超细ANPyO/HMX混晶炸药的制备与性能

为提高超细ANPyO/HMX的能量输出,采用溶剂/非溶剂法和水悬浮法制备了超细ANPyO/HMX混晶炸药。用SEM、XRD、红外光谱对其结构进行表征,并测试了其比表面积、真空安定性、撞击感度、冲击波感度、爆速和飞片起爆感度。结果表明,XRD和红外光谱特征峰的位移现象说明超细混晶炸药中ANPyO分子的氨基与HMX分子的硝基形成了分子间氢键;ANPyO/HMX混晶炸药(ANPyO与HMX质量比为70∶30)撞击感度为138cm,真空安定性为1.72mL/g(200℃)和4.50mL/g(250℃)。装药密度为1.84g/cm3时,混晶炸药冲击波感度为7.1mm,爆速为8 080m/s,最低起爆电压为2.91kV,是一种感度适中、易于被短脉冲起爆、能量输出高的超细混晶炸药。     

HMX/ANPZO共晶炸药的制备及表征

运用分子动力学方法,计算了1,3,5,7-四硝基-1,3,5,7-四氮环杂辛烷(HMX)分子、2,6-二氨基-3,5-二硝基-吡嗪-1-氧(ANPZO)分子以及HMX/ANPZO共晶分子的分子间作用力、结合能和内聚能密度。通过气相扩散法制备了HMX/ANPZO共晶炸药,用红外光谱(IR)、差示扫描量热(DSC)和X射线衍射(XRD)表征了其结构,并测试了其机械感度。结果表明,HMX/ANPZO共晶分子间的相互作用力大于HMX分子间以及ANPZO分子间的相互作用力。与HMX和ANPZO相比,HMX/ANPZO共晶炸药的晶体结构和热分解特性变化较大,特性落高为59cm,与HMX相比提高了96.7%;理论爆速达9 060m/s。     

Pickering乳液聚合法制备TATB/HMX基复合微球

为了提升HMX的安全及应用性能,采用Pickering乳液聚合法,以固体粒子氧化石墨烯(GO)为稳定剂,分别以聚醋酸乙烯酯(PVAc)和聚苯乙烯(PSt)为黏结剂制备了两种TATB/HMX基复合粒子;通过扫描电子显微镜(SEM)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)和X射线光电子能谱仪(XPS)对样品进行了表征,并测试了其撞击感度和摩擦感度。结果表明,制备的TATB/HMX基复合粒子均为表面均匀密实的球形颗粒,所含HMX和TATB的炸药晶型均未改变;与HMX原料相比,复合粒子的表观活化能(E_a)提高,其中TATB/HMX/PVAc/GO复合粒子的E_a提高了44.18kJ/mol, TATB/HMX/PSt/GO的E_a提高了40.5kJ/mol;撞击感度和摩擦感度明显降低,以PVAc为黏结剂更适合复合粒子的制备,其临界撞击能量由5.5J提升至60J,临界摩擦压力由128N提升至324N,说明制备的复合微球的热安全性和机械安全性大大提高。     

原位合成钝感混合炸药HMX/TATB

利用超声波法制备单质炸药TATB,用高频率超声波反应器,采用原位合成方法制备了钝感HMX/TATB混合炸药.讨论了反应时间、反应温度以及料比对合成TATB的影响.测试了混合炸药的压制成型性和耐热性能.结果表明,超声波法合成的TATB粒度为5～6μm,混合炸药中TATB的质量分数小于15%,降感效果明显,耐热性能良好;使...     

