Condensed-phase decomposition in thermally-aged explosives
In previous work, the isothermal decomposition of nitrocellulose (NC) was examined using two substantially different experimental techniques that are being developed to investigate condensed-phase chemistry occurring during the thermal decomposition of a variety of explosives. The confined isothermal aging technique involved confined thin-film samples heated to temperatures of 150 to 170{degrees}C, for 1 to 72 hours. Condensed-phase chemistry was monitored real-time using FTIR. Results indicated that the first step in decomposition was scission of the O-NO{sub 2} bond and subsequent formation of carbonyl and hydroxyl products. Scission of the O-NO{sub 2} bond appeared to occur by a first-order reaction. Additional unconfined rapid isothermal decomposition experiments with NC have been completed and are described in this paper. Those additional experiments extended the previous work and investigated the effect of varying film thickness (from about 0.2 to 0.6 microns), varying temperature (from about 420 to 640{degrees}C), and using {sup 15}NO{sub 2}-labled NC. The results indicated that decomposition of NC appears to involve at least two principal mechanisms: (1) O-NO{sub 2} bond scission, which is accompanied by carbonyl or hydroxyl formation, and (2) polymer fragmentation. These two mechanisms occur simultaneously. At temperatures of 170{degrees}C, or lower, polymer fragmentation appears negligible, but at temperatures of 420{degrees}C, or higher, polymer fragmentation is appreciable and occurs at rates comparable to those for O-NO{sub 2} bond scission. While polymer fragmentation may be associated with O-NO{sub 2} bond scission, at higher temperatures, additional steps must be involved in the fragmentation mechanism. At each end of the temperatures range from about 150 to 420{degrees}C, the rate of O-NO{sub 2} bond scission appears reasonably consistent with a mechanism dominated by a first-order decomposition step.
- Research Organization:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Sponsoring Organization:
- USDOE, Washington, DC (United States)
- DOE Contract Number:
- AC04-94AL85000
- OSTI ID:
- 188502
- Report Number(s):
- SAND-95-0886C; CONF-9510228-3; ON: DE96002471
- Resource Relation:
- Conference: Joint Army Navy NASA Air Force propulsion systems hazards subcommittee meeting, Huntsville, AL (United States), 23-27 Oct 1995; Other Information: PBD: [1995]
- Country of Publication:
- United States
- Language:
- English
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