The corrosion behavior of Co-Mo alloys in H₂-H₂O-H₂S environments

Abstract

The corrosion behavior of Co alloyed with up to 40 wt.% Mo alloys was studied in H₂-H₂O-H₂S gas mixtures over the temperature range between 600‡C and 900‡C. The parabolic rate constants for corrosion decreased with increasing amounts of Mo. The compositions of all gas atmospheres fall in the sulfide(s stability region of the ternary M-O-S phase diagrams at all temperatures investigated. All the corrosion scales were composed of sulfides, while no oxide was detected. The sulfide scales formed were duplex at all temperatures except at 900‡C. The outer layer consisted primarily of cobalt sulfide, while the inner layer was complex and heterophasic, the phases formed being highly composition dependent. MoS₂ predominated in the inner layer for all alloys. However, a metallic Mo layer was formed in the innermost layer of Co-40 Mo. Activation energies were different for all alloys, increasing with increasing Mo content. Identical kinetics were observed for Co-30Mo corroded at 700–800‡C. A Chevrel-phase Co_1.62Mo₆S₈ was present in scales formed on the samples exhibiting the temperature-independent kinetics. A possible model in which Co_1.62Mo₆S₈ forms preferentially in H₂-containing mixed gas is suggested. Alloys corroded at 900‡C formed a lamellar-structure scale which contained Co and CoMo₂S₄ layers perpendicular to the alloy surface. A eutectoid decomposition of an unknown Co-Mo sulfide may be responsible for the presence of the lamellar structure.