Compared SIMS and NanoSIMS Analyses of Duplex Oxide Layers Growth After Sequential Oxidation Tests Using Oxygen Isotope Tracers

A precise methodology for determining the growth mode of oxide layers on metallic materials at high temperatures is proposed. The approach combines sequential isotopic oxidation tests (using ¹⁶O and ¹⁸O isotopes) with secondary ion mass spectrometry (SIMS and nanoSIMS) analyses. NanoSIMS provides high-resolution localisation of oxygen diffusion pathways and oxide growth zones. However, its limited accessibility and specialised instrumentation can pose practical constraints. In contrast, dynamic SIMS offers broader accessibility and the ability to directly quantify oxygen isotope ratios across depth profiles. The detection of both conventional atomic (O⁻) and diatomic (O₂⁻) oxygen signals in dynamic SIMS analysis proved highly effective in offering insights on oxide growth mode, closely replicating nanoSIMS results. The diatomic signal analysis complements the atomic signal data by improving the understanding of oxidant transport within the oxide layer. The methodology was validated through its application to a Co-10Cr alloy oxidised at 900 °C in O₂, under sequential exposures to ¹⁶O and ¹⁸O isotopes. Both SIMS and nanoSIMS revealed the formation of a duplex oxide layer, consisting of an outer layer formed by outward Co cation diffusion and an inner layer growing by inward oxygen penetration, particularly in the grain-boundary regions of the outer oxide layer. The alloy is proposed to oxidise according to the Available Space Model.