Shelf Life Prediction of Picric Acid via Model-Based Kinetic Analysis of Its Thermal Decomposition

Materials (Basel). 2022 Dec 13;15(24):8899. doi: 10.3390/ma15248899.

Abstract

A priori knowledge of the shelf life of energetic materials (EMs) is relevant due to its direct association with safety and functionality. This paper proposes a quick and reliable approach to predicting the shelf life of EMs whose thermal decomposition is an autocatalytic process once their failure threshold has been defined as a function of the limiting extent of conversion. This approach is based on the assumption of a kinetic law consistent with the autocatalytic behavior and on the subsequent extraction, via a suitable procedure of parameter identification, of the kinetics of thermal decomposition from differential scanning calorimetry (DSC) data gathered under dynamic conditions at three different heating rates. Its reliability is proven for picric acid (PA) through the comparison of kinetic predictions with evaluations of conversion obtained by using high performance liquid chromatography (HPLC) analysis for samples subjected to isothermal and non-isothermal accelerated aging tests, as well as for a sample of naturally aged material, i.e., PA, stored at room temperature for more than 10 years.

Keywords: aging; differential scanning calorimetry; energetic materials; high performance liquid chromatography; model-based kinetic analysis; picric acid; shelf life prediction; thermal decomposition.