Stability of vacancy-hydrogen clusters in nickel from first-principles calculations

The interactions of hydrogen (H) atoms with vacancies are investigated by means of ab initio calculations. The lowest segregation energies are −0.27 and −0.41 eV at single vacancies and divacancies, respectively. These values are in excellent agreement with those corresponding to the two characteristic peaks of the thermal desorption spectra. The microscopic interpretation of the experimental data is therefore clarified. An energetic model is built from the ab initio data and used to study the influence of H bulk concentration and temperature on the concentration of vacancy-H clusters. Analytical expressions, validated by Monte Carlo simulations, are given. The mean vacancy occupation and the H-induced vacancy enrichment are calculated at two temperatures representative of H embrittlement experiments and stress corrosion cracking at high temperatures. The stability domain of VH6VH6 clusters is found to significantly overlap with the experimental conditions for embrittlement. Therefore, vacancy clustering at high concentrations can be qualitatively discussed based on VH6VH6–VH6VH6 interactions that are found weakly repulsive. Consequences on H damage in Ni are discussed. The effect of metal vibrations on segregation and local hydride stability is qualitatively evaluated by off-lattice Monte Carlo simulations using a semi-empirical Ni–H potential. They are shown to shift local hydride stability towards higher H concentrations.