Date of Award

Fall 2014

Degree Type


Degree Name

Doctor of Philosophy (PhD)


Aeronautics and Astronautics

First Advisor

Timothee L. Pourpoint

Committee Chair

Timothee L. Pourpoint

Committee Member 1

Steven F. Son

Committee Member 2

William Anderson

Committee Member 3

Stephen D. Heister


Traditional hypergolic propellant combinations, such as those used on the space shuttle orbital maneuvering system first flown in 1981, feature hydrazine based fuels and nitrogen tetroxide (NTO) based oxidizers. Despite the long history of hypergolic propellant implementation, the processes that govern hypergolic ignition are not well understood. In order to achieve ignition, condensed phase fuel and oxidizer must undergo simultaneous physical mixing and chemical reaction. This process generates heat, intermediate condensed phase species, and gas phase species, which then may continue to react and generate more heat until ignition is achieved. The process is not well understood because condensed and gas phase reactions occur rapidly, typically in less than 200 &mgr;s, on much faster timescales than traditional diagnostic methods can observe. A detailed understanding of even the gas phase chemistry is lacking, but is critical for model development. ^ Initial research has provided confidence that a study of condensed phase hypergolic reactions is useful and possible. Results obtained using an impinging jet apparatus have shown a critical residence time of 0.3 ms is required for the reaction between monomethylhydrazine (MMH) and red fuming nitric acid (RFNA, ~85% HNO3 + 15% N2O4) to achieve conditions favorable for ignition. This critical residence time spans the time required for liquid phase reactions to occur at the fuel/oxidizer interface and can give some insight into the reaction rates for this propellant combination. Experiments performed in a forced mixing constant volume reactor have demonstrated that the chamber pressurization rate for MMH/RFNA can be significantly reduced by diluting the MMH with deionized water. This result indicates that propellant dilution can slow the chemical reaction rates to occur over observable time scales.^ The research described in this document consists of two efforts that contribute knowledge to the propulsion community regarding the hypergolic liquid propellant combination of MMH and RFNA or pure nitric acid. The first and most important effort focuses on furthering the understanding of condensed phase reactions between MMH and nitric acid. To accomplish this goal diluted MMH and nitric acid were studied in a Fourier transform infrared spectrometer. By tracking the generation or destruction of specific chemical species in the reacting fluid we can measure the reaction progress as a function of reactant concentration and temperature. This work provides the propulsion community with a quantitative global condensed phase reaction rate equation for MMH/nitric acid. The second effort focuses on improving understanding the recently proposed gas phase hypergolic reaction mechanisms using a streak camera based ultraviolet and visible spectrometer. The time resolution on the streak camera system allows for detailed investigation of the pre-ignition and early stage gas phase species present during the reaction between MMH and RFNA.