Estimation of the kinetic parameters for thermal decomposition of HNIW and its adiabatic time-to-explosion by Kooij formula

A differential/integral method to estimate the kinetic parameters(apparent activation energy Eaand pre-exponential factor A) for thermal decomposition reaction of energetic materials based on Kooij formula are applied to study the nonisothermal decomposition reaction kinetics of hexanitrohexaazaisowurtzitane(HNIW) by analyzing nonisothermal DSC curve data. The apparent activation energy(Ea) obtained by the integral isoconversional non-isothermal method based on Kooij formula is used to check the constancy and validity of apparent activation energy by the differential/integral method based on Kooij formula. The most probable mechanism function of thermal decomposition reaction of HNIW is determined by a logical choice method. The equations for calculating the critical temperatures of thermal explosion(Tb) and adiabatic time-toexplosion(tTIad) based on Kooij formula are used to calculate the values of Tband tTIadto evaluate the thermal safety and heat-resistant ability of HNIW. All the original data needed for analyzing the kinetic parameters are from nonisothermal DSC curves. The results show that the kinetic model function in differential form and the values of Eaand A of decomposition reaction of HNIW are 3(1 a)[ ln(1 a)]2/3, 152.73 kJ mol 1and 1011.97s 1, respectively, and the values of self-accelerating decomposition temperature(TSADT), Tband tTIadare 486.55 K, 493.11 K and52.01 s, respectively.

从恒速升温速率下的DSC曲线峰温计算含能材料放热分解反应动力学参数的理论和数值方法(英文)

根据Kooij公式和van′t Hoff公式,从恒速升温速率下的DSC曲线峰温导出了计算含能材料放热分解反应动力学参数的两个数学表达式,提出了计算相应动力学参数的数值方法。对1,3,5-三硝基-1,3,5-三氮杂环己酮-2(Keto-RDX),由导出的两个表达式、Kissinger法、Ozawa法、Tang法、Hu-Gao-Zhang法、非线性等转化率积分法(NL-INT)所得的活化能E值彼此接近,表明Kooij′s公式中的a值取0.5,van′t Hoff公式的b值取0.003,可得到合理的动力学参数。