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The aging mechanism of explosive charges in pyrotechnic mechanical devices (PMDs) is pre-oxidations of their fuels (TiH2 for THPP, Zr for ZPP, and B for BKNO3) by external oxygen. The effect of water on the aging of explosive charges was thus investigated by TEM-EDS/XPS and DFT-based molecular modeling under accelerated aging with 71 °C and 100% relative humidity. The formation of oxide shell and its thickness on the surface of fuels by the aging were observed by TEM-EDS. It failed to detect any oxide on the surface of TiH2 (no sign of Ti-O peaks in XPS) regardless of the aging time, while the thickness of oxide shell increases linearly with the time for ZPP and is saturated at a certain point for BKNO3. It suggested that THPP is highly robust to aging compared to the others (the order of THPP >> BKNO3 > ZPP). Then, DFT-based vacuum slab calculations visualized the diffusion of oxygen from the surface of fuels into the interior, confirming that the activation barrier for the oxygen diffusion is much lower for Zr and B than TiH2 (37, 107, and 512 kcal/mol for Zr, B, and TiH2, respectively), in agreement with experimental results.

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A Combined Study of TEM-EDS/XPS and Molecular Modeling on the Aging of THPP, ZPP, and BKNO3 Explosive Charges in PMDs under Accelerated Aging Conditions