Chelating Energetic Material Nickel Semicarbazide 2,4,6‐Trinitroresorcinol: Synthesis, Structure, and Thermal Behavior

Abstract

AbstractThrough a one‐pot reaction of NiCO3·2Ni(OH)2·H2O, aminourea hydrochloride (SCZ·HCl) and 2,4,6‐trinitroresorcinol (TNR), a halogen‐free and lead‐free chelating energetic material (CEM) [Ni(SCZ)3]TNR was synthesized. We confirmed the structure of [Ni(SCZ)3]TNR by infrared spectroscopy, X‐ray diffraction, and elemental analysis. The complex is triclinic with P$\bar{1}$(2)/n space group. Cell parameters are: a = 1.04008(17) nm, b = 1.3719(2) nm, c = 1.4897(2) nm, V = 2.0337(6) nm3, Z = 4. The central nickel atom is six‐coordinate with three oxygen atoms of carbonyl groups and three terminal nitrogen atoms of the hydrazine groups from three SCZs to form a distorted octahedron. Differential scanning calorimetry and analysis applied to assess the thermal decomposition behavior. The DSC curve with a linear heating rate of 10 °C·min–1 shows that [Ni(SCZ)3]TNR is thermally stable with one exothermic peak temperatures of 78.8 °C and two exothermic peak temperatures of 216.8 °C and 308.1 °C. The kinetic parameters were obtained by non‐isothermal reaction kinetics. The equation can be expressed as lnk = 24.49–243.3 × 103/RT. Moreover, the values of the critical temperature of thermal explosion, ΔS≠, ΔH≠, ΔG≠, and the enthalpies of formation were obtained as 206.5 °C, –145.543 J·mol–1·K–1, 237.18 kJ·mol–1, 305.84 kJ·mol–1, and –2.65 MJ·kg–1, respectively.