Effects of FeO and CaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al₂O₃) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al₂O₃ spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al₂O₃ spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al₂O₃ inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al₂O₃ spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.     

Kinetics of CO-CO<Subscript>2</Subscript> reaction with CaO-SiO<Subscript>2</Subscript>-FeOx melts

Measurements of the rate of interfacial reaction between CO₂-CO mixtures and CaO-SiO₂-FeOx slags have been made using the ¹³CO₂-CO isotope exchange technique. Ranges of slag compositions from 0 to 100 wt pct ‘FeO’ and CaO/SiO₂ between 0.3 and 2.0 were examined in the experiments. For each slag, the dependence of the apparent rate constant on temperature and equilibrium oxygen potential was studied. The relationship between the rate constant and oxygen potential was found to be in the form k _a=k _a ^o (a_o)^-α. The parameter a, with values between 0.5 and 0.9, was dependent on the slag composition. The activation energy of the reaction was independent of iron oxide content and dependent on slag basicity.     

Influence of CaF<Subscript>2</Subscript> and Li<Subscript>2</Subscript>O on the Viscous Behavior of Calcium Silicate Melts Containing 12 wt pct Na<Subscript>2</Subscript>O

Understanding the viscous behavior of silica-based molten fluxes is essential in maintaining the reliability of steel casting operations and in preventing breakouts. In particular, high concentrations of aluminum in recently developed transformation induced plasticity (TRIP) and twinning induced plasticity (TWIP) steels tend to promote reduction of silica in the mold fluxes that result in the formation of alumina, which in turn increases the viscosity. To counteract this effect, significant amounts of fluidizers such as CaF₂ and Li₂O are required to ensure that mold fluxes have acceptable lubrication and heat transfer characteristics. The viscous behavior of the slag system based on CaO-SiO₂-12 wt pct Na₂O with various concentrations of CaF₂ and Li₂O has been studied using the rotating spindle method to understand the effects on the viscosity with these additives. CaF₂ additions up to 8 wt pct were effective in decreasing the viscosity by breaking the network structure of molten fluxes, but CaF₂ concentrations above this level had a negligible effect on viscosity. Li₂O additions up to 2 wt pct were also effective in decreasing the viscosity, but the effect was comparatively negligible above 2 wt pct. Using Fourier transform infrared (FTIR) analysis of as-quenched slag samples, it was concluded that the viscosity was controlled more effectively by changing the larger complex silicate structures of rings and chains than by changing the amounts of simpler dimers and monomers.     

Manganese Recovery by Silicothermic Reduction of MnO in BaO-MnO-MgO-CaF<Subscript>2</Subscript> (-SiO<Subscript>2</Subscript>) Slags

The effects of reducing agent, CaF₂ content, and reaction temperature upon the silicothermic reduction of MnO in the BaO-MnO-MgO-CaF₂ (-SiO₂) slags were investigated. Mn recovery was proportional to Si activity in the molten alloy. Moreover, 90 pct yield of Mn recovery was obtained under 5 mass pct CaF₂ content and 1873 K (1600 °C) reaction temperature. Increasing CaF₂ content above 5 pct yielded little or no further increase in Mn recovery, because it was accompanied by increased slag viscosity owing to the precipitation of high melting point compounds such as Ba₂SiO₄.     

Study on Formation Mechanism of CaO-SiO<Subscript>2</Subscript>-Based Inclusions in Saw Wire Steel

Attempts were made to elucidate the formation mechanism of CaO-SiO₂-based inclusions in saw wires by both laboratory experiments and industrial trials. The key point was to make clear the origin of CaO in such oxide inclusions. Probable origins of [Ca] in steel were first discussed, which can be taken into steel from the steel-slag reaction or ferrous alloy. As a result, slag-steel chemical reaction equilibrium was carefully evaluated at 1873 K (1600 °C) to classify the changes of dissolved aluminum ([Al]), total magnesium (Mg), and total calcium (Ca) in steel and the caused composition variations of inclusions. With the rise of slag basicity from 0.5 to 1.8, [Al] was remarkably increased from 0.00045 to 0.00139 mass pct, whereas Mg varied in the range of 0.00038 to 0.00048 mass pct. By contrast, Ca was constantly kept below 0.00003 mass pct. Accordingly, Al₂O₃ and MgO in inclusions witnessed obvious rises from 5 to 23 mass pct and from 2 to 8 mass pct, respectively. By contrast, inclusions were free of CaO when slag basicity was below 1.5. With slag basicity further increased to 1.8, CaO witnessed a negligible rise to only 1.0 mass pct on average. This phenomenon agreed well with thermodynamic calculations, which revealed that chemical reaction between steel and CaO in slag (for example, between [Si] and CaO) was weak to hardly supplying sufficient [Ca] to steel to increase CaO in inclusions. Ca contained in ferrous alloys as contaminations was not the cause of CaO-SiO₂-based inclusions, either. The industrial trial results indicated that CaO-SiO₂-based inclusions have been readily produced in short time just after BOF tapping. Also, a percentage of them changed slightly with the proceeding of refining. Based on the good agreement of laboratory, industrial, and thermodynamics calculations results, it can be reasonably concluded that CaO-SiO₂-based inclusions in saw wire were exogenous particles from entrapped/emulsified top slag, but not products of slag-steel-inclusion chemical reactions.     

