5-肼基四唑高氯酸含能配合物的合成、表征及性能

以5-肼基四唑(5-HT)为配体,制备5种含能配合物[Cd(HT)_6](ClO_4)_2(1),[Zn(HT)6](ClO_4)_2(2),[Ni(HT)_3](ClO_4)_2(3),[Co(HT)_6](ClO_4)_2(4),[Mn(HT)_6](ClO_4)_2(5)。采用元素分析和傅里叶变换红外光谱对5种配合物进行结构表征。通过差示扫描量热分析(DSC)研究其热分解性能,测试了其摩擦感度和撞击感度。在B3LYP/6-311++g**水平上理论研究了5-HT电子结构性质、自然键轨道电荷以及分子前线轨道。结果表明,5种配合物具有较高热稳定性,分解温度均高于200℃。5-HT四唑环上的N(3)和N(4)原子更容易同时参与金属原子配位,形成以5-肼基四唑为配体的配位化合物。90°摆角、1.96 MPa条件下,配合物4的摩擦感度为96%,800 g落锤下,撞击感度H50为25 cm,其机械感度与肼基四唑汞(HTMP)和高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)(BNCP)相当,有望应用于起爆药领域。     

高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)分子和晶体结构与性能的理论研究

运用密度泛函理论(DFT)分别对高氯酸·四氨·双(5-硝基四唑)合钴(Ⅲ)(BNCP)分子和晶体进行了理论计算.首先选取4种常见密度泛函方法对BNCP气相分子进行优化,结果表明TPSS(Tao,Perdew,Staroverov,Scuseria)方法最适合此体系.随后运用Materials Studio中DMOL3模...     

三种联结方式对典型双四唑含能材料晶体结构和性能的影响

为了研究不同联结方式对双四唑含能材料结构和性能的影响,比较分析了5,5′-联四唑-1,1′-二氧羟铵盐(TKX-50)、5,5′-偶氮四唑-1,1′-氮氧化物二羟氨盐(ATZO-1)、5,5′-偶氮四唑-5-氮氧化物钠(ATO-Na)等三个化合物的晶体数据,从键长、键角、二面角、氢键作用等微观层面总结了偶氮键(─N=N─)和氧化偶氮键(─N=N(O)─)的引入对双四唑化合物结构的影响。研究发现两个四唑环分子直接相连形成的联四唑结构最为致密,对称和致密结构使其具有高的晶体密度,采用玻恩-哈伯循环(Born-Haber cycle)和热力学中盖斯(Hess)定律计算了TKX-50、ATZO-1和5,5′-偶氮四唑-5-氮氧化物二羟氨盐(ATO-1)的生成热,根据Kamlet-Jacobs公式(K-J方程)计算了其爆轰参数,比较发现,─N=N─和─N=N(O)─引入到联四唑中可降低其晶体密度,在一定程度上提高其生成焓,由于晶体密度相差较大,TKX-50仍具有最高的爆轰性能。     

1,1′-DM-5,5′-AT和2,2′-DM-5,5′-AT结构及其热稳定性的量子化学研究

采用量子化学从头算方法全优化计算了1,1′-二甲基-5,5′-偶氮四唑(1,1′-DM-5,5′-AT)和2,2′-二甲基-5,5′-偶氮四唑(2,2′-DM-5,5′-AT)的构型,并对其结构特征、分子轨道性质和稳定性进行了分析.计算发现这2个化合物均为平面结构,四唑环具有键长平均化的芳香性特征,满足4n 2规则.计算的四唑环芳香性指标、环上的净电荷和分子的电子相关能均显示1,1′-DM-5,5′-AT具有较好的热稳定性,理论研究得出的结论与实验结果一致.     

