Influence of Thermally Grown Steel Oxides on Hydrogen Permeation Flux

Hydrogen–steel interactions remain a critical concern for the safe deployment of hydrogen–natural gas mixtures in pipeline infrastructures. Thermally grown iron oxides may be a good barrier to hydrogen ingress into the crystalline lattice of pipeline steels, but their actual effectiveness depends strongly on their composition and stability under service conditions. Several experimental approaches have been proposed to investigate the correlation between thermally grown oxides and hydrogen permeation. Among these, electrochemical permeation testing offers a more complex but safer methodology compared to pressurized hydrogen gas tests. However, when the oxide is directly exposed to the charging side (cathodic charging conditions), permeation behaviour often appears comparable to that of bare steel, and rapid oxide degradation occurs. This study introduces an alternative permeation testing configuration that enables direct assessment of thin thermally grown oxides while preserving their structural integrity. By deliberately placing the oxide on the anodic detection side, mechanical removal during hydrogen evolution is suppressed, allowing the intrinsic resistance of the oxide to hydrogen transport to be evaluated. Carbon steel samples were thermally oxidized at 250 °C for controlled exposure times, and the resulting oxide scales were characterized by Raman spectroscopy, revealing variations in hematite and magnetite fractions. Hydrogen permeation was evaluated using a Devanathan–Stachurski cell by positioning the oxidized surface either on the cathodic charging side or on the anodic detection side. Under these conditions, significant variations in apparent steady-state permeation current density were observed as a function of oxidation time and oxide composition.