采用高能氧化剂ADN部分代替AP,分别设计了AP/RDX、AP/RDX/Al、ADN/AP/RDX、ADN/AP/RDX/Al四种组分体系,利用差示扫描量热技术,研究ADN与高能组分的相互作用,尤其是对组分体系放热量的影响.结果表明,ADN的加入使ADN/AP/RDX组分体系的放热量增加了1.6倍,使ADN/AP/RDX/Al组分体系的放热量增加了1.68倍.同时,采用热-红-质联用技术,通过对分解产物的结构鉴定及整个过程中红外光谱强度和质谱质子流强度变化规律的研究,发现ADN的加入导致组分体系热分解反应生成更多的标准摩尔生成焓小的生成物,使得热分解反应的焓值更小,放热量增加.

为研究NEPE推进剂在诱发压力载荷作用下的老化性能,在75℃、1 MPa下进行了双应力加速寿命试验,研究了温度和压力对NEPE推进剂燃烧性能、能量性能、力学性能和安全特性的影响;采用交联密度、动态力学性能及扫描电镜分析了NEPE推进剂力学性能的变化机理.结果表明,在75℃、1 MPa下,30 d加速老化过程中,在温度和压力的共同作用下,NEPE推进剂爆热为6007～6192 kJ/kg、燃速为10.36～10.64 mm/s、安定剂质量分数为0.43％～0.48％,均不随老化时间的增加而变化;抗拉强度随老化时间的增加而降低,老化30 d后,抗拉强度由0.612 MPa降至0.433 MPa,变化率29.2％,表明力学性能的变化是推进剂的主要失效模式;温度和压力双应力载荷作用下失效机理为温度使黏合剂降解,交联网络中结点受到破坏及固体颗粒分解引起脱湿,压力的存在强化了脱湿现象,导致力学强度快速下降.

To study the thermal decomposition of dihydroxylammonium 5,5′‑bistetrazole‑1,1'‑diolate (TKX‑50), thermal decomposition experiments such as thermogravimetry and differential scanning calorimetry were carried out, respectively. Meanwhile, MATLAB software was employed to decouple the overlapping parts and the Málek method was used to study the kinetics of the thermal decomposition of TKX‑50. The results show that the thermal decomposition process of TKX‑50 is divided into two stages. The complete thermal decomposition curves of the two stages are obtained by MATLAB software, and the basic parameters such as Tonset, Tp, and ΔH are acquired at different heating rates. The thermal decomposition of TKX‑50 follows the autocatalytic reaction model, and the kinetic parameters including activation energy, pre‑exponential factor and kinetic model are obtained, respectively. For the first stage,Ea=174.99 kJ∙mol-1,lnA=40.75,f(α)=α0.917(1-α)0.509， for the second stage,Ea=149.60 kJ∙mol-1,lnA=31.84,f(α)=α0.357(1-α)0.117.

A new approach to evaluate the stability period of propellant is presented to solve the problems of poor safety,fussy operation and time-consuming of the existing methods for evaluating the stability of propellants.The propellant samples with different stabilizer contents were prepared by thermal accelerated aging test,and the kinetic equation of propellant aging was studied.A quantitative model for the determination of stabilizer content in propellant is established using near-infrared spectroscopy and chemometrics algorithm.The best quantitative model is obtained by analyzing and optimizing the proposed model.Applied results show that the determination coefficient (R2) of the model is 0.999 6,and the maximum predicted error is no larger than 0.04％.It proves that the proposed model can be used for the nondestructive,rapid and real-time evaluation of the stability period of propellant.