1,2,4,5-四嗪的四唑类衍生物高能量密度材料的分子设计

运用密度泛函理论DFT-wB97/6-31+G**方法研究了30种1,2,4,5-四嗪衍生物的几何结构、前线轨道能量和生成焓(ΔH_f)。在此基础上运用Kamlet-Jacobs方程估算了衍生物的爆轰性能。分析了标题化合物的键离解能。运用统计热力学,计算了部分标题化合物在200~800 K的热力学性质。比较了1,2,4,5-四嗪衍生物的爆轰性能和热稳定性。结果表明,它们的生成焓为920.46~2610.45 kJ·mol~(-1),爆速为7.69~9.31 km·s~(-1)。—NO_2和—N=N—不利于增加衍生物的稳定性。随温度升高,标准摩尔热容(c_p)、标准摩尔熵(S_m)和标准摩尔焓(H_m)逐渐增大。化合物i2(3-(5-硝基-1,2,3,4-四唑)-6-硝基-1,2,4,5-四嗪)、ii2(3-(偶氮-5-硝基-1,2,3,4-四唑)-6-硝基-1,2,4,5-四嗪)和iv2(3,6-偶氮-双(5-硝基-1,2,3,4-四唑)-1,2,4,5-四嗪)可以作为高能量密度材料候选物。     

多叠氮基嗪异构化反应的密度泛函理论研究

用密度泛函理论(DFT),对3,6-二叠氮基-1,2,4,5-四嗪(DiAT)和2,4,6-三叠氮基-1,3,5-三嗪(TAT)的叠氮→四唑异构化反应(关环反应)进行了研究。在B3LYP/6-311G**水平下优化了反应通道上各驻点(反应物、过渡态、产物)的几何构型,计算了各物种的总能量,并对总能量进行零点能校正。设计等键反应计算了各物种的生成焓,分析叠氮基向四唑环的转化对化合物分子构型、生成焓的影响。研究表明:3,6-二叠氮基-1,2,4,5-四嗪(DiAT)经两步环化反应生成四唑异构体,其反应能垒分别为100.5,117.4 kJ.mol-1。2,4,6-三叠氮基-1,3,5-三嗪(TAT)经三步环化反应生成四唑异构体,其反应能垒分别为101.8,99.7,108.7 kJ.mol-1。叠氮基环化为四唑环时,分子生成焓增大。从热力学上判断,TAT关环反应比DiAT关环反应更难进行。用自洽反应场(SCRF)方法对叠氮→四唑异构化反应进行溶剂化效应的计算,分析了二甲亚砜对分子性质的影响。     

1，1＇-DM-5，5’-AT和2，2＇-DM-5，5＇-AT结构及其热稳定性的量子化学研究

采用量子化学从头算方法全优化计算了1，1＇-二甲基-5，5’-偶氮四唑（1，1＇-DM-5，5＇-AT）和2，2’-二甲基-5，5’-偶氮四唑（2，2＇-DM-5，5＇-AT）的构型，并对其结构特征、分子轨道性质和稳定性进行了分析。计算发现这2个化合物均为平面结构，四唑环具有键长平均化的芳香性特征，满足4n＋2规则。计算的四唑环芳香性指标、环上的净电荷和分子的电子相关能均显示1，1＇-DM-5，5＇-AT具有较好的热稳定性，理论研究得出的结论与实验结果一致。     

四氮烯起爆药的电喷雾电离质谱裂解研究

为了更好地了解含能材料燃烧和爆炸机理,对四氮烯进行了电喷雾电离质谱分析。根据质谱图中碎片离子的信息,总结了四氮烯的裂解途径,发现四氮烯裂解时主要有NH2、HCN、HCN2、N3、N4中性碎片的丢失,推测它的裂解机理是C—N、N—N键的断裂反应和分子内重排反应;同时发现四唑环碎片离子m/z68.9的相对丰度较高,初步断定四氮烯分子结构中的四唑环是相对比较稳定的结构;并且由m/z68.9峰和m/z95.8峰的相对丰度接近,推测分子中C(5)—N(1)键和N(2)—N(3)键的键能相当(以四氮烯命名),且容易断裂,生成四唑自由基、氨基胍自由基和N2。     

