Combustion characteristics of EMOFs/oxygenated salts novel thermite for green energetic applications

Abstract

Metal-based thermites, especially those based on aluminum, have been recently included in materials for energetic applications such as pyrotechnics, propellants, and explosives. In parallel, several advances in the field of Metal-Organic Frameworks (MOFs) and Coordination Polymers (CPs) have as well paved the road for their use in developing novel energetic materials. In this context, we are introducing new thermites compositions with low ignition temperature, stable propulsive force, and high reactivity. These thermites are based on the [Cu4Na(Mtta)5(CH3CN)]n (Mtta = 5-Methyl-1H-tetrazole) energetic metal-organic framework (EMOF-1) as a fuel instead of pure metals. We first report the synthesis of an energetic MOF via the microwave-assisted technique as a more rapid and greener method. The efficiency of composites based on EMOF-1 and Al together with various oxygenated salts were investigated. Multiple instruments are involved to characterize the morphology and the structure of EMOF-1 and the developed systems, such as SEM-EDX, FTIR, and XRD. The combustion behavior of the novel composites was evaluated by TGA/DSC, bomb calorimetry and laser ignition. Additionally, the apparent kinetic parameters (activation energy & frequency factor) were calculated by the Kissinger and Ozawa approaches. The results revealed that the new thermite mixtures exhibit superior combustion characteristics of one and half to two-folds the average heat of combustion compared to aluminum-based ones, at almost half the ignition temperature. In this sense, the combustion reaction proceeds faster, easier (reduced activation energy), the ignition temperatures are noticeably lowered, and the heat released has considerably improved. In addition, they exhibited stable force with longer burning time. Among them, EMOF-1/KIO4 thermite exhibits the highest heat release (4.7 kJ/g), while EMOF-1/NH4NO3 thermite shows the lowest onset reaction temperature (224 ᵒC). EMOF-1/KClO4 yields the highest average force (8.4 N), calculated pressure (1365 kPa), pressurization rate (0.32 kPa/μs) and the longest burning time assigned to EMOF-1/K2S2O8 (40 ms).