O controle das características da escória de refino primário pode ser realizado pela adição de fluxantes, sendo comumente utilizado a Fluorita (CaF2), isto porque a Fluorita aumenta a solubilidade de CaO e, por conseguinte, aumenta a capacidade de desfosforação de escória. Apesar disso, alguns estudos advertem sobre o risco de liberação de gás tetra fluoreto de silício, que tem caráter nocivo para o meio ambiente. Outro problema relatado é o aumento do desgaste do revestimento refratário impactando nos custos de produção. Neste trabalho de mestrado o uso de Sodalita Nefelínica como fluxante foi comparado com a Fluorita em relação ao desgaste de refratários a base de MgO-C e à fluidez. Os ensaios consistiram em dopar escória de conversor LD com diferentes quantidades de Fluorita e Sodalita (1, 2, 3, 4 % em massa). Os resultados demonstraram que a Fluorita fornece uma escória com menor ponto de fusão e mais fluida, porém ela causa maior desgaste no revestimento refratário, mais que o dobro do desgaste causado pela Sodalita. Acredita-se que isso tenha ocorrido devido a Fluorita ser capaz de aumentar a dissolução tanto do CaO presente na escória quanto do MgO presente no refratário. Este processo é intensificado pela baixa viscosidade apresentada com este fluxante. / The control of the slag characteristics from primary refining can be accomplished by adding fluxes, being commonly used Fluorite (CaF2). This happens because the fluorite increases the solubility of CaO and thus increases the ability of the slag dephosphorization. Nevertheless, some studies warn about the risk of releasing silicon tetra-fluoride gas which has harmful character to the environment. Another problem reported is the increased wear of the refractory lining impacting on production costs. In this master dissertation the use of Sodalite Nepheline as flux was compared with Fluorite concerning MgO-C based refractories wear and fluidity. The tests consisted of doping LD converter slag with different amounts of Fluorite and Sodalite (1, 2, 3, 4 % mass). The results showed that the Fluorite provides a slag with a lower melting point and becomes more fluid, but it causes greater wear on the refractory lining, more than double the wear caused by Sodalite. It is believed that this has occurred due Fluorite be able to enhance the dissolution of the CaO in slag as well as MgO present in the refractory. This process is intensified by the low slag viscosity presented with this flux.

O controle das características da escória de refino primário pode ser realizado pela adição de fluxantes, sendo comumente utilizado a Fluorita (CaF2), isto porque a Fluorita aumenta a solubilidade de CaO e, por conseguinte, aumenta a capacidade de desfosforação de escória. Apesar disso, alguns estudos advertem sobre o risco de liberação de gás tetra fluoreto de silício, que tem caráter nocivo para o meio ambiente. Outro problema relatado é o aumento do desgaste do revestimento refratário impactando nos custos de produção. Neste trabalho de mestrado o uso de Sodalita Nefelínica como fluxante foi comparado com a Fluorita em relação ao desgaste de refratários a base de MgO-C e à fluidez. Os ensaios consistiram em dopar escória de conversor LD com diferentes quantidades de Fluorita e Sodalita (1, 2, 3, 4 % em massa). Os resultados demonstraram que a Fluorita fornece uma escória com menor ponto de fusão e mais fluida, porém ela causa maior desgaste no revestimento refratário, mais que o dobro do desgaste causado pela Sodalita. Acredita-se que isso tenha ocorrido devido a Fluorita ser capaz de aumentar a dissolução tanto do CaO presente na escória quanto do MgO presente no refratário. Este processo é intensificado pela baixa viscosidade apresentada com este fluxante. / The control of the slag characteristics from primary refining can be accomplished by adding fluxes, being commonly used Fluorite (CaF2). This happens because the fluorite increases the solubility of CaO and thus increases the ability of the slag dephosphorization. Nevertheless, some studies warn about the risk of releasing silicon tetra-fluoride gas which has harmful character to the environment. Another problem reported is the increased wear of the refractory lining impacting on production costs. In this master dissertation the use of Sodalite Nepheline as flux was compared with Fluorite concerning MgO-C based refractories wear and fluidity. The tests consisted of doping LD converter slag with different amounts of Fluorite and Sodalite (1, 2, 3, 4 % mass). The results showed that the Fluorite provides a slag with a lower melting point and becomes more fluid, but it causes greater wear on the refractory lining, more than double the wear caused by Sodalite. It is believed that this has occurred due Fluorite be able to enhance the dissolution of the CaO in slag as well as MgO present in the refractory. This process is intensified by the low slag viscosity presented with this flux.

