Studies on Energetic Compounds Part 27: Kinetics and Mechanism of Thermolysis of Bis(Ethylenediamine)Metal Nitrates and Their Role in the Burning Rate of Solid Propellants

Four bis(ethylenediamine)metal(II) nitrate (BEMN) complexes, i.e. [M(EDA)₂](NO₃)₂, where M=Cu, Co, Ni and Zn, have been prepared and characterized. Thermolysis of these complexes induced by heat and drop‐weight impact has been investigated by TG‐DTG, DTA, explosion delay (D_E), explosion temperature (T_E) and impact sensitivity measurement. The kinetics of early thermolysis reaction prior to fast decomposition have been evaluated. Contracting area (CA, n=2) and contracting cube (CC, n=3) equations were found to give the best fits in isothermal TG data among all tested nine mechanism‐based kinetic models. The values of activation energy (E_a), T_E, D_E and activation energy for explosion (E*) have been found to be quite lower for the copper complex as compared to cobalt, nickel and zinc complexes. A mechanism of thermolysis has also been proposed. All these complexes were found to be insensitive towards impact of 2 kg weight up to the height of 110 cm. These complexes were used as energetic burning rate modifiers in the combustion of hydroxy‐terminated polybutadiene (HTPB)‐ammonium perchlorate (AP) composite solid propellants. A two‐fold increase in burning rate was observed with copper and cobalt complexes at low concentration (2% by wt.). The in situ freshly formed metal oxides with large number of active sites in their crystallites seem to be better additives for combustion of propellants.