Effect of Sample Mass, Confinement, and Preheating Time on the Thermal Response of LLM‐105: Experiments and Kinetic Analysis

ABSTRACT Various small‐scale experiments were performed to provide data for developing a model to predict the thermal response of LLM‐105 over a wide range of conditions. The thermal decomposition of LLM‐105 was studied as a function of sample mass, confinement of volatile products, and preheating time in both isothermal and ramped heating experiments. The thermal decomposition of LLM‐105 is a two‐step process, as shown by the two exothermic peaks in the heat flow profiles, which were fitted to two nth‐order autocatalytic reaction models with a similar activation energy of ∼289 kJ/mol. The magnitude and shape of these peaks varied with sample mass and confinement. Increasing sample mass enhanced the second exotherm with respect to the first one, while increasing the level of confinement promoted a transition from a sublimation‐dominated regime towards thermal decomposition. The effect of LLM‐105 particle size on the rate of weight loss was evident for open‐pan experiments, where bigger particles sublimed at lower temperatures than smaller particles. Thermal response and solid residue composition of LLM‐105 samples were analyzed following preheating for different durations. Longer preheating times caused a shift of the second exotherm to lower temperatures and a decrease in the reaction enthalpy, confirming that LLM‐105 decay is a consecutive reaction mechanism, probably autocatalytic. The kinetic model derived from ramped experiments was validated against the measured LLM‐105 fraction remaining and the enthalpy remaining of the solid residue as a function of preheating times and showed good agreement.