硝基化合物热力学性质的估算(Ⅰ)

硝基化合物是常用的含能材料,其生成热的估算具有重要的意义.本文根据次级基团加和法的原理,提出了硝仿基的基团生成热值及各种情况下邻位和间位硝基之间相互作用的能量修正值;应用这些值对脂肪族硝基化合物的生成热进行了估算,取得了满意的结果,其拟合方程的回归系数达到0.997 0.     

CL—20及CL—20推进剂的燃烧研究

ＣＬ—２０及ＣＬ—２０推进剂的燃烧研究六硝基六氮杂异伍兹烷（Ｃ６Ｈ６Ｎ１２Ｏ１２）即ＣＬ—２０是一种高密度多环硝胺立体笼形化合物。与ＨＭＸ相比，它具有较高的密度和生成热。由于其结构之中不含有卤素，因而其燃烧产物呈现最小的信号特征，且与ＡＰ相比它对环境...     

国外高能量密度材料与目标化合物CL—20的进展

介绍了国外高能量密度材料(HEDM)发展的新动态。以多硝基/硝胺基多环化合物和主体笼形化合物等的开发研究作为契机,HEDM发展进入了一个新的阶段。CL-20即六硝基六氮杂异伍兹烷(HNIW)是一个很有前途的多环硝胺主体笼形化合物,本文着重评述它的结构、性能、应用及合成途径。认为通过它的六氮杂前驱物体系的基团转化而引入硝基的途径是可取的。     

二(2,2-二硝基丙基)硝胺的合成及热性能

以2,2-二硝基丙醇为原料,经缩合、硝化反应合成了二(2,2-二硝基丙基)硝胺(BDNPN)。用红外光谱、核磁共振、元素分析对中间体及目标化合物的结构进行了表征。优化了反应条件,硝化反应的最佳条件为nBDNPA:nHNO3=1∶30,反应温度为50℃,反应时间为1 h,收率92.1%。用DSC和TG-DTG考察了目标化合物的热性能。结果表明,BDNPN的热分解峰温为212.3℃,具有较好的热稳定性。     

硝基立方烷及其氮杂衍生物的能量特性计算研究

硝基立方烷及其氮杂衍生物是高能量密度材料的重要目标化合物类型之一。据此详细计算分析了硝基立方烷（从二硝基到八硝基立方烷）和四硝基四氮的杂立方烷分别在产单元推进剂，ＨＴＰＢ／Ａｌ，ＰＥＧ／ＮＧ／Ａｌ，ＧＡＰ／ＮＧ／Ａｌ体系中的能量特性。结果表明，硝基取代数大于４的立方烷和四硝基四氮杂立方烷的能量特性明显优于ＨＭＸ。     

燃烧催化剂苯甲酸铜盐及其衍生物的热分解研究(Ⅱ)──双取代基苯甲酸铜盐的热分解机理

羟基氨基苯甲酸铜、二羟基苯甲酸铜、二硝基苯甲酸铜和对硝基苯甲酸铜的DSC和TG热分解研究表明，与苯甲酸铜一样，它们分解都生成一种稳定的二聚作中间产物──双核铜五元环络合物，前二者还能生成一种八元环二聚体络合物。芳香基上由于引入硝基，使主要分解反应阶段由吸热效应变成放热反应，具有二个硝基取代基者，这种放热效应较只有一个硝基者更强烈。本文还初步探讨了苯甲酸铜及其衍生物分解历程与双基推进剂燃烧过程催化效果的关系。     

1,5-二氨基四唑含能配合物的制备、表征及其催化性能研究

合成出2种以1,5-二氨基四唑(DAT)为配体,苦味酸根为外界,钴和铜为中心离子的含能配合物,并对其结构进行了表征.运用示差扫描热分析(DSC)方法,就目标化合物对高氯酸铵(AP)、奥克托金(HMX)和六硝基六氮杂异伍兹烷(HNIW)热分解的影响进行了研究.利用电荷耦合器件(CCD)燃速测定系统,研究了目标化合物对缩水...     

