Absorption kinetics and hydride formation in magnesium films: Effect of driving force revisited

Abstract

Electrochemical hydrogen permeation measurements and in situ gas-loading X-ray diffraction measurements were performed on polycrystalline Mg films. Hydrogen diffusion constants, the hydride volume content and the in-plane stress were determined for different values of driving forces at 300K. For α-Mg–H, a hydrogen diffusion constant of DHMg=7(±2)·10-11m2s−1 was determined. For higher concentrations, different kinetic regimes with reduced apparent diffusion constants DHtot were found, depending on the driving force, decreasing to about DHtot=10−18m2s−1. This lowest measured diffusion constant is two orders of magnitude larger than that of bulk β-MgH2, and the difference is ascribed to a contribution from a fast diffusion along grain boundaries. The different kinetics regimes are attributed to the spatial distribution of hydrides. A heterogeneous hydride nucleation and growth model is suggested that is based on hemispherical hydrides spatially distributed according to the nuclei densities expressed as a function of the driving force. The model allows us to qualitatively explain the complex stress development, the different diffusion regimes and the blocking-layer thickness. As the blocking-layer thickness inversely scales with the driving force, small driving forces allow the hydriding of large film volume fractions. Maximum stress situations occur for hydride distances reaching four times the hydride radius and for hydride distances equaling the film thickness.