Comparative Study of Molecular Fragmentation in Sub-Initiated Tatb Caused by Impact, Uv, Heat and Electron Beams

Liquid state thermochemical decomposition of neat 1,3,5,5-tetranitrohexahydropyrimidine (DNNC) and its DNNC-d2, DNNC-d4, DNNC-d6 structural isotopomers: Mechanistic entrance into the DNNC molecule

“…In the case of structurally related RDX, sub-initiation by impact displays trigger linkage or first reaction N O bond rupture to form the analogous trinitroso intermediate compound [45]. More drastic sub-initiated shock reveals a melamine type of product where C H bond rupture [20], the rate-controlling step reflected by KDIE-based thermochemical decomposition investigations [11,12], apparently follows the initial N O bond rupture, and again, leaves the skeletal ring structure intact as discussed in Section 1.…”

“…In every case, the same mechanistic rate-controlling bond rupture found in the ambient pressure decomposition process for each compound, proved to be a significant ratecontrolling mechanistic feature observed in rapid deflagration [8,14], high-pressure combustion [14][15][16], and thermal explosion events [3,14]. Furthermore, it is detected as being a significant contributing mechanistic feature in impact or shock explosive initiation sensitivity [12,[17][18][19][20][21][22][23]. Identification of the pathway directing initial bond rupture, of the subsequent rate-controlling bond rupture, and of the resultant product composition formed during the thermochemical decomposition processes are critical for obtaining energetic compounds with improved thermochemical and initiation sensitivity properties.…”

“…Thirdly, sub-initiation impact and shock studies, where the charred inner surfaces of hot spots caused by a rapid thermochemical decomposition process, also reveal condensed phase intermediate condensed phase products with intact ring structures for TNT [22], TATB [21], and RDX [14,20]. In the case of structurally related RDX, sub-initiation by impact displays trigger linkage or first reaction N O bond rupture to form the analogous trinitroso intermediate compound [45].…”

“…Secondly, past condensed phase product isolation studies with TNT [41,42] and TATB [19] show intact ring structures where decomposition reactions occur only with the pendant methyl, amino, and nitro groups and include those consis- tent with the KDIE-determined rate-controlling C H (TNT) [10] and N H (TATB) [3] bond ruptures. Ring structures are left intact, and initial reactions with nitramines appear to involve the pendant NO 2 group [5,8] and subsequent rate-controlling ring hydrogen atom rupture by NO 2 radical abstraction [8].…”

Solid State Thermochemical Decomposition of Neat 1,3,5,5-Tetranitrohexahydropyrimidine (DNNC) and Its DNNC-d6 Perdeuterio-Labeled Analogue

“…In every case, the same rate-controlling bond rupture found in the ambient pressure thermochemical decomposition process for a given energetic compound [2,12,[16][17][18][19]] also appears to be the rate-controlling step for high-pressure combustion [4,12,20] and the predominant rate-controlling feature in explosive initiation events [2,12,19,[21][22][23][24][25][26].…”