A substrate steel of the comprising from 0.01 to 0.60 wt. % of La, from 0.0 to 0.65 wt. % of Ce; from 0.06 to 1.8 wt. % of Nb up to 2.5 wt. % of one or more trace elements and carbon and silicon may be treated in an oxidizing atmosphere to product a coke resistant surface coating of MnCr2O4 having a thickness up to 5 microns.