混合炸药中RDX对其热安全性的影响研究

采用差示扫描量热仪(DSC)研究了RDX对混合炸药体系的热分解性能的影响,用Kissinger法和Ozawa法计算并分析了其热分解动力学参数。结果表明,加入RDX后的混合炸药体系的初始反应温度、峰温、表观活化能、指前因子、自加速分解温度、热爆炸临界温度均随着RDX含量的增大而降低,说明了RDX的加入使混合炸药的热安全性变差了。     

含能增塑剂BDNPF/A与几种高能炸药相容性研究

采用差示扫描量热法(DSC)和X射线衍射法(XRD),研究了含能增塑剂双(2,2-二硝基丙基)缩甲(乙)醛(BDNPF/A)与6种高能炸药[1-氧-2,6-二氨基-3,5-二硝基吡嗪(LLM-105)、三氨基三硝基苯(TATB)、2,6-二氨基-3,5-二硝基吡啶-1-氧化物(ANPy O)、奥克托今(HMX)、六硝基六氮杂异伍兹烷(CL-20)和3-硝基-1,2,4-三唑-5-酮(NTO)]的相容性。DSC结果表明:BDNPF/A与TATB混合体系相容,与LLM-105混合体系轻微敏感,与ANPy O和HMX混合体系敏感,与CL-20和NTO混合体系危险。XRD结果表明:BDNPF/A与HMX、CL-20和NTO之间存在相互作用。上述试验研究表明,BDNPF/A与CL-20和NTO相容性差,不推荐一起使用。     

基于虚拟仪器的慢速烤燃系统的设计及应用

为了满足不敏感炸药的发展需求,在GJB 772A-1997及行业内标准烤燃装置的基础上,设计并开发了一套慢速烤燃系统。该系统基于LabVIEW程序的控制软件,由以控制器、数据采集卡、热电偶及数字I/O卡等为主的典型硬件构成。参照美军标MIL-STD-2105D和国内行业标准,对该系统的适用性开展了试验研究;采用RDX基与HMX基两种典型的混合炸药装药进行了慢速烤燃试验。结果表明,该慢速烤燃系统具有广泛的温度适用范围,试验数据拟合相关系数不低于0.999 8,在0.055、0.200、1.000、2.000℃/min和3.000℃/min等几种升温速率条件下,炸药均能实现较高精度的线性升温。与RDX基混合炸药相比,HMX基混合炸药响应程度有所缓和。该慢速烤燃系统满足试验需求,可为研究炸药的热不敏感性提供有效手段。     

分子氧在Con小团簇吸附的密度泛函研究

采用基于密度泛函理论（DFT）的Dmol3程序广义梯度近似PBE泛函,系统研究了Con（n =1~5）团簇及其对分子氧（O2）（垂直和平行）吸附后的ConO2团簇几何结构、稳定性和电子性质。结果表明：Con团簇的结合能随团簇数目的增加而增大,变化趋势趋于平缓,稳定性增强;分子氧在Con团簇顶位、桥位、空位的吸附稳定性、Co—O键长、O—O键长、分子氧的电荷转移都随团簇数目增大呈现规律性变化,说明分子氧被活化;Con团簇和分子氧之间的电荷转移越多,相互作用越强,吸附能和结合能也越大;分子氧垂直吸附型Co2O2 B团簇的吸附能和结合能最强,分别是-6.744 eV和4.611 eV,分子氧所得电荷最强为 -1.130 e。     

