Presence of inclusions in high manganese steel are a major concern in the steel making industry, since these particles affect the processing and properties of the steel. During the refining of high manganese steel in the ladle furnace, the types of inclusions present and their growth in the liquid steel, or during solidification of the steel, caused by the addition of manganese and other alloying elements are to be examined. This research developed a kinetic model for the presence and growth of inclusions in the liquid high manganese steel for the ladle metallurgy process. The diffusion of dissolved elements, and the seed of inclusions for the growth and consumption of inclusions, were both addressed in the model. The present model for inclusions was coupled to the updated kinetic model for slag-steel reactions in the ladle furnace for high manganese steel. The coupled model allows for verifying the process analysis plant data for the highest manganese concentration presently available in the steel industry. Finally, an analysis of the coupled kinetic model was performed to compare the effect of the different processing conditions, and the presence and growth of inclusions in the high manganese steel from the ladle metallurgy process. / Thesis / Master of Applied Science (MASc)

The cleanliness of steel impacts the success of steel production and the physical and chemical properties of the final product. Improving the cleanliness of steel, therefore, becomes a necessity in the present time, with an ever-increasing demand for high-quality steel products. The cleanliness can be improved by removing the harmful inclusions through flotation or by modifying their composition and morphology to less detrimental forms. The present study focuses on better understanding the second approach, a specific modification method commonly known as the calcium (Ca) treatment in advanced high strength steel (AHSS) production. The chemical and morphological evolutions of Al2O3 inclusions under experimental and industrial conditions, as well as the formation of CaS and MnS inclusions, were studied in this work. Six laboratory experiments with different combinations of calcium and sulfur contents of liquid steel were conducted. Samples were taken at different time durations after calcium addition. The inclusions on the sample cross-sections were analyzed using an automated SEM-EDS system to obtain their chemical, size distribution, population, and morphological information. Similar steps were taken in the analysis of industrial samples. The findings obtained based on the automated SEM-EDS analyses were further supported and validated against other analysis results such as manual SEM analysis, thermodynamics, and kinetics calculations. The modification mechanism for Al2O3 inclusions was established in the first part of the study. After adding 10 ppm, 20 ppm, and 35 ppm Ca, small-sized calcium aluminates CAx (C and A denote CaO and Al2O3, respectively) inclusions become the primary oxygen bearer instead of Al2O3 inclusions. The modification extent of the CAx inclusions depends on the Ca content. CaS inclusions also form at the early stage of calcium treatment. In the later stage, CaS inclusions act as the Ca source to modify the remaining Al2O3 inclusions to CAx inclusions and simultaneously modify the existing CAx inclusions until equilibrium is reached. CaO inclusions only form in steel containing 20 ppm S and 35 ppm Ca; the primary oxygen bearer will change from Al2O3 to CaO, followed by a transformation from CaO to CaS. In other S and Ca contents, CaO inclusions do not form. This finding clarified that modification of Al2O3 inclusions is mainly driven by dissolved Ca and CaS inclusions, with CaO showing a minor direct impact. Moreover, the experimental studies showed that total area fractions of liquid and semi-liquid inclusions, which are inclusions that are partially liquid and partially solid, are correlated with the thermodynamic stability of CaS inclusions. The fraction of liquid inclusions decreases after the area fraction of CaS inclusions drastically increases when steel chemistries allow stable CaS inclusions to precipitate. The correlation between the steel chemistries and inclusions was improved by iv incorporating more data from industrial heats. Three modification indexes were proposed to estimate the control of CAx, CaS, and MnS inclusions. The fraction of CAx inclusions with more than 50 pct liquid, and the area fraction of CaS and MnS inclusions in tundish samples were correlated with the Ca, Al, Mn, and S contents of liquid steel. Later, these modification indexes were incorporated to evaluate the effectiveness of calcium treatment quantitatively. This makes the present study the first to discuss the correlations between Ca, Al, Mn, and S contents and the number of inclusions in the open literature. The correlations were validated against industrial data, they may be used in industry to determine the optimum Ca content for inclusion control and modification. Based on the experimental and industrial data, the coarsening of CaS inclusions was initially governed by mass transport, then shifted to collision-related mechanisms. When agitation is absent, Brownian motion shows the most significant impact on the growth of CaS inclusions, while turbulent flow is the critical cause of collision and coagulation when the melt is stirred, such as in industrial conditions. It has been found that CAx inclusion growth mainly occurs in the early stage after Ca addition. The potential reason is that the lack of attraction prevents coagulation after CAx inclusions are modified to liquid and semi-liquid. / Thesis / Doctor of Philosophy (PhD)

