石墨烯基联四唑含能配位聚合物的制备、表征及催化活性

采用溶剂热法制备了一系列新型石墨烯基联四唑钝感含能配位聚合物,该含能配位聚合物以钴和镍两种金属离子为典型配位中心,氧化石墨烯(GO)为结晶掺杂物,配体选用1,1′-二羟基-5,5′-联四唑(DHBT)和5,5′-联四唑(H_2BT)。通过调节合成工艺参数,成功制备出GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT与β-GO-Ni-BT五种含能催化剂。采用粉末衍射(XRD)、X射线光电子能谱(XPS)、扫描电镜(SEM)/能谱(EDS)和差热扫描量热仪(DSC)-热重分析仪TG等技术对这五种含能催化剂形貌结构进行了表征,并采用DSC-TG研究了GO-Co-DBT、GO-Co-BT、GO-Ni-DBT、α-GO-Ni-BT对高氯酸铵(AP)和黑索今(RDX)催化热分解性能的影响。结果表明,石墨烯诱导联四唑配合物结晶可减少晶体缺陷,从而降低热点产生几率,提高热稳定性。其中,GO-Co-DBT、GO-Ni-DBT与GO-Ni-BT分解温度高于200℃。石墨烯基联四唑配合物含能催化剂对AP与RDX的热分解反应具有显著的催化作用,通过转移O元素与NH_4~+反应来提高生成NH_3和H_2O的反应深度,使AP两个放热峰重叠,总放热量增加,催化效应显著。AP的归一化放热量增至2757.0 J·g~(-1),转晶对应的吸热峰热值降低至23.2 J·g~(-1),RDX的归一化放热量提高至2898.0 J·g~(-1),相对于纯AP,RDX放热量提高50%以上,在保证催化效果的同时提高体系的热稳定性。     

球磨法制备高氯酸铵基分子钙钛矿微纳米颗粒及安全性能分析

为了改善高氯酸铵基分子钙钛矿((H2dabco)[NH4(ClO4)3],DAP)作为含能材料的安全性能,用球磨法制备出微纳米级DAP颗粒材料,采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、傅里叶红外光谱仪(FT-IR)以及Raman光谱仪分别对其形貌、结构进行表征。采用热重分析-差示扫描量热(TG-DSC)对其热分解性能进行表征,按GJB770B-2005爆炸概率法测试其撞击感度。结果表明,球磨法得到的细化DAP为0.5~10μm的微纳米级椭球颗粒,球磨后颗粒表面近似光滑,展现了良好的晶型稳定性;细化后DAP热分解峰温度为370.6℃,与原料DAP(热分解峰温度385.4℃)相比明显降低;与原料DAP(撞击感度为56%)相比,细化后DAP的撞击感度(28%)大幅降低。     

某镁铝贫氧推进剂吸湿与点火失效分析

为分析某航天型号镁铝贫氧推进剂失效机理,利用显微形貌分析、X射线衍射(XRD)、热分析和高速摄影等测试了贫氧推进剂的成分、热分解规律以及常压点火性能。结果表明,吸湿后推进剂中的高氯酸铵(AP)发生结块,Mg被氧化后与水作用生成Mg(OH)_2。未吸湿的推进剂在420℃前仅有AP的晶型转变及热分解失重,而吸湿后推进剂热稳定性变差,90℃下即开始失重,420℃前有四个分解步骤:水分挥发、Mg(ClO_4)_2热分解及AP与Mg(OH)_2分解。采用电点火头在常压下点燃后,未吸湿推进剂可以稳定燃烧,而吸湿后的推进剂无法被引燃。分析认为,导致推进剂点火失效的原因是AP结块和活性镁含量降低,因此镁铝贫氧推进剂在潮湿环境下的贮存应给予重点关注和定期抽样监测。     

高氯酸铵疏水表面的制备及表征

为降低高氯酸铵(AP)的吸湿性,采用聚苯乙烯(PS)和十二氟庚基丙基三甲氧基硅烷(氟硅烷,FAS:C14F12H20SiO3)对其表面包覆。将高氯酸铵(AP)和聚苯乙烯(PS)复合,再用FAS处理得到AP/PS/FAS粒子和复合薄膜。通过吸湿率和接触角测试研究了其吸湿性。用扫描电镜-能谱(SEM-EDS)分析研究其微观形貌结构。结果表明,AP/PS/FAS复合薄膜的吸湿率最小,且基本不吸水。未处理AP的接触角为0°,AP/PS/FAS复合薄膜与水的接触角为(113±2)°。AP/PS/FAS复合薄膜表面具有类似荷叶表面的微观形貌结构,其表面含有氟硅烷分子,有利于AP疏水表面的形成。     

CuO/PG纳米复合材料的制备及其对AP催化分解性能的影响

为改善纳米CuO的催化效果,以多孔石墨烯(PG)为载体,采用络合沉淀法分别制备CuO形貌为片状、线状、棒状和球状的CuO/PG纳米复合材料,并通过差示扫描量热法(DSC)测试了CuO/PG纳米复合材料对高氯酸铵(AP)热分解的影响,分析了其催化机理。结果表明,与相同形貌的纳米CuO相比,CuO/PG纳米复合材料的比表面积更大,对AP热分解的催化效果更好。在四种CuO/PG纳米复合材料中,球状氧化铜粒径最小,约4 nm,其复合材料的比表面积最大,约115 m~2·g~(-1),故催化活性位点最多,催化AP分解效果最好,使其高温分解放热峰温度下降至310.1℃。     

