The advancement in computational thermodynamics can help researchers to test their hypotheses regarding complex steelmaking operations in a more quantified manner. The main aim of the current work was to use develop a kinetic model that can predict changes in steel, slag and inclusions during ladle refining and use this model as a tool to develop better understanding of the steelmaking process itself. The important reactions during ladle refining are: steel-refractory reaction, slag-refractory reaction, flotation of inclusions to slag, steel-inclusion reaction, steel-slag reaction and inclusions originating from slag. The chemical reactions between two phases were considered to be mass transfer controlled. The macro-processing feature in FactSage was used to do multiple equilibrium calculations and calculate the change in steel, slag and inclusion composition. Targeted experiments and industrial trials were conducted to find model parameters. For laboratory experiments, the rate of magnesium-transfer to oxide inclusions in steel due to steel-crucible and steel-slag reaction was studied. It was concluded that the presence of spinel layer on MgO crucible at the steel-crucible reaction can help in significantly reduce the rate of Mg pick-up due to steel-crucible reaction. For industrial trials, a comparison between the rate of steel-slag reaction and inclusion flotation rate showed that the steel-slag reaction could be significantly slowed due to slag inhomogeneity. The kinetic model was also used to identify artifacts in steel and slag sampling during ladle refining. One of the main limitations of the kinetic model was the over-prediction of calcium pick-up in steel due to steel-slag reaction. Induction furnace experiments were conducted using MgO, ZrO2 and CaO crucible with different slag composition and silicon concentration to study the extent of calcium pick-up due to steel-slag and steel-crucible reactions. The steel-CaO crucible equilibrium experiment was used to estimate Ca-O interaction parameter. The equilibrated steel was reoxidized with known amount of oxygen to allow all the dissolved calcium to precipitate as oxide inclusions. Inclusion analysis of sample taken after reoxidation was used to estimate dissolved calcium in steel. The measured dissolved calcium was used to estimate Ca-O interaction parameter. A private database for liquid steel was created in FactSage and used for kinetic modeling of laboratory scale steel-slag-crucible experiments. The use of private database for kinetic model helped in avoiding excess calcium pick-up in steel due to steel-slag reaction. However, the model and database should be tested for conditions where significant calcium pick-up is experimentally observed. In the present work, the inclusion removal was assumed to be first order reaction with fixed rate constant. In practice, the inclusion removal is expected to be a more complicated process of agglomeration and flotation. Similarly, the steel-inclusion reactions were considered in equilibrium for each time step of calculation. Sometimes, the composition difference inside single inclusions was found. Some characterization tools were used that could be useful in future to study the agglomeration of inclusions and composition differences inside single inclusion. The agglomeration behavior of inclusions at the steel-argon interface inside confocal laser scanning microscope was compared to the agglomeration in bulk samples from laboratory and industrial steel samples. The size and morphology of inclusion clusters were studied using X-ray micro CT. The composition and morphology of single inclusion was studied using focused ion beam methods: Ga-FIB instrument and plasma-FIB instrument.

&Ccedil / EMTAS Steel Plant produces alloy steels used principally by the automotive industry. Demands of customers for cleaner steel with &ldquo / fewer, smaller and homogenously distributed inclusions&rdquo / are getting tighter with time. The tight demands of the customers are checked by ultrasonic testing and faulty regions are cut off and scrapped which results in production losses in steel plants. Decreasing production losses due to scrapping by producing cleaner steels is therefore a major concern. The objective of this study is to investigate factors affecting the cleanliness of the steels produced by &Ccedil / EMTAS. With this objective, the steelmaking practice used was thoroughly investigated and the possible origins of inclusions in the final product was tried to be found. Based on the findings, process parameters like temperature, time, quantities of additives to steel, intensity of stirring etc. were varied with the objective of determining the optimum production practice.

