Effect of surface hydrogen on the anomalous surface segregation behavior of Cr in Fe-rich Fe-Cr alloys

TL;DR

This study uses ab initio calculations to show that surface hydrogen significantly lowers the energy barrier for chromium segregation in Fe-Cr alloys, affecting their surface composition relevant for nuclear reactors.

Contribution

It reveals how hydrogen adsorption influences Cr segregation barriers in Fe-Cr alloys, a factor not previously considered in modeling these materials.

Findings

Hydrogen reduces the barrier for Cr segregation to surface and subsurface layers.

Cr enhances hydrogen adsorption, further lowering segregation barriers.

Subsurface layer remains the main control point for segregation despite hydrogen presence.

Abstract

The segregation behavior of Cr in dilute Fe-Cr alloys is known to be anomalous since the main barrier for surface segregation of Cr in these alloys arises not from the topmost surface layer but from the subsurface layer where the solution energy of Cr is much more endothermic as compared to the topmost surface layer. The Fe-Cr alloys are candidate structural materials for the new generation of nuclear reactors. The surfaces of these alloys will be exposed to hydrogen or its isotopes in these reactors, and although hydrogen is soluble neither in Fe nor in Fe-Cr alloys, it is known that the adsorption energy of hydrogen on the surface of iron is not only exothermic but relatively large. This clearly raises the question of the effect of the hydrogen adsorbed on the surface of iron on the segregation behavior of chromium towards the surface of iron. In this paper we show, on the basis of our ab initio density functional theory calculations, that the presence of hydrogen on the surface of iron leads to a considerably reduced barrier for Cr segregation to both the topmost surface layer and the subsurface layer, but the subsurface layer still controls the barrier for surface segregation. This reduction in the barrier for surface segregation is due to the nature of the Cr-H couple that acts in a complex and synergistic manner. The presence of Cr enhances the exothermic nature of hydrogen adsorption that in turn leads to a reduced barrier for surface segregation. These results should be included in the multiscale modeling of Fe-Cr alloys.