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An explosive co-crystal of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX) and 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) was prepared by the ball milling method. The raw materials and co-crystals were characterized using scanning electron microscopy (SEM), X-ray diffraction (XRD), differential scanning calorimetry (DSC) and Raman spectroscopy. Impact and friction sensitivity of the co-crystals were tested and analyzed. The results showed that the HMX/TATB co-crystals are spherical in shape and 100-300 nm in size. The co-crystals are different from anintimate mixture of HMX/TATB and they exhibit a new co-crystal structure. HMX/TATB co-crystals are formed by N-O···H hydrogen bonding between −NO2 (HMX) and −NH2 (TATB). The drop height of ultrafine HMX/TATB explosive co-crystals is 12.7 cm higher than that of ultrafine HMX, whilst the explosion probability of friction is 20% lower than that of ultrafine HMX. Ultrafine HMX/TATB explosive co-crystals are difficult to initiate under impact and friction conditions.
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