The high-temperature corrosion behavior of Co-Nb alloys in mixed-gas atmospheres

The corrosion of Co-Nb alloys containing up to 30 wt.% Nb in H₂-H₂S-H₂O gas mixtures was studied over the temperature range of 600–800°C. The gas composition falls in the stability region of cobalt sulfide and Nb₂O₅ in the phase diagrams of the Co-O-S and Nb-O-S systems at all temperatures studied. Duplex scales, consisting of an outer layer of cobalt sulfide and a complex, heterophasic inner layer, were formed at all temperatures studied. In addition to cobalt sulfide and CoNb₃S₆, a small amount of NbO₂ was found in the inner layer. The reason for the formation of NbO₂ over that of Nb₂O₅ in the scale is that the outer sulfide scale lowers the oxygen activity within the scale into the NbO₂-stability region. Two-stage kinetics were observed for all alloys, including an initial irregular stage usually followed by a steady-state parabolic stage. The steady-state parabolic rate constants decreased with increasing amounts of Nb, except for Co-20Nb corroded at 700°C. Nearly identical kinetics were observed for Co-20Nb corroded at 600°C and 700°C. The presence of NbO₂ particles leads only to a limited decrease of the available cross-section area for the outward-diffusing metal ions. The activation energies for all alloys are similar and are in agreement with those obtained in a study of the sulfidation of the same alloys. The primary corrosion mechanism involves an outward Co transport.