Analysis of Volatile Degradation Products From Green Stabilizers in Smokeless Propellants With Comprehensive Two‐Dimensional Gas Chromatography

The European Chemicals Agency regulations have recently begun encouraging greener chemistry across all sectors. Armament manufacturers are very interested in moving forward by replacing propellant stabilizers with natural products, which aligns with the green chemistry principle of designing safer chemicals. This article highlights variabilities in the volatiles emitted from propellant powders during aging (from STANAG 4582 [NATO Standardization Agreement]) containing three green stabilizers: α‐ionone, α‐tocopherol, and hydroxyl‐terminated polybutadiene. Headspace solid‐phase microextraction was applied in combination with comprehensive two‐dimensional gas chromatography–time‐of‐flight mass spectrometry (GC × GC–TOFMS) to analyze the volatile organic compound (VOC) fraction coming from the aging of propellants with three different green stabilizer additives. Principal component analysis (PCA) was used to compare the evolution of VOC profiles over time. The VOC profile from samples less than 5 years aged did not cluster closely on the PCA score plot, indicating variation in their VOC profile based on the number and amount of compounds. Samples greater than 5 years aged demonstrated stable composition with a similar number and amount of compounds present in the VOC profile. The VOC profile demonstrated a shift from fresh to degraded samples, demonstrating that this workflow could be useful to monitor aging progression in the routine quality control of stabilizers.