In this paper, laser cladding technology was used to prepare an Fe-based coating on H13 steel substrate and its corrosion behavior in molten zinc was studied. The results show that a laser-cladding Fe-based coating can effectively protect the substrate from the corrosion of molten zinc, which is mainly related to its microstructure. The typical microstructure of the coating is composed of α-(Fe, Cr) solid solution matrix and CrFeB eutectic phases continuously distribute around the matrix. When molten zinc is in contact with the surface of the coating, it corrodes the α phase matrix preferentially and CrFeB eutectic phases with better corrosion resistance interweave with each other to form a three-dimensional skeletal structure that can play the role of diffusion barrier and slow down the diffusion rate of liquid zinc. The corrosion by molten zinc leads to the formation of a transition layer and an outer corrosion layer above the coatings. With the prolongation of the corrosion time, a large number of microcracks are generated inside the transition layer and fracture gradually occurs under the action of thermal stress. The partial spalling of the transition layer and the corrosion of α phase matrix occur at the same time, making the corrosion depth of the coating increase continuously. However, the dense corrosion layer above the coating and the dispersed boride fragments can still function as a barrier to the inward diffusion of molten zinc.

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