Redox-Induced Microstructure and Phase Dynamics in Nickel: Insights from In Situ Synchrotron X-ray Diffraction.

Using in situ synchrotron X-ray diffraction, we interrogate the microstructural and phase evolution of polycrystalline nickel (Ni) during redox cycling in O2, H2, and H2O environments. Oxidation in O2 promotes strong (111) texturing in both the NiO overlayer and the underlying Ni substrate. However, this crystallographic alignment is lost following reduction in H2 and subsequent reoxidation, demonstrating irreversible microstructural changes. H2 exposure leads to proton dissolution into the Ni lattice, triggering a localized phase transition from face-centered cubic (FCC) to hexagonal close-packed (HCP) Ni in hydrogen-saturated regions. In H2O-containing atmospheres, dissociative H2O adsorption produces protons that permeate the NiO layer, forming γ-NiOOH within the NiO lattice and HCP Ni beneath the NiO overlayer as protons accumulate. Kinetic analysis via the Johnson-Mehl-Avrami-Kolmogorov model uncovers distinct growth mechanisms: preoxidized Ni surfaces follow one-dimensional (1D) kinetics for NiO, γ-NiOOH, and HCP growth, whereas pristine Ni exhibits three-dimensional (3D) kinetics due to island-like nucleation and growth of NiO. These results highlight the critical interplay between H2O dissociation, hydrogen permeation, and redox-driven phase transformations, with practical implications in engineering nickel-based catalysts and hydrogen storage systems through controlled microstructural and phase evolution.