用最佳工艺条件:70℃,二甲基亚砜(DMSO)为溶剂,甲醇为非溶剂,糊精为表面活性剂,搅拌强度1 000 r/min,改善了RDX的晶貌和内部质量,降低了撞击感度.通过控制溶液的初始浓度可制得不同粒度的RDX,粒径为100～120 μm晶体的撞击感度比原料降低了34%.     

重结晶工艺对太安撞击感度的影响

用溶剂-非溶剂法重结晶粗制太安,研究了溶剂-非溶剂体系、重结晶温度、搅拌速度和非溶剂滴加速度4个因素对重结晶太安撞击感度的影响.测定了不同工艺条件下重结晶太安的特性落高,通过金相显微镜和偏光显微镜分析了不同结晶工艺所得太安晶体的形貌及表观缺陷,讨论了重结晶工艺对太安晶体撞击感度的影响.结果表明,以乙酸乙酯为溶剂,三氯甲烷为非溶剂,温度50℃, 非溶剂稀释速度0.05 mL/min,搅拌速度100 r/min条件下制备的重结晶太安的特性落高为14.6 cm,比常用的丙酮-水重结晶太安的撞击感度显著降低.     

溶剂-非溶剂法CL-20/TATB共同结晶降低CL-20感度的实验研究

为了降低高能炸药六硝基六氮杂异伍兹烷(HNIW,CL-20)的机械感度,以DMSO为溶剂,水、水+离子液体、水+乙酸、水+乙酸+离子液体分别为非溶剂,对CL-20和钝感炸药TATB进行了共同结晶研究。采用溶剂-非溶剂法重结晶,制备得到CL-20/TATB共同结晶晶体,通过红外光谱、扫描电镜、热重-差热分析及撞击感度分析。分析表明,所得晶体为几百纳米到几微米、分散性良好的、多边形或圆形片状晶体,特性落高为26.5~36.5 cm,撞击感度显著降低。     

NTO包覆HMX的钝感研究

为降低HMX的机械感度并维持其爆炸性能,采用溶液重结晶法用较钝感的3-硝基-1,2,4-三唑-5-酮(NTO)包覆HMX,并测试了其机械感度和爆速。通过SEM观察了包覆HMX的粒径、形貌及包覆钝感的工艺条件。结果表明,包覆HMX的表面形态主要受水与N-甲基吡咯烷酮(NMP)体积比、搅拌速率和冷却速率的影响。当水和NMP体积比为5、搅拌速率为300r/min、冷却速率为6K/min时,包覆HMX的表面形态最好;以水和NMP为溶剂,包覆HMX的H50值提高了14.8cm,撞击感度降低了66%,且摩擦感度从100%降低至50%。包覆HMX的爆速降低了2.8%,基本可以维持爆炸性能不变。     

高能氧化剂表面包覆研究进展

表面包覆是降低高能氧化剂机械感度的一种重要方法.对推进剂组分中的氧化剂固体颗粒进行表面包覆,不仅能降低单组分的机械感度,也能提高推进剂的力学性能和改善推进剂工艺性能.综述了高能氧化剂的表面包覆方法及其研究进展.     

Prediction of Sensitivity of Energetic Compounds with a New Computer Code

Impact, electrostatic, and shock sensitivities of energetic compounds are three important parameters for the assessment of hazardous energetic materials. A novel easy to handle and user‐friendly computer code, written in Visual Basic, is introduced to predict these parameters, by solely using the molecular structure of an energetic molecule. It is able to predict impact sensitivity for different types of energetic compounds including nitropyridines, nitroimidazoles, nitropyrazoles, nitrofurazanes, nitrotriazoles, nitropyrimidines, polynitro arenes, benzofuroxans, polynitro arenes with α‐CH, nitramines, nitroaliphatics, nitroaliphatic containing other functional groups, and nitrate energetic compounds. It can also provide reliable results for electrostatic and shock sensitivities of some classes of high explosives including nitroaromatic and nitramine compounds. The prediction of this code give good values for some newly reported energetic compounds, where experimental data are available.     

