Effect of Temperature,Density and Confinement on Deflagration to Detonation Transition of an HMX‐Based Explosive

In order to obtain the characteristics of the deflagration‐to‐detonation transition (DDT) of PBX‐2 (an HMX‐based explosive) under different conditions, DDT tests were carried out as a function of charge density, temperature, and shell confinement. In these tests, the energetic materials were electrically ignited. The DDT response characteristics for PBX‐2 with 53 % and 99 % of theoretical maximum density (TMD) were evaluated by different shell thickness confinements at ambient temperature and at 85 °C. The test results with different densities, confinements and temperatures exhibited a wide range of reaction violence. Firstly, at both ambient temperature and at 85 °C under 10 and 20 mm shell thickness confinement, PBX‐2 did not undergo fully DDT at 99 % TMD, only a low velocity detonation (LVD) occurred. Secondly, PBX‐2 at 53 % TMD underwent DDT, and significant influence on the minimum run distance to detonation by the shell confinement thickness was observed. Strong confinement is favorable for the transition of DDT but the confinement does not influence reaction degree. Thirdly, the reaction degree of PBX‐2 at 85 °C was remarkably lower than that at ambient temperature. This insensitizing effect of temperature is induced by the melting and flowing of bonders which reduces the porosity and inhibits an important step of DDT, namely, high turbulent combustion.     

四氧化三锰的制备及其对奥克托今的热分解行为研究

以氯化锰为锰源、六次甲基四胺(HMT)为沉淀剂,采用均相沉淀法在90℃制备了Mn3O4,用X-射线衍射、扫描电镜和透射电镜等对产物的结构和形貌进行表征,利用DSC技术研究了产物对奥克托今(HMX)的热分解行为的影响。结果表明,制备产物为四方结构Mn3O4,直径约为300 nm的近似球形。Mn3O4的加入,对HMX的分解峰形变化不大,但分解温度增大,分解活化能增加。     

A Groundbreaking Stepwise Protocol to Prepare HMX from DPT: New Mechanism Hypothesis and Corresponding Process Study

1,3,5,7‐Tetranitro‐1,3,5,7‐tetraazacyclooctane(HMX) is one of the most powerful and widely used explosives. 3,7‐Dinitro‐1,3,5,7‐tetraazabicyclo[3.3.1] (DPT) is an important precursor in the production of HMX. A new reaction mechanism including nitrolysis, nitrosolysis and nitrolysis processes in fuming HNO₃ was put forward. The stable key intermediate 1‐nitroso‐3,5,7‐trinitro‐1,3,5,7‐tetraazacyclooctane (MNX) was isolated and characterized. Based on the new mechanism, a stepwise method to prepare HMX from DPT was developed. The influence factors on the yields of MNX such as reaction temperature, loading amounts of HNO₃, NaNO₂ and NH₄NO₃ were investigated. Under the optimized conditions, MNX was obtained with a satisfactory yield of 84.0 %. MNX could be efficiently and smoothly nitrolyzed in fuming nitric acid and afforded pure β‐HMX with excellent yield up to 92.8 %. The overall yield of the stepwise procedure was as high as 78.0 %, much higher than traditional one‐pot nitrolysis protocols.     

3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷硝解过程的理论研究

在密度泛函理论B3LYP/6-31G水平下,对3,7-二硝基-1,3,5,7-四氮杂双环[3.3.1]壬烷(DPT)硝解制备1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)的过程进行量子化学研究,主要计算了DPT以及重要反应中间体的电子云密度、键长、键级和二阶微扰能。结果表明,由于受键长和键解离能的影响,DPT在硝解过程中可能同时生成八元环和六元环的中间体;八元环中间体受键解离能与二阶微扰能的影响,在硝解制备HMX的同时有副产物产生。因此,DPT硝解制备HMX不仅受实际实验过程影响,还受到分子本身结构的影响,通过计算可以看出,量子化学参数在微观上体现了HMX的总收率不理想的内在原因。     

