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The internal surfaces of modern submerged entry nozzles (SENs) were coated with a glass/silicon powder layer to prevent SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. The results indicated that penetration of the formed alkaline rich glaze into the alumina/graphite base refractory occurs during preheating. More specifically, the glaze reacts with graphite to form carbon monoxide gas. Thereafter, dissociation of CO at the SEN/molten metal interface takes place. This leads to reoxidation of dissolved rare earth metals, which form ‘in situ’ rare earth metal oxides at the interface between the SEN and the molten steel. In addition, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to the formation of a high viscous alumina rich glaze during the SEN preheating process. This, in turn, creates a very uneven surface at the SEN internal surface. The ‘in situ’ formation of the rare earth metal oxides together with the uneven internal surface of the SEN may facilitate the accumulation of the primary inclusions on the refractory walls.

A large number of accretion samples formed inside alumina/graphite clogged Submerged Entry Nozzles (SEN) were examined using FEG-SEM-EDS and Feature analysis. The SENs were used for continuous casting of stainless steel grades alloyed by Rare Earth Metals (REM). The internal surfaces of the SENs were coated by a glass/silicon powder layer to prevent the SEN decarburization during the preheating process. The results indicated a harmful effect of the SENs decarburization on the accretion thickness. In addition, the post-mortem results clearly revealed the formation of a multi-layer accretion. Also, the study indicated the penetration of the protecting glaze into the Alumina/graphite refractory materials. The interaction of the penetrated glaze with alumina in the SEN refractory materials leads to formation of high viscous alumina-rich glaze during the SEN preheating process. This interaction may lead to formation of an uneven surface inside the SEN. These areas consist of alumina particles, silica particles and the penetrated glaze in between. The results showed that these areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. Furthermore, the penetration of the glaze may lead to reactions between alkalines in the glaze and the graphite. This leads to a supply of oxygen at the interface between the SEN and the molten steel. This, in turn, may lead to reoxidation of the REM alloying elements in molten steel under the formation of “in situ” REM oxides. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the SEN´s uneven inside surface, may create a large REM-rich surface in contact with the primary inclusions in molten steel. This may facilitate the attraction and agglomeration of the primary REM oxides inclusions on the SEN internal surface and thereafter the clogging.

Carbon oxidation is a main industrial problem for Alumina/Graphite Submerged Entry Nozzles (SEN) during pre-heating. Thus, the effect of ZrSi2 antioxidants and the coexistence of antioxidant additive and (4B2O3 •BaO) glass powder on carbon oxidation were investigated at simulated non-isothermal heating conditions in a controlled atmosphere. Also, the effect of ZrSi2 antioxidants on carbon oxidation was investigated at isothermal temperatures at 1473 K and 1773 K. The specimens’ weight loss and temperature were plotted versus time and compared to each others. The thickness of the oxide areas were measured and examined using XRD, FEG-SEM and EDS. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 •BaO) glass powder of the total alumina/Graphite base refractory materials, presented the most effective resistance to carbon oxidation. The 121% volume expansion due to the Zircon formation during heating and filling up the open pores by (4B2O3 •BaO) glaze during green body sintering led to an excellent carbon oxidation resistance.

Decarburization behaviours of Al2O3-C, ZrO2-C and MgO-C refractory materials constituting a commercial Submerged Entry Nozzle (SEN), have been investigated in different gas atmospheres consisting of CO2, O2 and Ar. The (CO2/ O2) ratio values were kept the same as it is in propane combustion flue gas at Air-Fuel-Ratio (AFR) values equal to 1.5 and 1 for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out non-isothermally in the temperature range 873 K to 1473 K at 15 (K•min-1) followed by isothermal heating at 1473 K for 60 min. The decarburization ratio (a) values of the three refractory types were determined by measuring the real time weight losses of the samples. The results showed that the decarburization ratio (a) values of the MgO-C refractory became 3.1 times higher for Oxygen-Fuel combustion compared to Air-Fuel combustion at an AFR equal to 1.5 in the temperature range 873 K to 1473 K. The decarburization ratio (a) values for Al2O3-C samples were the same as for the isothermal heating at 1473 K and non-isothermal heating in the temperature range 1473 K to 1773 K with a 15 (K•min-1) heating rate. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times instead of heating at lower temperatures for longer holding times. Diffusion models were proposed for estimating the decarburization rate of Al2O3-C refractory in the SEN. The activation energy for Al2O3-C samples heated at an AFR equal to 1.5, for Air-Fuel and Oxygen-Fuel combustions were found to be 81.8 (KJ•mol-1) and 88.8 (KJ•mol-1), respectively during non-isothermal heating in the temperature range 873 K to 1473 K.

Carbon oxidation is a main industrial problem for alumina-graphite refractory base materials used in commercial Submerged Entry Nozzles (SEN) during preheating. Thus, the effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation were investigated. Laboratory preheating trials were performed at non-isothermal heating conditions in a controlled atmosphere. Also, the applied temperature profile for the laboratory trials were defined based on industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The (CO2/O2) ratios were kept the same as for a propane combustion flue gas at an Air-Fuel-Ratio (AFR) value equal to 1.5 for heating in an air-fuel mixture and in air. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. The YSZ plasma-PVD coated alumina-graphite refractory base materials, presented the effective resistance to carbon oxidation at different coating thicknesses from 160-480 μm in both combustion flue gas and air atmospheres. For the YSZ plasma coating that contained a thinner coating layer such as 160 μm, the uneven surface of the substrate may be reflected more than it could be reflected for a thicker coating. However, for the YSZ plasma coating with a coating thickness of 290 μm, the uneven surface of the substrate may be reflected much less than it could be reflected for thinner coatings. A 250μm and a 290μm YSZ coating may prevent the decarburization of an alumina-graphite refractory base materials during preheating in air at a maximum heating temperature of 1020°C. Moreover, in an oxidizing atmosphere with an AFR value equal to 1.5 at a maximum temperature of 1020°C and a holding time of 7200 seconds. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface and prevention of the decarburization even during heating in air. In addition, the interactions between the YSZ coated alumina-graphite refractory base materials in contact with a cerium alloyed molten stainless steel were surveyed. The YSZ coating provided a total prevention of the alumina reduction by cerium. Therefore, the prevention of the first clogging product formed on the surface of the SEN refractory base materials. Therefore, the YSZ plasma-PVD coating can be recommended for coating of the hot surface of thecommercial SENs.