The effect of gas stirring in the ladle furnace on inclusion content in austenitic and duplex stainless steel has been investigated at Sandvik Materials Technology AB. The effect was mainly investigated by varying duration of stirring time and intensity of stirring. Any effect on inclusion content was determined by examining total oxygen content before and after the ladle treatment, along with mapping the chemical composition, size and size distribution of the inclusions. Any effect on slag composition was also determined. The effect of gas stirring was measured on a number of heats with continuous sampling during normal production. Data regarding oxygen content during the ladle refining process and the duration of the processes was used to determine a quantifiable relationship between stirring time, stirring intensity and resulting change in oxygen content. The result of the investigation was recommendations regarding the use of varied stirring intensities and duration of gas stirring for achieving negative net loss in oxygen content before and after ladle treatment.

<p>The inclusions are harmful to the steel cleanliness; process parameters such as stirring and steel and slag oxidation must be controlled to obtain a final number of inclusions in the steel whose size is smaller than the critical size for each steel product.</p> <p>A simple mathematical model was developed to analyze the impact of bubbling, slag and initial oxidation level on inclusion distribution control (quantity and size of them) during the process in a Ladle Metallurgy Furnace (LMF).</p> <p>The initial inclusion size distribution is calculated and adjusted with the samples analyzed by SEM-EDAX, this initial distribution decreases by removal mechanisms such as bubbling and slag and they can increases by reoxidation.</p> <p>The model allows predicting the inclusion removal by bubbling mechanism as a function of gas flow rate and inclusion size and it proves which a softer stirring is better for removal inclusion than stronger one. An interesting point analyzed is the effect of stirring level on small and large inclusions.</p> <p>According to the inclusion number removal by slag, it is possible to appreciate like larger inclusions are removed easier than smaller ones. This mechanism is the most important to remove inclusions calculated by this model.</p> / Master of Science (MSc)

Two industrial studies and one set of lab scale trials have been done. In addition, a theoretical study has been done. The main focus has been on non metallic inclusion composition during the ladle refining operation in industrial steel production. Sampling has been done together with careful inclusion determination. The inclusion composition is related to different variables. In the industrial trials samples have been taken at different steps during the ladle refining period. Steel and slag composition as well as temperature and oxygen activity have been determined. The thesis is based on five supplements with different major objectives, all related to the inclusion composition. The equilibrium top slag-steel bulk and inclusions-steel bulk were investigated by comparison between calculated and measured oxygen activity values. The oxygen activity and relation to temperature has also been discussed as well as oxygen activity and temperature gradients. The effect of vacuum pressure on inclusion composition has been evaluated in a theoretical study as well as lab scale trials. The inclusion composition has been studied during the industrial ladle treatment process. The inclusion composition was related to top slag composition and other parameters during ladle treatment. The major findings in the thesis are the lack of equilibrium conditions with respect to top-slag and steel bulk before vacuum treatment. The inclusions have been found to be closer to equilibrium with the steel bulk. Al/Al2O3 equilibrium has been found to control the oxygen activity after Al-deoxidation. Evaluation of inclusion composition during the ladle refining has revealed that the majority of the inclusions showed a continuous composition change throughout the ladle refining process, from high Al2O3, via MgO-spinel to finally complex types rich in CaO and Al2O3. The final inclusion composition after vacuum treatment was found to be close to the top slag composition. Vacuum pressure has been found to have a theoretical effect on inclusion composition at very low pressures. / QC 20100712

