Preparation of reduced sensitivity co-crystals of cyclic nitramines using spray flash evaporation

The present day weapon technology demands novel energetic materials that exhibit simultaneous high explosive yield and reduced sensitivity. This article demonstrates application of spray evaporation to prepare reduced sensitive co-crystals of high performance nitramine explosives like HMX and CL-20 with a relatively less insensitive explosive 1,1-diamino-2,2-dinitroethylene or FOX-7. Stronger intermolecular hydrogen bonding in FOX-7 is responsible for limited solubility in most of organic solvents. Large solubility differences of FOX-7 with HMX and CL-20 restricts it's co-crystallization through classical methods that yields thermodynamically favorable product. Spray flash evaporation, a kinetic crystallization method, has been therefore adopted and could successfully produce CL-20/FOX-7 (2:1) and HMX/FOX-7 (4:1) co-crystals. The fine powdered materials obtained were characterized by SEM, powder XRD, Raman spectroscopy, DSC-TGA etc. Multipoint Raman spectra showed consistent occurrence of spectral features indicating stoichiometric co-existence of ingredients in the crystal lattices. DSC analysis showed absence of all thermally assisted solid-solid phase transformation in the co-crystals as they were observed in pristine materials. The thermal stability calculated in terms of activation barrier for decomposition, revealed the CL-20/FOX-7 co-crystal to be intermediately stable on comparison to their constituents while, the HMX/FOX-7 co-crystal is more stable. Compared to pure HMX and CL-20, both the co-crystals have shown higher insensitivity to impact force, suggesting them to be suitable for future generation insensitive munitions.