High-temperature sulfidation of Fe-Nb alloys

The sulfidation behavior of Fe-Nb alloys containing up to 30 w/o Nb was studied over the range of 600–900°C in 0.01 aim. S₂ vapor. All alloys were two-phase, consisting of an Fe-rich solid solution and Fe₂Nb, and followed the parabolic rate law at all temperatures. Scales consisted of two layers-an outer layer of FeS and an inner, complex layer which contained some FeS, FeNb₂S₄ (possibly some FeNb₃S₆), NbS₂, and intermetallic particles which were either completely or only partially sulfidized. Platinum markers were located always at the interface between the two layers, which corresponded to the original metal surface. Activation energies were 18±3 kcal/mol in close agreement with the 19.8 reported for pure iron. The sulfidation rate decreased markedly with increasing Nb content of the alloys. The decrease is attributed to increasing amounts of Fe₂Nb with increasing Nb, the net effect being that the diffusion path for outward iron diffusion through the inner layer is reduced as the Nb content increases. An analysis of the structure of NbS₂ reveals that it is easily intercalated with Fe between loosely bonded layers of S-Nb-S. The S-Nb-S layers are covalently bonded which results in very low diffusivities of either S or Nb in pure NbS₂. Although intercalated Fe tends to change the Van der Waal's type bonding between layers to more ionic or covalent, Fe diffuses readily between the layers in NbS₂. Intercalation of Fe also increases the concentration of sulfur defects in NbS₂, which in turn increases the diffusivity of sulfur. Nb was observed to be immobile. Thus, it is thought that either outward iron diffusion or inward sulfur diffusion in the inner layer is the rate-controlling step, in spite of the close agreement of activation energies with that of the sulfidation of pure iron.