CL-20/RDX共晶炸药的制备与性能测试

为了研究六硝基六氮杂异伍兹烷/环三亚甲基三硝胺(CL-20/RDX)共晶炸药的性能,采用喷雾干燥法制备了质量比为1∶1的CL-20/RDX共晶炸药;通过扫描电镜(SEM)观察了共晶炸药的形貌;采用粉末X-射线衍射法与红外光谱法测试了共晶炸药的结构;采用差示扫描量热法(DSC)测试了共晶炸药的热性能;通过感度实验分别测试了共晶炸药的撞击感度与摩擦感度。结果表明,CL-20/RDX共晶呈球形,粒径在1～5μm; CL-20/RDX共晶的衍射图与CL-20和RDX的衍射图均不完全相同,衍射峰有明显的位移;CL-20/RDX共晶炸药的热分解温度为222.8℃,比CL-20低30℃左右,比RDX低20℃左右,说明共晶的生成对其热性能有较大影响;CL-20/RDX共晶炸药的撞击感度为76%,特性落高为26.9cm,摩擦感度为64%,其机械感度较CL-20有大幅降低,表明共晶炸药的感度显著降低,安全性能得到明显提高,进一步说明共晶在含能材料改性和降感方面的优势。     

CL-20对硝酸酯炸药性能的影响

以HMX硝酸酯炸药配方为基础,用六硝基六氮杂异伍兹烷(CL-20)部分替代HMX,计算了含CL-20的硝酸酯炸药的密度、爆热和爆速,并与测试结果进行了对比;测试了其机械感度。结果表明,随着CL-20含量的增加,硝酸酯炸药的实测密度、爆热、爆速均明显增加;当CL-20质量分数为50%时,硝酸酯炸药的实测密度、爆热和爆速分别为1.907g/m3、6 826J/g和9 125m/s,撞击感度由34%提高到40%,摩擦感度由28%提高到60%。     

分子动力学法研究掺杂缺陷对HMX/NQ共晶炸药性能的影响

为了研究掺杂晶体缺陷对HMX/硝基胍(NQ)共晶炸药性能的影响,分别建立了"完美"型与含有掺杂缺陷的HMX/NQ共晶炸药模型;采用分子动力学方法,预测了各种模型的稳定性、感度、爆轰性能和力学性能,得到了不同模型的结合能、引发键键长分布、引发键键连双原子作用能、内聚能密度、爆轰参数和力学参数并与"完美"型模型进行了比较。结果表明,与"完美"型晶体相比,缺陷晶体的结合能减小幅度为1.28%～11.05%,表明分子之间的相互作用力减弱,炸药的稳定性降低;缺陷晶体的引发键键长增大幅度为0.46%～5.29%,而键连双原子作用能减小幅度为0.63%～17.24%,内聚能密度减小幅度为0.83%～10.85%,表明炸药的感度升高,安全性降低;缺陷晶体的密度、爆速和爆压减小幅度分别为0.89%～7.06%、0.68%～5.41%、1.85%～14.18%,表明威力与能量密度降低;由于晶体缺陷的影响,拉伸模量、体积模量和剪切模量减小幅度分别为0.106～4.368GPa、0.086～2.573GPa和0.082～1.835GPa,柯西压增大幅度为0.108～1.787GPa,表明炸药的刚性与硬度降低,延展性增强。因此,晶体缺陷会对HMX/NQ共晶炸药的稳定性、感度和爆轰性能产生不利影响。     

CL-20/DNT共晶炸药的制备及其性能研究

以丙酮为溶剂,通过蒸发结晶法制得六硝基六氮杂异伍兹烷(CL-20)/二硝基甲苯(DNT)共晶炸药。利用扫描电镜(SEM)、X射线衍射(XRD)和热重/差示量热法(TGA/DSC)研究了共晶炸药的形貌、结构和热分解特性,测试了CL-20/DNT共晶炸药的机械感度和5s爆发点温度,并计算了其爆轰性能。结果表明,共晶炸药的微观形貌不同于原料CL-20,呈条状晶体;衍射峰明显不同于CL-20/DNT物理混合物的衍射峰,表明有新物相生成。在DSC曲线上,CL-20/DNT共晶几乎没有DNT的熔化吸热峰,而CL-20/DNT物理混合物中有明显的熔化峰,且二者的放热峰峰形和峰位不同;与原料CL-20相比,共晶炸药的分解峰温提前了21℃,放热量(ΔH)和最大热流量(Qmax)分别增加了39%和104%。与CL-20/DNT物理混合物相比,共晶炸药的5s爆发点温度和表观活化能分别增加3.9℃和65.7kJ/mol,撞击感度降低88.9%,摩擦感度降低40%,说明共晶炸药热稳定性增强。CL-20/DNT共晶炸药的理论爆速达到8 340m/s。     