Improved Approach to Predict the Power of Energetic Materials

Nowadays, the ballistic mortar is the preferred test for the explosive power measurements but there is no reliable method for its prediction. For an energetic compound, the formation of low molecular mass gaseous products and a high positive heat of formation per unit weight of the energetic compound are important parameters to have a high value of power. A novel method was developed to predict the power by the ballistic mortar test for pure and mixture of energetic materials. It can be used for some important classes of energetic compounds including nitroaromatics, acyclic and cyclic nitramines, nitrate esters, and nitroaliphatics. The presented method is based on the molecular structure of the desired compound and there is no need to use experimental data such as the condensed phase heat of formation. For 84 pure and 24 mixtures of energetic compounds, the calculated power relative to 2,4,6‐trinitrotoluene (= 100) show good agreement with respect to the measured values.     

Physicochemical Parameters of Nitramines Influencing Shock Sensitivity

TNO Prins Maurits Laboratory has actively followed and contributed to the research on the development of insensitive munitions (IM). One of the initial research topics at TNO focused on the improvement of the shape of RDX crystals and its relation to the shock sensitivity. The variation of crystal shape has been studied by crystallization from different solvents and/or by post‐treatment of the crystals. The role of the mean particle size on shock sensitivity was also included in these analyses. The decrease in shock sensitivity is even more pronounced when controlling the internal quality of crystals. In the meantime research has shifted to other energetic materials as well – in particular HMX and CL‐20 – in this way revealing step by step the important physicochemical parameters which play a role in determining the shock sensitivity of formulations containing these types of nitramines. Various characterization techniques, to determine the internal and external quality of crystals will be discussed, and their relation to shock sensitivity in PBXs will be shown. Two different grades of I‐RDX have been subjected to different characterization tests. The objective is to gain more understanding about which of the physicochemical parameters enables one to discriminate between a reduced sensitivity RDX and normal RDX.     

A New Computer Code for Assessment of Energetic Materials with Crystal density,Condensed Phase Enthalpy of Formation,and Activation Energy of Thermolysis

Crystal density and enthalpy of formation of the condensed phase of energetic compounds are two important input parameters for the performance prediction in several computer codes for rapid hazard assessment of energetic materials. A novel easy‐to‐handle user‐friendly computer code in Visual Basic is introduced to predict these parameters for various energetic compounds including nitroaliphatics, nitrate esters, nitramines, polynitroarenes, and polynitroheteroarenes. The calculated values can be used as inputs for other thermochemical/hydrodynamic computer codes. This computer code is also able to calculate the activation energies of thermal decomposition of polynitroarenes and nitramines in condensed state. The number of carbon, hydrogen, oxygen, and nitrogen atoms and specification of some molecular fragments are input parameters for this code without using any experimental data. The new algorithms on the base of easy‐to‐get input parameters are tested for some new energetic compounds, which provide more reliable results as compared to the best available methods.     

A New General Correlation for Predicting Impact Sensitivity of Energetic Compounds

This paper describes an improved simple model for prediction of impact sensitivity of different classes of energetic compounds containing nitropyridines, nitroimidazoles, nitropyrazoles, nitrofurazanes, nitrotriazoles, nitropyrimidines, polynitroarenes, benzofuroxans, polynitroarenes with α‐CH, nitramines, nitroaliphatics, nitroaliphatic containing other functional groups, and nitrate energetic compounds. The model is based on some molecular structural parameters. It is applied for 90 explosives, which have different molecular structures. The predicted results are compared with outputs of complex neural network approach as one of the best available methods. Root mean squares (rms) of deviations of different energetic compounds are 24 and 49 cm, corresponding to 5.88 and 12.01 J with 2.5 kg dropping mass, for new and neural network methods, respectively. The novel model also predicts good results for eight new synthesized and miscellaneous explosives with respect to experimental data.     

