TNBA/TNAZ最低共熔物的制备及性能

Preparation and Properties of TNBA/TNAZ Lowest Eutectic Mixture

采用静电喷雾方法制备了2,4,6-三硝基-3-溴苯甲醚(TNBA)与1,3,3-三硝基氮杂环丁烷(TNAZ)不同质量比的低共熔物。根据低共熔物的差示扫描量热(DSC)曲线绘制了二元温度-组成(T-X)、熔融焓-组成(H-X)相图,从而得到最低共熔物的质量比。采用扫描电镜(SEM)、能量色散光谱(EDS)、高效液相色谱(HPLC)、X射线粉末衍射(XRD)、红外光谱(IR)、X射线光电子能谱(XPS)、DSC和热重-质谱联用(TG-MS)等方法对最低共熔物形貌、组分含量、元素分布、晶体结构和热分解性质进行了研究,并对最低共熔物的机械感度、热感度和爆轰性能进行了测试和理论计算。结果表明:TNBA/TNAZ最低共熔物的最佳质量比为60.95∶39.05;其微观形貌无尖锐棱角,组分比例与静电喷雾前一致,表面元素分布均匀,晶体结构与原料基本一致;最低共熔温度为350.18 K,相比原料TNBA、TNAZ降低了22.72 K和24.82 K;热分解反应速率常数为0.33 s^(-1),活化焓为60.10 kJ·mol^(-1),活化能为64.44 kJ·mol^(-1),活化吉布斯自由能为135.21 kJ·mol^(-1),活化熵为-143.78 J·(mol·K)^(-1);最低共熔物的撞击感度(H50)为42 cm,摩擦感度(FS)为20%,5 s爆发点温度为558 K;爆轰性能(氧平衡-34.83%,爆热5101.78 kJ·kg^(-1),爆速7598.37 m·s^(-1))介于原料TNBA与TNAZ之间,理论爆轰产物主要为N2、C(d)、CO、CO_(2)及H_(2)O。

The eutectic mixtures of 2,4,6-trinitro-3-bromoanisole (TNBA) and 1,3,3-trinitroazetidine (TNAZ) with different mass ratios were prepared by the electrostatic spray method.T-X and H-X phase diagrams were drawn according to the differential scanning calorimetry (DSC) curves of the eutectic mixtures to obtain the mass ratio of the lowest eutectic.Scanning Electron Microscopy (SEM),Energy Dispersive Spectroscopy (EDS),High Performance Liquid Chromatography (HPLC),X-ray Powder Diffraction (XRD),Infrared (IR),X-ray Photoelectron Spectroscopy (XPS),DSC,and thermogravimetry-mass (TG-MS) spectrometry were used to determine the morphology,component content,element distribution,crystal structure and thermal decomposition properties of the lowest eutectic.And the mechanical sensitivity,thermal sensitivity and detonation performances of the lowest eutectic were tested and theoretically calculated.The results show that 60.95∶39.05 is the optimal mass ratio of TNBA/TNAZ lowest eutectic mixture;the microscopic morphology has no sharp edges and corners;the component proportion is the same as before electrostatic spraying;the surface elements are evenly distributed;and the crystal structure is basically the same as that of the raw materials.The eutectic temperature is 350.18 K,which is 22.72 K and 24.82 K lower than that of raw materials TNBA and TNAZ.The thermal decomposition reaction rate constant (k),activation enthalpy(ΔH≠),activation energy(EK),activated Gibbs free energy(ΔG≠),and activation entropy(ΔS≠)of the lowest eutectic are 0.33 s^(-1),60.10 kJ·mol^(-1),64.44 kJ·mol^(-1),135.21 kJ·mol^(-1),and-143.78 J·(mol·K)^(-1),respectively.The impact sensitivity (H50),friction sensitivity (FS),and 5s explosion temperature of the lowest eutectic mixture are 42 cm,20%,and 558 K,respectively.Its detonation performance (OB=-34.83%,Q=5101.78 kJ·kg^(-1),VD=7598.37 m·s^(-1)) is between TNBA and TNAZ.The main detonation products are N2、C(d)、CO、CO_(2)and H_(2)O.