蜂窝状ZnCo2O4的制备及对AP和CL-20热分解行为的影响

为了研究双金属氧化物在固体推进剂中的催化性能,采用溶剂热法及热退火工艺成功制备出在镍泡沫(NF)上生长的蜂窝状ZnCo_2O_4(honeycombs ZnCo_2O_4,ZnCo_2O_4(HCs)),并通过X射线粉末衍射(XRD),X射线光电子能谱仪(XPS),傅里叶红外光谱仪(FT-IR),扫描电子显微镜(SEM)及N2吸附-脱附测试对其物相组成和形貌结构进行了表征分析。采用差示扫描量热法(DSC)研究了制备的ZnCo_2O_4(HCs)对高氯酸铵(AP)和六硝基六氮杂异伍兹烷(CL-20)的催化性能。结果表明,当ZnCo_2O_4(HCs)用量为20%时,ZnCo_2O_4(HCs)/AP和ZnCo_2O_4(HCs)/CL-20最低热分解峰温,分别为575.01,521.55 K。与纯AP和CL-20相比,ZnCo_2O_4(HCs)/AP和ZnCo_2O_4(HCs)/CL-20复合物的放热分解峰温分别提前了101.87,3.73 K,热分析动力学计算表明它们的表观活化能分别降低了17.88,6.23 kJ·mol~(-1)。与文献报道的纳米微晶状(NCs)、纳米线状(NWs)及纳米球状(NSs)ZnCo_2O_4相比,蜂窝状ZnCo_2O_4呈现出良好的催化活性,这可归因于ZnCo_2O_4(HCs)的多孔结构和大比表面积,能够为热分解反应提供丰富的活性位点。     

四氧化三钴@碳化蝶翅的制备及催化高氯酸铵分解的性能

采用水热法制备了四氧化三钴@碳化蝶翅(Co_3O_4@CW)纳米复合材料。利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、比表面及孔径分析仪表征了其结构和成分。采用同步热分析仪(DSC-TG)研究了该复合材料对高氯酸铵(AP)热分解的催化性能。结果表明,Co_3O_4@CW具有微孔-介孔-大孔的多级孔结构,Co_3O_4纳米粒子均匀紧密地负载于碳化蝶翅的骨架上,其中Co_3O_4的负载量约为72.0%。Co_3O_4@CW可显著降低AP的高温分解峰温度,当Co_3O_4@CW的添加量为3%时,AP的高温分解峰提前147℃,AP的热分解放热量从173.4 k J·mol~(-1)增加到369.3 k J·mol~(-1),表现出了良好的催化性能。     

含能快递

正劳斯阿拉莫斯国家实验室继续近红外激光低能起爆的四嗪类配合物的研发劳斯阿拉莫斯国家实验室曾报道了近红外激光起爆阀值比PETN低了近2 J·cm~(-2)的[(TriTzPyr)_3Fe][ClO_4]_2和[(NH_2TriTzPyr)_3Fe][ClO_4]_2的研发(Tri为三唑,Tz为四嗪,Pyr为吡唑,2017年第3期含能快递),为增加氧平衡,他们又在此研究基础上,通过以下反应制备出了     

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)。     

含能配合物［Cu（MIM）2（AIM）2］（DCA）2的合成、结构及对AP热分解的催化

为探索固体推进剂燃烧催化剂,以1-甲基咪唑(MIM)、1-烯丙基咪唑(AIM)、硝酸铜和二氰胺钠(NaDCA)为原料,合成了一种新型双配体含能配合物[Cu(MIM)2(AIM)2](DCA)2,并通过红外光谱、X射线单晶衍射和粉末衍射对其结构进行了表征.采用差示扫描量热法(DSC)、热重分析法(TGA)对该含能配合物的热分解过程进行了分析,在40～500℃的温度范围内,DSC曲线中有一个吸热熔化峰(峰值温度:93.5℃)和一个放热分解峰(峰值温度:199.4℃).对配合物进行了感度测试,其摩擦感度为240 N,撞击感度>40 J.对比研究了双配体的[Cu(MIM)2(AIM)2](DCA)2与单配体的[Cu(MIM)4](DCA)2、[Cu(AIM)4](DCA)2对高氯酸铵(Ammonium Perchlorate,AP)热分解的催化作用,结果表明双配体的含能配合物具有更好的催化效果,使AP的分解峰值温度提前到285.6℃,放热量升高到2458 J·g-1,热分解活化能降低到81.5 kJ·mol-1,表现出作为复合推进剂催化剂的潜力.     

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.     

Method for Measuring Velocity of Warhead Fragments Based on Photoelectric Detection

For measuring velocity and impacting position of single fragment of warhead, a non-contact measuring method is proposed, in which a six-light-screen array, a position indicator, a multi-channel chronograph and a computer are used.The principle of measurement is described. The key device of the system is a light screen array sensor which consists of six light screens allocated with certain geometrical parameters. When the fragment flies through the light screen array, the time of passing through each of the screens is recorded by the multi-channel chronograph. According to the time data and the geometrical parameters of the array, the velocity vector and the location of the fragment can be calculated immediately. The presented method can be used to locate the fragment and to measure the real velocity on its flying direction. It can also be used to measure the velocity of a fragment swarm after the system is engineered further.     

数码电子雷管中影响点火头性能因素分析

阐述了数码电子雷管中,点火药剂细结晶三硝基间苯二酚铅（LTNR）的制备工艺;从点火药剂的种类、加入黏合剂的质量分数、桥丝直径、点火头的电阻值、防潮漆的蘸涂等方面对点火头性能的影响因素进行了探讨;通过震动试验、并联起爆试验、延期精度检测与考核,试验结果表明：一次性合成的细结晶LTNR是制造数码电子雷管点火头较为理想的点火药剂,按技术要求生产的点火头性能指标能够满足行业标准要求。     

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.