The growth of protective ultra-thin alumina layers on γ-TiAl(111) intermetallic single-crystal surfaces

An XPS and AES study of the early stages of oxidation of gamma-TiA1(111) surfaces at 650 degrees C under 1.0 x 10(-7)- 1.0 x 10(-6) mbar O-2 is reported. The data evidence a first regime of oxidation characterized by the growth of a pure alumina layer followed by a second regime of simultaneous oxidation of both alloying elements. In the first regime, continuous alumina layers from similar to 0.4 to similar to 1.5 nm thick have been observed by angle-resolved XPS. The composition of the metallic phase underneath the growing oxide is modified by a depletion of Al and the injection of Al vacancies in the metal during the growth of the transient alumina formed at 650 degrees C. The onset of Ti oxidation was repeatedly observed for a critical concentration in the modified region of the alloy underneath the alumina layer: Ti75 +/- 2Al25 +/- 2 (Ti50Al17 +/- 2V(Al)(33 +/- 2)), showing that decreasing the number of Ti-Al bonds in the modified intermetallic region increases the activity of Ti up to a critical point where its oxidation at the oxide/metal interface becomes competitive with that of Al. The growth of Ti3+ and Ti4+ oxide particles observed above the alumina layer by angle-resolved XPS indicates the transport of titanium cations trough the alumina layer and their subsequent reaction with oxygen at the outer gas/oxide interface. Improving structural ordering in the intermetallic phase slows down the growth kinetics of the alumina layer and the related Al-depletion of the substrate, and increases the resistance of the alloy to the subsequent oxidation of Ti. This is assigned to two combined effects: a slower diffusion of Al in the better ordered metallic phase and the growth of less defective alumina layers allowing to slow down the ionic transport through the oxide. Highly stable and corrosion resistant alloy surfaces covered by a 0.4 nm thick alumina layer have been obtained by slowly oxidizing the alloy at lower partial pressure (<5.0 x 10(-10) mbar O-2). (c) 2005 Elsevier B.V. All rights reserved.