The present thesis was to study non-metallic inclusions during vacuum degassing in ladle treatment. Emphasize was mostly given to liquid CaO-Al2O3 inclusions. A series of industrial experiments were carried out at Uddeholm Tooling AB, Hagfors, Sweden. To gain an insight into the industrial findings, laboratory investigations were also performed. Large number of steel samples were collected and examined. Liquid calcium aluminate inclusions with low SiO2 and high SiO2 were often found with spinel inclusions before vacuum degassing. Laboratory experiments showed that spinel would react with the dissolved Ca in the liquid steel forming calcium aluminate inclusions. This laboratory results agreed with the industrial observation that spinel phase was quite often found in the center of the calcium aluminate phase. After vacuum degassing, most of the inclusions were calcium aluminate liquid inclusions. When dissolved Al level was low, 2 types of liquid calcium aluminate inclusions with considerably different SiO2 contents were found to coexist even at the end of the process. In view of the lack of the thermodynamic data for SiO2 activities in the low silica region, thermodynamic measurements were conducted in the CaO-Al2O3-SiO2-MgO system. The experimental results could reasonably explain the coexistence of the two types of the liquid oxide inclusions. While the total number of inclusions decreased during vacuum degassing, the number of bigger inclusions (&gt;11.3 μm) increased generally in used ladles. This finding was in accordance with the previous studies, wherein, ladle glaze was found to be responsible for the supply of bigger inclusions. The behaviors of several types of inclusions in liquid steel were examined using a laser scanning confocal microscope (LSCM). While alumina inclusions tended to impact on each other, agglomerate and grow very quickly, none of the other types of inclusions, such as spinel and calcium aluminate was observed to agglomerate. The results of LSCM study agreed well with the industrial observation. Examination on a huge number of inclusions did not show any indication of impact and physical growth of the inclusions, except the alumina inclusions. The removal of inclusions around open-eye in a gas-stirred ladle was experimentally studied by a cold model with oil and water. Most of the simulated inclusions were brought up to the oil phase by gas-water plume. Inclusion removal into oil layer took place when the inclusions passed through the sphere-bed of the oil layer around the open-eye. A calculation showed that the contribution of metal-gas plume in inclusion removal was much larger than that of buoyancy mechanism. The results of the industrial experiments revealed that the inclusions distribution strongly depended on stirring condition. When a ladle was stirred by both gas and induction, inclusion removal near slag layer was significant. / QC 20100803

In the present thesis, the correlation between ladle glaze and non-metallic inclusions in the ladle treatment was studied. A number of industrial trials with full scale ladle and laboratory works were performed to investigate the inclusions in the ladle treatment. BaO was used as tracer in the ladle slag to investigate the effect of slag on inclusion composition and the formation of non-metallic inclusions by ladle glaze. BaO was detected in the inclusions of all followed heats. This observation showed strong evidence for the generation of non-metallic inclusions by the ladle glaze. The increase of the fractions of BaO containing inclusions and their average content of BaO in the first heat with tracer suggested that the effect of slag on the composition of inclusions was a very slow process. The detachment of ladle glaze and the chemical transformations of oxide solution in the MgO matrix were investigated. The experimental results evidently showed that the ladle glaze could be the source of inclusions continually during the ladle treatment. Samples of liquid oxide solution to simulate the liquid oxide inclusions carried over from EAF were equilibrated with molten steel under controlled atmosphere. The results along with thermodynamic calculation suggested that the SiO2 content of inclusions from EAF could be considerably reduced by dissolved aluminium in the steel. This would explain the vanishing of inclusions containing high SiO2 content after deoxidation. Due to the lack of experimental data, the viscosities of slags in the Al2O3-CaO-MgO-SiO2 system were measured using the rotating cylinder method in the temperature range of 1720 to 1910 K. Eight different slag compositions related to the secondary steel making operations were selected. Viscosities in this system and its sub-systems were expressed as a function of temperature and composition based on the viscosity model developed earlier at KTH. The activities of oxide components in the Al2O3-CaO-MgO-SiO2 systems at 1873 K were measured by equilibrating liquid slag and metal. Either silicon or copper was used as the metal phase and the oxygen partial pressure was controlled with different mixing rates of Ar and CO gas flow in equilibrium with graphite. Iso-activity lines were drawn from the measured activity values in the isothermal section of the slag systems. Nine series of industrial trials were carried out using the same ladle in each series to examine the effect of ladle slag on the number of non-metallic inclusions in the next heat. It was found that the number of inclusions increased with SiO2 content of the ladle slag in the previous heat. No clear trends were found for the effects of viscosity and MgO activity of the previous slag on the number of inclusions. Theoretical analysis based on the experimental results suggested that the formation of 2CaO∙SiO2 followed but the dusting of the compound made the refractory more porous, which was reasonable for the number of non-metallic inclusions.

