Oxidation Behavior of Nanocrystalline Alloys

Thermo-mechanically stabilized nanocrystalline (NC) alloys are increasingly valued for their enhanced mechanical strength and high-temperature stability, achieved through thermodynamic and kinetic stabilization methods. However, their fine-grained structure also increases susceptibility to internal oxidation due to higher atomic diffusivity associated with a greater volume fraction of grain boundaries (GBs). By incorporating solutes that form protective oxides, or the so-called thermally growing oxides (TGO), this vulnerability can be mitigated. The TGO scale acts as a diffusion barrier for oxygen that slows down the oxidation kinetics and prevents internal oxidation that impairs the structural integrity of the metal. This review examines advancements in oxidation-resistant NC alloys, focusing on the interplay between grain size and alloy chemistry. We explore how grain refinement influences diffusion coefficients, particularly the enhanced GB diffusion of Ni and Cr in Ni-Cr-based alloys, which improves oxidation resistance in NC variants like Ni-Cr and Cu-Cr compared to coarse-grained counterparts. We also analyze the role of third elements as oxygen scavengers and the impact of reactive elements such as Hf, Zr, and Y in NiAl alloys, which can slow down diffusion through early establishment of protective TGO layers and enhance oxidation resistance. The concomitant effect of grain size refinement, modifications in alloy stoichiometry, and enhanced atomic diffusion is shown to manifest via drastic reductions in oxidative mass gain, and visualization of the stable, protective oxide scales is delivered through characterization techniques such as TEM, SEM, and EDS. A brief overview is provided regarding stress effects and the role of induced stress in driving oxide scale spallation, which can negatively impact oxidation kinetics. Lastly, we propose future research directions aimed at developing micro-structurally stable NC alloys through multi-solute strategies and surface modification techniques, targeting robust materials for high-stress applications with improved oxidation resistance.