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Four stages of the kinetics of solute segregation at (001), (0114), (017), (015), (014) and (013) surfaces of an Fe–6 at.% Si alloy were distinguished. They are controlled by nucleation and growth of stable Six Ny surface compounds at all surfaces. Their formation is accompanied by the shift of kinetic energy of the Si LVV Auger peak. To explain segregation behaviour in particular cases, individual surfaces are considered to be composed of combinations of the two principal planes (001) and (013).