Iron-based alloys sulphidation

Although iron sulphide also forms a eutectic with the metal this melts at 988°C, and at temperatures in the region of 700 to 800°C alloys with substantial proportions of nickel replaced by iron and a chromium level maintained at about 20% show advantages over nickel-chromium-base alloys in resistance to sulphur attack. 

Of course, if the protective scale of chromia or alumina is not penetrated by SO2, sulphide cannot form at the scale-metal interface. This was found for Ni-20 wt% Cr, Co-35 wt% Cr and Fe-35 wt% Cr alloys exposed to pure SO2 at 900 °C and emphasizes the resistance of a chromia scale to permeation. On the other hand, alloys in the Fe-Cr-Al, Ni-Cr-Al and Co-Cr-Al systems were exposed to atmospheres in the H2-H2S-H2O system. These atmospheres had compositions that supported the formation of chromia or alumina together with the sulphides of Fe, Ni and Co at the scale-metal interface. In these cases, a protective layer of chromia or alumina that formed initially was penetrated by sulphur to form iron, nickel, and cobalt sulphides at the scale-metal interface. Furthermore, iron, nickel, and cobalt ions apparently diffused through the oxide layer to form their sulphides on the outside of the protective scale. Thus the original protective scale was sandwiched between base-metal sulphides. 

Reid and Schey studied the role of substrate composition and other factors in the formation and performance of films on various metal substrates, including copper, aluminium, titanium and mild steel, tested against themselves and against an alloy steel. They used a twist-compression test to assess performance, and concluded that substrate hardness and composition had the greatest influence on film formation and life. They believed that film formation and especially durability are improved by chemical reaction if a substrate, such as copper or iron, has a strong tendency to react to form a sulphide, provided that the reaction kinetics are favourable. However, they found no direct evidence of reaction or of sulphide formation. Their conclusions were based on the fact that the durability of the films was found to be in the sequence aluminium, titanium, iron, copper, which is the same as the order of the free energies of formation of their sulphides. 

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