Thermal diffusivity measurements of some synthetic CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> slags

In an attempt to systematize the knowledge of the heat conduction of liquid silicates, the effective thermal diffusivities of some synthetic slags containing CaO, Al₂O₃, and SiO₂ have been measured, using the three-layer laser-flash method on a differential scheme in the temperature range of 1625 to 1825 K. The effective thermal diffusivities measured, which are a combination of the phononic and photonic heat-transfer mechanisms, were found to increase with increasing temperature for all the presently investigated slags. The slag compositions were chosen in such a way that the changes in the effective thermal diffusivities would reflect the changes in the structure of the slags. It was observed that, at a CaO/Al₂O₃ molar ratio of 4.42, an increase of the SiO₂ content had very little effect on the effective thermal diffusivity values. On the other hand, addition of SiO₂ to a slag with the CaO/Al₂O₃ molar ratio of 2.59 resulted in a significant increase in the effective thermal diffusivity. The addition of Al₂O₃ to slags with a constant CaO/SiO₂ molar ratio resulted in a marked increase in the effective thermal diffusivity. Both these trends indicate that there might be an influence of the network formation in silicate melts on the effective thermal diffusivity.     

Nitrogen solubility in metallurgical slags equilibrated with Fe–Al or Fe–Ca melts

Considerations are directed to the denitrogenation potential of metallurgical slags with respect to steel melts under reducing conditions. Experiments were made to determine partition ratios of nitrogen between molten slag and iron. The investigated systems were aluminate-based slags, containing CaO, MgO, SrO, BaO, CaF₂ or ZrO₂, in equilibrium with Fe–AI melts and Ca–CaO–CaF₂ slags equilibrated with Fe–Ca melts. Denitrogenation efficiency of aluminate-based slags is comparatively low and essentially determined by oxygen potential and basicity of the slag. Denitrogenation efficiency of Ca–CaO–CaF₂ slags is much higher and is dependent on calcium activity.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Concentration on Density and Structure of (CaO-SiO<Subscript>2</Subscript>)-xAl<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The effect of Al₂O₃ concentration on the density and structure of CaO-SiO₂-Al₂O₃ slag was investigated at multiple Al₂O₃ mole percentages and at a fixed CaO/SiO₂ ratio of 1. The experiments were conducted in the temperature range of 2154 K to 2423 K (1881 °C to 2150 °C) using the aerodynamic levitation technique. In order to understand the relationship between density and structure, structural analysis of the silicate melts was carried out using Raman spectroscopy. The density of each slag sample investigated in this study decreased linearly with increasing temperature. When the Al₂O₃ content was less than 15 mole pct, density decreased with increasing Al₂O₃ content due to the coupling of Si (Al), whereas above 20 mole pct density of the slag increased due to the role of Al³⁺ ion as a network modifier.     

Effect of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO slags on the formation of MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> inclusions in ferritic stainless steel

A thermodynamic equilibrium between the Fe-16Cr melts and the CaO-Al₂O₃-MgO slags at 1823 K as well as the morphology of inclusions was investigated to understand the formation behavior of the MgO-Al₂O₃ spinel-type inclusions in ferritic stainless steel. The calculated and observed activities of magnesium in Fe-16Cr melts are qualitatively in good agreement with each other, while those of aluminum in steel melts exhibit some discrepancies with scatters. In the composition of molten steel investigated in this study, the log (X _MgO/X _{Al 2}O₃) of the inclusions linearly increases by increasing the log [a _Mg/a _Al ² ·a _O ² ] with the slope close to unity. In addition, the relationship between the log (X _MgO/X _{Al 2}O₃) of the inclusions and the log (a _MgO/a _{Al 2}O₃) of the slags exhibits the linear correlation with the slope close to unity. The compositions of the inclusions are relatively close to those of the slags, viz. the MgO-rich magnesia-spinel solid solutions were formed in the steel melts equilibrated with the highly basic slags saturated by CaO or MgO. The spinel inclusions nearly saturated by MgO were observed in the steel melts equilibrated with the slags doubly saturated by MgO and MgAl₂O₄. The spinel and the Al₂O₃-rich alumina-spinel solid solutions were formed in the steel melts equilibrated with the slags saturated by MgAl₂O₄ and MgAl₂O₄-CaAl₂O₄ phases, respectively. The apparent modification reaction of MgO to the magnesium aluminate inclusions in steel melts equilibrated with the highly basic slags would be constituted by the following reaction steps: (1) diffusion of aluminum from bulk to the metal/MgO interface, (2) oxidation of the aluminum to the Al³⁺ ions at the metal/intermediate layer interface, (3) diffusion of Al³⁺ ions and electrons through the intermediate layer, and (4) magnesium aluminate (MgAl₂O₄ spinel, for example) formation by the ionic reaction.     

