The power of model-fitting kinetic analysis applied to complex thermal decomposition of explosives: reconciling the kinetics of bicyclo-HMX thermolysis in solid state and solution

摘要: Thermal decomposition of cis-1,3,4,6-tetranitrooctahydroimidazo-[4,5-d]imidazole (Bicyclo-HMX) both in solid state and solution has been studied with a set thermal analysis methods. Differential scanning calorimetry data obtained at several heating rates were analyzed using the model-fitting kinetic technique free open-source THINKS thermokinetic software. The parameters for noncatalytic stage thermolysis are found to be Ea = 168.7 ± 1.4 kJ mol−1, log (A, s−1) = 15.7 ± 0.2, prove activation energy agrees theoretical prediction barrier N–NO2 bond rupture BC-HMX molecule. is complex process, typical explosives. A formal three-step scheme proposed, which explains numerous experimental findings (thermal behavior various confinement degree, morphology changes under heating) previous literature results as well. first step process obeys third-order nucleation-growth model Ea = 186.6 ± 1.2 kJ mol−1 s−1) = 16.7 ± 0.3. Overall, power demonstrated extension proposed methodology other energetic materials patterns suggested.