Unveiling Hf-O Clusters Nucleation from Fe-Cr-Al Alloys by Molecular Dynamics Simulations

The precipitation of nanoscale HfO2 plays a critical role in the high-temperature creep properties of Fe-Cr-Al electrical heating alloys. However, the atomic-scale initial nucleation and growth mechanisms remain unclear, hindering the precise design of precipitates based on Hf microalloying. In this study, classical molecular dynamics simulations implemented in LAMMPS were employed to investigate the formation and evolution of Hf-O clusters at 1773 K, 1873 K, and 2000 K. The Fe-Cr-Al-Hf-O system was described by hybrid potential functions, whose reliability was verified by lattice-parameter calculations in good agreement with literature values. The simulation results demonstrate that Hf atoms and O atoms attract each other, forming stable Hf-O clusters. At higher temperatures, the diffusion capabilities of Hf and O atoms are enhanced, the number of Hf-O bonds grows, and the size of the largest cluster expands, indicating that elevated temperatures promote cluster growth. The calculated diffusion activation energy of Hf and O atoms indicates that increasing temperature promotes O atom diffusion more significantly. Analysis of the cluster radius of pair gyration and average atomic energy reveals that Hf-O clusters formed at 1873 K exhibit more compact and stable structural characteristics. Radial distribution function analysis further revealed that the atomic arrangement of neighboring atoms in Hf-O clusters closely resembles the relaxed HfO2 crystal structure at the same temperature, indicating that Hf-O clusters serve as critical nucleation cores promoting the precipitation of HfO2 crystals. This study elucidates the dynamic formation mechanism and structural evolution of Hf-O clusters in Fe-Cr-Al alloys at the atomic scale, providing valuable guidance for the optimized design of precise control over HfO2 nanoprecipitates.