二(5-胺基-1,2,3,4-四唑)二肼盐的热分解行为

为详细了解二(5-胺基-1,2,3,4-四唑)二肼盐(Hy_2BTA)的热分解行为,采用热重-差示扫描量热-傅里叶红外光谱-质谱(TG-DSC-FTIR-MS)联用的方法,测定了该化合物在不同升温速率下的热分解曲线、分解气体产物的种类及其含量变化。结果表明:随着温度升高,Hy_2BTA的热分解包括2个吸热过程和2个连续地放热过程,分别对应于Hy_2BTA分子第一个离子键断裂脱除NH_2NH_2;第二个离子键断裂脱除NH_2NH_2的过程中,四唑环开始以断裂—N—N—键的方式释放N_2;四唑环及剩余骨架裂解产生N_2、HN_3、NH_3和HCN;剩余骨架分解产生HN_3、N_2和NH_3,裂解产物聚合成含氮高聚物。利用Kissinger方法计算4个过程的表观活化能分别为115.12,193.75,334.16 kJ·mol~(-1)和243.40 kJ·mol~(-1)。     

直链取代五唑共价化合物的稳定性和热解机理理论研究

五唑离子化合物是当前新型含能材料的一个研究热点,其制备通常以五唑共价化合物为前体实现.多数情况下,五唑共价化合物的稳定性对能否成功制备五唑离子化合物有很大影响.采用密度泛函理论B3LYP/6-31G**方法重点研究了18个直链取代五唑共价化合物(R—N5或N5—R—N5)的侧链化学键的解离能EBD和N5环的分解能垒Ea,分析了侧链对其稳定性和热解机理的影响.发现当R为羟基或氨基时,侧链容易断裂,N5环也容易破裂,难以得到N5-;当R为烷基时,N5环裂解的Ea相对较大,更可能得到N5-,且侧链C—N键和N5环的稳定性受烷基链长短影响不大;在双环分子中,两个N5环的裂解是先后发生的,后一个环的裂解能垒比前者高,裂解生成氮气和叠氮化物;分子侧链上的C—C键会先于C—N键断裂,从而可能使C—N键的EBD明显降低而对N5环的Ea影响不大,因此,在由五唑共价化合物制备五唑盐的过程中,先切断C—C键可能更利于得到N5-.     

气相色谱/质谱法分析偏二甲肼初期氧化产物

利用气相色谱／质谱表征偏二甲肼及其初期氧化产物,确定主要氧化产物浓度。结果表明,偏二甲肼在空气中氧化不大于100h的初期阶段,氧化产物有7种;二甲胺、偏腙和亚硝基二甲胺浓度缓慢上升,其后随着偏二甲肼氧化的继续进行,二甲胺浓度下降,亚硝基二甲胺浓度迅速上升,并有新的氧化产物出现。含氮有机物质谱中均含有m/z=42-43的碎片离子峰,说明偏二甲肼和含氮有机氧化物分子N-N键受热易于断裂。     

偶氮四唑胍盐的热分解机理

采用热重分析(TG),差示扫描量热法(DSC),固体原位池/红外和质谱(直接进样和热裂解-色谱-质谱联用方式)研究了偶氮四唑胍(GZT)的热分解行为,凝聚相产物和气相产物的变化,提出了GZT的热分解机理。结果表明,GZT分解失重的第一阶段由偶氮四唑的放热分解反应和胍分解的吸热过程构成。在单独热作用下,GZT首先发生质子转移形成偶氮四唑和胍,然后分别分解。偶氮四唑的四唑环经过开环反应,可能形成中间产物叠氮四唑(CHN7),最终生成三聚氰胺和叠氮铵等高沸点物质。在离子源轰击作用下除了四唑环开环解离外,C—N azo也会发生断裂,进而裂解。     

苦味酸和斯蒂酚酸电喷雾电离质谱裂解研究

为了更好地了解含能化合物分解机理,用电雾电离质谱研究了2,4,6-三硝基苯酚（苦味酸,PA）和2,4,6-三硝基间苯二酚（斯蒂芬酸,H2TNR）的裂解途径,分析了裂解机理。两种化合物裂解机理是消去OH自由基的“邻位效应”和C—NO2键的断裂反应,主要有NO2、OH、O、NO、CO、CNO、CNO2等自由基的丢失。发现当分子中-NO2基团的数量一定时,邻位-OH基团的数目越多,“邻位效应”越明显,越容易首先失去OH自由基,而C—NO2键的断裂反应则越难进行,首先丢失NO2自由基的机率越小。     

原位红外漫反射光谱研究HMX的分解动力学

采用原位红外漫反射光谱研究了炸药1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)的热分解动力学.结果表明升温中HMX会发生C-N键和N-N键的断裂,释放出CO2、N2O、CO、NO、HCHO、HONO、NO2和HCN八种气体,HMX的分解动力学方程为kC.N=e34.6exp(-152/RT).     

