Grain boundary segregation beyond the dilute limit: Separating the two contributions of site spectrality and solute interactions

Abstract Solute segregation at grain boundaries (GBs) is known to have a profound impact on material properties, and as such is becoming routinely used as an element in alloy design. Beyond the dilute limit, the extent of solute GB segregation is known to be concentration dependent. Using hybrid Monte Carlo/Molecular Statics simulations of Mg segregation in Al, we decouple the two contributions to this composition dependence: (i) spectrality of atomic environments at the boundary and (ii) solute-solute interactions. Although only contribution (ii) is typically considered in the literature, we argue that both contributions are equally important to understand concentration dependence and correctly quantify GB solute segregation in a binary alloy. Finally, a thermodynamic segregation isotherm is outlined that accounts for both the spectrality of grain boundary sites and solute-solute interactions. Unlike classical isotherms like those of McLean or Fowler-Guggenheim, which can be successfully fitted to GB segregation data only over a limited range of composition and temperature, our proposed model is shown to be accurate across the composition-temperature space.