Impurity atoms segregated in grain boundary (GB) regions can dramatically change the physical and chemical properties of the GBs. Such changes often appear to be attributed to the GB energy reduction and/or solute drag effect. Phase-field models have been utilized to clarify both the thermodynamic and kinetic effects of the GB segregation. In this study, we developed phase-field models for GB segregation that are diffuse interface versions of the classical two-phase model of GB segregation. The thermodynamic state at any point in the system is represented as a mixture of a GB phase and a matrix phase. There are two choices for the thermodynamic relation between the GB phase and the matrix phase that constitute the point: the equal composition condition in model I and the equal diffusion potential condition in model II. Most of the previous PFMs for GB segregation appear to be specific cases of model I. We examined the thermodynamic properties of models I and II, and compared them with each other and the classical two-phase model. Although all the models resulted in the same GB composition, the GB energy and its dependency on the composition at the equilibrium state are quite different from each other. In model I, there is a lower bound to the GB energy, which originates from the equal composition condition. The GB energy from model II shows no such lower bound, and it is represented as the vertical distance between the parallel tangent lines on the free energy diagram, as in the classical two-phase model. Nevertheless, the compositional dependence in the model II is quite different from that in the classical two-phase model. This originates from the different choices for the composition-independent parameter in the models: a constant gradient energy coefficient in model II and a constant GB width in the classical two-phase model. Model I is not suitable for simulations of alloys that show a reduction of the GB energy due to GB segregation below a certain limit (in dilute alloys, about half of the GB energy of pure solvents). Model II is a correct choice for such alloys.
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