石墨烯负载Pdn(n=1—3)原子/团簇吸附三氯甲烷分子的第一性原理研究

采用基于密度泛函理论的第一性原理研究了三氯甲烷(CHCl₃)分子在负载Pd_n(n=1—3)原子/团簇的石墨烯表面的吸附行为。研究表明，CHCl₃分子与本征石墨烯(PG)之间仅为物理吸附，而采用Pd原子/团簇对本征石墨烯进行修饰，可以提高CHCl₃分子与石墨烯之间的吸附性能，使得CHCl₃分子与负载Pd_n(n=1—3)的石墨烯(PG-Pd_n(n=1—3))之间形成稳定的化学吸附。在PG-Pd_n(n=1—3)三种吸附体系中，吸附能计算表明Pd₃团簇修饰的石墨烯基底对CHCl₃分子的吸附效果最好，电荷转移分析表明CHCl₃分子向PG-Pd₃转移了大量电荷，电荷密度计算证实CHCl₃分子与PG-Pd₃之间形成了稳定的化学吸附。CHCl₃分子吸附在PG-Pd_3<...     

分子动力学模拟Pb纳米薄膜的结合能和晶格参数的尺寸效应

利用Materials Explorer分子动力学软件包,模拟研究了尺寸为0.5～15nm的Pb纳米薄膜的结合能和晶格参数的尺寸效应.研究表明,Pb纳米薄膜的结合能和晶格参数都随薄膜厚度的减小而降低,但降低的幅度要比同尺寸的Pb纳米团簇小.在模拟过程中,由于薄膜充分弛豫,模拟的结合能比SAD模型的计算结果要高一些.     

3，4-二硝基吡唑的晶体形貌、力学性能和感度的计算模拟

利用Material Studio(MS)软件中Morphology模块所包含的Growth Morphology （GM）、Bravais-Friedel Donnay-Harker (BFDH)和Equilibrium Morphology (EM)3种方法,计算了3,4 二硝基吡唑（DNP）的晶面参数,预测了晶体的生长习性和自然生长晶形。采用分子动力学方法模拟计算了DNP、1,3,5-三硝基甲苯（TNT）和2,4-二硝基苯甲醚（DNAN）的力学性能和感度。结果表明:3种方法计算得到的DNP晶体的形貌分别近似为梭形、短圆柱形和椭球形,综合分析,DNP晶体的形貌更可能为梭球形;DNP的拉伸模量E大于TNT和DNAN,体积模量K大于TNT而小于DNAN,剪切模量G要大于TNT和DNAN,其韧性要弱于TNT和DNAN;DNP和DNAN的引发键最大键长相同且比TNT低,DNP的内聚能密度与DNAN基本持平且均大于TNT。     

高速撞击下温压炸药的响应敏感性

采用自行设计的动态加载装置对HMX基、HMX/NTO基和HMX/FOX-7基3种温压炸药撞击响应规律进行了研究,获得炸药的临界点火速度,并通过密闭燃烧罐分析撞击后回收试样的燃烧特性。结果表明:3种温压炸药药柱在高速撞击下均经历了冲击、塑性变形、破碎飞散和点火反应阶段;HMX基、HMX/NTO基和HMX/FOX-7基温压炸药的临界点火速度分别为302.9、312.3 m/s和315.3 m/s,NTO和FOX-7能够提高温压炸药的临界点火速度;分析撞击后回收试样的燃烧特性发现,与HMX基温压炸药相比,HMX/NTO基和HMX/FOX-7基温压炸药升压时间分别增加了103.6%和103.3%,升压速率分别降低了17.3%和21.1%,且撞击后的燃烧速率显著降低。     

3，4-二硝基吡唑(DNP)的研究进展

随着武器装备的不断发展,对弹药能量和安全性的要求也越来越高,传统TNT基熔铸炸药存在易损性差、长期储存渗油、爆轰性能不理想等缺点,已不能满足当前不敏感弹药的发展要求;因此,研究炸药的新型载体是当前熔铸炸药发展的一个重要方向。3,4-二硝基吡唑(DNP)是一种新型的熔铸炸药载体。根据国内外的相关报道,阐述了DNP的合成方法、基本性能、机械感度、热安全性、相容性、应用性等研究发展现状。研究结果表明:目前,经N-硝化、热重排、C-硝化三步法合成DNP的工艺更加稳定,得率较高;DNP的熔点为86.5 ℃,理论密度为1.87 g/cm³,实测爆速为7 633 m/s（ρ=1.65 g/cm³）,爆热为4 326 kJ/kg,理论爆压为28.7 GPa;DNP的机械感度与TNT相当,具有较好的机械安全性;DNP热分解分两个阶段,第一阶段分解放热峰为319.8 ℃,第二阶段分解放热峰为407.2 ℃,与TNT和DNTF相比,DNP的热分解峰温高,热安定性好;DNP与RDX、HMX、CL-20、Al、AP、微晶蜡具有较好的相容性,可以与这些组分组成混合炸药,具有广泛的适用性。     

