States and transport of hydrogen in the corrosion process of an AZ91 magnesium alloy in aqueous solution

Mott–Schottky measurement and secondary ion mass spectroscopy (SIMS) were used to investigate the states and transport of hydrogen during the corrosion behavior of an AZ91 magnesium alloy in 0.1 M sodium sulfate solution. The results showed that when samples were immersed or charged in solution, hydrogen atoms diffused into the film and reacted with vacancy to cause the increases of the carrier concentration (excess electron or hole carrier) and diffusion rate of hydrogen. Some hydrogen atoms diffused to interior of matrix and enriched in β phase while others resorted in the corrosive film. With the increase of immersion or charging time, magnesium hydride would be brittle fractured when the inner stress caused by hydrogen pressure and expansion stress of formation of magnesium hydride was above the fracture strength, which provided the direct experimental evidence of the hydrogen embrittlement (HE) mechanism of magnesium and its alloys. After immersion in solution, the transfer of excess electrons to the interfaces of corrosion film and solution would destroy the charge equilibrium in the film and stimulate the adsorption of SO42-, which resulted in the initiation of localized corrosion; after cathodic charging and then immersion, the enrichment of hydrogen atoms at interior of corrosion film would combine into hydrogen gas to form high pressure and result in the rupture of corrosion film, and localized corrosion initiated and developed at surface. Therefore, localized corrosion nucleated earlier on the charged samples than on the uncharged samples. Hydrogen invasion accelerated the corrosion of matrix.