Healing layer formation in Fe–Cr–Si ferritic steels

Abstract

The addition of small amounts of Si can dramatically improve the oxidation resistance of Fe and Fe–Cr steels. It is found that steels with Si contents above a certain critical value oxidise at a much slower rate and also become virtually immune to breakaway oxidation in high pressure CO₂, The critical Si content for this behaviour is found to vary with the Cr content (wt-%) of the steel, from about 2·5% for mild steel to 0·7% for 9%Cr steel to 0·3% for 11%Cr steel in the temperature range 575–650°C. The lower Si content required for Cr steels than for mild steels is advantageous, because it is small enough not to degrade the other metallurgical properties such as creep strength. The beneficial effect of Si is thought to arise from the formation of a near continuous ‘healing’ layer of amorphous SiO₂ at the oxide/metal interface which acts as a diffusion barrier to further transport of metal ions to the scale. The conditions required for the development of such layers are analysed using standard models of selective oxidation. The synergistic effect of Cr and Si is ascribed to the action of Cr as a secondary getter, in which it reduces the oxygen solubility in the metal and so reduces the Si content required to form a healing layer. Chromium also discourages the SiO₂ from converting to fayalite (Fe₂SiO₄) which is a much poorer diffusion barrier. The conventional theory of selective oxidation and secondary gettering is found to describe reasonably well the compositional limits of healing layer behaviour in these ferritic steels. However, the silica also seems to encourage the formation of a chromia based layer at the base of the overlying oxide and the oxidation rate during healing seems to be limited eventually by this chromia layer rather than the silica layer, as would be expected in the conventional model.

MST/1074