聚醋酸乙烯酯与黑索今体系的分子动力学模拟

聚醋酸乙烯酯(PVAc)与黑索今(RDX)的界面相互作用会直接影响RDX的表面包覆效果,因此,在原子、分子层次研究其作用方式,可以发现相互作用机制。利用分子动力学模拟方法,以径向分布函数描述组分间相互作用的方式;研究不同温度下PVAc与RDX晶面的相互作用,并计算PVAc在RDX晶体表面的扩散速率。结果表明,在298~353 K温度下,PVAc与RDX的结合能随温度升高略有降低;通过对有效各向同性模量和柯西压的分析得到,加入PVAc能够有效改善RDX的力学性能。此外,在343 K的温度下,PVAc在RDX表面的扩散速率最大,体系的力学性能最为优异。     

RDX和HMX混合物中HMX的分离研究

根据HMX和RDX在不同溶剂中的溶解机理的差异,选用两种代表性物质对RDX和HMX混合物进行分离研究,确立以N,N-二甲基甲酰胺(DMF)为溶剂的分离RDX和HMX混合物的最佳工艺条件。最佳工艺条件为物料比14,溶解温度95～100℃,解离剂为水,解离温度90℃,解离时间2 h。运用高效液相色谱(HPLC)对分离得到的HMX进行了纯度测定,HMX纯度可达98%;通过偏光显微镜观察显示分离得到的HMX为β-晶型。分离得到的HMX在民用混合炸药中得到了再利用,可以替代直接生产的HMX。     

熔铸载体2,4-二硝基苯甲醚的热安全性研究

为全面了解2,4-二硝基苯甲醚(DNAN)的热安全性,通过分子结构分析和DSC对DNAN的理化特性进行研究;并采用自行设计的热感度试验装置和1L烤燃试验装置,分析炸药在220、230℃和240℃等不同温度下的烤燃响应情况,观察了炸药在大尺寸烤燃过程中的变化情况;采用公斤级低易损性试验验证了DNAN基熔铸炸药的安全性。结果表明,DNAN分子结构稳定,在365.1℃发生热分解反应,5 s爆发点为374.1℃,活化能为215.0 kJ/mol;DNAN的烤燃过程经历4个阶段,分别为固-液相变阶段、慢速分解阶段、快速分解阶段和喷发及点火阶段;DNAN炸药良好的热安全性使DNAN基熔铸炸药在热刺激作用下反应温和,为其在低易损炸药上的应用奠定了基础。     

爆轰法制取氧化铝

为进一步探求纳米氧化铝的尺寸和晶型与混合炸药爆轰参数之间的有机联系,以九水硝酸铝和黑索金为原材料,按1∶8的质量比将两者均匀混合配制出密度约为0.8g/cm3的混合炸药在爆炸罐内进行爆轰实验研究,爆轰实验产物为灰色粉末。通过高分辨率透射电镜和X光衍射仪器对产物进行检测分析,分析结果表明产物为纳米氧化铝,氧化铝颗粒形状呈标准球形,大部分颗粒尺寸小于100nm,少量颗粒尺寸大于100nm,颗粒平均尺寸为30nm左右,氧化铝晶型为γ型。实验结果进一步证明了混合炸药中黑索金含量越高,爆轰合成的纳米氧化铝尺寸越大。     

The fate and transport of RDX, HMX, TNT and DNT in the volcanic soils of Hawaii: a laboratory and modeling study