A limpeza dos aços está diretamente associada ao conteúdo de óxidos dos mesmos, sendo que os diferentes tipos de inclusões não-metálicas presentes podem prejudicar desde os processos de fabricação e conformação até as características necessárias para a aplicação do produto final. As inclusões se formam e se modificam ao longo dos processos de fabricação, e estão relacionadas principalmente às práticas de refino secundário e de lingotamento. Essas inclusões estão sempre presentes nos aços, de modo que é impossível se produzir um aço completamente livre das mesmas. Atualmente, existe uma série de pesquisas buscando o desenvolvimento de práticas e de processos para incrementar a limpeza dos aços. Entre essas está o desenvolvimento de novos materiais refratários adequados às diversas etapas de uma Aciaria. Com especial importância na limpeza dos aços estão as práticas e tecnologias aplicadas no lingotamento contínuo. Neste trabalho foi avaliada a influência do uso de nitrogênio injetado através de poros no colo das válvulas submersas sobre a lingotabilidade e limpeza dos produtos laminados a partir de tarugos. Para este estudo foram testadas diferentes vazões de gás e depois mensurado seu efeito. As técnicas utilizadas para a avaliação foram: verificação da abertura dos tampões; índice de sucateamento nas linhas de inspeção; severidade em ultrassom pelo método de imersão; análise dos teores de oxigênio total e nitrogênio e análise pelo método de distribuição de valores extremos da maior inclusão estimada. Os resultados práticos foram então comparados entre os lotes escolhidos para o teste. Verificou-se através dos dados coletados boa compatibilidade entre as diferentes variáveis e coerência dos resultados com os relatos da literatura. O uso de gás nitrogênio se mostrou ser potencialmente benéfico para a melhoria da limpeza e lingotabilidade do aço, apesar de mais testes serem necessários para a validação das hipóteses levantadas. / The steel cleanliness is directly associated to its inclusion content. The different kind of non-metallic inclusion can harm from the manufacturing and forming processes up to the demanding characteristics for the final products. The inclusions are formed and modified along the steel manufacturing process, and they are related mainly to the secondary refining and casting of steel. These inclusions are always present in the steel, so it is hardly possible to produce steels completely free of them. Nowadays, there are several fields of research concerning with the development of practices and processes to improve steel cleanliness. The development of new lining materials which are suitable for each melting shop step is one of these fields. With special importance over the steel cleanliness issue, the practices and technologies applied to the continuous casting process can be cited. In this work, the influence of nitrogen injection though the pores of the submerged entry nozzle over the castability and cleanliness of rolled products was evaluated. For this study, different gas flows were tested and then measured its effects. The techniques used for the evaluation were: stopper rod opening; rejection index during the inspection lines; severity in immersion ultra-sonic inspection; total oxygen and nitrogen content analysis and largest inclusion diameter estimated by extreme values distribution. The practical results for each lot of steel were then compared. It was verified from, the collected data, good compatibility between these different variables and coherency of the results with the experiences reported in the literature. The use of nitrogen gas showed itself to be potentially good for the improvement of cleanliness and castability of steel, though more trials are necessary for the validation of the considered hypothesis.

