Thermal Decomposition Mechanism of Molecular Perovskite Energetic Material (C₆NH₁₄)(NH₄)(ClO₄)₃(DAP‐4)

Abstract

The recently developed ammonium perchloratebased molecular perovskite has been demonstrated to exhibit excellent comprehensive performance as an energetic material. This ABX 3 -type molecular perovskite energetic material consists of a high symmetry ternary structure framework stabilized through ionic bonds. In this work, the thermal decomposition mechanism of (C 6 NH 14 )(NH 4 )(ClO 4 ) 3 (DAP-4) was extrapolated by analyzing its thermal decomposition characteristics, gas products, kinetic parameters, and condensed phase change results along with temperature-varying, with the help of DSC-TG-MS-FTIR and in-situ FTIR experiment. The results show that a rapid reaction occurs once the decomposition of DAP-4 starts at 383.7 °C, with the maximum thermal weight loss rate reaches 97.4 %. By using Kissinger's and Ozawa's method, the calculated activation energy of thermal decomposition of DAP-4 was estimated to be 124.3 kJ/mol and 128.6 kJ/mol, respectively, demonstrating good reliability of our results. The gas products during the thermal decomposition were found mainly include NH 3 , H 2 O, HNCO, HCN, CO, HCl, and CO 2 . The decomposition process of DAP-4 contains three stages. The first stage involves crystal form changes and H + transfer of DPA-4, followed by the collapse of the cage skeleton in the second stage. The third stage mainly involves a rapid redox reaction at high temperatures to generate great heat.

Mixed-Metallic Energetic Metal–Organic Framework: New Structure Motif for Potential Heat-Resistant Energetic Materials

“…22 Nevertheless, the development of advanced energetic materials is growing rapidly, particularly evident in the proliferation of energetic crystals using various techniques. These include nitrogen-rich fused molecules 23−25 and related cocrystals, 26 binary salts, 27,28 ionic liquids 29,30 and perovkite energetic mateials, 31,32 etc. While some of these energetic crystals have balanced stability and detonation capability, the majority of them face difficult synthesizes or high costs, making them unlikely to find widespread application.…”

“…Nevertheless, the development of advanced energetic materials is growing rapidly, particularly evident in the proliferation of energetic crystals using various techniques. These include nitrogen-rich fused molecules − and related cocrystals, binary salts, , ionic liquids , and perovkite energetic mateials, , etc. While some of these energetic crystals have balanced stability and detonation capability, the majority of them face difficult synthesizes or high costs, making them unlikely to find widespread application. , As a result, the development of a specific class of new heat-resistant explosives with fine-tuned properties such as excellent thermal stability, insensitivity, detonation performance, and straightforward approaches has been greatly influenced by environmental concerns.…”

Effect of Cubic Crystal Morphology on Thermal Characteristics and Mechanical Sensitivity of PYX

“…The absorbance achieves a larger value at the temperatures of 384 • C and 427 • C, corresponding to the first and second decomposition stages, respectively. For the first decomposition stage, the main gaseous products include CO 2 (2356 and 671 cm −1 ), N 2 O (2201 cm −1 and 2240 cm −1 ), NO (1843 cm −1 and 1923 cm −1 ), HCN (720 cm −1 ) and H 2 O (3511 cm −1 ~3824 cm −1 ) [29]. For the second decomposition stage, the absorption peaks of NO and H 2 O disappear, indicating that there may be no NO and H 2 O produced.…”