Effect of Thermal History and Mass Scale on the Thermal Safety of 1,3,5,7‐Tetranitro‐1,3,5,7‐Tetrazocane

Abstract

The effect of thermal history and mass scale on the thermal safety of Octogen (HMX) were explored by microcalorimetric and differential scanning calorimetry. The autocatalytic properties were verified by isothermal experiments, and the thermal decomposition kinetics was analyzed by Kissinger, Ozawa and Friedman methods. The results indicated that the thermal decomposition process was accomplished under solid state conditions with the heating rates in the range of 0.1–1 °C/min, and the apparent activation energy calculated by isothermal experiment was basically consistent with that calculated by dynamic method. Thermal history experiments presented that the thermal decomposition had autocatalytic properties, which was verified by isothermal experiments. Moreover, thermal history which had great influence on the thermal decomposition kinetics made the apparent activation energy decrease significantly, resulting in safety risk augmentation. Additionally, mass scale had a salient effect on the thermal stability. With the increase of sample mass, the degree of hazard augmented. It is necessary to keep the heat source off and avoid the large mass storage in the industrial production.

Thermal Safety Performance Evaluation for Typical Free Radical Polymerization Initiator of Tert‐butyl Peroxypivalate

“…The Kissinger method [25] is based on the Arrhenius equation. [26] Assuming that the rate constant follows the Arrhenius law and the exothermic reaction can be considered as a single step process.…”