Possible origin and roles of nano-porosity in ZrO 2 scales for hydrogen pick-up in Zr alloys

A mechanistic understanding of Wagnerian build-up and subsequent non-Wagnerian break-down of barrier oxide upon oxidation of zirconium alloys by water is reiterated. Hydrogen assisted build-up of nano-porosity is addressed. Growth of sub-nanometer wide stalactitic pores owing to increasing aggregation of neutral oxygen vacancies offering a means to permeate hydrogen into the alloy is explored by density functional theory. The Wagnerian channel utilizes charge separation allowing charged oxygen vacancies and electrons to move separately from nominal anode to nominal cathode. This process becomes increasingly controlled by the charging of the barrier oxide resulting in sub-parabolic rate law for oxide growth. The break-down of the barrier oxide is understood to be preceded by avalanching hydrogen pick-up in the alloy. Pore mediated diffusion allows water to effectively short circuit the barrier oxide.