采用TG-DSC-FTIR-MS联用技术研究了Al-Li合金粉体燃料对高氯酸铵(AP)热分解特性的影响,探讨了其对AP的催化热分解机理.DSC,TG-DTG曲线表明,Al-Li的存在使得AP的低温分解及高温分解峰温分别降低7.7,11.2℃,分解热ΔH增加35.6%,说明Al-Li对AP的热分解过程有显著的促进作用.通过FTIR,MS对AP及Al-Li/AP的分解气体产物进行表征及对比,二者表现出明显不同.FTIR显示,低温分解过程中,Al-Li/AP相比于纯AP,出现了明显的NH3红外特征吸收;MS显示,高温分解过程中,Al-Li/AP比纯AP明显少了m/z=35(Cl)的离子流.更多还原

采用微热量热仪(HFC)研究了9/7单基发射药的等温热分解动力学和样品质量对其分解的影响.实验结果表明:在热流达到峰值之前,9/7单基发射药热分解可以分成3个阶段,其机理函数均服从Mampel power法则,初期的反应机理为0级,中期为1/2级,后期为2/3级;增加样品的质量会缩短热流达到峰值的时间和反应深度,但是对初期的零级反应没有影响;初期分解的表观活化能Ea=145.5 kJ/mol,指前因子lnA=29.7s-1.

采用-55 ～71 ℃温度循环老化试验,研究了RDX基浇铸高聚物粘结炸药(PBX)老化时,随时间的外观变化、结构完整性、质量/体积变化率、机械感度、力学性能及发射安全性.进行了65,75,85,95 ℃老化试验和老化样扫描电镜(SEM)及动态力学分析(DMA)的研究.结果表明,25个温度循环后,PBX炸药装药内部无可见裂纹和气孔,结构完整性未发生变化,质量/体积变化率小于1％,撞击感度增加到16％,在锤重400 kg和落高3 m的撞击条件下,未发生爆炸,PBX的抗压强度增加、压缩率下降,力学性能显著劣化.65℃恒温老化252 d后,抗压强度增加47.5％,压缩率下降9.8％.随老化时间延长,β松弛的动态力学损耗峰值(tanδ)降低,网络交联程度提高,与填料之间的结合更为紧密,显示后固化交联反应是力学性能劣化的原因之一.

为满足1，1－二氨基－2，2－二硝基乙烯（FOX －7）高纯度标准物质定值研究需要，研究了电位滴定过程各因素对测量精度的影响，根据产生不确定度分量的性质，通过 A 类和 B 类不确定度评定，对各不确定度分量进行了分析和量化，获得了本测定方法的合成标准不确定度及扩展不确定度。

A gel permeation chromatography(GPC) test method was established with polyethylene glycoKPEG) as standard sample.The relative molecular mass and its distribution of 3-azidomethyl-3-methyloxetane homopolymer(PAMMO) were determined.The effect of column temperature and sample concentration on the test results was studied.The best experimental conditions were determined.The relative molecular mass of PAMMO samples from different batchs were tested.A comparison of the values obtained by GPC test method and the ones obtained by a combination method of GPC and Multi-angle Laser Light Scatterometer(GPC/MALLS),vapour phase osmometry(VPO) and titration method of hydroxyl end-group was performed.Results show that the repeatability of GPC test method is good.The relative standard deviations(RSD) of number-average molecular mass(Mn),weight average molecular mass(Mw) and polydispersity index(PD) are all less than 5%,revealing that the traditional GPC test method can be used to determine the relative molecular mass and its distribution of PAMMO and to guide the improvement of PAMMO synthesis process and choice of post-processing method.

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.

Uncertainty of determination of copper in some propellant was evaluated.The uncertainty components including sample weighing,sample solution volume,the curve intends to match,measurement repeatability were analyzed and quantified.The combined uncertainty was calculated.The expanded uncertainty of measurement was 0.08%(k=2) as the copper mass fraction was 0.96%.

用硫酸亚铁作滴定剂,电位滴定仪指示滴定终点测定硝化棉含氮量,对硝化棉氮含量测定过程和标定过程中的不确定度的来源进行了分析,确定了含氮量测量过程中不确定度的主要来源为:重复性、样品质量、体积.对引入不确定度的各个不确定分量,用统计方法及所获得的各种信息,逐个进行不确定度的量化.通过测量和计算得到硝化棉含氮量测量结果为(12.97±0.05)％.

