以3-甲酰胺基-5-氨基-1, 2, 4-1H-三唑为原料,经缩合、环化、酯化、氨化和氧化等反应获得目标化合物3-氰基-5-氨基-1,2,4-1H-三唑（ATCN）,通过优化制约合成工艺的氧化反应体系、反应温度以及反应时间,将收率由文献值37.0%提高至81.6%。采用核磁共振（NMR）、红外吸收（IR）和元素分析等手段表征了结构,通过差示扫描量热法（DSC）和原位红外技术研究ATCN热分解和热裂解特性,并进行热分析动力学计算。结果表明,ATCN第1个热分解峰值温度为163.01℃,对应为氨基和氰基的断裂;第2个热分解峰值温度为244.29℃,对应为三唑环结构的裂解。此外,通过热力学参数计算获得ATCN第1个热分解过程的活化能、活化焓、活化吉布斯自由能和活化熵分别为156.21、153.26、109.80 kJ·mol -1 和103.40 J·K -1 ·mol -1 。

The solubilities of energetic material N-nitrodiethanolamine dinitrate (DINA) were measured in ten commonly used pure organic solvents including methanol, ethanol, ethyl acetate, dichloromethane, acetone, dimethyl sulfoxide, 1,4-dioxane, toluene, 1,2-dichloroethane, and acetonitrile and three binary mixed solvents between 283.15 and 313.15 K by the gravimetric method. The solubility of DINA showed a temperature dependence for all test solvents. The experimental mole fraction solubility data were correlated with a simple Apelblat equation, showing a good fitting between the experimental data and Apelblat equation. The order of the solubility of DINA was 1,2-dichloroethane > acetone > 1,4-dioxane approximate to acetonitrile > ethyl acetate approximate to dichloromethane > methanol + acetone > ethanol + acetone > ethanol + ethyl acetate > dimethyl sulfoxide > toluene > methanol approximate to ethanol. Particularly, 1,2-dichloroethane, acetone, and 1,4-dioxane were preferred as the cooling recrystallization solvents for DINA, while toluene, methanol, and ethanol could be considered for the antisolvent method. All of the obtained results would benefit the purification and crystallization of DINA, which would extend its applications in the field of pyrotechnics.

Laser Raman spectroscopy is an in-situ non-destructive fast detection technology,which has significant application prospects in the field of explosives analysis and detection.Research progress on the applications of conventional laser Raman spectroscopy and its derivative techniques including Fourier transform Raman spectroscopy (FT-Raman),confocal micro Raman,surface enhanced Raman scattering(SERS),portable Raman and remote Raman in the field of explosives analysis were reviewed.The advantages and limitations of different type of laser Raman spectroscopic techniques were analyzed.The laser Raman spectra data of several typical explosives such as TNT,CL-20,HMX,PETN and RDX were compared.It is considered that the future research should focus on the establishment of Raman quantitative analysis methods for explosives,the preparation of high-performance substrate materials for surface enhanced Raman and the improvement of portable Raman spectroscopy.

针对硝化甘油生产过程中硝化酸检测存在安全隐患和检测时间长的问题,采用近红外光谱技术研究了硝化酸的快速检测方法,建立了硫酸、硝酸和硝化甘油组分的定量模型并进行了应用验证,并与化学分析法进行了对比.结果 表明,所建模型的交互验证决定系数(R2)分别为0.966 6、0.958 5和0.9791,交互验证的均方根误差(RMSECV)分别为0.195％、0.329％和0.064％,外部验证的均方根误差(RMSEP)分别为0.271％、0.388％和0.121％.显著性检验(t(H2SO4)=0.59,t(HNO3)=1.64,t(NG)=1.59)表明,在显著水平为0.05时,近红外光谱法与化学分析法无显著差异.每个样品的检测时间统计不超过2 min.表明该方法快速、准确,能够满足硝化甘油在线质量检测和自动化生产的要求.

Aiming at the disadvantages of traditional preparation of gunpowder samples,e.g.,low safety,time-consuming,and easy to contaminate samples,etc.,a rapid gunpowder samples preparation device has been developed.The device consists of the main body and remote console.To realize man-machine isolated operation,the remote console controls the main body through shielded cable. The programmable logic controller(PLC)is used as the core of control,for driving step-motor,implementing logical control,and data communication;the configuration software KingVIEW is applied to build up the human-computer interface,which is combined with the pan-and-tilt camera to form an independent monitoring system by means of the display and operating functions of the touch screen.The tests prove that by setting different spindle rotation speeds and lateral movement speeds,it is possible to achieve controllable and uniform particle size of the cutting device,effectively shortening the sample preparation time, and significantly improving the efficiency.The sample preparation process has less manual operations,the sample exposure time is short,and the sample is not easy to be contaminated.Compared with the traditional preparation method of the gunpowder sample,it is a safe and efficient new device for rapid preparation of gunpowder samples.

