Articles

All articles  |  Recent articles

Corrosion of Cement-Bonded Refractory Castables due to Hydrogen-Containing Atmosphere

T. Tillmann, T. Leber, T. Tonnesen

Chair of Ceramics, Institute of Mineral Engineering, RWTH Aachen University, Forckenbeckstrasse 33, 52074 Aachen, Germany

received October 3, 2024, received in revised form June 18, 2025, accepted July 18, 2025

Vol. 16, No. 3, Pages 161-172   DOI: 10.4416/JCST2024-00022

Abstract

This study examined the influence of a hydrogen-containing atmosphere on cement-bonded refractory castables. Two series of tests were conducted using different materials, a fireclay and a high-alumina castable with SiC. Each test series consisted of three samples exposed in a tube furnace at temperatures of 1 100 °C and 1 500 °C for 24 and 72 hours. The temperature of 1 100 °C represents the upper temperature limit of a direct reduction plant, while 1 500 °C should provoke corrosion. An optical examination revealed a change in colour, due to the formation of oxygen vacancies. At 1 100 °C, there were only minor changes, with no significant loss of mass or change in porosity. At 1 500 °C a greater loss of mass was observed, particularly at the gas inlet, and an increase in porosity was determined. The chemical composition of the high-alumina material undergoes a transformation, with the loss of SiO₂, SiC, and alkalis. Depending on the temperature and holding time, non-oxide agglomerates of iron and phosphorus, form on the surface. Similarly, agglomeration occurs in the castable with a high alumina content and SiC. In contrast to the other test series these agglomerates do not consist of iron and phosphorus, but of iron and silicon.

Keywords

Hydrogen, refractories, corrosion, high temperature.

References

¹ Houghton, J.: Global warming, Rep. Prog. Phys., 68, 1343 – 1403, (2005). doi: https://doi.org/10.1088/0034 – 4885/68/6/R02.

² Calvin, K. et al.: IPCC, 2023: Climate Change 2023: Synthesis Report. Contribution of Working Groups I, II and III to the Sixth Assessment Report of the Intergovernmental Panel on Climate Change [Core Writing Team, H. Lee and J. Romero (Eds.)]. IPCC, Geneva, Switzerland. https://www.ipcc.ch/report/ar6/syr/(2023) doi: https://doi.org/10.59327/IPCC/AR6 – 9789291691647.

³ Fakten zur Stahlindustrie in Deutschland 2022 | Wirtschafts­ver­einigung Stahl. Wirtschaftsvereinigung Stahl | Informationen des Verbandes der stahlerzeugenden Unternehmen in Deutschland https://www.stahl-online.de/publikationen/fakten-zur-stahlindustrie-in-deutschland-2022/(2022).

⁴ Mahapatra, M.K.: Review of corrosion of refractory in gaseous environment, Int. J. Appl. Ceram. Technol., 17, 606 – 615, (2020) doi: https://doi.org/10.1111/ijac.13418.

⁵ Crowley, M. S.: Hydrogen-silica reactions in refractories, Bull. Am. Ceram. Soc., 46, 679 – 682, (1967).

⁶ Misra, A.: Thermodynamic analysis of chemical stability of ceramic materials in hydrogen containing atmospheres at high temperatures. (1990).

⁷ Schneider, H., Schreuer, J., Hildmann, B.: Structure and properties of mullite — A review, J. Eur. Ceram. Soc., 28, 329 – 344, (2008) doi: https://doi.org/10.1016/j.jeurceramsoc.2007.03.017.

⁸ Leber, T., Madeo, S., Tonnesen, T., Telle, R.: Corrosion of bauxite-based refractory castables and matrix components in hydrogen containing atmosphere, Int. J. Ceram. Eng. Sci., 4, 16 – 22, (2022). doi: https://doi.org/10.1002/ces2.10111.

⁹ Ribeiro Gomes, M. et al.: Towards H2 implementation in the iron- and steelmaking industry: state of the art, requirements, and challenges for refractory materials, J. Eur. Ceram. Soc., 44, 1307 – 1334, (2024). doi: https://doi.org/10.1016/j.jeurceramsoc.2023.10.044.

¹⁰ Gulbransen, E.A., Jansson, S.A.: The high-temperature oxidation, reduction, and volatilization reactions of silicon and silicon carbide, Oxid. Met., 4, 181 – 201, (1972). doi: https://doi.org/10.1007/BF00613092.

¹¹ Davis, R.F., Aksay, I.A., Pask, J.A.: Decomposition of mullite, J. Am. Ceram. Soc., 55, 98 – 101, (1972). doi: https://doi.org/10.1111/j.1151 – 2916.1972.tb11218.x.

¹² Chen, Y., Liu, W., Zuo, H.: Phosphorus reduction behavior of high-phosphate iron ore during hydrogen-rich sintering, Int. J. Miner. Metall. Mater., 29, 1862 – 1872, (2022). doi: https://doi.org/10.1007/s12613 – 021 – 2385 – 0.

¹³ Jacobson, N.S., Eckel, A.J., Misra, A.K., Humphrey, D.L.: Reactions of SiC with H2/H2O/Ar mixtures at 1300 °C, J. Am. Ceram. Soc., 73, 2330 – 2332, (1990). doi: https://doi.org/10.1111/j.1151 – 2916.1990.tb07596.x.

¹⁴ Herbell, P., Eckel, J.: Effect of Hydrogen on the Strength and Microstructure of Selected Ceramics, (1990).

¹⁵ Dooley, D., Balooch, M., Olander, D.R.: Chemical Reduction of Refractory Oxides by Atomic Hydrogen. https://www.osti.gov/biblio/6267436 (1978).

Copyright

Göller Verlag GmbH