First-Principles Study of Rare-Earth Doping Effects on Nitrogen Adsorption and Diffusion in Chromium

To address the premature corrosion failure of chromium-based coatings in harsh environments (e.g., high temperatures, chloride-containing solutions), this work systematically investigates how rare-earth (RE, i.e., Ce and La) elements regulate nitrogen (N) adsorption and diffusion behavior in Cr during the early stages of nitriding, a critical corrosion protection strategy, using first-principles density functional theory (DFT). Results show that RE preferentially occupies Cr substitutional site, increasing the Young’s modulus from 293.5 GPa (pristine Cr) to 344.9 GPa (Ce-doped) and 348.7 GPa (La-doped). Surface RE doping on Cr(110) significantly enhances N adsorption energy from −3.23 eV to −3.559/−3.645 eV (Ce-/La-doped), whereas subsurface doping slightly weakens the adsorption. Moreover, the energy barrier for N penetration into subsurface is reduced from 2.11 eV to 2.03/1.91 eV (Ce-/La-doped), thereby facilitating nitridation. Notably, RE is found to strongly trap vacancies and N atoms, leading to increased migration barriers and thus hindering their long-range transport. These findings demonstrate that RE exhibits a dual role during nitriding: promoting N incorporation at the surface while restricting its deep diffusion into the bulk. The study provides theoretical insights into the atomistic mechanisms by which RE elements modulate nitriding efficiency in Cr-based alloys, offering guidance for the design of RE-doped surface-modified coatings with improved corrosion resistance.