Facilitating polymorphic crystallization of HMX through ultrasound and trace additive assistance

Low sensitivity octahydro-1,3,4,7-tetranitro-1,3,5,7-tetrazocine (HMX) has garnered significant attention from researchers due to its reduced shock sensitivity. However, the crystallization process poses challenges due to the high solidity and viscosity of the metastable alpha phase. Despite efforts to address this with additional energy sources like ultrasonic irradiation, prolonged exposure duration often results in small particle sizes, hindering the production of HMX with a consistent particle size distribution, thus limiting its applicability. To overcome these challenges, a method combining ultrasonic irradiation and trace H+ additive was proposed and investigated for their impact on the polymorphic transformation of HMX. The H+ additive was found to modify barriers, thus there was a lack of competitive driving force for the nucleation or growth of the metastable alpha form, thereby shortening the transformation pathway and duration. Moreover, the H+ additive significantly accelerated the nucleation rate of the beta form (67.7 orders of magnitude faster with 0.10 wt %o H+) and the growth rate of beta form HMX (5.8 orders of magnitude faster with 0.10 wt %o H+). While H+ additive alone was insufficient to induce spontaneous nucleation of the beta form, combining it with short-duration ultrasonic irradiation further promoted beta nucleation and shortened the polymorphic transformation duration (almost 20 orders of magnitude shorter). This rational approach led to effective control of the transformation process. The resulting low sensitivity HMX crystals exhibited varying mean sizes ranging from 20 to 340 mu m, with purity exceeding 99.6 %, an apparent density greater than 1.8994 g/cm3, and few internal defects, fully meeting the requirements of low-sensitivity HMX, thus significantly expanding its potential applications. Our study sheds light on the mechanisms governing HMX polymorphic transformation in the presence of additives and ultrasonic irradiation, offering guidance for the rational control of this complex transformation.