Effect of Mn addition on microstructure and corrosion behavior of AlCoCrFeNi high-entropy alloy

In this study, the effects of Mn content on the microstructure and corrosion resistance of AlCoCrFeNiMnx (x = 0, 0.25, 0.5, 0.75, and 1) high-entropy alloys were investigated. The results indicate that with increasing Mn content, the HEAs consistently comprise nanophase BCC geometry with different shapes embedded in the ordered B2-phase matrix, and the morphology of the microstructure changes from a coarse dendritic structure to a fine dendritic structure, then to a completely columnar dendrite structure. The microhardness of the HEAs increases gradually to 620 HV0.2 when x = 1, owing to the solid-solution and fine-grain strengthening. The corrosion resistance of the HEAs in 3.5 wt% NaCl solution first increases and then decreases, reaching a maximum with the lowest self-corrosion current density of 2.869 × 10−8 A∙cm−2 when x = 0.5. Improvement in corrosion resistance is related to a reduction in degree of composition segregation in the microstructure of HEAs, which leads to the formation of a dense and complete passivation film on the surface of the alloys. However, when the Mn content is in the range of 0–0.5, the pitting potential of the HEAs gradually decreases, although the passivation current density also gradually decreases. Higher Mn content (x > 0.5) leads to a transition of the HEAs from passivation to active dissolution. This indicates that the stability of the passivation film on the HEAs decreases with higher Mn content. XPS analysis revealed a gradual decline in the relative content of Cr2O3 and a gradual increase in the presence of unstable oxides such as MnO and Mn2O3 in the passivation film, leading to this phenomenon. The present work reveals that the addition of Mn in the AlCoCrFeNi HEA affects not only the microstructure and composition segregation but also the composition and stability of the passivation film, leading to a non-monotonic variation in the corrosion performance of the present HEAs with respect to the Mn content.