Electrochemical Synthesis of the Energetic Combustion Catalyst Co(BODN)·9H2O and Its Catalytic Effect on Ammonium Perchlorate Thermal Decomposition.

Safe, efficient, and green synthetic energetic combustion catalysts are of great importance for the application of ammonium perchlorate (AP) in solid propellants. In this study, a novel, simple, efficient, and green electrochemical method for synthesizing energetic combustion catalysts was designed and implemented to successfully synthesize Co(BODN)·9H2O (BODN = [2,2'-bi{1,3,4-oxadiazole}]-5,5'-dinitramide), a novel energetic combustion catalyst. The target products were characterized via single-crystal X-ray diffraction, powder X-ray diffraction, Fourier transform infrared spectroscopy, optical microscopy, scanning electron microscopy, differential scanning calorimetry, and thermogravimetric analysis. Results reveal that Co(BODN)·9H2O crystallizes in the triclinic P1̅ space group and has a density of 1.836 g cm-3. The size of the Co(BODN)·9H2O crystal increases gradually with the increase in the reaction current and the prolongation of the reaction time, respectively. However, the change in reaction current and time does not affect the crystal form. In addition, with the increase in Co(BODN)·9H2O content, the peak temperature of high-temperature decomposition (HTD) and apparent activation energy of AP/Co(BODN)·9H2O gradually decrease, and the heat release during thermal decomposition gradually increases. The HTD peak temperature and apparent activation energy of AP/Co(BODN) 9H2O (10%) decrease by 97.9 °C and 94.2 kJ·mol-1, respectively, compared with those of pure AP, and the heat release during thermal decomposition increases by 1613 J·g-1. Furthermore, compared with those of the propellant containing pure AP, the burning rate and flame temperature of the propellant containing AP/Co(BODN)·9H2O (10%) increase by 8.15 mm s-1 and 458.44 °C, respectively. Real-time Fourier transform infrared spectroscopy reveals that CoO catalyzes the thermal decomposition of AP mainly by promoting electron transfer to accelerate the oxidation of NH3 and the conversion of N2O to NO. In brief, this work provides new insights into synthesizing energetic combustion catalysts. Moreover, Co(BODN)·9H2O synthesized through the electrochemical method exhibits considerable application prospects for improving the thermal and energy performance of AP and the combustion performance of propellants.

Enhanced thermal, safety and anti-hygroscopicity performance of core-shell ammonium perchlorate with a double coating layer.

A new core-shell structure AP/Cu-DABT/Cu(Pa)2 (10 wt% each) (AP = ammonium perchlorate, DABT = 3,3'-diamino-5,5'-bis(1H-1,2,4-triazole), Pa = palmitic acid) with two coating layers was synthesized through two self-assembly reactions to improve the thermal decomposition performance, safety performance and moisture absorption resistance of AP. The results show that the surface of AP particles is uniformly and densely covered by Cu-DABT and Cu(Pa)2 coatings successively. Compared with pure AP, the HTD (high-temperature decomposition) peak temperature and activation energy of the AP/Cu-DABT/Cu(Pa)2 (10 wt% each) composite material were reduced by 74.7 °C and 117.67 kJ mol-1, respectively, and the heat release increased by 1421.02 J g-1. In addition, the burning rate and maximum flame temperature of the propellant containing the AP/Cu-DABT/Cu(Pa)2 (10 wt% each) composite were increased by 8.7 mm s-1 and 815.8 °C, respectively, compared with the propellant containing pure AP. Moreover, compared with pure AP, the contact angle of the AP/Cu-DABT/Cu(Pa)2 (10 wt% each) composite with water increased by 89.15°, and the water content decreased by 0.38 wt%. The impact sensitivity and friction sensitivity of the composite material were reduced by 16.9 cm and 96%, respectively. Analysis shows that the Cu-DABT coating plays a major role in improving the thermal properties of the composite material, the burning rate and flame temperature of the propellant, while the Cu(Pa)2 coating plays a major role in improving the hygroscopic performance and safety performance of the composite material. The composite material has good thermal decomposition properties, anti-hygroscopic properties and safety properties, so the composite material is very promising as a potential additive for solid propellants.

Design, preparation, and combustion performance of energetic catalysts based on transition metal ions (Cu2+, Co2+, Fe2+) and 3-aminofurazan-4-carboxylic acid.

Development of energetic catalysts with high energy density and strong catalytic activity has become the focus and frontier of research, which is expected to improve the combustion performance and ballistic properties of solid propellants. In this work, three energetic catalysts, M(H2O)4(AFCA)2·H2O (AFCA = 3-aminofurazan-4-carboxylic acid, M = Cu, Co, Fe), are designed and synthesized based on the coordination reaction of transition metal ions and the energetic ligand. The target products are characterized by single crystal X-ray diffraction, Fourier transform infrared spectroscopy, differential thermal analysis, optical microscopy, and scanning electron microscopy. The results reveal that Cu(H2O)4(AFCA)2·H2O crystallizes in the monoclinic space group, Dc = 1.918 g cm-3. Co(H2O)4(AFCA)2·H2O, and Fe(H2O)4(AFCA)2·H2O belong to orthorhombic space groups, their density is 1.886 g cm-3 and 1.856 g cm-3, respectively. In addition, the designed catalysts show higher catalytic activity than some reported catalysts such as Co(en)(H2BTI)2]2·en (H3BTI = 4,5-bis(1H-tetrazol-5-yl)-1H-imida-zole), Co-AzT (H2AzT = 5,5'-azotetrazole-1,1'-diol), and [Pb(BTF)(H2O)2]n (BTF = 4,4'-oxybis [3,3'-(1-hydroxy-tetrazolyl)]furazan) for the thermal decomposition of ammonium perchlorate (AP). The high-temperature decomposition peak temperatures of AP/Cu(H2O)4(AFCA)2·H2O, AP/Co(H2O)4(AFCA)2·H2O, and AP/Fe(H2O)4 (AFCA)2·H2O are decreased by 120.3 °C, 151.8 °C and 89.5 °C compared to the case of pure AP, while the heat release of them are increased by 768.8 J g-1, 780.5 J g-1, 750.9 J g-1, respectively. Moreover, the burning rates of solid propellants composed of AP/Cu(AFCA)2(H2O)4·H2O, AP/Co(AFCA)2(H2O)4·H2O and AP/Fe(AFCA)2(H2O)4·H2O are increased by 2.16 mm s-1, 2.53 mm s-1, and 1.57 mm s-1 compared with the case of pure AP. This research shows considerable application prospects in improving the combustion and energy performance of solid propellants, it is also a reference for the design and preparation of other novel energetic catalysts.