DNAN/TNAZ最低共熔物的制备及性能

Preparation and Properties of DNAN/TNAZ Lowest Eutectic Mixture

制备了2,4-二硝基苯甲醚(DNAN)和1,3,3-三硝基氮杂环丁烷(TNAZ)摩尔比分别为0∶1、1∶3、1∶2、2∶3、1∶1、3∶2、2∶1、3∶1、1∶0的低共熔物;通过对不同摩尔比的DNAN/TNAZ二元低共熔物进行DSC测试,绘制了T—X与H—X相图;通过相图得出了DNAN/TNAZ最低共熔体系的摩尔比,并对其最低共熔物进行了热动力学分析、XRD分析以及TG-MS分析,同时对不同摩尔比的DNAN/TNAZ低共熔物进行了机械感度测试以及爆轰性能计算。结果表明,当DNAN与TNAZ摩尔比为56.65∶43.35时,获得最低共熔物,其最低共熔点为65.14℃,最低共熔物的热分解反应速率常数较小(k=0.40s-1),反应过程需要吸收热量,活化自由能(ΔG≠)为20.29kJ/mol,活化焓(ΔH≠)为61.92kJ/mol,活化熵(ΔS≠)为78.76J/(mol·K),反应过程熵值增加;XRD测试表明最低共熔物在35.43°处产生了一定的分子间作用力;热分解的主要产物为H2O、C2H6、NO、N2、CO、N2O、CO2、CH4,同时还有少量的NO2。DNAN/TNAZ最低共熔物的撞击感度(H50)为56cm,摩擦感度为0,理论爆速为7310.8m/s,理论爆热为6273.7kJ/kg。

The eutectic mixture of 2,4-dinitroanisole(DNAN)and 1,3,3-trinitroazetidine(TNAZ)with the molar ratios of 0∶1,1∶3,1∶2,2∶3,1∶1,3∶2,2∶1,3∶1,1∶0 were prepared.The T—X and H—X phase diagrams were drawn according to the DSC test results performed on DNAN/TNAZ binary eutectic mixtures with different molar ratios.The ratio of DNAN/TNAZ lowest eutectic mixture was further obtained from the phase diagram,and thermodynamic analysis,XRD analysis and TG-MS analysis were applied to the eutectic mixture.The mechanical sensitivity test and detonation performance calculation were performed on DNAN/TNAZ eutectic mixtures with different molar ratios.The results show that the lowest extectic mixture can be obtained when the molar ralio of DNAN to TNAZ is 56.65∶43.35 with the lowest extectic temperature of 65.14℃.The eutectic mixture has a small thermal decomposition reaction rate(k=0.40s-1),and the reaction process needs to absorb heat.In addition,the activation free energy(ΔG≠)is 20.29kJ/mol,the activation enthalpy(ΔH≠)is 61.92kJ/mol,the activation entropy(ΔS≠)is 78.76J/(mol·K),and the value of entropy increases during the reaction.XRD test shows that the lowest eutectic mixture produces a certain intermolecular force at 35.43°.Besides a small amount of NO2,the main decomposition products are H2O,C2H6,NO,N2,CO,N2O,CO2,CH4.The impact sensitivity(H50)of the lowest eutectic mixture of DNAN/TNAZ is 56cm,friction sensitivity is 0,theoretical detonation velocity is 7310.8m/s,and theoretical detonation heat is 6273.7kJ/kg.