FOX-7的热分解机理

采用热原位红外、热裂解色谱-质谱、热重分析(TG)、差示扫描量热法(DSC)研究了FOX-7的热分解过程,通过测定程序升温过程中凝聚相的化学结构变化和生成的气相产物,研究了FOX-7的热分解机理。研究结果表明,FOX-7在转晶后可能发生了缩合反应,使其处于缩合产物的平衡状态,随着温度的升高该平衡被打破,FOX-7开始分解成一些小官能团产物和小分子产物;气相产物中首先检测到NO,说明热分解的"脱硝"过程存在硝基与亚硝基互变反应过程。     

侧链含硝基氮杂基团的聚醚粘合剂的性能及应用：新型硝基粘合剂…

对新型的侧链含硝基氮杂基团的富能聚醚粘合剂－端羟基２－甲硝胺基乙基缩水甘油醚均聚醚和端羟基共聚醚的性能进行了研究。结果表明，ＮＰＥ的热稳定性和化学稳定性良好，优于普通碳氢聚醚粘合剂和新型氟碳聚醚粘合剂；其固化后的力学性能好。简要地叙述了以ＮＰＥ－Ｂ为粘合剂的固体火箭推进剂的配方和性能。     

5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4-三唑(DNAT)的合成和性能研究

以3,5-二氨基-1,2,4-三唑为原料,经过重氮化、选择性还原、酸性氧化3步,合成出目标化合物5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4三唑(DNAT),通过红外光谱、元素分析、质谱分析进行了结构鉴定,并进行了DSC-TGA、燃烧性能分析、感度测试等性能研究.实验结果表明,5,5'-二硝基-3,3'-偶氮基-1-氢-1,2,4-三唑(DNAT)化合物具有密度高(1.88 g/cm3)、正的生成焓(446.448 kJ/mol)、热稳定性能好的特点,是一种性能良好的高氮含能化合物.     

载人飞船密封舱漏热问题研究

密封舱漏热是载人飞船热控系统设计中必须考虑的一个关键因素,是影响飞船热平衡和舱内温度的一项重要参数。建立了求解密封舱漏热的热物理模型,分析了各种参数对密封舱漏热的影响。结果表明：（1） 在一定温度范围内,密封舱漏热与舱内空气温度近似呈线性关系;（2） 返回舱漏热高于轨道舱,主要原因是导热热阻的基数偏小;（3） 漏热随外热流增大而减小,返回舱漏热波动较大,调节其热控涂层的α_S和ε_h值将导致返回舱漏热和漏热波动出现相反变化,为同时减小漏热和漏热波动,推荐采用较低α_S和ε_h 值的热控涂层;（4） 返回舱漏热受舱内壁对流换热系数影响较大,特别在2W/(m^2·K)附近。
     

C／C复合材料石墨化度的测定和评价

用Ｘ射线衍射方法对不同热处理温度下Ｃ／Ｃ复合材料石墨化度进行了测定，并对衍射峰进行了分峰处理。得出该材料由三种不同组元构成，即树脂炭，碳纤维和热解炭，求出各组元的石墨化度值及所占比例，进而得到试样的加权平均石墨化度。     

TG-DSC-IR-MS联用研究RDX-CMDB推进剂催化热分解

采用热重-差示扫描量热-红外-质谱(TG-DSC-IR-MS)联用技术,研究了三元复合燃速催化剂(2,4二羟基苯甲酸铅、对氨基苯甲酸铜和炭黑)对RDX-CMDB推进剂热分解的作用,并比较了纳米和普通催化剂作用效果的差异.结果表明,该复合燃速催化剂使RDX-CMDB推进剂热分解特征量发生明显变化;改变了推进剂中RDX的初期热分解机理,使放热的CN 键断裂在与吸热的NNO2 键断裂的竞争反应中占优;也使双基组分放出有负生成热的CH2O的相对量增加,分解过程放热量或放热速度提高,促进了燃速的提高.与普通催化剂相比,纳米催化剂作用效果更好.     

