Dissimilar AZ31B-Mg and Ni-coated Q235A-steel alloys were joined in a lap configuration using a laser welding-brazing process. The effects of the Ni coating thickness on the joint appearance, interfacial reactions and mechanical properties were investigated with the assistance of thermodynamic calculations. In the direct irradiation region, Ni atoms diffused and were accumulated near the interface due to the driving force of the chemical potential. Al atoms from the filler were attracted by the concentrated Ni atoms, which resulted in the formation of the FeAl phase. In the middle region and weld toe region, a Fe(Ni) solid solution formed at the interface. Heterogeneous reaction products were produced at the seam near the interface, varying from only the AlNi phase to the AlNi+(α-Mg+Mg2Ni) eutectic with the increase of the coating thickness. Additionally, a bulky Mg2Ni phase also formed in the matrix of Mg-Ni eutectic with a coating thickness of 40 μm. Strong mutual attraction occurred between the Al and Ni atoms at the seam, resulting in a higher driving force for generating the AlNi phase than for generating the Mg-Ni phase. All joints were finally fractured at the seam. The maximum value of the tensile-shear fracture load approached 230 N/mm with a Ni coating thickness of 20 μm, reaching an 88.5% joint efficiency relative to the Mg base metal.
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