Zr alloy protection against high-temperature oxidation: Coating by a double-layered structure with active and passive functional properties

Abstract

In this work, a new concept of metal surface protection against degradation caused by high-temperature oxidation in water environment is presented. We were the first to create a double-layered coating consisting of an active and passive part to protect Zr alloy surface against high-temperature oxidation in a hot water environment. We investigated the hot steam corrosion of ZIRLO fuel cladding coated with a double layer consisting of 500 nm nanocrystalline diamond (NCD) as the bottom layer and 2 μm chromium-aluminum-silicon nitride (CrAlSiN) as the upper layer. Coated and uncoated ZIRLO samples were exposed for 4 days at 400 °C in an autoclave and for 60 min at 1000 °C (nuclear reactor accident temperature) in a hot steam furnace. We have shown that the NCD coating protects the Zr alloy surface against oxidation in an active way: carbon from NCD layer enters the Zr alloy surface and, by changing the physical and chemical properties of the Zr cladding tube surface, limits the Zr oxidation process. In contrast, the passive CrAlSiN coating prevents the Zr cladding tube surface from coming into physical contact with the hot steam. The advantages of the double layer were demonstrated, particularly in terms of hot (accident-temperature) oxidation kinetics: in the initial stage, CrAlSiN layer with low number of defects acts as an impermeable barrier. But after a longer time (more than 20 min) the protection by more cracked CrAlSiN decreases. At the same time, the carbon from NCD strongly penetrates the Zr cladding surface and worsen conditions for Zr oxidation. For the double-layer coating, the underlying NCD layer mitigates thermal expansion, reducing cracks and defects in upper layer CrAlSiN.