DNP/DNTF低共熔物的二元相图及熔融动力学

Binary Phase Diagram and Melting Kinetics of DNP/DNTF Eutectic

为获得3,4-二硝基吡唑(DNP)/3,4-二硝基呋咱基氧化呋咱(DNTF)二元混合体系的相图,深入了解其低共熔物的熔融过程,采用差示扫描量热法(DSC)研究了不同比例的DNP/DNTF混合体系的液化及熔融过程,建立了液化温度Tl与组成x的T-x相图、熔融焓ΔH与组成x的H-x相图;研究了不同升温速率5,10,15,20℃·min^(-1),不同添加剂奥克托今(HMX)、高氯酸铵(AP)和硝基胍(NQ)对低共熔物熔融过程的影响;通过Kissinger方程和Šatava-Šesták方程计算得到了低共熔物熔融过程的动力学参数活化能Ea、指前因子A和最概然机理函数。结果表明,从T-x相图得到的DNP/DNTF低共熔物的质量百分比为70.38/29.62,低共熔温度为76.38℃;由H⁃x相图得到的低共熔物组成为70.57/29.43。随升温速率的升高,熔融反应的开始温度和峰温延迟;HMX和NQ的加入使低共熔物的熔点明显后移,AP的加入对熔点影响不大。DNP/DNTF低共熔物的熔融动力学参数Ea和A为19.13 kJ·mol^(-1)和109.74 s^(-1),最概然机理函数的积分形式为:G(α)=(1-α)^(-1)-1。

In order to get the phase diagrams of 3,4-dinitropyrazole(DNP)/3,4-bis(3-nitrofurazan-4-yl)furoxan(DNTF)binary mixture system and understand the eutectic melting process,DSC was used to investigate the liquefaction and melting process of DNP/DNTF mixed system with different proportions.The T⁃x phase diagram and H⁃x phase diagram were established,and the effects of different heating rates and additives on melting process of eutectic were studied.Finally,the kinetic parameters Ea and A of eutectic melting process were calculated by Kissinger equation andŠatava-Šestak equation.Results show that the mass percentage of DNP/DNTF eutectic is 70.38/29.62 and the eutectic temperature is 76.38℃based on T⁃x phase diagram,which is good consistent with that from H⁃x phase diagram as 70.57/29.43.With the increase of heating rate,the initial temperature and peak temperature of melting process are delayed correspondingly.After the addition of Octogen(HMX)and nitroguanidine(NQ),the melting point of the low eutectic is significantly delayed,while ammonium perchlorate(AP)has little effect on the melting point.The melting kinetic parameters Ea and A of DNP/DNTF eutectic are 19.13 kJ·mol^(-1) and 109.74 s^(-1) respectively,and the integral form of the most probable mechanism function is:G(α)=(1-α)^(-1)-1.