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1.
由原子化反应法求算高能化合物的生成热   总被引:2,自引:2,他引:0  
基于DFT-B3LYP/6-31G*及HF/6-31G*水平的理论计算结果,借助原子化反应及严格的物理化学公式,对49种已有实验值的高能化合物的生成热进行了计算。与实验值的关联比较表明B3LYP/6-31G*水平的计算结果(x)与实验值(y)之间存在良好的线性关系;对49个标题物,线性方程为y=-75.79 0.98x,相关系数R=0.990,标准偏差SD=28.21。以此线性方法预测了高能化合物的生成热,所得结果与实验值偏差较小,表明B3LYP/6-31G*结合原子化反应是兼顾适用性和可靠性的计算高能化合物生成热的较好方法。基于HF/6-31G*水平的原子化反应法不适于计算高能化合物的生成热。  相似文献   

2.
邱玲  肖鹤鸣 《含能材料》2006,14(2):158-158
基于简单的量子化学计算,提出一种快速、方便、准确地预测高能化合物晶体密度的新方法。由计算所得密度和生成热,预估化合物的爆速和爆压,形成定量地进行高能量密度材料(HEDM)分子设计的有效手段。选择了已有实验晶体密度的32种高能化合物(DNU,DATNTAN,TNAZ,DNCP,DNDC,RDX,TNTACH,β-HMX,DNFP,TN650,TN550,DINGU,TNGU,BCHMX,TNAD,cis1357TNAD,trans1357TNAD,(r,r)-TNBI,TNSD,TNSU,TNDBN,TNPD,HHTDD,TNTriCB,TNCB,N-DNAT,TEX,ε-HNIW,HANA,ONC,DNBF和TNT),采用量子化学中四种半经验分…  相似文献   

3.
有机叠氮化物几何构型和生成热的分子轨道研究   总被引:4,自引:2,他引:2       下载免费PDF全文
用AM1、PM3、MND烽MINDO/3四种半经验分子轨道(MO)方法对55种有机叠氮化合物的分子可构型进行了全优化计算,与已有的气相实验构型进行比较,发现AM1法偏差较小,PM3和MNDO次之。AM1法计算所得生成热与基团加和法求得的结果最接近,MINDO/3计算结果偏差最大。  相似文献   

4.
FOX-7或1.1-二氨基-2.2-二硝基乙烯是一种低感度和高性能的新型炸药。本文报道了它的合成,感度(摩擦落锤和SSGT),热稳定性和相容性,以及它的结晶密度,ρ=1.885g/cm^3(粉末X-射线)和它的生成热。AHf=-32kcal/mole(弹式量热法)。相容性的测量用微热量计进行测量,并且显示与聚合物,增塑剂和二异氰酸盐的相容性极佳。用DSC测量活化能(Ea=58kcal/mole)用伍德合金浴测量点火温度(Tign=205℃)。为了说明根据实验观测到的相容性和感度的数据。我们进行了量子力学计算(从B3LYP/6-3l C**级开始)。量子力学(QM)的计算也与X-射线测定的长度和角度相同。用热化学符号(Cheetah 1.40)和实验测得的密度和生成热值计算爆速和爆压(DCJ=8870m/s,pCJ=34.0GPa)。  相似文献   

5.
以3-氰基~(-1),2,4-三唑为原料,经肟化、重氮化-氯化、硝解、还原、氟化等反应合成了一种含氟偕二硝甲基官能团的新型含能化合物——3-氟偕二硝甲基~(-1),2,4-三唑(FDNMT),利用红外光谱、核磁(~1H NMR、~(13)C NMR)、元素分析和质谱等方法表征了化合物的结构;优化了肟化反应的合成条件:3-氰基~(-1),2,4-三唑和盐酸羟胺摩尔比为1∶1.15,p H值为8,反应时间为2 h,反应温度为60℃,收率为49.0%;获得了FDNMT的单晶并进行了晶体结构解析,该化合物晶体为正交晶系,空间群为Pbcn,晶体学参数为:a=7.4821(11),b=9.8106(15),c=38.683(6),V=2839.5(7)~3,Z=16,μ=0.178 mm~(-1),F(000)=1536;采用Gaussian 09程序中的CBS-4M方法计算了该化合物的生成热,基于密度和计算的生成热,利用Kamlet-Jacobs爆轰方程预估该化合物的爆轰性能:密度1.81 g·cm~(-3),生成热-8.7 k J·mol~(-1),爆速8365.0 m·s~(-1),爆压31.1 GPa,爆热为5614.4 k J·kg~(-1)。  相似文献   

6.
王霆威  李燕  陈东  张祺  朱顺官 《含能材料》2019,27(12):1031-1035
以3-氨基-1H-1,2,4-三氮唑-5羧酸为原料首次合成不对称结构的联三唑类富氮含能化合物3-氨基-3′-硝胺基-5,5′-联-1H-1,2,4-三唑(3),并通过红外,核磁,质谱等表征产物结构。采用差示扫描量热─热重分析联用法研究了其热稳定性和分解历程。结果表明,化合物3的分解温度达到160℃;利用氧弹量热仪测得标准摩尔燃烧焓Δ_CH_m~θ为-1952.25 kJ·mol~(-1),根据Hess定律计算得标准摩尔生成焓Δ_fH_m~θ=-336.245 kJ·mol-1,采用粉末密度仪测得粉末密度为1.6137 g·cm~(-3),用EXPLO 5程序预测爆压为9.6 GPa,爆速为5745.5 m·s~(-1),撞击感度为80 J,摩擦感度为360 N,表明该物质是一种新型不敏感含能材料。  相似文献   

