Reactivity analysis of ammonium dinitramide binary mixtures based on ab initio calculations and thermal analysis

Abstract

Ammonium dinitramide (ADN) is a promising high energy oxidizer for rocket propellants because it offers a good oxygen balance and has a significant energy content. As a result, ADN-based energetic ionic liquid propellants (EILPs) have been studied, based on ADN combined with urea and monomethyl ammonium nitrate (MMAN). The thermal decomposition of ADN in the condensed phase affects the combustion of both pure ADN and ADN-based EILPs; thus, it is important to understand the reactions of EILPs in the condensed phase. The present study assessed the reactivity of ADN mixtures in the condensed phase, focussing on hydrogen abstraction reactions with NO2· formed from the thermal decomposition of ADN. The potential energy surfaces of these reactions were obtained using ab initio calculations. The effects of functional groups and of carbon chain length on hydrogen abstraction by NO2· were examined. Mixtures of ADN with urea and acetamide (AA) as amide compounds, and with MMAN and monoethanol amine nitrate (MEAN) as nitrate salts, were examined. Thermal analysis was conducted to investigate the properties of these mixtures, using differential scanning calorimetry (DSC). The calculation results shows that AA and MEAN are more reactive with ADN than urea and MMAN, which is supported by the DSC data. Hydrogen abstraction by NO2· is evidently an important condensed phase reaction in ADN mixtures, and substances having alkyl groups and longer carbon chains are more highly reactive.