Considering the shortcomings of existing measurement systems for propellants,a grating ruler-based dimensional measurement system for propellants was developed and its overall structure and the operating principle were provided.The measuring result verified by standard 2/1 Zhang propellants shows that,as compared to the traditional dimensional measurement system,no obvious difference exists between them and the resolution of the system developed is 1μm along with the measuring ranges from 0.02 to 100mm.

Nano-CuO was prepared using polyethylene glycol (PEG) as template.Nano-Al/CuO composite was prepared by self-assembling using a kind of polymer as coating material.The structure and morphology of the composite were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectrometer (EDS), X-ray diffraction (XRD), etc.The thermal properties of samples prepared by self-assembling method (with coating materials) and ultrasonic blending method (without coating materials) were studied and compared by thermogravimetry (TG) and differential scanning calorimetry (DSC).Exothermic quantity of the composite with different Al-CuO molar ratio was investigated.Results show that the exothermic peak occurring the thermite reaction of nano-Al and CuO is at about 576.4℃ and the exothermic quantity is 1093J/g.The composite with coating material has a higher exothermic quantity than that without coating material.The exothermic quantity of the thermite reaction is a maximum, reaching 1093 J/g when the molar ratio of Al and CuO is 1.0∶1.2.

针对市售标气很难满足实际应用需求的问题,基于质量流量控制器的控制原理,研制一套高精密动态可持续输出的配气系统.给出系统的总体结构及其工作原理,并利用电化学传感器和统计学原理,对该系统的稳定性和准确度进行了考察,结果表明:在30min的考察期内,配气浓度标准偏差小于0.40％,在95％的置信区间内与电化学传感器测定值的准确度相当.

For rapid detection of α‐HMX phase impurity content in HMX ,based on the preparation of samples for building model ,the mathematical model between HMX spectra and α‐HMX impurity phase content was established with partial least squares (PLS) method using near infrared spectroscopy technique .The representativeness of sam‐ples for building model ,the selection of the spectral range and the optimization process of the model were discussed . The results show that the model has a broadly representativeness ,the prefered spectral ranges are 6476-6446 and 4602-4424cm -1 ,the correlation coefficient of cross‐validation is 0 .996 ,the root mean square error of cross‐vali‐dation(RMSECV) is 0 .20% ,and the root mean square error of prediction (RMSEP) of external‐validation is 0 .27% .The error of the method is less than 0 .13% and the standard deviation is 0 .1% .The method has the ad‐vantages of simple operation ,rapid ,non‐destructive and green enviromental protection ,and can be used to detect the α‐HMX phase impurity content in HMX .

Aiming at the factors bothering the quantitative analysis of the active metal powder,a PLC-based quantitative analysis system was developed,which has PPI communication protocol adopted to implement the master-slave communication between the computer and PLC and to demonstrate the metal powder activity through the gas content calculated by testing the gas pressure and temperature in the reaction tank.

To evaluate the effect of environmental humidity on the stability of AlH3 ,the hygroscopic hydrolysis process of AlH3 was studied by dryer balance method and dynamic hygroscopic analysis method.The isothermal hygroscopic curves and the critical relative humidity (CRH)at different temperatures were obtained.AlH3 and its hydrolytic products under the conditions of different environmental humidity were characterized by scanning electron microscopy (SEM),X-ray diffraction (XRD)and organic element analyzer.Results show that when the environ-mental humidity is lower than critical relative humidity,the stability of AlH3 is better,whereas when the environmental humidity is greater than critical relative humidity,an obvious hydrolysis reaction appears in AlH3 and the Al(OH)3 gradually generates at the AlH3 crystal surface.At the same time,the critical relative humidity of AlH3 is inversely proportional to environmental temperature.

建立气相色谱法测定某点火剂中三乙基硼含量的方法.由于三乙基硼化学活性高,定量困难,采用惰性氛围控制和溶剂稀释的方式,以甲苯为稀释溶剂,三乙基硼可与溶剂很好地分离,并在5～50 mg/mL范围内呈现良好的线性,相关系数r=0.9992,方法的检出限为0.16 μg/mL.采用外标法定量,测定三乙基硼标准溶液的回收率为99.13％～100.19％,测定结果的相对标准偏差小于2％(n=7).该方法可用于点火剂中三乙基硼含量的质量控制.

为了实现对温压战斗部及其装药的毁伤评估,采用静爆实验对某温压战斗部静爆耗氧量进行了试验研究,得到环境中氧气浓度-时间动态曲线.根据试验条件下温压战斗部的耗氧量及耗氧持续时间,分别对装药的能量释放效率以及战斗部毁伤威力进行了评估.结果表明,温压战斗部装药能量释放效率和毁伤威力分别是高聚物粘结炸药(PBX)战斗部的1.13倍和1.55倍,与利用冲击波、温度等参数评估结果相当.

