Carbon Solubility in the CaO-SiO2-3MgO-CaF2 Slag System

The carbon solubility in the CaO-SiO₂-3MgO-CaF₂ slag system at 1773 K (1500 °C) was investigated under CO/Ar and CO/N₂ gases. Higher extended basicity [(CaO + MgO)/SiO₂) increased the carbon solubility in the slag as the activity of free oxygen ions ( $ \varvec{a}_{{{\mathbf{O}}^{2 - } }} $ ] promoted the reaction of the free carbide mechanism. Higher CaF₂ also resulted in higher carbon dissolution into the slag as fluorine ions interact with the bridged oxygen (O⁰) in the melt structure to increase the activity of the free oxygen ions in the melt. Structural information obtained from the Fourier transformed infra-red (FT-IR) and Raman revealed a depolymerization of the network structure as the simpler structural units of NBO/Si = 4 increased and the Si-O-Si bending vibrations decreased with higher basicity and CaF₂ content. This correlated well with higher free oxygen ions (O^2?) in the slag system and subsequently higher carbon dissolution. A correlation of the theoretical optical basicity (Λ_th) with the logarithm of the carbon content in slag showed a relatively similar trend and an increase of carbon was observed with higher optical basicity.     

Thermodynamic behaviour of carbonate in CaO based slag

Carbonate solubility was measured for CaO bearing slag systems at 1600 °C under different thermodynamic conditions by using equilibration techniques. Carbonate solubility increased with activity of (CaO). The reaction mechanism of the carbonate dissolution in slag can be expressed as a reaction between CO₂ gaseous phase and oxygen ion to form carbonate (CO₃^2-). Carbonate capacities of various slags depended not only on oxygen ion but also activity coefficient of carbonate ion. The activity coefficient of carbonate ion in CaO-SiO₂ slag changed with CaO content, but that of CaO-Al₂O₃ slag did not change remarkably. Substitution of MgO by CaO for solubility of carbonate had a similar effect as in the case of carbide in CaO-SiO₂-MgO slag. The critical oxygen potential for carbide and carbonate stability was found to be 10-¹⁰ bar.     

Solubility of nitrogen in CaO-SiO2-CaF2 slag system

Equilibrium experiments between gas and slag were carried out to understand the thermodynamic behaviour of nitrogen in the CaO-SiO₂-CaF₂ slag system at 1600°C. The solubility of nitrogen in this slag system increased as the oxygen potential decreased and as the reaction temperature increased. The values of the nitride capacity have a minimum at about 2.0 slag basicity, having higher values in both more acidic and basic regions. This may be explained by two mechanisms for nitrogen dissolution; incorporated nitride ion and free nitride ion state. In slag with 2.0 basicity or less, MgO content increased the nitride capacity slightly. At higher slag basicity, however, nitride capacity decreased with MgO content. The effects of BaO to substitute CaO on nitride capacity showed similar behaviour as MgO. This complex relationship between basicity of slag and nitride capacity is explained by using optical basicity. It was found that nitride capacity and optical basicity had a close relationship even in the different basic oxide systems.     

The Effects of CaF2, Basicity, and Atmospheric Conditions on the Solubility of Carbon and Nitrogen in the CaO-SiO2-Al2O3-Based Slag System

The solubility of carbon and nitrogen in the CaF₂-CaO-SiO₂-Al₂O₃ slag system was studied. The effects of the CaF₂, extended basicity (CaO/(SiO₂ + Al₂O₃)), and atmospheric conditions on the dissolution behavior of the carbon and nitrogen, as well as the correlations of the behaviors with the slag structure observed at 1773 K (1500 °C), are presented. Increases in the extended basicity and the CaF₂ increased the solubility of carbon in the slag. In the case of nitrogen dissolution, a characteristic parabolic curve with an identifiable minimum was observed for the slag. This curve shape correlated with a change in the dominant mechanism of dissolution from an incorporated to a free nitride. The solubility of carbon in the mixture of CO with N₂ was significantly higher than that of carbon in the mixture of CO with Ar and is likely due to the formation of cyanide. Thus, when carbon is present in significant quantities in the slag, the solubility of nitrogen in the slag increases. The degree of depolymerization of the slag with increased content of CaO/(SiO₂ + Al₂O₃) and CaF₂ was verified using Fourier transform infrared and Raman spectroscopy.     

Thermodynamic behaviour of zinc in Fe‐C and CaO‐FeO‐CaF2 slag at high temperatures

The distribution ratio of zinc between Ag‐Zn and Fe‐Zn alloys was measured to clarify the thermodynamic behaviour of zinc in Fe‐C melt at high temperatures. Also, the distribution ratio between Ag‐Zn alloy and CaO‐FeO‐CaF₂ slag was measured to understand the dissolution mechanism of zinc in molten slags. The activity coefficient of zinc in Ag‐Zn alloy was preliminarily measured as a fundamental thermodynamic data for the activity of zinc in Fe‐C melt. From the dependence of the activity coefficient of zinc in Fe‐C melts on temperature and carbon content, the following equation could be obtained at 1473 ‐ 1623 K: The distribution ratio of zinc between Ag‐Zn alloy and CaO‐FeO‐CaF₂ slag increased by increasing both the oxygen potential and slag basicity. The stoichiometric coefficients of the dissolution reaction were obtained by considering the relationship between zinc distribution ratio and slag basicity or oxygen partial pressure, when one of these two independent variables was fixed. The dissolution reaction of zinc into the slags could be described as follows:      

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.     

