In this study, we successfully produced Fe-based amorphous composite coatings on the surface of 45 steel using laser cladding technology, and the impact of the relative content of Cr and Mo elements on the microstructure, hardness, and wear resistance of composite coatings has been investigated. The results show that the microstructure of the coating changes from dendrite to amorphous nanocrystalline when the content of Cr and Mo is 20 and 15 wt. %, respectively. However, when the Mo element continues to be added, elemental segregation will be caused, resulting in a large number of brittle Fe–Cr–Mo intermetallic compounds and MoSi2 ceramic phases in the coating. Therefore, the appropriate element ratio can not only increase the amorphous phase content in the coating but also prevent elemental segregation. Among the three types of amorphous composite coatings studied, the Fe45Cr20Mo15B10Si10 (wt. %) composite coating exhibited the most favorable performance, primarily due to its highest amorphous content (43.33%). Through the interaction of the amorphous phase, α-Fe, Fe–Cr solid solution, and a small proportion of intermetallic compounds, this coating achieved a hardness of 1282.8 HV0.2, approximately five times that of the 45 steel substrate, and demonstrated superior wear resistance.
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