Abstract
The potential of tetrazole-based ligands for forming energetic complexes applied in pyrotechnics and propellants is demonstrated with the use of 5,5’-(1,3-phenylene)bis(1H-tetrazole) (H2BTB) to generate an energetic complex with high energy. A new energetic complex of PbII-tetrazolate, [Pb2(BTB)2(H2O)8]·5H2O (1), was synthesized and structurally characterized by single crystal X-ray diffraction. Structural analysis reveals that the central PbII ions present two distinct coordination environments in the asymmetric unit, including distorted pentagonal bipyramid and distorted tetragonal pyramid geometries, respectively. To identify potential combustion catalyst as additives in propellants, we employed differential scanning calorimetry technique to evaluate the influence of the complex on thermal decomposition of ammonium perchlorate (AP) and cyclotrimethylenetrinitramine (RDX). The kinetic parameters of an exothermic process for the catalytic system of RDX+1 were investigated by the Kissinger’s and Ozawa-Doyle’s methods. For both AP and RDX, the decomposition temperature decreased obviously in the presence of 1, and the released heat could effectively compensate the propellants. Our observations demonstrate that 1 shows good catalytic activity toward the thermal decomposition of AP and RDX.
Highlights
IntroductionThe design and preparation of energetic materials that combine high performance and low sensitivity have been widely studied for military and civilian applications over the last decades.[1,2] Nitrogen-rich heterocycles, featuring high nitrogen content and heats of formation, can generally derive energy from ring or cage strain and the oxidation of their carbon backbone to mainly yield environmentally friendly N2 molecules as end-product of propulsion or explosion.[3,4,5,6] Given the generation of gasses, these derivatives show potential applications as promising materials in explosives, solid propellants, and other thermal decomposition and combustible systems.7-10 5,5’-(1,3-Phenylene)bis(1H-tetrazole) (H2BTB), exhibits a high nitrogen content of 52.3% and containsVol 31, No 8, 2020 Experimental CautionH2BTB in its dehydrated form shows increasing friction and impacts sensitivity; PbII-based H2BTB complex is energetic material
The Pb1II ion locates in a ψ-PbNO5 distorted pentagonal bipyramid geometry, while the coordination configuration of Pb2II can be described as a ψ-PbNO3 distorted tetragonal pyramid
Differential scanning calorimetry (DSC) results showed that the 1 significantly accelerated the decomposition of ammonium perchlorate (AP) with the decomposition temperature reducing from 442 to 343 °C and the decomposition heat increasing from 1522 to 2524 J g−1, which was vastly superior to PbO catalyst
Summary
The design and preparation of energetic materials that combine high performance and low sensitivity have been widely studied for military and civilian applications over the last decades.[1,2] Nitrogen-rich heterocycles, featuring high nitrogen content and heats of formation, can generally derive energy from ring or cage strain and the oxidation of their carbon backbone to mainly yield environmentally friendly N2 molecules as end-product of propulsion or explosion.[3,4,5,6] Given the generation of gasses, these derivatives show potential applications as promising materials in explosives, solid propellants, and other thermal decomposition and combustible systems.7-10 5,5’-(1,3-Phenylene)bis(1H-tetrazole) (H2BTB), exhibits a high nitrogen content of 52.3% and containsVol 31, No 8, 2020 Experimental CautionH2BTB in its dehydrated form shows increasing friction and impacts sensitivity; PbII-based H2BTB complex is energetic material. The design and preparation of energetic materials that combine high performance and low sensitivity have been widely studied for military and civilian applications over the last decades.[1,2] Nitrogen-rich heterocycles, featuring high nitrogen content and heats of formation, can generally derive energy from ring or cage strain and the oxidation of their carbon backbone to mainly yield environmentally friendly N2 molecules as end-product of propulsion or explosion.[3,4,5,6] Given the generation of gasses, these derivatives show potential applications as promising materials in explosives, solid propellants, and other thermal decomposition and combustible systems.7-10 5,5’-(1,3-Phenylene)bis(1H-tetrazole) (H2BTB), exhibits a high nitrogen content of 52.3% and contains. Vol 31, No 8, 2020 Experimental Caution. H2BTB in its dehydrated form shows increasing friction and impacts sensitivity; PbII-based H2BTB complex is energetic material.
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