Abiotic synthesis of organic compounds from carbon disulfide under hydrothermal conditions

Abiotic formation of organic compounds under hydrothermal conditions is of interest to bio, geo-, and cosmochemists. Oceanic sulfur-rich hydrothermal systems have been proposed as settings for the abiotic synthesis of organic compounds. Carbon disulfide is a common component of magmatic and hot spring gases, and is present in marine and terrestrial hydrothermal systems. Thus, its reactivity should be considered as another carbon source in addition to carbon dioxide in reductive aqueous thermosynthesis. We have examined the formation of organic compounds in aqueous solutions of carbon disulfide and oxalic acid at 175 degrees C for 5 and 72 h. The synthesis products from carbon disulfide in acidic aqueous solutions yielded a series of organic sulfur compounds. The major compounds after 5 h of reaction included dimethyl polysulfides (54.5%), methyl perthioacetate (27.6%), dimethyl trithiocarbonate (6.8%), trithianes (2.7%), hexathiepane (1.4%), trithiolanes (0.8%), and trithiacycloheptanes (0.3%). The main compounds after 72 h of reaction consisted of trithiacycloheptanes (39.4%), pentathiepane (11.6%), tetrathiocyclooctanes (11.5%), trithiolanes (10.6%), tetrathianes (4.4%), trithianes (1.2%), dimethyl trisulfide (1.1%), and numerous minor compounds. It is concluded that the abiotic formation of aliphatic straight-chain and cyclic polysulfides is possible under hydrothermal conditions and warrants further studies.     

Effect of variable thermal properties of the solid phase on composite solid propellant combustion

Effects of variable thermal properties (specific heat and thermal conductivity) of the solid phase on the combustion of composite solid propellants are studied analytically. Both steady and unsteady burning are considered. It is shown that the effects of variable thermal properties are small and can be accounted for by choosing proper average values of specific heat and thermal conductivity.     

Effect of variable solid phase thermal properties on propellant combustion

Mathematical models derived for describing the combustion of solid rocket propellants have in the past assumed that the thermal properties, specific heat, and thermal conductivity are constant throughout the solid phase portion of the combustion zone. The values for specific heat and thermal conductivity can vary as much as 50–100 percent for the temperatures in the solid phase combustion wave, values from about 250 to 1100 K. Thus, the variation in solid phase properties due to the temperature variation in the solid phase have significant effects on the burning rate, the temperature sensitivity and the pressure coupled response. The paper is concerned with predicting the effect of the variable solid phase properties on the combustion properties. Parametric calculations were made to illustrate the effect of the magnitude of the variation of solid phase properties with temperature. The results indicate that significant differences exist between the values for the combustion parameters calculated using variable thermal properties as compared to those calculated using constant thermal properties.     

热处理工艺对2A70铝合金自由锻件力学性能的影响

研究了不同热处理工艺参数对2A70铝合金自由锻件力学性能的影响。首先采用正交试验分析了各因素对两个目标值(抗拉强度、延伸率)的影响;然后利用极差分析方法分析试验结果,指出各个因素对力学性能影响的主次顺序,并确定最优的热处理生产条件。试验结果表明:通过锻件锻后增加退火处理、适当提高固溶温度和选用合适的时效保温时间,该合金的力学性能得到了较大的改善,在保证抗拉强度大于等于375MPa要求的同时,延伸率由4%提高到了8.5%。     

