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Behavior of basic refractories at high temperatures in steelmaking processes — thermodynamics and implications for the usability of olivine as refractory material

¹ Mineralogisch-Petrologisches Institut und Museum, Universitat Bonn, Poppelsdorfer Schloss, D-53115 Bonn, Germany
² Institut fur Mineralogie und Geochemie, Universitat Koln, Zülpicher Strasse 49b, D-50674 Köln, Germany
³ Landeszentrum für Hochleisrungs-Elektronenmikroskopie NRW, Institut fur Anorganische Chemie, Universitat Bonn, Römerstrasse 164, D-53117 Bonn, Germany
⁴ Weerulin Feuerfeste Materialien GmbH & Co. KG, Frohnhauser Weg 298, D-45472 Mülheim an der Ruhr, Germany

^* corresponding author, e-mail: pack{at}min.uni-koeln.de

Basic unshaped refractories are used as tundish lining in the continuous casting steelmaking process. These refractories are composed of forsteritic olivine and periclase. Slag covers the steel bath in the tundish in order to protect the melt from reoxidation. Using TEM, we demonstrate that the fayalite component of the olivine is reduced to metallic iron giving the olivine a dusty appearence in transmitted light. The reduced olivine appears stable under high temperature reducing conditions. We suggest that diffusion of Mg²⁺ from the outer part of the olivine into empty Fe²⁺ lattice positions in the interior prohibits formation of SiO₂ as by-product of the fayalite reduction. Some of the silica may also have left the olivine in form of gaseous SiO. Periclase reacts with Al₂O₃ from the tundish slag to form spinel. We show that Mn from the steel melt is oxidized and enriched in tundish slag as well as in the refractory. The steel melt is the only source of Mn in the slag. Thermodynamic calculations show that equilibrium fractionation of Fe and Mn between steel melt and slag results in effective separation of Fe (in steel) and Mn (in oxides/silicates).

Key-words: basic refractory, olivine, periclase, continuous casting, clogging, non-metallic inclusions, tundish, slag.

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