金属配合物类炸药的爆轰性能计算及数值模拟

拟合了高氯酸[四氨·双(5-硝基四唑)]合钴(Ⅲ))(BNCP)、高氯酸·四氨·双叠氮基合钴(Ⅲ) (DACP)以及四氨·双(3,5-硝基三唑)合铜(Ⅱ)三种金属配合物炸药的固体爆轰产物Co和Cu的Cowan状态方程参数和热力学函数系数,利用VLW爆轰产物状态方程程序计算了其爆速、爆压等爆轰参数值,同时根据计算得到的等...     

2-偕二硝甲基-5-烷氧基四唑的合成

以2-偕二硝甲基-5-硝基四唑(HDNMNT)和醇钠为原料,合成出2-偕二硝甲基-5-甲氧基四唑(DNMMOT)、2-偕二硝甲基-5-乙氧基四唑(DNMEOT)、2-偕二硝甲基-5-异丙氧基四唑(DNMPOT)、2-(2-偕二硝甲基四唑-5-氧基)乙醇(SDEH)以及1,2-双(2-偕二硝甲基四唑-5-氧基)乙烷(DEH)5种化合物,产率分别为91.6%、92.1%、91.7%、31.7%及57.4%。采用红外光谱、核磁共振、元素分析及液相色谱质谱联用技术等对其结构进行了表征,并推测该反应机理为HDNMNT与醇钠的亲核取代反应。采用B3LYP方法预估了这5种2-偕二硝甲基-5-烷氧基四唑化合物的爆轰性能,发现DEH与RDX爆速和爆压相当。     

Open Rule-setting System Applied to Conceptual Design of Engines

Open rule-setting method advanced in this paper concentrates on providing designers of engines with a convenient way to express their design innovations and develop the expected prototypes in the early CAD stage, and constitute effective models for the following analysis process of CAE and CAPP. The problems arisen in the process of conceptual design with the traditional experience-based development method are analyzed. Based on those analyses, open rule-setting method is presented and some associated technical problems are discussed. The functional framework of open rule-setting system was built as software engineering methods. The speciality of the engine product as a kind of complex product and the requirement of the engine product based on its structural particularity to rule-setting system are considered carefully. A demonstration is supplied to illustrate how the open rule-setting method enhances the efficiency and quality of the engine conceptual design.     

Research on Linux Network Device Driver

By analyzing the working principle of Linux network device driver, discussing the Linux network driver structure and its key technologies, the general network driver structure and its design methodologies in Linux system are summarized. Through modifying the network device driver of Linux device driver 3rd version snull, c and improving the COW technology, the Zero-Copy technology in Linux （kernel version 2.6.11 ） is implemented. In the end, the success test tells us that the thorough analysis of network device driver is the foundation of many applications, and it also provides a certain improvement to a lot of real applications, even to military application development.     

Algorithm for Multi-laser-target Tracking Based on Clustering Fusion

Multi-laser-target tracking is an important subject in the field of signal processing of laser warners. A clustering method is applied to the measurement of laser warner, and the space-time fusion for measurements in the same cluster is accomplished. Real-time tracking of multi-laser-target and real-time picking of multi-laser-signal are introduced using data fusion of the measurements. A prototype device of the algorithm is built up. The results of experiments show that the algorithm is very effective.     

Influence of Installing Error on the Surface Shape Precision of the Axial Symmetry Aspheric Workpiece in Lapping

A method to calculate the surface shape error, which is caused by the installing error between the workpiece and the lapping tool in the process of form lapping, is proposed. The mathematical model which the installing translation error influences on the workpiece surface shape error is established. The changing rule of the error is simulated through the calculating example of the paraboloid workpiece. The results indicate that the surface shape error of the workpiece is increasing with the increase of the installing translation error, it is also increasing gradually along the center point of the curve surface to the edge, and the influence is severer to the curve surface with great curvature than that of the small curvature when the translation error is the same.     

