Chemical Characterization and Thermal Stressing Studies of Perfluorohexane Fluids for Space-Based Applications

Perfluorohexane (PFH), C6F14, is a perfluorocarbon fluid. Several PFH fluids with different isomer concentrations were evaluated for use in an upcoming NASA space experiment. Samples tested included two commercially obtained high-purity n-perfluorohexane (n-PFH) fluids and a technical grade mixture of C6F14 branched and linear isomers (FC-72(TradeMark)). These fluids were evaluated for exact chemical composition, impurity purity and high temperature degradation behavior (pyrolysis). Our investigation involved simulated thermal stressing studies of PFH fluids under conditions likely to occur in the event of an atmospheric breach within the International Space Station (ISS) and subsequent exposure of the vapors to the high temperature and catalyst present in its Trace Contaminant Control Subsystem (TCCS). Exposure to temperatures in the temperature range of 200-450 C in an inert or oxidizing atmosphere, with and without the presence of catalyst was investigated. The most aggressive conditions studied were exposure of PFH vapors to 450 C in air and in the presence of TCCS (palladium) catalyst. Gas chromatography-mass spectrometry (GC-MS) and gas chromatography (GC) analyses were conducted on the perfluorohexane samples before and after pyrolysis. The FC-72 and n-PFH samples showed no significant degradation following pyrolysis even under the most aggressive study conditions. Some trace level impurities associated with the PFH samples such as linear perfluorocarbon monohydrides or monoiodides were destroyed by pyrolysis at the upper limit. Other trace level impurities such as olefinic or cycloolefinic perfluorocarbons were converted into oxidation products by pyrolysis. The purity of PFH following pyrolysis actually increased slightly as a consequence since these trace contaminants were effectively scrubbed from the samples. However, since the initial concentrations of the thermally-impacted impurities were so low, the net effect was trivial. A potential byproduct of exposure of perfluorohexane fluids to high temperatures is the production of perfluoroisobutene (PFiB), which is extremely toxic. An ultra-high sensitivity PFiB-specific analysis based on GC-MS with negative ion chemical ionization (NICI) detection was used to evaluate the samples following thermal stressing. The perfluorohexanes examined here under conditions reflective of the ISS TCCS environment showed no signs of PFiB production with an analytical detection limit of 10 part per billion (ppb v/v).