Steel industries consume refractory materials on a large scale. High temperature resistant refractory materials are essential for linings of the steelmaking vessels, to protect them from corrosive environments, high temperatures, molten steels and slags during transportation and steelmaking operations. Furthermore, with the increasing demand in steel production the usage of refractory materials has substantially increased, resulting in an increasing demand for refractory raw materials. However, with the hike in prices and abundancy for raw materials there is a need for recycling and reusing of spent refractory materials, which are otherwise sent to landfill. Nowadays the environmental as well as economic aspect regarding the recycling of spent refractories are of interest for the steel industries for achieving a solution towards zero waste. Several projects have been launched to investigate and generate new ideas with different ways to recycle refractory materials, but there is much more research and planning that needs to be done in order to find a large scale solution towards achieving zero waste. One of the simplest solutions to avoid landfilling of spent refractory is to introduce and manage a good sorting of the breakout scrap refractory, which can later be recycled or reused depending on their condition. The thesis work was carried out in collaboration of KTH – The Royal Institute of Technology/ Stockholm/ Sweden and Jernkontoret – The Swedish Steelmaking Association / Stockholm / Sweden. The work includes a collection of information regarding the current refractory waste management situation within some of the Swedish steel producers as Ovako AB, Uddeholm AB and SSAB. The information were collected on the basis of their refractory usage and practises. The thesis as well provides some suggestions for recycling and reusing of spent refractory waste materials collected from literature. Additionally some experimental work was carried out on whether an MgO-C refractory brick made of recycled materials can perform similarly against slag as a brick made from virgin materials. Experimental corrosion trials with one industrial slag composition were carried out using a hot-finger test apparatus for bricks with different amounts of recycling content in comparison to a brick made of virgin materials. After experiments, the samples were analysed using a Light Optical Microscope (LOM). A similar performance of all bricks against the slag composition was observed. Additional laboratory tests with different slag compositions, holding times and stirring rates are required to reach more profound conclusions. Industrial trials are essential with bricks containing recycled raw materials to reach a final performance status. / Stålindustrin konsumerar eldfasta material i stor skala. Högtemperatur resistenta eldfasta material är nödvändiga för att fodra skänkugnen, för att skydda den från frätande miljöer, höga temperaturer av smält stål och slagg, samt transport och blandning av smält stål under ståltillverkning. Vidare har användningen av eldfasta material ökat avsevärt med den ökande efterfrågan inom stålproduktion, vilket har resulterat i en ökande efterfrågan på eldfasta råvaror. Men i och med prishöjningen och avhållsamheten för råvaror behövs en idé om återvinning och återanvändning av eldfasta material som annars skickas till deponi. Numera är den miljömässiga och ekonomiska aspekten av återvinning av förbrukade eldfasta ämnen av intresse för stålindustrin för att kunna nå en lösning mot zero waste. Flera projekt har påbörjats för att undersöka och generera nya idéer med olika sätt att återvinna eldfasta material, men det finns mycket mer forskning och planering som behöver göras för att hitta en storskalig lösning mot netto noll avfall. En av de enklaste lösningarna för att undvika deponering av använt eldfast material är att införa och hantera en bra sortering av använt eldfast avfall, som senare kan återvinnas eller återanvändas beroende på dess tillstånd. Avhandlingsarbetet utfördes i samarbete med KTH – Kungliga tekniska högskolan / Stockholm / Sverige och Jernkontoret – Svenska stålföreningen / Stockholm / Sverige. Informationen samlades in angående användning och praxis av eldfasta material. Avhandlingen innehåller också några förslag för återvinning och återanvändning av använt eldfast avfall som samlats in från litteraturen. Dessutom utfördes experiment för huruvida en eldfast infodring av återvunnen MgO-C kan motstå reaktioner mot slagg som en infodring tillverkad av ny utvunna råvaror. Experimentella korrosionsförsök med en industriell slaggkomposition utfördes av en ugn designad för hot finger test för eldfasta material gjorda av olika mängd återvunnet material samt inget återvunnet material alls. Efter experimenten analyserades proverna med ett ljusoptiskt mikroskop (LOM). En liknande prestanda för alla tegelstenar mot slaggkompositionen observerades. Ytterligare laboratorietester med olika slaggkompositioner, hålltider och omrörningshastigheter krävs för att nå en djupare slutsats. Industriella försök är väsentliga med eldfast tegel som innehåller återvunna råvaror för att kunna nå en slutlig prestandastatus.

