Towards a heat- and mass-balanced kinetic model of TATB decomposition

TATB (1,3,5-triamino-2,4,6-trinitrobenzene) was thermally degraded by two small-scale analytical methods - simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) and a hot-stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. SDT used ramped heating, isothermal soaking, and thermal pretreatment at various conditions. The heat flow and mass loss were monitored during various treatment conditions to derive chemical decomposition kinetics and Arrhenius parameters. FTIR experiments used isothermal heating, and changes were monitored spectroscopically. Solid samples generated at specific conditions were collected from both methods and were analyzed by DMSO extraction followed by chemical speciation by optical and mass spectrometric methods. Characterization provided the following reaction insights:1. TATB decreases in a sigmoidal pattern in isothermally heated samples. Other soluble products gradually increase in concentration and then abruptly decline in concentration during the second exotherm, such as diamino-dinitro-benzofurazan and amino-nitro-benzodifurazan.2. FTIR showed gradual changes in the amino and nitro functionality, shifting positions and decreasing intensity for the first 40 min. Then the solid gradually appeared more like an amorphous C with N incorporated, similar to previous studies on thermally degraded TATB-type materials.3. Extracted residues (DMSO-soluble components removed) examined by FTIR showed an abrupt change in chemical composition between 40- and 45-min isothermal treatment, indicating early forming solids are different than later forming residues.4. A reliable mass- and energy-balanced global reaction network must include at least two autocatalytic reactions, either in parallel or series, and at least one must have an explicit initiation reaction having a low activation energy. image

Automated summary

The thermal degradation of TATB was analyzed using two small-scale analytical methods: simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT), and a hot-stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. The results showed that TATB displayed a sigmoidal decrease in concentration during isothermal heating, while other soluble products increased and then abruptly declined in concentration. FTIR analysis revealed gradual changes in the amino and nitro functionality of TATB, and the extracted residues examined also showed a change in chemical composition between different treatment times. The establishment of a reliable mass- and energy-balanced global reaction network for TATB degradation requires the consideration of autocatalytic reactions with low activation energies.