HMX粒度对其机械感度的影响研究

本文分别采用H3．5-10W落锤式撞击感度仪和摆式摩擦感度仪对不同粒度HMX的撞击感度和摩擦感度进行了实验研究，得到了相应的变化规律，并对实验结果进行了分析。     

外电场影响HMX/MDNI复合物感度的理论研究

为研究外电场对炸药感度的影响,采用量子力学方法在M06-2X∥B3LYP/6-311++G(d,p)水平上对奥克托今(HMX)/1-甲基-4,5-二硝基咪唑(MDNI)分别施加不同大小的外电场(-0.010~0.010 a.u.),得到不同外电场下的稳定构型。分析了各稳定构型的分子间相互作用、引发键解离能、硝基基团电荷、电子密度拓扑、电子密度转移及表面静电势的变化。结果表明:随着正向外电场的增强,HMX的引发键键长变短,解离能增加,感度降低,负向外电场时则相反;采用B3LYP方法所得3种复合物的解离能与外电场的相关系数分别达到了0.995、0.977和0.982;负向外电场作用下硝基基团所带负电荷减少,使炸药感度增加;电子密度拓扑分析表明,外电场作用下,HMX与MDNI分子间仍存在微弱的氢键作用;电子密度转移分析表明正向外电场增强了引发键的强度;分子表面静电势则进一步表明在正向外电场作用下炸药感度降低,负向时感度增加。     

Energetic nitrocellulose coating: effective way to decrease sensitivity and modify surface property of HMX particles

Modifying the surface properties of energetic materials has theoretical and practical significance in the field of their application. In this paper, irregular cyclotetramethylene tetranitramine (HMX) particles were successfully coated by energetic nitrocellulose (NC), leading to the uniform NC-coated HMX particles. As coating materials, energetic (NC was chosen to decrease the sensitivity and modify the surface property of HMX particles, in order to expand their application furthermore. Scanning electron microscopy, laser particle size analysis, energy dispersive spectrometer, and Fourier-transform infrared (FT-IR) spectra were utilized to investigate the morphology, size, and coating quality of NC-coated HMX particles. These results indicated the effective preparation of composites structure. Moreover, the thermal behaviors of NC-coated HMX particles were investigated by simultaneous thermogravimetric and differential scanning calorimetry analysis, coupled with FT-IR and mass spectroscopy. These results showed that NC did not induce chemical properties change of HMX, only physical hydrogen bond was formed in the coating process. Finally, the friction sensitivity, impact sensitivity, and surface properties NC-coated HMX were investigated, and the results suggested that NC-coated HMX particles had better safety and depicted stronger interaction with the binder matrix than original HMX, owing to the stability of NC on the outer layer.     

奥克托今转晶研究

采用α－ＨＭＸ为原料，以醋酐法工艺的废酸为溶剂，溶解α－ＨＭＸ和在废酸中氧化α－ＨＭＸ的所含杂质，运用升降温冷却结晶技术，进行转晶取得成功。并摸索出制备中等粒度级别的工艺条件，产品酸度均小于或等于０．０２％，熔点大于或等于２７３℃。为醋酐法制备ＨＭＸ生产工艺的改进和降低ＨＭＸ生产成本奠定了基础。     

不同组分比的HMX/DMI共晶炸药结构与性质的理论研究

利用分子动力学,研究了分子摩尔比对HMX/DMI共晶炸药几个重要晶面成键能的影响,对于不同分子的摩尔比的力学性质也进行了估算,借助M06-2x/6-311+G(2df,2p)方法对HMX/DMI复合物的溶剂效应也进行了研究。计算结果表明,(020)和(100)取代基模型具有最高的成键能和稳定性,1∶1和2∶1的化合物最稳定且具有最高的力学性能。分子间相互作用能和N–NO_2键离解能的变化对HMX/DMI共晶炸药的稳定性有较大影响。制备稳定的HMX/DMI共晶炸药应选用较低介电常数作溶剂。     

Stimulating the anaerobic biodegradation of explosives by the addition of hydrogen or electron donors that produce hydrogen

The anaerobic biodegradation of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), and 2,4,6-trinitrotoluene (TNT) by a methanogenic mixed culture was investigated. Microcosms containing a basal medium and the mixed culture were amended with ethanol, propylene glycol (PG), butyrate or hydrogen gas as the electron donor and a mixture of TNT (50 microM), RDX (25 microM), and HMX (8 microM). After 29 days TNT and RDX were completely transformed to unidentified endproducts in the bottles amended with ethanol, hydrogen, or PG, while 53%, 40%, and 22% of the HMX was transformed, respectively. There was no loss of RDX or HMX in the electron donor unamended control bottles. The ethanol and PG were transformed to near stoichiometric amounts of acetate and propionate, suggesting the immediate electron donor supporting the transformation of the explosives was the H2 evolved during the metabolism of the parent substrate. Our findings suggest that the addition of H2 or electron donors that produce H2 may be a useful strategy for enhancing the anaerobic biodegradation of explosives in contaminated groundwater and soils.