Decades  ago,  1  ton  of  steel  required  80  kg  of  refractory  material.  While  the  scenario  has completely changed over the years. Today, 1 ton of steel needs approximately 11 kg of refractory material   depending   on   the   steelworks.   Refractories   are   accustomed   to   high-temperature processes,  for  example,  producing  steel,  glass,  etc.  The amount of  spent  refractories has  also increased  with the increase in demand for its production. For the manufacturing of refractories, there is a tremendous use of virgin raw materials but with the increase in price and reducing raw material   sources,   it  will   be  difficult  to   continue  in  that   way  in  the  future.  While,  the environmental  concerns  in  steel  industries  are  increasing  on  a  rapid  scale  such  as  global environmental pollution, natural  resource conservation, and the most important increase in cost for  landfilling.  Therefore,  achieving  zero  waste  and  proper  usage  of  material  from  spent refractories is necessary for economic and environmental reasons in future. This project work focuses on collecting information regarding the refractory waste management for  aid  towards   more   sustainable  Swedish  steel  industries.  The  project  is  carried  out  in collaboration  with  KTH  Royal  Institute  of  Technology  and  the  Swedish  steel  producers association  Jernkontoret.  This  work  focuses  on  a   survey   of  well-known  Swedish  steel companies Sandvik Materials Technology (SMT) AB and Höganäs AB. The scientific work concentrates on the investigation of MgO-C bricks mixed waste, collected from Mireco AB, up to a grain size of 20 mm. Three samples of varying compositions and different grain sizes were collected  from  the  recycling  site  and  processed  for  carbon  reduction.  On  several  trails,  the maximum  carbon  elimination  was  achieved at a  temperature higher than  800°C with holding time longer than 5h. The fines underwent mechanical pressing of 40 MPa to form pellets of 16 mm and 32 mm in diameter. The main traced elements of MgO, SiO2, CaO, Al2O3  and Fe2O3  can be utilized for applications in the agricultural industry. MgO is present in the maximum quantity (70-80%).  By  possible  extraction  of  MgO  from  the  fines  can  be  employed  in  the  crucible industry,  construction industry  and steel  industry for slag  formation. The MgO  in the form of supplements for magnesium deficient soils or calcium magnesium oxide for neutralizing the pH of  the  soil  by  balancing  the  acidity  can  be  employed.  The  compatibility of the  fines can be helpful  to  resolve  transportation  issues and benefit  convenient addition to processes. Overall, this  work  brings  to  the  fore  a  high  potential  for  using  such  waste  refractory  materials  forapplications besides landfilling with an emphasis on agriculture. / För decennier sedan krävde 1 ton stål 80 kg eldfast material. Medan scenariot har förändrats helt genom åren. Idag behöver 1 ton stål cirka 11 kg eldfast material beroende på stålverk. Eldfasta produkter är vana vid högtemperaturprocesser, till exempel produktion av stål, glas etc. Mängden förbrukade  eldfasta  produkter  har  också  ökat  med  ökad  efterfrågan  på  dess  produktion.  För tillverkning av eldfasta produkter finns det en enorm användning av jungfruliga råvaror men med prisökningen  och  minskade  råvarukällor  blir  det  svårt  att  fortsätta  på  det  sättet  i  framtiden. Medan  miljöproblemen  inom  stålindustrin  ökar  i  snabb  skala,  såsom  global  miljöförorening, bevarande av naturresurser och den viktigaste ökningen av kostnaderna för deponering. Därför är det  nödvändigt  att  i  framtiden  uppnå  noll  slöseri  och  korrekt  användning  av  material  från förbrukade eldfasta anläggningar av ekonomiska och miljömässiga skäl. Detta projektarbete fokuserar på att samla in information om eldfast avfallshantering för stöd till mer  hållbar  svensk  stålindustri.  