Toward better halon substitutes: Effects of carbon chain length on pyrolytic and fire-suppressing mechanisms of perfluoroalkanes

The use of halon fire extinguishants has led to the depletion of the ozone layer, prompting numerous international organizations to invest significant efforts in finding suitable halon alternatives. Among the counterparts, perfluorinated compounds stand out due to their environmental friendliness, specifically, CF3CF3, CF3CF2CF3 and CF3CF2CF2CF3 have been identified by NASA as the most promising candidates within this chemical family. This study digs into the impact of carbon chain length on thermal decomposition and fire suppression mechanisms of perfluoroalkanes with the three agents as model substances, employing experimental and theoretical analyses. Thermal decomposition products within the temperature range of 600 degrees C- 900 degrees C and fire suppression performances, including fire-extinguishing concentrations (9.38 vol.%, 7.81 vol.%, and 6.87 vol.%, respectively), variation of the flame morphology and temperature, are intensively analyzed and compared for the three perfluoroalkanes. Theoretical calculations indicate a decrease in carbon chain stability with the increasing chain length, and CF3CF2CF2CF3 manifests the most diversified self-decomposition paths at low energy barriers. Moreover, a wider spectrum of free radicals can be generated from the longer carbon chain via the C-C cleavage, which can efficiently react with and continuously consume flame radicals (H center dot and OH center dot) to interrupt the combustion chain reaction. These findings enrich the structure-performance relationship of perfluoroalkanes, highlight the potential of specific perfluorinated compounds as viable halon alternatives and offer theoretical guidance for the selection and design of environmentally benign and efficient halon substitutes.