Oxidation Kinetics of AISI 441 Ferritic Stainless Steel at High Temperatures in CO2 Atmosphere

Ferritic stainless steels used as interconnectors in SOFC stacks are subjected to air and fuel atmospheres at 800 °C. The use of hydrogen as fuel gas may be substituted by fermentative biogas consisting of mainly CO₂ and CH₄. In this gas mixture, carbon dioxide leads to steel oxidation whereas methane induces carburization. The objective of this study was to investigate the oxidation kinetics of the AISI 441 ferritic stainless steel under pure CO₂ in order to understand oxidation mechanisms. The results show that the kinetic behaviour is linear at low temperatures (800–900 °C) and initially linear then parabolic at higher temperatures (925–1,000 °C). Oxide scale consisted of major Cr₂O₃-rich oxide, topped with MnCr₂O₄ and a dispersion of TiO₂. The chromium-rich oxide was analysed by using the photoelectrochemical method. It exhibits N-type semi-conductor. Oxidation kinetics is modelled by the mixed surface and oxide-diffusion limited steps.     

Behaviour of ferritic stainless steels subjected to dry biogas atmospheres at high temperatures

The objective of this study is to understand the high temperature corrosion behaviour of the ferritic stainless steel type AISI 441 (18CrTiNb), a candidate for SOFC interconnectors, under dry synthetic fermentation biogas (CH₄ + CO₂ mixtures), possibly used at the anode side of the cell. Thermodynamic analysis showed that, in such mixtures, the partial pressure of oxygen lies in the range of 10^?23 to 10^?20 bar for temperature between 700 and 900 °C and that the formation of solid carbon may take place in several conditions. XRD results confirmed the formation of Cr₂O₃ and Mn‐Cr spinel, with a mixture of internal carbides. In this temperature range, kinetic experiments showed linear mass change. Comparing with the linear rate constants of 441 oxidised in pure CO₂, corrosion in biogas was larger and increased with increasing the methane content in the biogas. The surface morphology of the corroded specimens showed a dense oxide scale at temperatures less than 800 °C, serving as an efficient barrier to carbon penetration. However, when the temperature reaches 900 °C, cracks and pores appear in the oxide scale, carbon can precipitate and diffuse easier than at 800 °C and may lead to internal carbide formation. In such biogas atmospheres, 800 °C seems the maximum operating temperature of devices containing this ferritic stainless steel.