Experimental Research on Output Performances of Giant Magnetostrictive Actuator

The paper introduces the performances of magnetostrictive actuators and its applications, discusses the design methods for the structure and internal magnetic circuit of a giant magnetostrictive actuator, and makes tests on the output displacement and force characteristics for an actuator using homemade magnetostrictive material. The experimental result shows that the actuator has satisfactory output precisions and ranges in transient and stable states, and can be used in lowfrequency vibration control system of precise equipment.     

Overview of Anti-tank Mines

First the different anti-tank mines laying possibilities are shortly summarized： hand emplaced, with mine layers, ground or helicopter relatively topographical well defined, and with cluster systems of projectiles, rockets and aircraft dispensers. Then examples of the three generations of anti-tank mines are presented：Ⅰ generation： detonating only beneath the track; Ⅱ generation： detonating beneath the track and belly; Ⅲ generation： mines with off-route actions. Weight and cost comparisons are strongly favoring the off-route Ⅲ-generation mines.     

A Finite Element Analysis on Static Strength of a Complex Section

A static finite element analysis （FEA） of an impulsive controller section is presented. The boundary condition and a part of the loads are applied. Considering the grades of the stress around the holes being large, the dense grids are adjusted accordingly. Four cases with different loads are compared, thus the influences of different loads on the section are analyzed. Numerical results show that the maximum stress of the section is lower than the strength limit of the material, and the section will not be broken with the static loads.     

Discussion on Mechanism of Breech-Blow Caused by Propellant Charge

From the view point of launch safety caused by fracture of propellant charge, this paper points out that the safety criterion of pressure wave is inadequate to evaluate the launch safety of propellant charge based on the initial negative differential pressure and sensitivity tests. Generally, the maximum barrel pressure does not depend upon the intensity of pressure wave correspondingly. The pressure wave intensity can not describe the fracture degree of propellant charge in chamber and reflect the mechanical environment of propellant charge fracturing exactly and wholly. The evaluation criterion for launch safety of propellant charge should be built on the basis of depicting the fracture degree of propellant bed.     

Experimental Studies of Toxicity on HNIW and Its Intermediates

The polycyclic nitramine hexanitrohexaazaisowurtane（HNIW） is a compound of high energy density. HNIW can replace 1, 3, 5-trinitro-1, 3, 5-triazacyclohexane（RDX） or HMX, hut its toxicity is unknown. In this paper, HNIW, hexabenzylhexaazaisowurtzitane （HBIW）, tetraacetyldibenzulhexaazaisowurtzitane （TADBIW）, tetraacetyldiformylhexaazaisowurtzitane（TADFIW） and tetraacetylhexaazaisowurtzitane（TAIW）, which are intermediates of the synthesis of the HNIW, were selected as the tested objects in acute toxicity test, acute eye stimulation test and skin irritation test according to the standards of ＂chemical product testing method-401 ： acute oral toxicity test＂, ＂chemical product testing means-405： acute eye irritation/corrosion test＂ and ＂chemical product testing means-404： acute dermal irritation/corrosion test＂ of National Circumstance Protect Bureau. The results show that all of the five objects have no toxicity, no stimulation to eye and skin under the tested conditions.     

Dynamic Simulation for Missile Erection System

In order to study the dynamic characteristics of the missile erection system, it can be considered as a rigid-flexible coupling multi-body system. Firstly, the actual system is abstracted as an equal and simplified one and then the forces applied to it are analyzed. Secondly, the rigid-flexible coupling dynamic simulation for erection system is accomplished by use of the system simulation software, for example Pro/E, ADAMS, ANSYS, MATLAB/Simulink, etc. Finally, having the aid of simulation results, the kinetic and dynamic characteristics of the flexible bodies in erection system are analyzed.The simulation considering the erection system as a rigid-flexible coupling system can provide valuable results to the research of its kinetic, dynamic and vibrational characteristics.