A signal acquisition system for near-infrared spectrometer based on digital envelope demodulation technique were designed and implemented,which is simple and flexible for the handling of digital signal. In the system designed,CPLD EPM240T100C5 N,which has enough I /O ports for the system expansion and generates timing pulse to control ADS8505,was applied; STC89LE54 RD + was used as the microcontroller. Quartus II development environment was used to design the CPLD internal program. Two tests of the influence of sampling period number to S /N and the influence of? sampling points number of single cycle to S /N,were designed for detecting and verifying of the system. Compared with the phase-sensitive detection,this method is simple and flexible,greatly retrenched the circuit of the spectrometer and reduced the debugging steps.

To deposit alumina thin films on ammonium dinitramide (ADN) by atomic layer deposition (ALD), trimethylaluminum and water were used as the precursors. The surface morphology and chemical compositions of the ALD alumina coated ADN were characterized by scanning electron microscope (SEM) and X-ray photoelectron spectroscope (XPS). The hygroscopic property of the ALD alumina coated ADN was studied by a vapor adsorption analyzer (VSA). The possible mechanism of ALD alumina film growth on the surface of ADN was discussed. The characterization results indicate that the ALD alumina film completely covers the surface of ADN. The thickness of the alumina film can reach hundreds of nanometers. After 48 h of air exposure, the shapes and topologies of the alumina coated ADN particles are maintained. The hygroscopicity of the ADN samples coated by 200 and 400 cycles of ALD alumina are 40.99% and 40.75%, respectively. Although the ALD alumina coating completely covers the surface of ADN and successfully maintains the shapes and topologies of ADN particles in a wet environment, the hygroscopicity of the ALD alumina coated ADN is not improved.

Through the study on near infrared diffuse reflectance spectroscopy for 107 kinds of nitrocellulose (NC) samples and their reference value of nitrogen content in NC,the mathematical model for the determination of nitrogen content in NC was established with Partial Least Squares (PLS)method.The results by pairt-test were compared with those by chemical analysis method.Results show that the correlation coefficient of cross-validation (R2 )is 0.998 1 and the Root-Mean-Squares Error of Cross-Validation (RMSECV)is 0.026%.The Root-Mean-Square Error of Predication(RMSEP)of external-validation is 0.023%.The results by pairt-test show that there is no obvious difference between NIR method and the chemical analysis method.NIR method can make the analyzation time shorten to 3 min and can replace chemical analysis method.

建立了HPLC法检测茚-C60双加成物(ICBA)纯度及异构体比例.实验条件:色谱柱cosmosil Buckyprep (4.6 mm I.D.×250 mm),检测波长245 nm,流动相为V(四氢呋喃):V(乙腈)=80∶20(测纯度)或66∶34(测异构体比例),试样用THF溶解.结果表明:ICBA纯度检测在32.3～290.8μg/mL范围内有良好的线性关系(R2=0.9955),定量限为2.4 μg/mL,回收率为99.7％～100.2％,RSD为1.8％(n=6);能检测出11个异构体,含量较多的10个异构体比例的RSD小于1.0％(n=6).分离机理主要是疏水效应和“π-π”作用.从ICBA、茚-C60单加成物(ICMA)、C60的光吸收图谱可以看出,随着茚加成数量的增加,有效光吸收范围变小,故不能为改善溶解性一味增加茚的加成数量.其中异构体7含量较高,且有效吸光范围较宽,与ICMA相似,推测其双茚的夹角较尖锐,较少破坏C60的共轭结构,从而较少破坏其电子亲和能,预估其光电性能较优.

The nitrogen content in nitrocellulose was determined by using the Vario MACRO cube element analyzer. The design of two stage combustion tubes made with stainless steel assures the complete combustion of nitrocellulose under large sample amounts and the safety of combustion. The maximum sample amount can reach 85 mg. The method possesses the advantages such as simplicity, rapidity, high degree of automation, high accuracy of results, and so on.

This paper reviews on the applications of Raman spectroscopy in the identification of explosive.The characteristics of the Raman spectrum used in explosive identification are explained and the technology applied in explosive structure characterization,remote probing and identification of trace explosive residues is analyzed.We put forward the prospects of Raman spectroscopy in the fields of rapid detection,trace detection,quantitative detection and remote detection aiming at the urgent demands of national defense,security inspection,criminal investigation and emergency incidents.

The method was established for determining the components of organic impurity without the self-reference material(RM) by GC–FID.The signal of GC–FID was caliberated with the compound whose structure was similar with the organic impurity to be determined,and after the mass response(Si) of GC–FID of the impurity counted by ECN,the components of impurity in sample were determined.DBS purity RM as the example,the sum of organic impurities in DBS RM was(0.29±0.07)%(k=2).The major sources of uncertainty of measurement were Si and the repeatability.