This work elucidated the underlying mechanism of the dramatic and divergent physicochemical properties of CL-20-based energetic cocrystals.

Cocrystals of hexanitrohexaazaisowurtzitane (CL-20) and 7H-trifurazano[3,4-b:3′,4′-f:3′′,4′′-d]azepine (TFAZ) in a 1 : 1 molar ratio were prepared by both slow evaporation and self-assembly methods. Structure determination showed that they belong to the monoclinic system (space group P2₁) with a crystal density of 1.932 g cm⁻³. The intermolecular hydrogen bonds and N–O⋯NO₂ type interactions are demonstrated as the predominant driving forces in the cocrystal formation. Furthermore, the cocrystals were successfully synthesized by a self-assembly method using only water as a solvent under mild conditions and the product yield was up to 92.3%. The two types of cocrystals were fully characterized by powder X-ray diffraction, infrared spectroscopy and scanning electron microscopy. Moreover, the thermal behavior, sensitivity, and calculated detonation performance of the cocrystals were evaluated. The cocrystals exhibit good thermal stability (T_d = 242.8 °C), low impact sensitivity (H₅₀ = 42 cm) and friction sensitivity (P_f = 38%), high crystal density, and high calculated detonation velocity (9103 m s⁻¹). This work opens up a new perspective in the environment-friendly preparation of energetic cocrystals on a large-scale, as well as providing potential low-sensitivity and high-energy explosives.

Molecular dynamics simulation was performed on 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), 2,4-dinitro-2,4-diazapentane (DNDAP), and CL-20/DNDAP cocrystal and composite under COMPASS force field at different temperatures. The binding energy (E_bind), radial distribution function (RDF), trigger bond length, cohesive energy density (CED) and mechanical properties were studied and compared. The results show that the binding energy of the cocrystal is evidently higher than that of the composite at the same temperature. RDF analysis reveals that hydrogen bonds and vdW forces between CL-20 and DNDAP exist in both CL-20/DNDAP cocrystal and composite, and the interactions in the cocrystal are stronger than those in the composite. The maximum trigger bond length decreases in the order ε-CL-20 > CL-20/DNDAP composite > CL-20/DNDAP cocrystal. Moreover, the rigidity and stiffness of the cocrystal and composite decrease compared to that of CL-20, while the ductility and elasticity are better than that of the two pure components. These results demonstrate that CL-20/DNDAP cocrystal might be very promising in explosive applications.

Safety concerns remain a bottleneck for the application of 2,4,6,8,10,12-hexanitro- 2,4,6,8,10,12-hexaazaisowurtzitane (CL-20)/1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX) cocrystal. Melamine–formaldehyde (MF) resin was chosen to fabricate CL-20/HMX cocrystal-based core–shell composites (CH@MF composites) via a facile in situ polymerization method. The resulted CH@MF composites were comprehensively characterized, and a compact core–shell structure was confirmed. The effects of the shell content on the properties of the composites were explored as well. As a result, we found that, except for CH@MF–2 with a 1% shell content, the increase in shell content led to a rougher surface morphology and more close-packed structure. The thermal decomposition peak temperature improved by 5.3 °C for the cocrystal enabled in 1.0 wt% MF resin. Regarding the sensitivity, the CH@MF composites exhibited a significantly reduced impact and friction sensitivity with negligible energy loss compared with the raw cocrystal and physical mixtures due to the cushioning and insulation effects of the MF coating. The formation mechanism of the core–shell micro-composites was further clarified. Overall, this work provides a green, facile and industrially potential strategy for the desensitization of energetic cocrystals. The CH@MF composites with high thermal stability and low sensitivity are promising to be applied in propellants and polymer-bonded explosive (PBX) formulations.

Exploring the facile synthesis of Pb-free energetic metal–organic frameworks (EMOFs) with both high nitrogen content and high thermostability is a significant but challenging task in the field of MOF-based green energetic materials. Herein, a new EMOF, [Zn₂(atz)₃(N₃)]_n (atz = 5-amino-1H-tetrazole), has been synthesized by simply using a commercial ligand (atz) under mild conditions. A probable mechanism for the formation of azide groups in the product has been proposed, in which the fraction of C–N and N–N bonds in atz is the key. The X-ray single crystal structure analysis reveals the EMOF's unique graphene-like and azide-group-bridged 2D bilayer structure with gourd-type micropores. More impressively, the EMOF shows a high nitrogen content of 59.33% and superior thermostability of up to 362 °C, both among the best of existing EMOFs. In addition, detonation property calculations and sensitivity tests have been carried out, which demonstrate its high-energy and low-sensitivity features. Moreover, [Zn₂(atz)₃(N₃)]_n shows the ability to accelerate the thermal decomposition of ammonium perchlorate (AP) and hexanitrohexaazaisowurtzitane (CL-20), making it a potential combustion promoter for green and insensitive propellants.

Weak interfacial interactions remain a bottleneck for composite materials due to their weakened performance and restricted applications. The development of core–shell engineering shed light on the preparation of compact and intact composites with improved interfacial interactions. This review addresses how core–shell engineering has been applied to energetic materials, with emphasis upon how micro-energetic materials, the most widely used particles in the military field, can be generated in a rational way. The preparation methods of core–shell structured explosives (CSEs) developed in the past few decades are summarized herein. Case studies on polymer-, explosive- and novel materials-based CSEs are presented in terms of their compositions and physical properties (e.g., thermal stability, mechanical properties and sensitivity). The mechanisms behind the dramatic and divergent properties of CSEs are also clarified. A glimpse of the future in this area is given to show the potential for CSEs and some suggestions regarding the future research directions are proposed.