A limpeza dos aços está diretamente associada ao conteúdo de óxidos dos mesmos, sendo que os diferentes tipos de inclusões não-metálicas presentes podem prejudicar desde os processos de fabricação e conformação até as características necessárias para a aplicação do produto final. As inclusões se formam e se modificam ao longo dos processos de fabricação, e estão relacionadas principalmente às práticas de refino secundário e de lingotamento. Essas inclusões estão sempre presentes nos aços, de modo que é impossível se produzir um aço completamente livre das mesmas. Atualmente, existe uma série de pesquisas buscando o desenvolvimento de práticas e de processos para incrementar a limpeza dos aços. Entre essas está o desenvolvimento de novos materiais refratários adequados às diversas etapas de uma Aciaria. Com especial importância na limpeza dos aços estão as práticas e tecnologias aplicadas no lingotamento contínuo. Neste trabalho foi avaliada a influência do uso de nitrogênio injetado através de poros no colo das válvulas submersas sobre a lingotabilidade e limpeza dos produtos laminados a partir de tarugos. Para este estudo foram testadas diferentes vazões de gás e depois mensurado seu efeito. As técnicas utilizadas para a avaliação foram: verificação da abertura dos tampões; índice de sucateamento nas linhas de inspeção; severidade em ultrassom pelo método de imersão; análise dos teores de oxigênio total e nitrogênio e análise pelo método de distribuição de valores extremos da maior inclusão estimada. Os resultados práticos foram então comparados entre os lotes escolhidos para o teste. Verificou-se através dos dados coletados boa compatibilidade entre as diferentes variáveis e coerência dos resultados com os relatos da literatura. O uso de gás nitrogênio se mostrou ser potencialmente benéfico para a melhoria da limpeza e lingotabilidade do aço, apesar de mais testes serem necessários para a validação das hipóteses levantadas. / The steel cleanliness is directly associated to its inclusion content. The different kind of non-metallic inclusion can harm from the manufacturing and forming processes up to the demanding characteristics for the final products. The inclusions are formed and modified along the steel manufacturing process, and they are related mainly to the secondary refining and casting of steel. These inclusions are always present in the steel, so it is hardly possible to produce steels completely free of them. Nowadays, there are several fields of research concerning with the development of practices and processes to improve steel cleanliness. The development of new lining materials which are suitable for each melting shop step is one of these fields. With special importance over the steel cleanliness issue, the practices and technologies applied to the continuous casting process can be cited. In this work, the influence of nitrogen injection though the pores of the submerged entry nozzle over the castability and cleanliness of rolled products was evaluated. For this study, different gas flows were tested and then measured its effects. The techniques used for the evaluation were: stopper rod opening; rejection index during the inspection lines; severity in immersion ultra-sonic inspection; total oxygen and nitrogen content analysis and largest inclusion diameter estimated by extreme values distribution. The practical results for each lot of steel were then compared. It was verified from, the collected data, good compatibility between these different variables and coherency of the results with the experiences reported in the literature. The use of nitrogen gas showed itself to be potentially good for the improvement of cleanliness and castability of steel, though more trials are necessary for the validation of the considered hypothesis.

A limpeza dos aços está diretamente associada ao conteúdo de óxidos dos mesmos, sendo que os diferentes tipos de inclusões não-metálicas presentes podem prejudicar desde os processos de fabricação e conformação até as características necessárias para a aplicação do produto final. As inclusões se formam e se modificam ao longo dos processos de fabricação, e estão relacionadas principalmente às práticas de refino secundário e de lingotamento. Essas inclusões estão sempre presentes nos aços, de modo que é impossível se produzir um aço completamente livre das mesmas. Atualmente, existe uma série de pesquisas buscando o desenvolvimento de práticas e de processos para incrementar a limpeza dos aços. Entre essas está o desenvolvimento de novos materiais refratários adequados às diversas etapas de uma Aciaria. Com especial importância na limpeza dos aços estão as práticas e tecnologias aplicadas no lingotamento contínuo. Neste trabalho foi avaliada a influência do uso de nitrogênio injetado através de poros no colo das válvulas submersas sobre a lingotabilidade e limpeza dos produtos laminados a partir de tarugos. Para este estudo foram testadas diferentes vazões de gás e depois mensurado seu efeito. As técnicas utilizadas para a avaliação foram: verificação da abertura dos tampões; índice de sucateamento nas linhas de inspeção; severidade em ultrassom pelo método de imersão; análise dos teores de oxigênio total e nitrogênio e análise pelo método de distribuição de valores extremos da maior inclusão estimada. Os resultados práticos foram então comparados entre os lotes escolhidos para o teste. Verificou-se através dos dados coletados boa compatibilidade entre as diferentes variáveis e coerência dos resultados com os relatos da literatura. O uso de gás nitrogênio se mostrou ser potencialmente benéfico para a melhoria da limpeza e lingotabilidade do aço, apesar de mais testes serem necessários para a validação das hipóteses levantadas. / The steel cleanliness is directly associated to its inclusion content. The different kind of non-metallic inclusion can harm from the manufacturing and forming processes up to the demanding characteristics for the final products. The inclusions are formed and modified along the steel manufacturing process, and they are related mainly to the secondary refining and casting of steel. These inclusions are always present in the steel, so it is hardly possible to produce steels completely free of them. Nowadays, there are several fields of research concerning with the development of practices and processes to improve steel cleanliness. The development of new lining materials which are suitable for each melting shop step is one of these fields. With special importance over the steel cleanliness issue, the practices and technologies applied to the continuous casting process can be cited. In this work, the influence of nitrogen injection though the pores of the submerged entry nozzle over the castability and cleanliness of rolled products was evaluated. For this study, different gas flows were tested and then measured its effects. The techniques used for the evaluation were: stopper rod opening; rejection index during the inspection lines; severity in immersion ultra-sonic inspection; total oxygen and nitrogen content analysis and largest inclusion diameter estimated by extreme values distribution. The practical results for each lot of steel were then compared. It was verified from, the collected data, good compatibility between these different variables and coherency of the results with the experiences reported in the literature. The use of nitrogen gas showed itself to be potentially good for the improvement of cleanliness and castability of steel, though more trials are necessary for the validation of the considered hypothesis.

