The phase and microstructural analysis of protective oxide coatings on molybdenum

Due to their high sensitivity to oxygen, the use of refractory metals requires an effective protection against oxidation. In the case of molybdenum this is achieved by using a silicon and boron based coating commercially marketed under the trade name SIBOR registered. In the moduction of a SIBOR registered -coating, a mixture of Si, B and C is plasma sprayed in air onto the Mo-surface to be protected and subsequently annealed in hydrogen. Previous investigations have shown that in doing so a stationary coating of Mo-borides and Mo-silicides is formed. However, the exact phase arrangement and composition has until now remained unclear. Energy dispersive X-ray spectroscopy (EDS) in the scanning electron microscope (SEM) is able to analyse the silicides in SIBOR registered, although due to the overlapping of the Mo-and B-spectral partial a clear identification of the borides was not possible. Using a combination of electron back scatter diffraction (EBSD) and wavelength dispersive X-ray spectroscopy (WDS) it is, however, shown that SIBOR registered is made up of a series of sublayers of Mo2B and MoB followed by Mo5Si3 and MoSi2, and that the other phases of the Mo-Si-B ternary system, i.e. Mo3Si and Mo5SiB2(T2), do not occur. Notably, the two borides and the Mo5Si3 exhibit a structure which is polycrystalline in the lateral direction yet normal to the surface forms of only a single layer of crystallites. In contrast, the final MoSi2-layer has a polycrystalline structure both in the lateral and in the normal directions. Furthermore, Mo5Si3 and MoSi2 both exhibit marked textures. (orig.)