Atomistic Studies on Hydrogen and Helium in Fe

Erin Hayward and Chu Chun Fu

CEA-Saclay, DEN/DMN, Service de Recherches de Mtallurgie Physique

Hydrogen
Hydrogen retention and embrittlement are relevant issues for todays fission reactors and tomorrows fusion industry Atomistic simulations -- density functional theory, molecular dynamics, and Monte Carlo -- can be used to give insight into fundamental lattice defect-impurity interactions This study focuses on the interplay between hydrogen and vacancies in body-centered cubic iron, keeping these questions in mind: How is the diffusion of hydrogen affected by vacancies, and vice versa? How is the form and behavior of a hydrogen-vacancy cluster affected by concentration? size?

Low Energy State Searches

Hydrogen + Helium
When hydrogen and helium are both present, additional damage to the material can occur; understanding this synergistic interaction will be vital for fusion environments Although H has only minimal self-attraction in the bulk, He tends to form clusters

We use an iterative method to search for low energy states of defect clusters, consisting of perturbation, minimization, and Monte Carlo selection criteria Minimization may be handled using different methods: Empirical interatomic potentials, molecular dynamics, LAMMPS Density functional theory, SIESTA
8 7 6
Helium atoms

Hydrogen is trapped at these clusters, perhaps attracted to the free volume between He and the Fe Displacement of Fe surrounding cluster (units of a0, MDMC result)

5 4 3 2 1 0 0 5 10 15 20 Hydrogen atoms 25

Diffusion and Electronic Structure of Hydrogen in -Fe

Bulk diffusion is very low barrier, and it may proceed via two competing paths We must account for zero-point energy (ZPE) corrections
2 1 0 -1 -2 2 1 0 -1 -2 Hydrogen in T-site Molecular Hydrogen and Perfect Bulk Iron

Saturation
Due to the tendency to hybridize with Fe, atomic H sticks to the surface of vacancy clusters; molecules are unstable

Hydrogen may assist in helium-induced Frenkel pair ejection

Hydrogen at Monovacancy

Vacancies act as strong traps for hydrogen, however, dissociation of a hydrogen-vacancy pair is more likely than coherent migration
0.8 EAM 0.7 DFT 0.6 0.5 E (eV) 0.4 0.3 0.2 0.1 0 O1 T1 T2 T4 O1

2 1 0 -1 -2

A substitutional He atom can trap up to 8 hydrogen atoms (as opposed to the 6 that a monovacancy can trap), even though the direct attraction between H and He is negligible
-2 0 2

-10

-8

-6

-4 E - EF (eV)

Saturation of the surface may be followed by molecule formation within the void

For more details, see our paper: Different environments result in changes to the electronic structure of hydrogen, with delocalization in space accompanied by delocalization in energy Models based on surface absorption sites are being developed to predict when saturation occurs Interplay between hydrogen and vacancies in -Fe Physical Review B 87, 174103 (2013) or contact us at: erin.hayward@cea.fr chuchun.fu@cea.fr