Visualising microstructural dynamics of titanium aluminium nitride coatings under variable-temperature oxidation

Understanding the link between titanium-aluminium nitride's (Ti1-xAlxN) physicochemical properties and structural dynamics during operation is essential to designing and fabricating advanced ceramic coatings. Here, we directly visualise the oxidation of Ti1-xAlxN (for x = 0, 0.18, 0.44, & 0.67) coatings from 100 to 1000 degrees C using environmental transmission electron microscopy (ETEM) imaging and energy dispersive X-ray spectroscopy (EDX) analysis. The high-frame-rate ETEM movies show that oxidation in TiN proceeds at the grain boundaries and cracks; in contrast, Ti1-xAlxN coatings transform from large as-deposited grains into oxide nanoparticles. Moreover, high-resolution ETEM imaging show the presence of anatase TiO2 at the early stages of oxidation across all compositions. Above similar to 850 degrees C, the oxide nanoparticles grow through crystal merging, diffusion and recrystallisation to form rutile TiO2. The EDX elemental maps coupled with secondary electron imaging reveal a uniform TiO2 sublayer decorated with increasing coverage of Al2O3 particles for x = 0.18 to 0.44. In contrast, coatings with x = 0.67 reveal a complete in-plane phase separation of Al- and Ti-oxides, which can rationalise their decreasing long-term oxidation resistance. Finally, the study provides unique insight into the real-time structural dynamics underpinning the oxidation resistance of Ti1-xAlxN coatings.