Analytical electron microscopy of the mixed zone in NiCoCrAlY-based EB-PVD thermal barrier coatings: as-coated condition versus late stages of TBC lifetime

The microstructural evolution of the alumina-zirconia mixed zone in a NiCoCrAlY-based electron beam physical vapor deposited (EB-PVD) yttria partially stabilized zirconia (Y-PSZ) thermal barrier coating (TBC) system from the as-coated condition into the advanced stages of TBC lifetime is monitored by analytical transmission electron microscopy (TEM). In the as-coated condition yttria-rich islands at the thermally-grown oxide (TGO)/TBC interface locally impede zirconia uptake of the scale during TBC deposition and give rise to the formation of an "off-plane" alumina-zirconia mixed zone textured perpendicular to the TGO/TBC interface. During prolonged isothermal/cyclic oxidation an increased chromium diffusion through the TGO scale turns the mixed zone into a reaction zone introducing a morphological instability of the mixed zone/TBC interface due to solutioning of the bottom TBC layer. This microstructural pattern is corroborated by a triple-stage growth model for the mixed zone during three successive stages in TBC lifetime: (i) during TBC deposition, the thickness of the mixed zone increases due to predominant outward aluminum diffusion and uptake of zirconia. No columnar alumina zone (CAZ) has formed at this stage, (ii) upon completion of the transition alumina-to-corundum phase transformation the thickness of the mixed zone remains constant while the change in diffusion mechanism for an inward oxygen diffusion process now initiates parabolic growth of the columnar alumina sublayer of the TGO scale, (iii) in the late stage of TBC lifetime an marked outward chromium diffusion from the bond coat causes the mixed zone to resume growth due to TBC destabilization and the formation of a (Al, Cr)(2)O-3 mixed oxide matrix phase. A transient YCrO3 phase is proposed for driving the destabilization of yttria-rich sections of the bottom TBC layer.