The determination of ice composition with instruments on cometary landers

The determination of the composition of materials that make up comets is essential in trying to understand the origin of these primitive objects. The ices especially could be made in several different astrophysical settings including the solar nebula, protosatellite nebulae of the giant planets, and giant molecular clouds that predate the formation of the solar system. Each of these environments makes different ices with different composition. In order to understand the origin of comets, one needs to determine the composition of each of the ice phases. For example, it is of interest to know that comets contain carbon monoxide, CO, but it is much more important to know how much of it is a pure solid phase, is trapped in clathrate hydrates, or is adsorbed on amorphous water ice. In addition, knowledge of the isotopic composition of the constituents will help determine the process that formed the compounds. Finally, it is important to understand the bulk elemental composition of the nucleus. When these data are compared with solar abundances, they put strong constraints on the macro-scale processes that formed the comet. A differential scanning calorimeter (DSC) and an evolved gas analyzer (EGA) will make the necessary association between molecular constituents and their host phases. This combination of instruments takes a small (tens of mg) sample of the comet and slowly heats it in a sealed oven. As the temperature is raised, the DSC precisely measures the heat required, and delivers the gases to the EGA. Changes in the heat required to raise the temperature at a controlled rate are used to identify phase transitions, e.g., crystallization of amorphous ice or melting of hexagonal ice, and the EGA correlates the gases released with the phase transition. The EGA consists of two mass spectrometers run in tandem. The first mass spectrometer is a magnetic-sector ion-momentum analyzer (MAG), and the second is an electrostatic time-of-flight analyzer (TOF). The TOF acts as a detector for the MAG and serves to resolve ambiguities between fragments of similar mass such as CO and N2. Because most of the compounds of interest for the volatile ices are simple, a gas chromatograph is not needed and thus more integration time is available to determine isotopic ratios. A gamma-ray spectrometer (GRS) will determine the elemental abundances of the bulk cometary material by determining the flux of gamma rays produced from the interaction of the cometary material with cosmic ray produced neutrons. Because the gamma rays can penetrate a distance of several tens of centimeters a large volume of material is analyzed. The measured composition is, therefore, much more likely to be representative of the bulk comet than a very small sample that might have lost some of its volatiles. Making these measurements on a lander offers substantial advantages over trying to address similar objectives from an orbiter. For example, an orbiter instrument can determine the presence and isotopic composition of CO in the cometary coma, but only a lander can determine the phase(s) in which the CO is located and separately determine the isotopic composition of each reservoir of CO. The bulk composition of the nucleus might be constrained from separate orbiter analyses of dust and gas in the coma, but the result will be very model dependent, as the ratio of gas to dust in the comet will vary and will not necessarily be equal to the bulk value.     

某卫星真空热试验中一些新要求的解决措施

某卫星在进行真空热试验时,对热流提出了三个方面的新要求：(1)对某些热流要求较低的加热区的加热笼进行修改,提高其低热流实现能力;(2)减小支架漏热;(3)实时计算设计热流和实际热流的周期积分偏差。由于修改时的约束条件较多,新的要求的满足非常困难。经过努力,最终解决了这些问题,通过对某些加热笼采取加热带双面涂黑漆的方法,实现了低热流;经过计算和针对性的设计,支架漏热不超过0．1188W;同时实现了设计热流与实际热流周期积分偏差的实时计算。     

Elucidation of an iterative process of carbon-carbon bond formation of prebiotic significance

Laboratory experiments carried out under plausible prebiotic conditions (under conditions that might have occurred at primitive deep-sea hydrothermal vents) in water and involving constituents that occur in the vicinity of submarine hydrothermal vents (e.g., CO, H(2)S, NiS) have disclosed an iterative Ni-catalyzed pathway of C-C bond formation. This pathway leads from CO to various organic molecules that comprise, notably, thiols, alkylmono- and disulfides, carboxylic acids, and related thioesters containing up to four carbon atoms. Furthermore, similar experiments with organic compounds containing various functionalities, such as thiols, carboxylic acids, thioesters, and alcohols, gave clues to the mechanisms of this novel synthetic process in which reduced metal species, in particular Ni(0), appear to be the key catalysts. Moreover, the formation of aldehydes (and ketones) as labile intermediates via a hydroformylation-related process proved to be at the core of the chain elongation process. Since this process can potentially lead to organic compounds with any chain length, it could have played a significant role in the prebiotic formation of lipidic amphiphilic molecules such as fatty acids, potential precursors of membrane constituents.