Projektet  genomförs i samarbete  med KTH Royal  Institute of Technology och den svenska stålproducentföreningen Jernkontoret. Detta arbete fokuserar på en undersökning  av  välkända  svenska  stålföretag  Sandvik  Materials  Technology (SMT) AB  och Höganäs AB. Det vetenskapliga arbetet koncentrerar sig på undersökningen av blandat avfall av MgO-C-tegel,  samlat  från Mireco  AB, upp till en kornstorlek på 20 mm. Tre prover med olika kompositioner  och  olika  kornstorlekar  samlades  från  återvinningsstället  och  bearbetades  för kolreduktion. På flera stigar uppnåddes den maximala kolelimineringen vid en temperatur högre än 800 ° C  med en hålltid  längre än 5 timmar.  Böterna  genomgick mekanisk  pressning av 40 MPa  för att bilda pellets med 16 mm och 32 mm i diameter. De viktigaste spårade elementen i MgO,  SiO2,  CaO,  Al2O3 och Fe2O3  kan användas för applikationer inom jordbruksindustrin. MgO finns i den maximala kvantiteten (70-80%). Genom möjlig utvinning av MgO från böterna kan användas i degelindustrin, byggindustrin och stålindustrin för slaggbildning. MgO i form av tillskott  för  magnesiumbristjord  eller kalciummagnesiumoxid för neutralisering av jordens pH genom balansering  av surheten  kan användas. Böternas kompatibilitet kan vara till hjälp för att lösa transportproblem och gynna praktiska tillägg till processer. Sammantaget ger detta arbete en hög   potential   för   att   använda   sådana   eldfasta   avfallsmaterial   för   applikationer   förutomdeponering med tonvikt på jordbruk

MgO-C based refractory materials, often used in secondary steel making, are exposed to variouswear mechanisms in its application. The wear could be divided into oxidative, chemical andabrasive categories, all behaving differently and all being influenced by different factors. Dueto the importance of minimizing material loss and to the environmental challenges to run asustainable industry, it is of interest to gain more knowledge of the behavior of the refractorymaterial in use. The present thesis work specifically investigated slag designed of the CaOSiO2-Al2O3-MgO (CSAM) system as well as the chemical and oxidative wear mechanisms ofthree different MgO-C based refractory materials from Höganäs AB, Halmstadverken, whichcontained 5, 10 and 12 wt% carbon (labeled T05, T10 and T12). Different CSAM slags weredesigned to meet certain process criteria such as MgO and CaO saturations and wereinvestigated through thermodynamic calculations using the FactSage software and throughlaboratory scaled slag smelting experiments. The oxidation effect on the refractory material wasalso studied through pre-heating simulations in chamber furnaces, similar to the pre-heating ofa re-built ladle furnace.The thermodynamic calculations made in FactSage 7.0, using the FactPS and FToxid databases, resulted in a few different slag designs with different properties. A few different slagsfulfilled the CaO and MgO saturation limits proposed by Höganäs AB and could be consideredto test experimentally for further evaluation. The simulations also showed trends on how theliquid viscosity behaved with different slag compositions and how the solids content changedwith temperature.The oxidation experiments were performed on the different MgO-C refractory types, where thebricks with 10% carbon also contained Al2O3 antioxidants. The experiments showed that themass loss during the pre-heating is greater for refractory with higher carbon content, withexception to T10, where the mass losses were measured to 3.76 – 4.01%, 1.06 – 1.28% and6.28 – 6.33% for T05, T10 and T12 respectively. Further, the oxidation depth of each materialwas measured to 9-10 mm, 2-3 mm and 2-5 mm for the T05, T10 and T12. The experimentsalso showed that T12 refractory in particular was very susceptible to abrasive wear after beingoxidized.The slag smelting experiments were carried out through two different methods, by melting slagin MgO-C crucibles and by melting pressed slag briquettes on top of refractory bricks. Theformer tests mainly showed that the methodology was not suitable for this type of refractorymaterial due to the crucibles cracking during the experiments. The latter experiments showedsome general behaviour of the different components in the slag, where Ca, Al and Fe stayednear the surface, and Si and Mg penetrated deeper. The spinel formation at the refractory surfacewas then concluded to be the reason for Al not penetrating deeper. Further it was concludedthat no significant difference in refractory dissolution was seen between slags with- and withoutMgO, other than possibly a small increase in refractory dissolution for the latter.

