Study on the Cocrystallization Mechanism of CL-20/HMX in a Propellant Aging Process through Theoretical Calculations and Experiments

Energetic materials undergo physical and chemical aging due to environmental effects, resulting in the degradation of safety and detonation performances. Therefore, studying the aging performance of energetic materials is of great importance for the efficient application of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)-based solid propellants. In this paper, XRD and FTIR of the CL-20-based propellant and CL-20/1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX)-based propellant samples showed CL-20/HMX cocrystal formation according to appearance of new peaks. SEM and EDS analyses showed that pores and dehumidification in the propellant occurred with the cocrystallization of CL-20 and HMX during the aging process. Furthermore, molecular dynamics simulation was used to predict the crystal transformation of the CL-20- and HMX-based propellant under a long-term storage process. The stability of epsilon-CL-20 was obtained by analyzing the crystal transformation rate. The binding energy, radial distribution function between CL-20 and HMX, as well as mechanical properties of the CL-20/HMX cocrystal and the mixture were calculated to reveal the stronger binding between CL-20 and HMX in the cocrystal. Meanwhile, the inducer effect of a nitrate ester during the cocrystallization process was analyzed. The theoretical calculation shows that during aging, epsilon-CL-20 tends to exist stably, while CL-20/HMX tends to form cocrystals because of the strong bond. The present work on the transformation and cocrystallization of CL-20 and HMX during long-term storage is beneficial for understanding the degradation mechanism of the propellant performances, facilitating safe storage and life evaluation of propellants.

Automated summary

In this study, the aging performance of energetic materials in CL-20-based solid propellants was investigated. The results showed the formation of a cocrystal of CL-20/HMX through XRD and FTIR analysis. SEM and EDS analyses revealed the occurrence of pores and dehumidification during the aging process. Molecular dynamics simulation and theoretical calculations demonstrated the stronger binding and mechanical properties of the CL-20/HMX cocrystal, as well as the inducer effect of a nitrate ester during cocrystallization. These findings contribute to a better understanding of the degradation mechanisms and safe storage of propellants.