四氮烯异构体的密度泛函理论研究（英）

采用密度泛函理论对四氮烯起爆药的异构体进行研究。在B3LYP/6-311 G**水平下对四氮烯三种异构体分子的几何结构进行全优化计算。计算结果表明,(Ⅲ)的总能量比(Ⅰ)和(Ⅱ)都低,这说明(Ⅲ)是最稳定的分子结构,这与四氮烯的晶体结构和(Ⅲ)非常相近这一事实一致。对三种异构体分子的红外振动计算结果表明,它们的分子中都不存在虚频,由此说明这三种异构体都是可能存在的结构。由三种异构体分子的NBO电荷可以看出,(Ⅲ)分子中的原子排列比(Ⅰ)和(Ⅱ)便于分子中电荷的分散。前线轨道分析结果表明:N(8)是(Ⅲ)分子中最活跃的原子,在(Ⅲ)被活化的时候,N(8)—N(12)键先断裂。     

咪唑桥连唑类含能化合物的合成与性能研究进展

咪唑基含能化合物具有优异的热稳定性、良好的修饰性和适当的环张力,是高能材料的重要研究方向。围绕联咪唑、咪唑联三唑、咪唑联四唑等咪唑桥连唑类含能化合物及其离子盐的合成、性能与应用基础等方面进行了综述。分析可知,以单键、双键连接的双环咪唑类化合物,比相应的单环咪唑化合物具有更好的热稳定性和机械感度、更高的密度和爆轰性能,能够实现能量与安全的较好协调,但在单一咪唑环上引入富氮的含能基团、连接基团和离子盐在保证安全性的同时尚未实现高能量和高氮含量的兼顾。而将两种氮杂环结构通过C—C键或C—N键进行键合的联唑类化合物往往可以兼具两种氮杂环母体结构的骨架特点,是今后新型高氮高能化合物的重要发展方向。同时提出了基于咪唑联三唑或咪唑联四唑骨架构建高氮含量、高能量和良好安全性相协调的咪唑桥连双环唑类含能化合物的有效策略。     

五唑钠的制备工艺及C─N键切断机理

以2,6?二甲基?4?五唑基苯酚钠盐为原料,间氯过氧苯甲酸(m?CPBA)与甘氨酸亚铁(Fe(Gly)_2)为氧化切断试剂和稳定催化剂,在低温条件下成功合成了五唑钠;探索了芳基五唑氧化切断C—N键的反应条件:芳基五唑、Fe(Gly)2与m?CPBA摩尔比为1∶3∶4.5,反应时间24 h,反应温度-45℃,粗品收率为28%;探索了不同氧化切割试剂对五唑钠产率的影响,并分析了五唑钠产率低的原因;利用X?射线单晶衍射仪(X?ray single crystal diffractometer,XRD)、核磁(~(15)N NMR和~1H NMR)、元素分析、红外、质谱等对五唑钠和芳基五唑切断副产物(2,6?二甲基对苯醌)的结构进行了表征;并在此基础上推测分析了m?CPBA与Fe(Gly)_2氧化切断芳基五唑C—N键的机理历程。     

AP对HATO热分解影响的机制

为详细了解高氯酸铵(AP)对5,5'-联四唑-1,1'-二氧二羟铵(HATO)热分解影响的机制,采用热重-质谱-傅里叶红外光谱(TG-MS-FTIR)联用技术、差示扫描量热法(DSC)、傅里叶红外光谱(FTIR)方法,对HATO和HATO/AP共混物的热分解特性、气体产物以及凝聚相变化进行了研究。结果表明,HATO具有两个连续热分解阶段,HATO/AP共混物则有3个热分解阶段;HATO、AP共混后,HATO使得AP熔融峰消失,AP可使HATO的热分解初始温度提前,热分解时间延长且不影响分解完全性;HATO热分解气体产物有CO_2、N_2O、HCN、NH_3、NO、N_2、H_2O,而HATO/AP共混物热分解产生气体主要有N_2、CO_2、N_2O、HCN、NH_3、H_2O、HCN、NO、HCl、NOCl;另外,采用等转化率法计算HATO和HATO/AP共混物四唑环基团的活化能分别为53.38 kJ·mol~(-1)和60.69 kJ·mol~(-1);通过对比HATO和HATO/AP共混物热分解特性以及凝聚相特征基团的变化,阐释了AP使HATO热分解温度提前的机理很可能是:AP的铵根离子与HATO之间发生了质子转移;推测AP导致HATO热分解时间延长的原因为:HATO/AP共混物产生的NH_3与热分解中间体1,1'-二羟基-5,5-联四唑(BTO)反应生成5,5'-联四唑-1,1'-二氧铵盐(ABTOX)。     