7.
根据制备过程,提出了配合物Cu(TO)2Cl2在混合溶液中的晶体生长的动力学模型。通过这个动力学模型,测定了一系列的动力学参数Ea=45.37kJ·mol-1,ln(A/s-1)=14.65,Δ≠Gm=82.11kJ·mol-1,Δ≠Hm=42.85kJ·mol-1,Δ≠Sm=131.58J·mol-1·K-1。另外,用RD496-Ⅲ型微量热计测定了该化合物在298.15K时的比热容,并计算了[Cu(TO)2]2 (aq)和Cu(TO)2Cl2(s)的标准生成焓。  相似文献   

8.
高通量含能分子设计需要兼顾准确性与效率的性能预测方法。结合原子化方案,对常见的3种不同水平的理论方法(半经验PM6方法、密度泛函理论方法B3LYP/6-31G(d,p)和高精度的完全基组CBS-4M方法)用于高通量含能分子设计筛选的生成焓(HOF)计算适宜性进行了评估。计算并比较了20种含能分子的固相HOF,发现不同理论水平预测结果存在较大差异;而基于10种常见含能分子的不同水平下的HOF,实验密度和Kamlet-Jacobs(K-J)、Becker-Kistiakowsky-Wilson(BKW)与Virial-Wu (VLW)3种模型预测的爆轰性能差别不大。其中B3LYP方法具有最佳适宜性,具有较高的计算效率且爆轰性能预测结果同CBS方法接近,如基于BKW模型计算的爆速和爆压的平均相对偏差仅为0.4%和1.2%。而低精度的PM6方法和高耗时的CBS方法难以满足兼顾高通量含能分子设计筛选中的精度和效率的要求。这表明,在高通量的含能分子设计筛选中,可考虑中等精度的方法进行快速的HOF预测。  相似文献   

9.
采用密度泛函理论B3LYP/6-31G*方法研究了季戊四醇的五个结构相似的硝酸酯基(-ONO2)和叠氮基(-N3)衍生物,包括四叠氮基季戊烷( TAPE)、三叠氮基季戊醇硝酸酯( PTAN)、二叠氮基季戊二醇二硝酸酯( PDADN)、叠氮基季戊三醇三硝酸酯( PATN)和季戊四醇四硝酸酯( PETN)。优化了分子几何构型。进行了振动分析。估算了密度、生成热、热力学函数、爆轰性能和比冲。计算了可能的热解引发键的键离解能( EBD )和氢转移反应的活化能( Ea )。结果表明,与PTAN 、PDADN、 PATN和 PETN比较,TAPE的生成热最大,比冲与PETN相当。 PATN的爆轰性能和稳定性与PETN接近,优于其它衍生物,包括PDADN。含-N3的TAPE的热解由氢转移导致-N3热裂解放出N2引发,其Ea 为130.57 kJ· mol-1。含-ONO2的其它衍生物的热裂解均由O-NO2键断裂开始, EBD为130.91~137.45 kJ· mol-1。这些能量值满足高能化合物的稳定性指标要求。  相似文献   

10.
含能材料理论设计中的几个问题(英)   总被引:1,自引:1,他引:0  
舒远杰  李华荣  熊鹰  周阳  钱文 《含能材料》2013,21(2):166-172
理论方法在新型含能材料的设计和研发中起到非常重要的作用。本研究介绍了含能材料理论设计中所遇到的问题,如从微观上估算含能化合物的密度、生成热、稳定性及爆轰性能等。并讨论了含能聚合物界观参数的计算方法:1) 基于优化的分子结构,求得含能金属配合物分子周围的电子云包覆体积,然后由公式求得包覆密度作为其晶体密度近似值; 2) 含能化合物的生成热根据原子化方案,进行数值计算; 3) 以五种小分子氮氢化合物和六种四嗪化合物的热分解机理为例,阐述采用将从头算分子动力学(ab initio MD)和从头算分子轨道理论(ab intio MO)结合起来研究含能化合物热分解机理的可靠性; 4) 含能材料的爆轰性能, 基于各个元素的Lennard-Jones势参数等,由反应物及产物的VLW状态方程,进行数值求解; 5) 采用DPD方法可用于研究含能聚合物的界面性质。上述性能的计算可为新型含能材料的探寻提供有价值的信息。   相似文献   

11.
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.  相似文献   

12.
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.  相似文献   

13.
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.  相似文献   

14.
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.  相似文献   

15.
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.  相似文献   

16.
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.  相似文献   

17.
An expression for estimating the aeroheating on a warhead nose at different supersonic speeds is proposed by incorporating CFD (computational fluid dynamics) and the least-square method. Compared with the traditional estimation formula, the expression is more accurate, convenient and can be used in the optimized design of warheads. The error from the result obtained in the test of a ball cartridge flight is less than 3 %. It satisfies the engineering requirements.  相似文献   

18.
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.  相似文献   

19.
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.  相似文献   

20.
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.  相似文献   

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