A New Computer Code for Prediction of Enthalpy of Fusion and Melting Point of Energetic Materials

The prediction of phase change properties of energetic materials is important for the assessment of hazardous energetic materials. A novel user‐friendly computer code, written in Visual Basic, is introduced to predict the melting point and the enthalpy of fusion of energetic materials by only using their molecular structure parameters. It can be used for different types of energetic compounds including polynitro arenes, polynitro heteroarenes, acyclic and cyclic nitramines, nitrate esters, and nitroaliphatic. The predicted results were compared with several of the best available methods, which confirmed the higher reliability of the new computer code for some new and well‐known energetic compounds with complex molecular structures. This code can be used for designing of energetic compounds with desirable phase change properties.     

Recent Developments for Prediction of Power of Aromatic and Non‐Aromatic Energetic Materials along with a Novel Computer Code for Prediction of Their Power

The explosive power or strength of an energetic material shows its capacity for doing useful work. This work reviews recent developments for prediction of power of energetic compounds. A new user‐friendly computer code is also introduced to predict the relative power of a desired energetic compound as compared to 2,4,6‐trinitrotoluene (TNT). It is based on the best available methods, which can be used for different types of energetic compounds including nitroaromatics, nitroaliphatics, nitramines, and nitrate esters. The computed relative powers are consistent with the measured data for some new materials containing complex molecular structures.     

Simple Relationship for Predicting Impact Sensitivity of Nitroaromatics,Nitramines, and Nitroaliphatics

This paper describes the development of a simple model for predicting the impact sensitivity of nitroaromatics, benzofuroxans, nitroaromatics with α‐CH, nitramines, nitroaliphatics, nitroaliphatics containing other functional groups, and nitrate energetic compounds using their molecular structures. The model is optimized using a set of 86 explosives for which different structural parameters exist. The model is applied to a test set of 120 explosives from a variety of the mentioned chemical families in order to confirm the reliability of a new method. Elemental composition and two specific structural parameters, that can increase or decrease impact sensitivity, would be needed in this new scheme. The predicted impact sensitivities for both sets have a root mean square (rms) of deviation from experiment of 23 cm, which shows good agreement with respect to the measured values as compared to the best available empirical correlations.     

A Simple Way to Predict Heats of Detonation of Energetic Compounds only from Their Molecular Structures

A simple method to predict heats of detonation of important classes of energetic compounds including nitroaromatics, nitramines, nitroaliphatics, and nitrate esters is introduced. It is based on the ratios of oxygen to carbon and hydrogen to oxygen as well as the contribution of some specific functional groups or structural parameters. Predicted heats of detonation of pure explosives and explosive formulations with water as product in the liquid state for 77 energetic compounds provide more reliable results than those obtained using two empirical and quantum mechanical methods. This new method improves an earlier effort of previous models through its application for different categories of energetic compounds, which contain the energetic bonds Ar NO₂, N NO₂, C NO₂, and C O NO₂. In addition, the novel model provided good results for some miscellaneous explosives and several new synthesized explosives, where experimental data were available.     

绿色火炸药及相关技术的发展与应用

综述了绿色火炸药及其生产工艺、销毁以及回收利用方面具有“绿色”特征的改进和应用研究成果。绿色火炸药包括洁净固体推进剂、无铅双基推进剂、TPE发射药、无毒发射药、无铅点火药和起爆药。绿色制造技术包括N2O5作硝化剂的含能硝基化合物化学合成，过硝酸盐作硝化剂、微生物作催化剂的生物合成技术，连续化柔性制造技术，基于双螺杆混合成型火炸药生产技术，火炸药生产中挥发性污染物的安全消除技术和纳米复合含能材料的Sol-Gel制备技术。绿色销毁和回收利用技术包括销毁产品的熔盐氧化技术、摧毁含含能化合物废水的光催化技术以及火炸药的回收再利用（R^3）技术。评述了上述火炸药及相关技术的最新状况和发展方向，附参考文献25篇。