Since pyrotechnic delays are utilized to control the initiation timing of the metal-rich chemical reactions, precise control of these reactions is desired even when the combustion mixture is subjected to extended storage conditions. However, alterations in physicochemical and geometrical properties, accompanied by changes in thermal behavior, significantly influence the reaction pathways. This study explores the reactions of tungsten (W)-based pyrotechnic compositions subjected to aging. In particular, the work identifies the altered reaction pathways and fundamental causes leading to deterioration in both thermodynamic and physicochemical characteristics due to aging under seasonal cycles. Surface analyses revealed the major aging products as KClO3, WO3, BaO, and Cr2O3, along with three distinct effects of aging: pre-oxidation of metals, a priori decomposition of oxidizers, and surface cracking. Thermal analyses using peak deconvolution techniques described the sub-reactions of the major exothermic reaction, such as chemical reactions #1: (W and KClO4) and #2: (W, KClO4, and BaCrO4) and (WO3 and BaO). Notably, samples aged longer than 2 weeks underwent an additional side reaction, #3: (KClO3 decomposition). The multi-step reaction kinetics obtained from the Friedman method disclosed notably distinct trends in both pristine and aged samples. Among the aging products, KClO3 played a decisive role in altering the Eα-α relationship from a monotonic increase to a convex pattern. The measured decrease in Eα due to the involvement of KClO3 was approximately 30 % (from 464.7 kJ/mol to 272.4 kJ/mol). This demonstrates that KClO3 is critical to performance degradation, as it can release excess oxygen at initiation and decompose at a later stage. This results in incomplete combustion and a decline in thermodynamic performance due to the resulting ad-hoc O/F ratio. Thus, these findings may help in designing the time delay margins and estimating the shelf-life of these compositions.
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