Grain-boundary segregation of 3d-transition metal solutes in bcc Fe: ab initio local-energy and d-electron behavior analysis.

We present ab initio calculations of grain-boundary (GB) segregation of the series of 3d transition-metal (TM) solutes in bcc Fe, taking advantage of the local-energy analysis. For [Formula: see text]11(3 3 2) and [Formula: see text]3(1 1 1) [Formula: see text] symmetrical tilt GBs, the segregation behaviors of 3d-TM solutes can be classified into three groups. The early TMs (Sc, Ti and V) are preferentially segregated to the looser sites of GBs antiferromagnetically, the late TMs (Co, Ni and Cu) are preferentially segregated to the tighter sites of GBs ferromagnetically, and the middle TMs (Cr and Mn) are segregated antiferromagnetically without fixed site preference. TMs at both ends of the 3d series show larger segregation-energy gains, while Mn shows a cusp at the center, which is similar to the ab initio interaction energies between the 3d-TM solutes and a screw-dislocation core in bcc Fe. By the local-energy analysis combined with the local densities of states, the segregation of the early TMs is mainly attributed to the stabilization of surrounding Fe atoms by the TM solute at the looser sites of GBs, and that of the late TMs is mainly attributed to the stabilization of the TM solute itself from bulk Fe to GB sites and the destabilization of Fe atoms around the TM solute in bulk Fe. The cusp at Mn is mainly caused by the destabilization of Fe atoms around the Mn solute in bulk Fe, due to nearly-localized high-spin d states of Mn, in contrast to substantial d-d hybridization for Mn in GBs. For each group of 3d-TM solutes, the effects on the magnetic and mechanical properties of Fe GBs are also analyzed by the d-electron behavior in common with the segregation mechanism.