Substitutional solutes in metals generally diffuse by successive exchanges with vacancies, that is, via the so called vacancy mechanism. However, recent density functional theory (DFT) calculations predicted an atypical behavior for the oversized solute atoms (OSAs) in bcc and fcc iron. These solutes exhibit a very strong attraction with a nearby vacancy (V) at a first neighbor (1nn) distance. The attraction is so large that the 1nn OSA-V pair is no longer stable and relaxes spontaneously towards a new configuration where the OSA sits in the middle of the two half-vacancies (V/2). As a consequence, the diffusion of OSAs cannot be described by the standard vacancy mechanism. A new migration mechanism with a new formulation of correlation effects is required. The present study rests on a revised expression of the diffusion coefficient of the OSAs in bcc and fcc lattices, which introduces the concept of macrojumps. The formalism is applied presently to the case of yttrium (Y: a principal alloying element of advanced steels) in iron, using DFT data. But it is directly transferable to other OSAs in cubic metal lattices. At variance with the standard substitutional solutes, the Y atom is found to diffuse more rapidly than iron at all temperatures by orders of magnitude in the two cubic-Fe structures. This finding is opposite to the recent common belief that yttrium is a slow diffusing species in Fe alloys, based on experimental evidences. Several suggestions are proposed to solve this apparent inconsistency.

• Received 16 November 2016
• Revised 7 April 2017

DOI:https://doi.org/10.1103/PhysRevB.95.214108