Detection of autocatalytic decomposition behavior of energetic materials using APTAC

Characterization of autocatalytic decomposition reactions is important for the safe handling and storage of energetic materials. Isothermal differential scanning calorimetry (DSC) has been widely used to detect autocatalytic decomposition of energetic materials. However, isothermal DSC tests are time consuming and the choice of experimental temperature is crucial. This paper shows that an automatic pressure tracking calorimeter (APTAC) can be a reliable and efficient screening tool for the identification of autocatalytic decomposition behavior of energetic materials. Hydroxylamine nitrate (HAN) is an important member of the hydroxylamine family. High concentrations of HAN are used as liquid propellants, and low concentrations of HAN are used primarily in the nuclear industry for decontamination of equipment. Because of its instability and autocatalytic decomposition behavior, HAN has been involved in several incidents. This paper presents calorimetric measurements for the thermal decomposition of 24 mass% HAN/water. APTAC heat-wait-search and heat-soak-search modes are used to characterize the thermal decomposition of HAN. By comparing the kinetic analysis for the two modes, it is concluded that HAN shows strong autocatalytic decomposition behavior. The most likely decomposition pathway of HAN is proposed to explain the observed autocatalytic behavior.