Evaluation of Volatile Species in Green Monopropellant Project

NASA is interested in green monopropellants to replace hydrazine in reaction control systems (RCSs). Some current NASA programs require reduced vapor pressure and low toxicity monopropellant (green) and superior performance (specific impulse and density) formulations. Earlier vapor phase studies of a candidate green monopropellant at the NASA White Sands Test Facility (WSTF) showed the presence of a volatile species that warranted further investigation. The purpose of this study was to further characterize the volatile species and to evaluate it. The evaluation was with respect to whether the volatile species was an impurity or how it is formed, and to use that information to examine whether its presence as an impurity can be eliminated during formulation. The evaluation also considered whether formation of the volatile impurity could be prevented while not compromising the propellant. To reduce variables associated with evaluation of the propellant formulation as a whole, a precursor to one of the individual components in the propellant formulation was subjected to a NASA Standard 6001B Flammability, Off-gassing, and Compatibility Requirements and Test Procedures "Determination of Off-gassed Products (Test 7)". Testing took place in the NASA WSTF Molecular Desorption and Analysis Laboratory. One gram of the precursor was placed in a flask within a specimen container. After thermal conditioning for 72 +/- 1 h at 50 +/- 3 deg C (122 +/- 5 deg F), the atmosphere inside the specimen container was analyzed for off-gassed compounds by cryotrap gas chromatography-mass spectrometry (GC-MS) and fixed sample loop GC-flame ionization detection (GC-FID). The specimen container used was glass to minimize potential catalytic surfaces. The identification of compounds was difficult due to the complexity of the vapor phase concentrations and overlapping chromatographic peaks and mass spectra. However, eleven compounds were specifically identified and five compounds or classes of compounds were reported as unidentified. Quantitation of most of the compounds, including unidentified compounds, was as methane. Quantitating compounds or classes of compounds that were detected but for which specific calibration is not established as methane is in accordance with the Test 7 standard protocol. The thermal decomposition temperature of the precursor was significantly higher than the test temperature. Based on thermal decomposition temperature and on an examination of the structure and chemistry of the identified volatile species, the presence of the volatile species appears to be chemically reasonable with respect to the propellant formulation and is at this time attributed to impurities. Further examination of the overall propellant formulation process (including the individual components' synthesis processes) and process quality control (including purity of reagents and possible decomposition reactions) is indicated