Developing grain boundary diagrams as a materials science tool: A case study of nickel-doped molybdenum

Impurity-based, premelting-like, grain boundary (GB) ``phases'' (complexions) can form in alloys and influence sintering, creep, and microstructural development. Calculation of Phase Diagrams (CalPhaD) methods and Miedema-type statistical interfacial thermodynamic models are combined to forecast the formation and stability of subsolidus quasiliquid GB phases in binary alloys. This work supports a long-range scientific goal of developing ``GB (phase) diagrams'' as a new materials science tool to help controlling the materials fabrication processing and resultant materials properties. Using nickel-doped molybdenum as a model system, a type of GB diagram (called ``{λ} diagram'') is computed to represent the temperature- and composition-dependent thermodynamic tendency for general GBs to disorder. Subsequently, controlled sintering experiments are conducted to estimate the GB diffusivity as a function of temperature and overall composition, and the experimental results correlate well with the computed GB diagram. Although they are not yet rigorous GB-phase diagrams with well-defined transition lines, the predictability and usefulness of such {λ} diagrams are demonstrated. Related interfacial thermodynamic models and computational approaches are discussed.