A method to determine the content of trace impurities in purity standard material 1,5-diazido-3-nitroaza pentane(DIANP) by gas chromatography(GC) was established.The sample was dissolved by THF,and separate by RTX–1 capillary column(30?m ×0.32?mm,5μm) with temperature programming.The external standard method was employed for quantitative analysis.Linear correlation coefficients(r) were in the range of 0.999?0–0.999?6.The recoveries were in the range of 81.6%–101.7%.The relative standard deviations of determination results were 2.16%–2.67%(n=6).The method is simple,rapid,and suitable for detecting trace impurities in 1,5-azido-3-nitro-aza pentane.

The purity reference material 3-nitro-1,2,4-triazol-5-one(NTO) was analyzed by the method of impurity deduction in order to acquire the purity and uncertainty.The purity was validated by potentiometric titration.The uncertainty of certification was evaluated.The purity and expanded uncertainty of NTO were 99.57% and 0.02%(k=2) respectively.

A method to determine the content of fifths inorganic anions in DIANP by ion chromatography was established.After added acetonitrile and water,the sample was passed though the On Guard Ⅱ RP column to wipe off DIANP and other organic compound then was determined directly.The separation was performed with KOH as isocratic mobile phase at a flow rate of 1.0mL/min and accomplished with a Dionex IonPac AS11-HC column.The calibration curve of DIANP was linear,results showed that correlation of fifths anions were higher than 0.999.The relation standard deviation were 1.57%～4.30%,NO-2,N-3,NO-3,SO2-4 the recoveries were 89.3%～98.6%.The method was simple,rapid and satisfaction.

In order to certificate the standard substance 1,5-diazido-3-nitrazpentane(DIANP),an electrode potential titration of determining the purity of DIANP was established.The conditions of the titration method were as follow:dimethysulfoxide(DMSO)as solvent,adding sodium hydroxide solution as reaction regent,and making N-3 in DIANP and Ag+ in AgNO3 react to form the precipitate of AgN3.The purity of standard substance DIANP calculated by the EQP curve was 99.85% and the relative standard derivation was 0.13%.There was no significant varation between the results obtained by electrode potential titration and HPLC method.The expanded uncertainty of this method was 0.3%.

In order to satisfy the requirement of quantity transfer and traceability,1,5-diazido-3-nitrazapentane(DIANP) certified reference material was synthesized with 1,5-dinitralo-3-nitrazapentane(DINA) as starting material,via azidation and purification.The determined purity is 99.85% via substractive process,U=0.01%(k=2),and the yield is 73%.The optimum preparation conditions are as follows: solvent,DMSO;reaction temperature,100℃;reaction time,6h;discoloration process: standing for 3～5d.The organic impurity was separated and characterized as 1-hydroxy-5-azido-3-nitrazapentane,the purity is 99.6%.

The candidateship of purity reference material RDX was prepared by the recrystallization technology,and it's uniformity was eligible.The purity of RDX reference material was analysised by the method of impurity deduction.The purity was validated by potentiometric titration.The purity and the expanded uncertainty of RDX were 99.69% and 0.03%(k=2)respectively.

In order to obtain the standard substance 3-nitro-1,2,4-triazol-5-one(NTO),it is necessary to establish the corresponding chemical certification method in its preparation.Using methanol as solvent and sodium methanol standard solution as titrant,the certification of NTO standard substance was investigated by non-aqueous titration.The results show that the method can exclude disturbance of impurity with better accuracy and precision,and the average purity value of NTO standard substance is 99.88% and the standard deviation is 0.16% after 27 times of repeated determinations.

A method to determine the content of hexahydro-1,3,5-trinitro-s-triazine(RDX) and hexahydro-1,3,5,7-tetronitro-sterazine(HMX) by electrode potential titration in non-aqueous solvent was established.The factors of affecting the experiment,such as non-aqueous solvent,titrant,concentration of titrant,endpoint of electrode potential,were determined.The optimal electrode potential titration conditions obtained were dimethylsulfoxide(DMSO) as non-aqueous solvent;sodoum mothoxide(CH3ONa) as titrant;CH3ONa concentration,0.30mol/L;EQP of electrode potential titration curve as endpoint.The purity of RDX obtained by eighteen times of measurements is 99.554% to 99.865% with the relative standard deriation(RSD) of 0.0976%.The purity of HMX is 99.565% to 99.888%,the value of RSD is 0.10%.The method is facile and dependable.