<p>The thesis is based on two supplements with two major objectives. In the first supplement equilibrium top slag-steel bulk and inclusions-steel bulk were investigated by comparison between calculated and measured oxygen activity values. This was done by applying different oxide activity models for slags combined with thermodynamic calculations. In the second supplement the inclusion composition is studied during the ladle refining process. The inclusion composition is related to top slag composition and other parameters during ladle</p><p>treatment.</p><p>The work was carried out by collecting data during well controlled sampling procedures at two different steel plants. Extensive inclusion analyses in Scanning Electron Microscope, SEM, were done. The data was used together with thermodynamics for a description of the interaction between slag-steel-inclusion interaction during ladle treatment.</p><p>Evaluation of inclusion composition during the ladle refining have revealed that the majority of the inclusions belonged to the system Al₂O₃-CaO-MgO-SiO₂and showed a continuous composition change throughout the ladle refining process, from high Al₂O_3, via MgO-spinel to finally complex types rich in CaO and Al₂O_3. The final composition after vacuum treatment was found to be close to the top slag composition. Small process parameter changes and practical variations during ladle refining were proven to give large differences of the inclusion composition.</p><p>Finally, it was concluded that equilibrium does not exist between top slag and steel bulk, with respect to oxygen, for the studied conditions. However, the equilibrium does exist between the steel bulk and inclusion.</p>

The thesis is based on two supplements with two major objectives. In the first supplement equilibrium top slag-steel bulk and inclusions-steel bulk were investigated by comparison between calculated and measured oxygen activity values. This was done by applying different oxide activity models for slags combined with thermodynamic calculations. In the second supplement the inclusion composition is studied during the ladle refining process. The inclusion composition is related to top slag composition and other parameters during ladle treatment. The work was carried out by collecting data during well controlled sampling procedures at two different steel plants. Extensive inclusion analyses in Scanning Electron Microscope, SEM, were done. The data was used together with thermodynamics for a description of the interaction between slag-steel-inclusion interaction during ladle treatment. Evaluation of inclusion composition during the ladle refining have revealed that the majority of the inclusions belonged to the system Al2O3-CaO-MgO-SiO2 and showed a continuous composition change throughout the ladle refining process, from high Al2O3, via MgO-spinel to finally complex types rich in CaO and Al2O3. The final composition after vacuum treatment was found to be close to the top slag composition. Small process parameter changes and practical variations during ladle refining were proven to give large differences of the inclusion composition. Finally, it was concluded that equilibrium does not exist between top slag and steel bulk, with respect to oxygen, for the studied conditions. However, the equilibrium does exist between the steel bulk and inclusion. / QC 20101109

Целью работы является изучение влияния донной продувки в промежуточном ковше на содержание неметаллических включений в транспортном металле и пути повышения качества данных марок стали. В качестве решения проблемы рассмотрена гипотеза о зависимости содержания неметаллических включений в стали от состава шлака на установке «печь-ковш»; создана физическая модель МНЛЗ; предложена схема расположения аргонных блоков в промежуточном ковше, что позволит создать оптимальные потоки металла для флотации неметаллических включений. / The aim of the work is to study the effect of bottom blowing in the intermediate bucket on the content of non-metallic inclusions in the transport metal and ways to improve the quality of these steel grades. As a solution to the problem, the hypothesis of the dependence of the content of non-metallic inclusions in steel on the composition of the slag at the furnace-ladle installation is considered; a physical model of the CCM is created; a scheme for the arrangement of argon blocks in the intermediate ladle is proposed, which will create optimal metal flows for flotation of non-metallic inclusions.