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The Role of O2 and H2O Impurities in Dictating the Oxidation Mechanism and Protective Capacity of 9Cr Steels in Hot CO2

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Abstract

The initial stages of oxidation of 9Cr steel in CO2, O2, CO2–O2 and CO2–O2–H2O is studied by gas phase analysis (GPA) at 550 °C using 13C16,16O2, 18,18O2 and 2H216O isotopic molecules in order to discriminate the reactions of all gas molecules. Protective and non-protective oxide scales are formed on 9Cr steel depending on the exact composition of the gas mixture. In pure CO2, 9Cr steel forms a slow growing chromium-rich oxide scale without any carburization. Adding O2 impurities in CO2 favors the formation of fast growing iron-rich duplex oxide scale coupled to strong carburization. Adding several % of O2 in CO2 favors again the formation of slow growing oxide scale but with different structure and composition than in pure CO2. GPA analyses combined with oxide scale analyses demonstrate that the composition and structure of the transient oxide scale formed on 9Cr surface is determined by the rate at which surface adsorbed oxygen atoms are supplied by the gas phase in the first minutes of exposure. The presence of the very oxidizing O2 molecules in CO2 increases drastically the surface oxidation rate, favoring formation of a non-protective oxide scale which transmits carbon permitting carburization of the steel. Adding water vapor to a CO2 gas environment slows carburization. Preferential adsorption of water vapor molecules over CO2/CO molecules in the inner oxide scale is proposed to explain this result. A unified mechanism for the formation of the transient oxide scale on 9Cr steel in CO2/O2/H2O gas mixtures is described.

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Acknowledgements

The authors are grateful to Ms R. Benyhia for carrying out part of the oxidation tests during their Master internship, Mr M. Tabarant for the GDOES analyses and Mr Schlegel for the Raman analyses.

Funding

This study was funded by the French Alternative Energies and Atomic Energy Commission.

Author information

Authors and Affiliations

  1. CEA, Service de Recherche en Corrosion et Comportement des Matériaux, Université Paris-Saclay, 91191, Gif-sur-Yvette, France

    F. Rouillard, L. Martinelli & F. Miserque

  2. Univ Versailles St Quentin En Yvelines UVSQ, Grp Etud Matiere Condensee GEMaC UMR8635, CNRS,, Univ Paris Saclay, 45 Av Etats Unis, 78035, Versailles, France

    F. Jomard

  3. Ugitech Res Ctr, Ave Paul Girod, 73403, Ugine, France

    L. Latu-Romain

  4. School of Materials Science and Engineering, University of New South Wales, Sydney, NSW, 2052, Australia

    D. J. Young

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  1. F. Rouillard
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  4. L. Martinelli
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Contributions

Conceptualization: F.R; Methodology: F.R; Formal analysis and investigation: F.R, F.J, L.L-R, F.M, L.M, DJ.Y; Writing—original draft preparation: F.R, L.L-R, L.M, DJ.Y; Funding acquisition: F.R; Resources: F.R; Supervision: F.R.

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Correspondence to F. Rouillard.

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Rouillard, F., Jomard, F., Latu-Romain, L. et al. The Role of O2 and H2O Impurities in Dictating the Oxidation Mechanism and Protective Capacity of 9Cr Steels in Hot CO2. High Temperature Corrosion of mater. 100, 557–595 (2023). https://doi.org/10.1007/s11085-023-10186-y

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