Searching for Low-Sensitivity Cast-Melt High-Energy-Density Materials: Synthesis, Characterization, and Decomposition Kinetics of 3,4-Bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide

Abstract

The most comprehensive approach to analyze and characterize energetic materials is suggested and applied to enable rational, rigorous design of novel materials and targeted improvements of existing materials to achieve desired properties. We report synthesis, characterization of the structure and sensitivity, and modeling of thermal and electronic stability of the energetic, heterocyclic compound, 3,4-bis(4-nitro-1,2,5-oxadiazol-3-yl)-1,2,5-oxadiazole-2-oxide (BNFF). The proposed novel, relatively simple synthesis of BNFF in excellent yields allows for an efficient scale up. Performing careful characterization indicates that these materials offer an unusual combination of properties and exhibit a relatively high energy density, high and controllable stability against decomposition, low melting temperature, and low sensitivity to initiation of detonation. First-principles calculations of activation barriers and reaction rate constants reveal the decomposition scenarios that govern the thermal stability and chemical behavior of BNFF, which appreciably differ from conventional nitro compounds. Details of the electronic structure and calculated electronic properties suggest that BNFF is an excellent candidate energetic material on its own and an attractive ingredient of modern energetic formulations to improve their stability and enable highly controllable chemical decomposition.

A Comparative Density Functional Theory and Density Functional Tight Binding Study of Phases of Nitrogen Including a High Energy Density Material N8

“…Also desired are low cost of inputs and of synthesis as well as low environmental impact of both inputs and the products of decomposition. New HEDMs are actively researched experimentally as well as computationally [2][3][4][5][6][7][8][9]. Most effective molecular HEDM contain nitrogen-and oxygen-containing heterocycles and/or NOx moieties [10].…”

“…Most effective molecular HEDM contain nitrogen-and oxygen-containing heterocycles and/or NOx moieties [10]. The decomposition of such molecules usually leads to the release of COx, NOx and cyanogen molecules which are toxic or environmentally damaging [2][3][4][5][6][7][8][9].…”

Recent Advances in the Synthesis of High Explosive Materials

“…The impact, friction, and ESD sensitivity of this material was found to be comparable to pentaerythritol tetranitrate (PETN). BNFF (aka DNTF) can be synthesized depicted in Scheme 17 [50]. Formation of furazan (63) from malononitrile, followed by diazotization and substitution furnished chloroxime (64).…”

“…Exposure of the chloroxime to silver carbonate afforded difurazano furoxan (65), which was nitrated to yield BNFF (66). BNFF (aka DNTF) can be synthesized depicted in Scheme 17 [50]. Formation of furazan (63) from malononitrile, followed by diazotization and substitution furnished chloroxime (64).…”

Searching for new energetic materials: Computational design of novel nitro-substituted heterocyclic explosives

“…Our recent study 17,25 revealed the four most plausible unimolecular decomposition channels of BNFF and its derivatives, illustrated in Fig. 2: (1) the dissociation of C-NO 2 bond, (2) nitro-nitrite (CONO) isomerization, (3) elimination of CN 2 O 2 through the concerted break of the outer oxadiazol rings, and (4) cleavage of the central ring.…”