High temperature corrosion of Fe-Cr-Mn-alloys in H2-H2S and H2-H2O-H2S gas mixtures

The sulfidation of Fe-20% Cr-30% Mn, Fe-25%Cr-20%Mn and Fe-25% Cr was studied at 700°C in H₂-H₂S and the oxidation and sulfidation in H₂-H₂O-H₂S after preoxidation in H₂-H₂O. The sulfidation rate is strongly increased for the Mn-containing alloys, layers of (Mn,Cr)S and (Mn,Fe)Cr₂S₄ are formed. Also the oxidation rate is enhanced compared to Fe-25% Cr by formation of MnCr₂O₄ instead of Cr₂O₃. The sulfidation after preoxidation leads to internal and external sulfidation of the Mn-containing alloys. With increasing oxygen pressure p(O₂) = 10^?26…10^?22 atm. of the H₂-H₂O-H₂S mixtures the sulfidation is suppressed, for the higher oxygen pressure 10^?23 and 10^?22 atm. fast oxidation prevails under formation of MnCr₂O₄. Manganese cannot increase the sulfidation resistance of alloys, in spite of the stability and low degree of disorder of its sulfide, since the mixed sulfide (Mn,Cr)S is formed which has a high degree of disorder, high diffusivities and high growth rate according to the doping effect of trivalent Cr³⁺.