The submerged entry nozzle (SEN) has been used to transport the molten steel from tundish to the mould. The main purpose of the SEN usage is both to prevent oxygen and nitrogen pick-up by molten steel and to achieve the desired flow condition in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. Furthermore, the steelmaking processes occur at high temperatures around 1873 K so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during pre-heating and casting is necessary for the design of the steelmaking processes. The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during pre-heating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied in supplement 1. The results of the study indicated the penetration of the formed alkaline-rich glaze into the Alumina/graphite base refractory during pre-heating. More specifically, the alkaline-rich 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 REM (Rare Earth Metal), which form the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, the interaction of the penetrated glaze with alumina in the SEN base refractory materials leads to a formation of a high-viscous alumina-rich glaze during the SEN pre-heating process. This in turn, creates a very uneven surface at the SEN internal surface. The “In Situ” formation of the REM oxides together with the uneven internal surface of the SEN may facilitate the accumulation of the primary inclusions. Supplement 1 revealed the disadvantages of the glass/silicon powder layer. On the other hand the carbon oxidation is a main industrial problem for un-coated Alumina/Graphite Submerged Entry Nozzles (SEN) during pre-heating. This led to the proposal of a new refractory material for the SEN. In supplement 2, the effect of ZrSi2 antioxidant 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 antioxidant on carbon oxidation was investigated at isothermal temperatures at 1473 K and 1773 K. The specimens’ weight losses and temperatures were plotted versus time and compared to each others. The thickness of the oxide areas were measured and also 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. In supplement 3, decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials constituting a commercial Submerged Entry Nozzle (SEN), have been investigated in different gas atmosphere 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 combustions. Laboratory experiments were carried out non-isothermally in the temperature range 873 K to 1473 K at 15 K/min followed by isothermal heating at 1473 K for 60 min. The decarburization ratio (α) values of the three refractory types were determined by measuring the weight losses of the samples. The results showed that the decarburization ratio (α) values of the MgO-C refractory became 3.1 times higher for oxygen-fuel combustion compared to air-fuel combustion both at AFR equal to 1.5 in the temperature range 873 K to 1473 K. The decarburization ratio (α) values for Al2O3-C samples were the same as for the isothermal heating at 1473 K and non-isothermal heating in the temperature range 473  to 1773 K with a 15 K/min 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. Jander’s diffusion model was proposed for estimating the decarburization rate of Al2O3-C refractory in the SEN. The activation energy for Al2O3-C samples heated at AFR equal to 1.5, for air-fuel and oxygen-fuel combustions were found to be 84.5 KJ/mol and 95.5 KJ/mol respectively during non-isothermal heating in the temperature range 873 K to 1473 K. / QC 20101008

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, 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. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide 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 oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base 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 a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. 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 the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as 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 the commercial SENs. / <p>QC 20111014</p>

The submerged entry nozzle (SEN) is used to transport the molten steel from a tundish to a mould. The main purpose of its usage is to prevent oxygen and nitrogen pick-up by molten steel from the gas. Furthermore, to achieve the desired flow conditions in the mould. Therefore, the SEN can be considered as a vital factor for a stable casting process and the steel quality. In addition, the steelmaking processes occur at high temperatures around 1873 K, so the interaction between the refractory materials of the SEN and molten steel is unavoidable. Therefore, the knowledge of the SEN behaviors during preheating and casting processes is necessary for the design of the steelmaking processes  The internal surfaces of modern SENs are coated with a glass/silicon powder layer to prevent the SEN graphite oxidation during preheating. The effects of the interaction between the coating layer and the SEN base refractory materials on clogging were studied. A