Oxidation kinetics and mechanism of nickel alloys

Abstract

The study covers the effect of alloying elements on the kinetics and mechanism of oxidation at 1150 °С for 30 hours of heat-resistant nickel alloys obtained using such technologies as centrifugal SHS metallurgy (SHS(M)), vacuum induction melting (VIM), elemental synthesis (ES), hot isostatic pressing (HIP). A comparative analysis was carried out for alloys based on nickel monoaluminide and standard AZhK and EP741NP alloys. It was found that kinetic dependences are described mainly by parabolic approximation. The logarithmic law of oxidation with the rapid (within 3–4 hours) formation of the primary protective layer is typical for alloys doped with molybdenum and hafnium. In the case of AZhK and EP741NP, oxidation proceeds according to a parabolic law at the initial stage (2–3 hours), and then according to a linear mechanism with the voloxidation and complete destruction of samples. Oxygen and nitrogen diffusion proceeds predominantly along the nickel aluminide grain boundaries and it is limited by the Al2O3 + Cr2O3 + XnOm protective film formation. SHS(M) alloys feature by a positive effect of zirconium and tantalum added as dopants on heat resistance. The Ta2O5 phase is formed in the intergranular space, which reduces the rate and depth of oxidation. The zirconium-containing top layer Al2O3 + Zr5Al3O0.5 blocks the external diffusion of oxygen and nitrogen, thereby improving heat resistance. Doping with hafnium also has a positive effect on oxidation resistance and leads to the formation of submicron and nanosized HfO2 inclusions that suppress the grain boundary diffusion of oxygen. MoO3, Mo3O4, CoMoO4 volatile oxides are formed in alloys with a high content of molybdenum and compromise the protective layer integrity. A comparative analysis of the oxidation kinetics and mechanism for samples consisting of the base β-alloy with Cr + Co + Hf additives showed a significant effect on the heat resistance of the sample preparation method. As the proportion of impurity nitrogen decreases and the Cr2O3 sublayer is formed, the oxidation mechanism also changes.