The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Al2O3. After oxidation at 750 °C, nucleation of voids at the Ni/Al2O3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO2 due to the outward self-diffusion of Ni2+ ions, followed by the formation of a mixture of metastable and stable α-Al2O3 at the oxide/metal interface that is attributed to a PO2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. The results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.
The in situ closed-cell gas reaction STEM characterization method presented in this study offers the potential to understand the fundamental high-temperature oxidation mechanisms and kinetics for a wide range of alloys.