Effect of Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> on Structure,Viscosity, and Crystalline Phase of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> Slags

Aiming at devising new mold flux for Ce-bearing stainless steel, a fundamental investigation on the effect of Ce₂O₃ on properties of the CaO-Al₂O₃-Li₂O-Ce₂O₃ slag was provided by the present work. The results show that adding Ce₂O₃ could decrease the viscosity of the slag due to its effects on decreasing the polymerization of the slag. The crystalline process was restrained by increasing the content of Ce₂O₃, and the crystalline phases also can be influenced by the slag structure. The crystalline phases were transferred from LiAlO₂ and CaO to LiAlO₂ and CaCeAlO₄ with the addition of Ce₂O₃ to the slag, which could be well confirmed by the structure of the unit cell of the crystals.     

Thermodynamic behaviour of carbon in CaO-SiO2 slag system

In order to understand the thermodynamic behaviour of carbon in steelmaking slag at high temperature, the carbon dissolution into CaO-SiO₂ slag system has been investigated including the effects of temperature and slag components on the carbon dissolution reaction. It was found that carbide solubility in the CaO-SiO₂ slag decreased with increasing oxygen potential to confirm the theoretical relationship of ?1/2, which reflected the ionic exchange reaction mechanism between carbon and oxygen ions. Carbide solubility in slag as a function of slag basicity for various slag systems appeared to confirm this mechanism. This reaction mechanism implied that the carbide dissolution proceeded due to the reaction of solid carbon and oxygen ions supplied from (CaO) in slag. The oxygen ion appears to be the driving force as it is influenced by the slag components as well as the temperature as shown in the concept of the carbide capacity of slag. The solubility of carbide in the CaO-SiO₂ slag increased with the addition of CaF₂; the role of CaF₂ for carbide dissolution into slag could be speculated to have complex effects on indirect increase in basicity in spite of (CaO) dilution. Substitution of CaO by MgO decreased the solubility of carbide in the CaO-SiO₂-MgO slag, possibly caused by the relatively low electro-negativity of MgO.     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature     

Thermodynamics of Boron Removal from Silicon Using CaO-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Slags

Slag refining is one of few metallurgical methods for removal of boron from silicon. It is important to know the thermodynamic properties of boron in slags to understand the refining process. The relation of the distribution coefficient of boron to the activity of silica, partial pressure of oxygen, and capacity of slags for boron oxide was investigated. The link between these parameters explains why the distribution coefficient of boron does not change much with changing slag composition. In addition, the thermodynamic properties of dilute boron oxide in CaO-MgO-Al₂O₃-SiO₂ slags was determined. The ratio of the activity coefficient of boron oxide and silica was found to be the most important parameter for understanding changes in the distribution coefficient of boron for different slags. Finally, the relation between the activity coefficient of boron oxide and slag structure was investigated. It was found that the structure can explain how the distribution coefficient of boron changes depending on slag composition.     

Phase equilibria and thermodynamic properties of the Cu<Subscript>2</Subscript>O-CaO-Na<Subscript>2</Subscript>O system in equilibrium with copper