This study explores the possibility of prediction and modification of some of the physicochemical properties of non-metallic inclusions by considering top slag-steel-ladle equilibria in an ASEA-SKF ladle furnace. To test the reliability of an available computational thermodynamic computer program, the first sub project was done. It was concluded that LiMeS, an interface for Thermo-Calc, is a useful tool for slag-steel equilibrium calculations. The second sub project was set out to find some model/s that could calculate the most accurate oxygen activity of molten steel compared to the measured one. This study concluded that both Wagner’s and Turkdogan's equations are useful. It was further seen that increasing the Al contents in the molten steel, increasing the CaO/Al2O3 ratio in the top slag, and reducing the temperature, resulted in reduction of the oxygen activity of the molten steel. In the third sub project a comparison was made between measured CaO and Al2O3 (normalised to CaO-Al2O3) in top slag, calcium aluminate inclusions, and the results of theoretical calculations. The average contents of CaO and Al2O3 in all inclusions were close to the composition of the phase Ca12Al14O33 and the contents of CaO and Al2O3 in the slags were close to the composition of the phase Ca3Al2O6 in the binary phase diagram of CaO-Al2O3. The forth sub project set out to study the effect of vacuum degassing time on non-metallic inclusions. It was concluded that during the vacuum degassing process the share of calcium aluminates compared to spinels, Ca content of the oxides, and the average equivalent circle diameters of the oxides were increasing, and oxides tended to form spherical shapes. Finally, based on the preceding four sub projects, the fifth sub project aimed to optimize the steel treatment in an ASEA-SKF ladle furnace. The final results showed that by adding 200 kg fluorite to the top slag of 1200 kg, it was possible to achieve a sulphur content of less than 10 ppm in the steel and a sulphur ratio between slag and steel of 1570, and at the same time reduce the oxygen activity of the molten steel and the degassing time. / <p>QC 20120917</p>