非溶剂制备细化HMX及其性能表征

以二甲基亚砜为溶剂,用喷雾重结晶细化法制备了HMX,研究了非溶剂(水、乙醇、氯代烷烃)的种类、溶剂与非溶剂的体积比以及非溶剂的温度对HMX晶体形貌的影响并分析了其影响机理。采用扫描电子显微镜(SEM)、激光粒度分析仪、X射线衍射仪(XRD)、差示扫描热量法(DSC)对其进行了表征和热分析。测试了细化HMX和原料HMX的撞击感度。结果表明,HMX细化最佳工艺条件是以35℃乙醇为非溶剂,溶剂与非溶剂体积比为1∶40,此时可获得中值粒径为616nm、粒径分布均匀、趋于球形且表面光滑的亚微米HMX;亚微米HMX表观活化能比原料HMX降低了13.75kJ/mol,与原料HMX相比具有更好的热安定性,特性落高从34.05cm升至79.10cm,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。     

TATB对HMX的钝感作用研究

通过机械感度、热感度、冲击波感度等方面的实验数据,分析研究了ＴＡＴＢ对ＨＭＸ的钝感作用,证明以ＨＭＸ／ＴＡＴＢ为主体炸药的塑性粘结炸药对目前钝感高能炸药的研究具有十分重要的意义。     

Effect of Crystal Quality and Particle Size of HMX on the Creep Resistance for TATB/HMX Composites

Two kinds of reduced sensitivity high explosive 1,3,5,7‐tetranitro‐1,3,5,7‐tetrazocane (RS‐HMX) with different particle sizes were selected to enhance the energy output and the mechanical properties of insensitive high explosive 1,3,5‐triamino‐2,4,6‐trinitrobenzene (TATB). Mechanical sensitivities, dynamic mechanical analysis, and non‐linear time dependent creep behaviors of TATB/HMX composites were investigated and discussed in relation to the structural characteristics. Compared with TATB/conventional HMX (C‐HMX) sample, both the impact and friction sensitivities of TATB/RS‐HMX were reduced. It revealed that TATB/fine grains RS‐HMX composites had the highest storage modulus and minimum steady‐state creep strain rate due to the increased coherence strength and the inhibited slide of the single layer of TATB crystal. The creep resistance also showed clear dependence on the particle size of RS‐HMX. The overall results indicated that RS‐HMX had good potential in high energetic, safe, and load‐bearing material applications.     

一种新型CL-20/TKX-50共晶炸药的制备、表征和性能研究

为降低六硝基六氮杂异伍兹烷(CL-20)的感度,通过溶剂-非溶剂法制备了CL-20和1,1′-二羟基-5,5′-联四唑二羟胺盐(TKX-50)共晶炸药;通过Materials Studio 5.0软件分析了CL-20和TKX-50分子的表面静电势,并预测了共晶分子间可能的非共价键作用;采用扫描电镜(SEM)、X射线衍射(XRD)、红外(IR)和拉曼光谱(Raman)对其形貌和结构进行了表征;采用DSC测试了其热性能,并测试了其撞击感度,预测了其爆轰性能。结果表明,制备的CL-20/TKX-50共晶呈扁平的片状形貌;XRD、IR和Raman谱图中出现峰的生成、消失、偏移和强度的改变,证明有新的晶格结构形成;升温速率8℃/min下,CL-20/TKX-50共晶的主要热分解峰温为222.8℃,与CL-20、TKX-50的热分解峰温240.3、234.9℃相比,分别提前了17.5℃和12.1℃,明显区别于具有两个放热过程的CL-20/TKX-50混合物的热分解行为;CL-20/TKX-50共晶炸药的感度显著低于原料CL-20,同时也优于β-HMX,说明其具有良好的安全性能;CL-20/TKX-50共晶的预测爆速和爆压分别为9264m/s和43.8GPa,较CL-20均略微下降,但和β-HMX相比,爆轰性能明显提高。表面静电势能和建模分析均表明,CL-20中—NO2的O与TKX-50中—NH+3的H之间易于形成氢键。     