The liquidus surfaces of the Cu₂O-CaO, Cu₂O-Na₂O, and Cu₂O-CaO-Na₂O phase diagrams in equilibrium with metallic Cu were measured by thermal analysis at compositions varying from approximately 0 to 35 wt pct Na₂O and 0 to 15 wt pct CaO. Solubilities in the solid binary terminal solutions were also measured by wavelength dispersive X-ray spectrometer analysis. Copper oxide activities in binary liquid slags were determined from the measured oxygen content of the metallic copper equilibrated with the slags. The ternary system is a simple eutectic system. No ternary compounds were observed. The Cu₂O-CaO binary eutectic was measured at 1140 °C±10 °C at 10±1 wt pct CaO and the Cu₂O-Na₂O binary eutectic was measured at 803 °C±15 °C at 28±2 wt pct Na₂O. The liquid slag was thermodynamically modeled with the modified quasi-chemical model, while the solid Cu₂O-rich solution was treated as Henrian ideal. All data from the present work and from the literature (phase diagrams and activities) for the binary systems were evaluated simultaneously by least-squares optimization in order to obtain the best model parameters. With only these binary parameters, the calculated ternary liquidus surface is in very good agreement with the measurements. Finally, using the model, the liquidus projection of the Cu₂O-CaO-Na₂O system in equilibrium with Cu was calculated as well as the oxygen content of the equilibrated Cu as a function of slag composition.     

Viscosity Estimations of Multi‐Component Slags

A model for viscosity estimation of molten aluminosilicate slag, which was developed in our previous study, was extended to estimate viscosity of multi‐component slag containing alkali oxide and calcium fluoride in this study. The charge compensations of alkali oxides for Al tetrahedral ions are explicitly taken into account in the equations. The effect of calcium fluoride on the viscosity of slag was modeled by considering Ca‐2F species and no network‐breaking effect of CaF₂ were considered. The present model was applied to estimate the viscosity of slags within Al₂O₃‐CaO‐FeO‐MgO‐SiO₂‐CaF₂‐Na₂O‐K₂O system. A good agreement with a mean deviation of ～20% was achieved by comparison between estimated and measured values.     

Phase equilibrium and distribution of minor elements between Ni-S melt and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-MgO Slag at 1873 K

Distribution of nickel and minor elements such as Au, Ag, Fe, Co, Cu, As, and Sb between the Ni-S alloy and the CaO-Al₂O₃ based slag phases in a magnesia crucible was studied at 1873 K. Partial pressure of SO₂ was controlled at 10.1 kPa, while partial pressures of O₂ and S₂ ranged between the point of NiO precipitation (po₂ of 10.1 Pa) and the point at which Ni₃S₂ is formed (ps₂ of 4.0 kPa). The nickel content in the slag and the sulfur and oxygen contents in the metal at a given po₂ or pso₂ decrease when the temperature is increased from 1773 to 1873 K. The distribution ratios of iron, cobalt, and copper, defined by (wt pct X in slag)/{wt pct X in alloy}, where X is the minor element in the slag, have larger values than that of nickel, while the values of Au, Ag, Sb, and As are lower than that of nickel. The distribution behavior of nickel and minor elements is discussed based on the concept of oxidic and sulfidic dissolution.     

The electrical conductivity of some liquids in the system CaF2+CaO+Al2O3

The conductivity of slags in the binary systems CaF₂+Al₂O₃, CaF₂+CaO and the ternary system CaF₂+CaO+Al₂O₃ has been measured, using a four-lead electrode technique at a frequency of 1 kHz. The cell design used ensured that only molybdenum metal was in contact with the slag at high temperature and that the slag was wholly contained in molybdenum. No frequency dispersion could be detected at frequencies between 0.8 to 10 kHz. It is suggested that the formation of complex ions (e.g. AlO₂F₂ ³⁻ and AlOF ₂ ⁻ ) might account for the observed effects in CaF₂+Al₂O₃, CaF₂+CaO+Al₂O₃ liquids as has been previously suggested. an oxide ion clustering mechanism may explain the conductivities found in CaF₂+CaO.     

The Effect of MgO on the Viscosity of the CaO‐SiO2‐20 wt%Al2O3‐MgO Slag System

The viscosities of CaO‐SiO₂‐20 wt%Al₂O₃‐MgO slags (CaO/SiO₂ = 1.0–1.2, wt%MgO = 5–13) were measured to estimate the effect of MgO on the viscous behaviour at elevated temperatures. The slag viscosity at 1773 K decreased with increasing MgO contents, which was typical of a basic oxide component at relatively low basicity (CaO/SiO₂) of 1.0. The FT‐IR spectroscopic analysis of the slag structure seems to verify this behaviour. However, an unexpected contradiction with the temperature dependence was observed above 10 wt%MgO and above CaO/SiO₂ of 1.2. Although the apparent activation energy was expected to decrease with additions of the basic oxide component MgO, the apparent activation energy increased. This unexpected behaviour seems to be related to the change in the primary phase field correlating to the phase diagram corresponding to the slag composition. Therefore, in order to understand the viscosity at both high Al₂O₃ and MgO, not only should the typical depolymerization of the slag structure with high MgO content be considered but also the primary phases of which the molten slag originates.