Thermal decomposition of energetic materials 35 A mechanism study of decomposition and the ignition-like transition in trinitromethyl alkyl compounds

✍ Scribed by T.B. Brill; R. Subramanian

• Publisher: Elsevier Science
• Year: 1990
• Tongue: English
• Weight: 418 KB
• Volume: 80
• Category: Article
• ISSN: 0010-2180
• DOI: 10.1016/0010-2180(90)90123-9

✦ Synopsis

Chemical features of the mechanism of the apparent transition from decomposition to deflagration frequently observed in compounds containing the trinitromethyl group have been elucidated by using rapid-scan FTIR spectroscopy with temperature profiling as a function of pressure. The compounds studied were [(NO2)aCCH20]xCH4_x, x = 2-4 (TEFO, TNEOF, TNEOC, respectively). TEFO, TNEOF, and TNEOC were studied in the most detail. They melt 40°C or more below the decomposition point when rapidly heated (70°-200°C/s). The first detected thermolysis step is homolysis of a few C-NO2 bonds per molecule liberating NO2(g). The temperature at which this occurs at 15 psi Ar is TEFO (145°C) < TNEOF (180°C) < TNEOC (200°C), which is consistent with C-C bond scission also occuring in the condensed phase. The resultant residue exotherms in a narrow temperature range (230°-250°C) irrespective of the static pressure (15-1000 psi Ar) or the original sample. This indicates that the ignition-like step involves the residue alone in the condensed phase without participation of the initially released NO2(g).