Highly Thermal Stable TATB‐based Aluminized Explosives Realizing Optimized Balance between Thermal Stability and Detonation Performance

In this work, a series of TATB‐based aluminized explosives were formulated from 1, 3, 5‐triamino‐2, 4, 6‐trinitrobenzene (TATB), aluminum powders and polymeric binders. The thermal stability, heat of detonation, detonation velocity and pressure of the TATB based aluminized (TATB/Al) explosives were systematically investigated by cook‐off, constant temperature calorimeter, electrometric method and manganin piezo resistance gauge, respectively. The selected PBX‐3 (70 wt% TATB/25 wt% Al/5 wt% fluorine resin) achieved optimized balance between thermal stability and detonation performance, with the thermal runaway temperature around 583 K. The thermal ignition of TATB‐based aluminized explosive occurred at the edge of the cylinder according to the experimental and numerical simulations. Moreover, the critical thermal runaway temperature for PBX‐3 was calculated based on the Semenov's thermal explosion theory and the thermal decomposition kinetic parameters of the explosive, which was consistent with the experimental value.     

Preparation and Performance of a HNIW/TNT Cocrystal Explosive

A novel cocrystal explosive composed of 2,4,6,8,10,12‐hexanitrohexaazaiso‐wurtzitane (HNIW) and 2,4,6‐trinitrotoluene (TNT) in a 1 : 1 molar ratio was effectively prepared by solvent/nonsolvent cocrystallization adopting dextrin as modified additive. The structure, thermal behavior, sensitivity, and detonation properties of HNIW/TNT cocrystal were studied. The morphology and structure of the cocrystal were characterized by scanning electron microscopy (SEM) and single crystal X‐ray diffraction (SXRD). SEM images showed that the cocrystal has a prism type morphology with an average size of 270 μm. SXRD revealed that the cocrystal crystallizes in the orthorhombic system, space group Pbca, and is formed by hydrogen bonding interactions. The properties of the cocrystal including sensitivity, thermal decomposition, and detonation performances were discussed in detail. Sensitivity studies showed that the cocrystal exhibits low impact and friction sensitivity, and largely reduces the mechanical sensitivity of HNIW. DSC and TG tests indicated that the heterogeneous exothermic decomposition of the cocrystal occurs in the temperature range from 170 °C to 265 °C with peak maxima at 220 °C and 250 °C and significantly increases the melting point of TNT by 54 °C. The cocrystal has excellent detonation properties with a detonation velocity of 8426 m s⁻¹ and a calculated detonation pressure of 32.3 MPa at a charge density of 1.76 g cm⁻³, respectively. Moreover, the results suggested that the HNIW/TNT cocrystal not only has unique performance itself, but also effectively alters the properties of TNT and HNIW. Therefore, the cocrystal formed by HNIW and TNT could provide a new and effective method to modify the properties of certain compounds to yield enhanced explosives for further application.     

A Novel Cocrystal Explosive of HNIW with Good Comprehensive Properties

In order to improve the safety of the high explosive 2,4,6,8,10,12‐hexanitrohexaazaisowurtzitane (HNIW), we cocrystallized HNIW with the insensitive explosive DNB (1,3‐dinitrobenzene) in a molar ratio 1 : 1 to form a novel cocrystal explosive. Structure determination showed that it belongs to the orthorhombic system with space group Pbca. Therein, layers of DNB alternate with bilayers of HNIW. Analysis of interactions in the cocrystal indicated that the cocrystal is mainly formed by hydrogen bonds and nitro‐aromatic interactions. Moreover, the thermal behavior, sensitivity, and detonation properties of the cocrystal were evaluated. The results implied that the melting point of the cocrystal is 136.6 °C, which means an increase of 45 °C relative that of pure DNB. The predicted detonation velocity and detonation pressure of the cocrystal are 8434 m s⁻¹ and 34 GPa, respectively, which are similar to that of the reported HNIW/TNT cocrystal, but its reduced sensitivity (H₅₀=55 cm) makes it an attractive ingredient in HNIW propellant formulations.