THE THERMAL-DECOMPOSITION OF THE NEW ENERGETIC MATERIAL AMMONIUMDINITRAMIDE (NH4N(NO2)2) IN RELATION TO NITRAMIDE (NH2NO2) AND NH4NO3

This qualitative study examines the response of the novel energetic material ammonium dinitramide (ADN), NH4N(NO2)2, to thermal stress under low heating rate conditions in a new experimental apparatus. It involved a combination of residual gas mass spectrometry and FTIR absorption spectroscopy of a thin cryogenic condensate film resulting from deposition of ADN pyrolysis products on a KCl window. The results of ADN pyrolysis were compared under similar conditions with the behavior of NH4NO3 and NH2NO2 (nitramide), which served as reference materials. NH4NO3 decomposes into HNO3 and NH3 at 182-degrees-C and is regenerated on the cold cryostat surface. HNO3 undergoes presumably heterogeneous loss to a minor extent such that the condensed film of NH4NO3 contains occluded NH3. Nitramide undergoes efficient heterogeneous decomposition to N2O and H2O even at ambient temperature so that pyrolysis experiments at higher temperatures were not possible. However, the presence of nitramide can be monitored by mass spectrometry at its molecular ion (m/e 62). ADN pyrolysis is dominated by decomposition into NH3 and HN(NO2)2 (HDN) in analogy to NH4NO3, with a maximum rate of decomposition under our conditions at approximately 155-degrees-C. The two vapor phase components regenerate ADN on the cold cryostat surface in addition to deposition of the pure acid HDN and H2O. Condensed phase HDN is found to be stable for indefinite periods of time at ambient temperature and vacuum conditions, whereas fast heterogeneous decomposition of HDN at higher temperature leads to N2O and HNO3. The HNO3 then undergoes fast (heterogeneous) decomposition in some experiments. Gas phase HDN also undergoes fast heterogeneous decomposition to NO and other products, probably on the internal surface (ca. 60-degrees-C) of the vacuum chamber before mass spectrometric detection.