A quantitative phase-field model for grain boundary trapping and diffusion of hydrogen

Abstract: Grain boundaries influence hydrogen transport in polycrystalline metals by acting as both trapping sites and interconnected diffusion pathways. Conventional interpretations of thermal desorption spectroscopy (TDS) and permeation experiments often treat traps as isolated defects, neglecting grain boundary connectivity and potentially misinterpreting experimental data. Here, we develop a quantitative phase-field model for hydrogen diffusion, grain boundary trapping, and grain boundary-assisted transport. The formulation preserves the physical grain boundary volume independently of the numerical interface thickness and accounts for anisotropic diffusion parallel and perpendicular to grain boundaries. Benchmark simulations verify quantitative behavior under interface upscaling. The model shows that grain boundary diffusion can significantly shift TDS peaks, making Kissinger-type analyses unreliable when grain boundary transport is significant. Effective diffusion coefficients are also shown to depend strongly on grain size, trapping free energy, temperature, and grain boundary mobility. These results highlight the coupled role of trapping thermodynamics, bulk diffusion, and grain-boundary transport.