The adsorption and degradation behavior of RDX, HMX, TNT and DNT and the impact of pH, ionic strength and dissolved organic matter on sorption were examined for two volcanic soils of a former military training area on Hawaii Island, Hawaii, USA. The transport of these chemicals in the soil was also studied in small packed columns and simulated using a water-flow and solute-transport model, HYDRUS_1D. The results show that HMX and RDX are both significantly more mobile than TNT and DNT. The adsorbability of the four chemicals was ranked as: RDXRDX>DNT>TNT. No significant trend was observed for the effect of ionic strength, pH and dissolved organic carbon (DOC) on the adsorption of explosive compounds within the concentrations and pH ranges evaluated. The simulation results show that TNT and DNT would not leach beyond a depth of 30cm soil profile whereas a significant amount of HMX and RDX would pass the 30cm depth. It seems that the risk for contamination of groundwater is much higher for both HMX and RDX than for DNT and TNT as the substratum in this area consists of highly permeable lavas.     

Aqueous solubility and alkaline hydrolysis of the novel high explosive hexanitrohexaazaisowurtzitane (CL-20)

The recently developed polycyclic nitramine CL-20 is considered as a possible replacement for the monocyclic nitramines RDX and HMX. The present study reports aqueous solubility data for CL-20, as well as the kinetic parameters for its alkaline hydrolysis with sodium hydroxide below and above its solubility limits. Aqueous solubility of CL-20 was measured in the temperature range of 4–69 °C and the data were fitted to a generalized solubility model. Alkaline hydrolysis experiments were conducted at 15, 20, 30 and 40 °C, with hydroxide concentrations ranging from 0.25 to 300 mM. Like RDX and HMX, alkaline hydrolysis of CL-20 follows second-order kinetics. CL-20 alkaline hydrolysis was found to proceed at a significantly faster rate than RDX. The temperature dependency of the second-order rate constants was evaluated using the Arrhenius model. The activation energy for CL-20 was found to be within close range of the activation energies reported for RDX and HMX.     

HMX based enhanced energy LOVA gun propellant

Efforts to develop gun propellants with low vulnerability have recently been focused on enhancing the energy with a further improvement in its sensitivity characteristics. These propellants not only prevent catastrophic disasters due to unplanned initiation of currently used gun propellants (based on nitrate esters) but also realize enhanced energy levels to increase the muzzle velocity of the projectiles. Now, in order to replace nitroglycerine, which is highly sensitive to friction and impact, nitramines meet the requirements as they offer superior energy due to positive heat of formation, typical stoichiometry with higher decomposition temperatures and also owing to negative oxygen balance are less sensitive than stoichiometrically balanced NG. RDX has been widely reported for use in LOVA propellant. In this paper we have made an effort to present the work on scantily reported nitramine HMX based LOVA gun propellant while incorporating energetic plasticizer glycidyl azide polymer to enhance the energy level. HMX is known to be thermally stable at higher temperature than RDX and also proved to be less vulnerable to small scale shaped charge jet attack as its decomposition temperature is 270 degrees C. HMX also offers improved impulse due to its superior heat of formation (+17 kcal/mol) as compared to RDX (+14 kcal/mol). It has also been reported that a break point will not appear until 35,000 psi for propellant comprising of 5 microm HMX. Since no work has been reported in open literature regarding replacement of RDX by HMX, the present studies were carried out.     

Synthesis of RDX by nitrolysis of hexamethylenetetramine in fluorous media

Perfluorooctanesulfonic acid (CF₃(CF₂)₇SO₃H, PfOS) catalyses the highly efficient nitrolysis of hexamethylenetetramine in fluorous media, affording high yield of explosive RDX. The reaction can be carried out at room temperature in the absence of acetic anhydride and produces smaller amounts of waste acid and nitrate than in traditional process. The fluorous phase containing catalyst could be easily and efficiently recovered for reuse by simple phase separation.