large number of accretion samples formed inside alumina-graphite clogged SENs were examined using FEG-SEM-EDS and Feature analysis. The internal coated SENs were used for continuous casting of stainless steel grades alloyed with Rare Earth Metals (REM). The post-mortem study results clearly revealed the formation of a multi-layer accretion. A harmful effect of the SENs decarburization on the accretion thickness was also indicated. In addition, the results indicated a penetration of the formed alkaline-rich glaze into the alumina-graphite base refractory. More specifically, the alkaline-rich glaze reacts with graphite to form a carbon monoxide gas. Thereafter, dissociation of CO at the interface between SEN and molten metal takes place. This leads to reoxidation of dissolved alloying elements such as REM (Rare Earth Metal). This reoxidation forms the “In Situ” REM oxides at the interface between the SEN and the REM alloyed molten steel. Also, 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. Furthermore, these uneven areas react with dissolved REM in molten steel to form REM aluminates, REM silicates and REM alumina-silicates. The formation of the large “in-situ” REM oxides and the reaction of the REM alloying elements with the previously mentioned SEN´s uneven areas may provide 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 oxide inclusions on the SEN internal surface and thereafter the clogging. The study revealed the disadvantages of the glass/silicon powder coating applications and the SEN decarburization. The decarburization behaviors of Al2O3-C, ZrO2-C and MgO-C refractory materials from a commercial Submerged Entry Nozzle (SEN), were also investigated for different gas atmospheres consisting of CO2, O2 and Ar. The gas ratio values were kept the same as it is in a propane combustion flue gas at different Air-Fuel-Ratio (AFR) values for both Air-Fuel and Oxygen-Fuel combustion systems. Laboratory experiments were carried out under nonisothermal conditions followed by isothermal heating. The decarburization ratio (α) values of all three refractory types were determined by measuring the real time weight losses of the samples. The results showed the higher decarburization ratio (α) values increasing for MgO-C refractory when changing the Air-Fuel combustion to Oxygen-Fuel combustion at the same AFR value. It substantiates the SEN preheating advantage at higher temperatures for shorter holding times compared to heating at lower temperatures during longer holding times for Al2O3-C samples. Diffusion models were proposed for estimation of the decarburization rate of an Al2O3-C refractory in the SEN. Two different methods were studied to prevent the SEN decarburization during preheating: The effect of an ZrSi2 antioxidant and the coexistence of an antioxidant additive and a (4B2O3 ·BaO) glass powder on carbon oxidation for non-isothermal and isothermal heating conditions in a controlled atmosphere. The coexistence of 8 wt% ZrSi2 and 15 wt% (4B2O3 ·BaO) glass powder of the total alumina-graphite refractory base 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 a (4B2O3 ·BaO) glaze during the green body sintering led to an excellent carbon oxidation resistance. The effects of the plasma spray-PVD coating of the Yttria Stabilized Zirconia (YSZ) powder on the carbon oxidation of the Al2O3-C coated samples were investigated. 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 the industrial preheating trials. The controlled atmospheres consisted of CO2, O2 and Ar. The thicknesses of the decarburized layers were measured and examined using light optic microscopy, FEG-SEM and EDS. A 250-290 μm YSZ coating is suggested to be an appropriate coating, as it provides both an even surface as well as 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 the commercial SENs.

The thesis addressed the effect of a varying MgO grade in MgO-C refractories on both their behavior in contact with a steel melt and the resulting effect on the non-metallic inclusion (NMI) population in the solidified steel. For this purpose, immersion tests were conducted in a semi-industrial steel casting simulator. In addition, the effect of the steel melting process parameters on the NMI population was thoroughly investigated, providing a guideline for the result interpretation for future experiments in the steel casting simulator. Here, a fundamental concept of data evaluation for the NMI characterization in a steel matrix using automated feature analysis was developed. The main NMI types detected in the solidified steel samples were alumina and MnSi-based inclusions. Their number density depended on the steel melt's temperature and amount of dissolved oxygen. A lower MgO grade refractory specimen in contact with the steel melt resulted in a higher proportion of low melting phases on its surface compared to a higher MgO grade specimen. These low-melting phases promoted the formation of MnSi-based inclusions and triggered NMI agglomeration leading to the formation of large alumina inclusions.