Synergistic coupling of micellar confinement and interfacial adsorption for fabricating high-density spherical nickel (II) tricarbohydrazide perchlorate

Precise control over crystal morphology is critical for energetic materials, as it governs packing behavior, thermal stability, and interfacial reactivity. However, morphology regulation of primary explosives remains challenging, particularly when simultaneous spheroidization and densification are required. Herein, nickel (II) tricarbohydrazide perchlorate (GTN) is employed as a model system to demonstrate a synergistic multiscale interfacial regulation strategy enabled by a binary surfactant system. By integrating maltodextrin (MD) and carboxymethylcellulose sodium (CMC), dense spherical GTN crystals are constructed through the cooperative coupling of molecular-level facet adsorption and mesoscale spatial confinement. Real-time crystallization monitoring, microscopic characterization, and first-principles calculations collectively elucidate the underlying growth and assembly mechanisms. The results reveal that MD selectively adsorbs on GTN crystal facets via hydrogen bonding, promoting intercrystalline adhesion and densification, while CMC generates a coordination-induced nanofiber network that guides spherical assembly. The synergistic interplay between these interfacial effects enables hierarchical crystal organization that cannot be achieved using single surfactants. As a consequence, the dense spherical crystals exhibit significantly improved bulk density, flowability, and thermal stability, alongside enhanced structural robustness under elevated-temperatures. This work establishes a generalizable interfacial regulation paradigm for hierarchical morphology control of primary explosives and provides insights applicable to a broad range of energetic materials.