Nitrosation and Nitration of Tetraacetyldibenzylhexaazaisowurtzitane

Tetraacetyldibenzylhitane (TADBIW) was subjected to debenzylation by nitrosating with inorganic materials available commercially to synthesize tetraacetyldinitrosohexaazaisowurtzitane (TADNSIW). TADNSIW was purified, and its structure was determined by FTIR, 1H NMR, MS and element analysis. The debenzylation reaction of TADBIW gave quantitative benzaldehyde as a by-product. This indicates that the reaction produces an imine cation as an intermediate. Hexanitrohexaazaisowurtzitane (HNIW) was prepared from unpurified TADNSIW with the yield over 96.0 % and the purity more than 98.0 %. And the mechanism of the reaction from TADNSIW to HNIW is proposed to be oxidation of nitroso and nitration of acetyl on the molecule of TADNSIW, This reaction system involved is simple, and the reaction can complete within a short time and under mild conditions. The product can be easily to separate and the waste disposed readily.     

A Robust Algorithm for Watermarking 2D Vector Maps with Low Shape-Distortions

The technique of watermarking has been introduced into 2D vector maps for many potential applications such as protecting the copyright of important GIS （geographical information system） data and tracing the data source of military maps. In most previous works, although the validity of the map data could be preserved during the embedding procedure, the shape-distortions of the map elements are usually neglected which would tend to degrade the invisibility of the watermarking schemes. A shape-preserving algorithm for watermarking 2D vector maps is presented in this paper. A 1D distance sequence extracted from the original map is adopted as the cover data instead of 2D coordinates. A watermark bit is represented by changing the distributions of the cover data. The embedding procedure induces lower shape-distortions than in former works. Experimental results indicate better invisibility of the proposed scheme, as well as its robustness to certain attacks such as map simplification, interpolation, additive noise and most geometric transforms.     

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.     

Improvement and Experiment of the Reamer in Vibra Cutter Against Wave Edge of Titanium Sheet Alloy Parts

By analyzing the influencing factors of part quality making of sheet alloy of titanium by vibra cutter, the shape of upper reamer is set as cylinder and wedge-shaped form, and the lower reamer as plain and hemicycle form, and its main structural parameters are defined as well. Then it is validated further that such improved vibra cutter reamer can be used to process curve-edged parts of titanium alloy sheet. The experimental result shows that the titanium alloy sheet parts processed by above equipment have no sharpen angles for convex parts and evident crevasse of concave-edged part. In summary, such improvement can eliminate the free-waved edge and improve the manufacture quality of titanium alloy sheet parts greatly.     

Experimental Study on the Small Flyer Initiating Behavior of Fine-grained Explosives

The initiating behavior of fine-grained explosives by small flyer is studied. The diameter of small flyer in this device is 1 ram. The test results indicate that the granularity of explosives has great effect on its flyer initiating sensitivity.The flyer initiating sensitivity of the fine-grained explosives is higher and the critical initiating energy is lower than that of common explosives. For common explosive, the flyer initiating sensitivity increases as the density is reduced. But for the fine-grained explosive, the test results are exactly opposite.     

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.     

Robust Graded Sliding Mode Tracking Control for Low Speed Spinning Ballistic Missiles

The nonlinear dynamic model of spinning ballistic missiles is established during the first boosting phase of the missile. Based on the conventional backstepping sliding mode control and the assumption of a two time-scale separation of missile dynamics, a graded sliding mode controller is designed with two sub-sliding surfaces which have invariability to external disturbances and parameter perturbations, and a matrix which comprises three first order low pass filters is introduced to prevent ＂explosion of terms＂. Owing to the upper bounds of the uncertainties are difficult to obtain in advance, adaptive laws are introduced to estimate the values of the uncertainties in real-time. Eventually, the numerical simulation results given to show the proposed controller can ensure the steady flight of missiles.