Decomposition and Energy-Enhancement Mechanism of the Energetic Binder Glycidyl Azide Polymer at Explosive Detonation Temperatures

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2020-07, Vol.124 (27), p.5542-5554
• Main Authors: Liu, Danyang, Geng, Deshen, Yang, Kun, Lu, Jianying, Chan, Serene Hay Yee, Chen, Chao, Hng, Huey Hoon, Chen, Lang
• Format: Article
• Language: English
• Subjects: A: Spectroscopy, Molecular Structure, and Quantum Chemistry
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/acs.jpca.0c02950

Replacing existing inert binders with energetic ones in composite explosives is a novel way to improve the explosive performance, on the proviso that energetic binders are capable of releasing chemical energy rapidly in the detonation environment. Known to be a promising candidate, the reaction mechanism of glycidyl azide polymer (GAP) at typical detonation temperatures higher than 3000 K has been theoretically studied in this work at the atomistic level. By analyzing and tracking the cleavage of characteristic chemical bonds, it was found that at the detonation temperature, GAP was able to release a large amount of energy and small molecule products at a speed comparable to commonly used explosives in the early reaction stage, which was mainly attributed to the decomposition of azide groups into N2 and the main chain breakage into small fragments. Moreover, N2 generation was found to be accelerated by H atom transfer at an earlier reaction step. The dissociation energy of the main chain was lowered with structure deformation so as to facilitate the fragmentation of the GAP chain. Based on this analytical study of reaction kinetics, GAP was found to have higher reactivity at the detonation temperature than at lower temperatures. The small molecules’ yield rate is of the same order of magnitude as an explosive detonation reaction, indicating that GAP has the potential to improve the performance of composite explosives. Our study reveals the chemical decomposition mechanism of a typical energetic binder, which would aid in the future design and synthesis of energetic binders so as to achieve both sensitivity-reducing and energy-enhancing performance goals simultaneously.