High-Temperature Scaling of Cu–Al and Cu–Cr–Al Alloys: An Example of a Non-Classical Third-Element Effect

Abstract

The oxidation of three Cu–xCr–2Al and three Cu–xCr–4Al alloys (x ≅ 0,4,8 at.%) has been investigated at 800°C in 1 atm O₂. Oxidation of a binary Cu–Al alloy containing 2.2 at.% Al produced external scales composed mainly of copper oxides with small amounts of Al-rich oxide in the inner region, while the internal oxidation of Al was almost absent. The addition of 3.9 at.% Cr to this alloy was able to decrease the oxidation rate but was insufficient to prevent the oxidation of copper. Conversely, addition of 8.1 at.% Cr to the same binary alloy promoted the rather fast formation of a protective Al₂O₃ layer in contact with the metal substrate, with a simultaneous large decrease in the oxidation rate, producing a form of third-element effect. On the contrary, all the Cu–xCr–4Al alloys formed an internal Al₂O₃ layer after an initial stage during which all the alloy components were oxidized, so that the only effect of the presence of chromium was to decrease the duration of the fast initial stage. The third-element effect due to chromium additions to Cu–2Al is related to a transition from the formation of external scales composed of mixtures of Cu and Al oxides to the external growth of Al₂O₃–rich scales as a consequence of a thermodynamic destabilization of copper oxides associated with the formation of solid solutions between Al₂O₃ and Cr₂O₃.