In present thesis, the fundamental studies on the reaction between MgO based refractories and slag were undertaken for the development of a carbon-free bonding MgO lining material. Alumina was selected as a potential binder material. Due to MgO-Al2O3 chemical reaction, the developed refractory was bonded by MgO·Al2O3 spinel phase. To begin with, an investigation of the dissolution process of dense MgO and MgO·Al2O3 spinel in liquid slag was carried out. To obtain reliable information for dissolution study, a new experimental method was therefore developed. In this method, a cylinder was rotating centrally in a special designed container with a quatrefoil profile. This method also showed a good reliability in revealing the dissolution mechanism by quenching the whole reaction system. The experimental results showed that the dissolution process of MgO and spinel was controlled by both mass transfer and chemical reaction. It was found that the rapid dissolution of spinel was mainly because of its larger driving force. To improve the resistance against slag penetration, two aspects were studied to develop carbon-free MgO refractory. First, colloidal alumina was used and the effect of its addition into MgO matrix was investigated. The use of colloidal alumina was to form bonding products in the grain boundary of MgO. The results showed that the alumina addition greatly improved the resistance of MgO based refractory against slag penetration in comparison with the decarburized MgO-carbon refractory. It was found that the improvement of resistance was mainly related to the spinel-slag reaction products of CaO·Al2O3 and CaO·MgO·Al2O3 solid phases at the grain boundaries. Second, the effect of particle size distribution on the penetration resistance of MgO was investigated. The most profound improvement against the slag penetration was obtained by using a proper particle size distribution. The results highlighted the importance of considering the refractory structure. Experiments were undertaken to investigate the dissolution mechanism of different types of MgO based refractories in liquid slag. It was observed that the dissolution of spinel bonded MgO refractory was much slower than the decarburized MgO-carbon refractory. The primary dissolution in spinel bonded MgO refractory occurred at the slag-penetrated layer, and the removal of this layer by peeling off enhanced the dissolution rate rapidly. / <p>QC 20170918</p> / European RFCS LEANSTORY project

In this study, the goal is to optimize the process and to reduce the clogging tendency during the continuous casting process. The focus is on clogging when the refractory base material (RBM) in the SEN is in contact with the liquid steel. It is difficult or impossible to avoid non-metallic inclusions in the liquid steel, but by a selection of a good RBM in the SEN clogging can be reduced.   Different process steps were evaluated during the casting process in order to reduce the clogging tendency. First, the preheating of the SEN was studied. The results showed that the SEN can be decarburized during the preheating process. In addition, decarburization of SEN causes a larger risk for clogging. Two types of plasma coatings were implemented to protect the RBM, to prevent reactions with the RBM, and to reduce the clogging tendency. Calcium titanate (CaTiO3) mixed with yttria stabilized zirconia (YSZ) plasma coatings were tested in laboratory and pilot plant trials, for casting of aluminium-killed low-carbon steels. For casting of cerium alloyed stainless steels, YSZ plasma coatings were tested in laboratory, pilot plant and industrial trials. The results showed that the clogging tendency was reduced when implementing both coating materials.   It is also of importance to produce clean steel in order to reduce clogging. Therefore, the steel cleanliness in the tundish was studied experimentally. The result showed that inclusions originated from the slag, deoxidation products and tundish refractory and that they were present in the tundish as well as in the final steel product. / <p>QC 20170227</p> / VINNOVA

科学研究費補助金 研究種目:一般研究(C) 課題番号:61550495 研究代表者:藤澤 敏治 研究期間:1986-1988年度

In this study, the goal is to optimize the process and to reduce the clogging tendency during the continuous casting process. The focus is on clogging when the refractory base material (RBM) in the SEN is in contact with the liquid steel. It is difficult or impossible to avoid non-metallic inclusions in the liquid steel, but by a selection of a good RBM in the SEN clogging can be reduced.   Different process steps were evaluated during the casting process in order to reduce the clogging tendency. First, the preheating of the SEN was studied. The results showed that the SEN can be decarburized during the preheating process. In addition, decarburization of SEN causes a larger risk for clogging. Two types of plasma coatings were implemented to protect the RBM, to prevent reactions with the RBM, and to reduce the clogging tendency. Calcium titanate (CaTiO3) mixed with yttria stabilized zirconia (YSZ) plasma coatings were tested in laboratory and pilot plant trials, for casting of aluminium-killed low-carbon steels. For casting of cerium alloyed stainless steels, YSZ plasma coatings were tested in laboratory, pilot plant and industrial trials. The results showed that the clogging tendency was reduced when implementing both coating materials.   It is also of importance to produce clean steel in order to reduce clogging. Therefore, the steel cleanliness in the tundish was studied experimentally. The result showed that inclusions originated from the slag, deoxidation products and tundish refractory and that they were present in the tundish as well as in the final steel product. / VINNOVA