Understanding the synergistic effect in green propellants 2-azido-N,N-dimethylethanamine and tetramethylethylenediamine: From drop test to gas-phase autoignition

2-Azido-N,N-Dimethylethanamine (DMAZ) and tetramethylethylenediamine (TMEDA) are promising green propellants for hypergolic applications, and blending DMAZ with TMEDA can achieve short ignition delay time (IDT) and comparable specific impulse to hydrazine-based fuels simultaneously. There are reports of a synergistic effect between DMAZ and TMEDA, but its mechanism is not well understood. In this work, drop tests and gas-phase autoignition experiments were combined to provide insights of this synergistic effect from different aspects. The drop tests of DMAZ/TMEDA blends with white-fuming nitric acid were conducted in a confined transparent chamber with controlled O₂ concentration. Results show that the hypergolic ignition is much faster for blends with 20–40 wt% DMAZ under all O₂ concentration conditions, and higher concentration of O₂ in the environment significantly promotes the hypergolic ignition process. To further investigate the chemistry between DMAZ/TMEDA with O₂, gas-phase IDTs were measured using a rapid compression machine and a shock tube in a wide temperature range of 500–1100 K and at pressure of 10 bar. TMEDA shows a higher reactivity at lower temperatures (<690 K), while the autoignition of DMAZ is much faster at higher temperatures (>690 K). A synergistic effect between DMAZ and TMEDA was also observed in the gas-phase autoignition, i.e., fuel blend with 30 % DMAZ showed equal or even lower IDTs than pure TMEDA at lower temperatures. The newly measured IDTs of DMAZ/TMEDA were further adopted to validate a previously developed chemical kinetic model for pure TMEDA and DMAZ, which exhibits good predictions for the blending effects nonetheless. Kinetic analyses reveal that the low-temperature reactivity contributed from the TMEDA can be enhanced by the heat release from DMAZ decomposition, causing the synergistic effect in gas-phase autoignition of DMAZ/TMEDA blends.