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.     

Nitrogen solubility in CaO-CaF2-SiO2 melts

The preceding paper^[5] demonstrated that nitrogen dissolves in silicate melts either as a free ion or complex anion, being incorporated into silicate networks. In the present study, the influence of CaF₂ addition to CaO-SiO₂ melts on the nitrogen solubility was investigated along the liquidus at 1573 K and within the liquidus at 1723 K at constant CaF₂ levels. In the latter case, as the SiO₂ content increases from CaO saturation, the total nitrogen content decreases to reach the minimum and then starts to increase up to the SiO₂ saturation. This is in accord with the abovementioned mechanism of nitrogen dissolution, which is supported by the changing behavior of free and incorporated nitrogen contents with the slag composition. The role of CaF₂ is complicated through the formation of fluorosilicates. The CaF₂ seems not to function simply as a diluent but to enhance the dissolution of nitrogen by releasing oxygen from silicate networks, promoting the formation of free nitride ions. Formerly Graduate Student, Department of Metallurgy, The University of Tokyo.     

Effect of Physicochemical Properties of Slag and Flux on the Removal Rate of Oxide Inclusion from Molten Steel

The slag-metal reaction experiments were carried out using a high-frequency induction furnace to confirm the effect of slag composition on the removal rate of inclusions in molten steel through the CaO-based slags. The apparent rate constant of oxygen removal (k _O) was obtained as a function of slag composition. It increased with increasing basicity, and the content of MgO and CaF₂, whereas it decreased by increasing the content of Al₂O₃ in the slag. The removal rate of inclusions was strongly affected not only by the driving force of the chemical dissolution but also by the viscosity of the slags and fluxes.     

Measurement of FeO activity and solubility of MgO in smelting slags

In bath smelting, the FeO activity of the slag must be known to predict the equilibrium of slag-metal reactions and for effective control of the rate of reduction in the system. Also, knowledge of the solubility of MgO in these slags is useful for reducing refractory consumption. A series of measurements of the FeO activity in simulated bath smelting slags (CaO-SiO₂-Al₂O₃-MgO_sat-FeO) were conducted by the electromotive force (EMF) technique. The influence of the slag composition on the relationship between the FeO activity coefficient and FeO content was studied. It has been found that the measured FeO activity coefficient decreases with increasing FeO content in the slag and increases slightly with increasing slag basicity, which is defined as (CaO + MgO)/(SiO₂ + Al₂O₃) on a mole fraction basis. The measured values of the FeO activity coefficient are in reasonable agreement with previously published data. The solubility of MgO was also measured and found to rang from 16 to 30 pct and decrease with increasing basicity.     

Interfacial Reaction between Refractory Materials and Metallurgical Slags containing Fluoride

Interfacial reaction between refractory materials such as zirconia, magnesia and doloma brick, and the metallurgical slags of the CaO‐SiO₂‐MgO‐CaF₂ system with varying CaF₂ content were investigated at high temperatures using various methodologies with static and dynamic modes. To figure out the corrosion mechanism due to interfacial reaction with the slag, the slag characteristics were examined in terms of flow temperature and viscosity and the corroded interface of zirconia, magnesia and doloma refractories were analyzed by SEM‐EDS and EPMA. With an addition of CaF₂, three different layers were formed at the interface between slag and zirconia refractory. Furthermore, the corrosion of zirconia refractory was found to be accelerated with an increase of CaF₂ which facilitated the dissolution of intermediate compounds. The penetration of slag through the grain boundaries of MgO refractory is enhanced by increasing the content of CaF₂ due to an increase in the fluidity of slag in the dynamic mode. On the other hand, in the static condition, a dense Ca₂SiO₄ layer is formed at the hot face of magnesia‐doloma refractory due to a reaction between silica in slag and lime in doloma, resulting in the protection of direct corrosion of refractory brick. However, the thickness of C₂S layer decreases with increasing content of CaF₂ due to an increase in fluidity of slag.     

A Study in the Thermodynamic Behavior of Nickel in the MgO‐SiO2‐FeO Slag System

The dissolution behavior of nickel in the MgO‐SiO₂‐FeO slag system was investigated by using the thermodynamic equilibrium technique. Nickel distribution ratio between molten MgO‐SiO₂‐FeO slag and molten Fe‐Ni alloy at 1773 K and 1873 K was measured to understand the dissolution mechanism of nickel into the slags. In particular, the effect of oxygen potential and basicity on the distribution of nickel was investigated. Nickel distribution between slag and Fe‐Ni alloy increased with higher oxygen potential showing a slope of 1/2. For basic slag systems near the olivine saturated composition, the nickel distribution ratio increased with higher basicity and for acidic slag systems near the cristobalite saturated composition, the nickel distribution ratio decreased with higher basicity. Thus, the nickel dissolution into the MgO‐SiO₂‐FeO slag system showed two independent mechanisms similar to that found in the CaO‐SiO₂‐CaF₂ system. The contour of the iso distribution ratio was represented in the MgO‐SiO₂‐FeO ternary phase diagram. From the results, an optimum slag composition was determined to be near the olivine saturated with approximately $X_{MgO} /X_{SiO_{2} } $ of 0.8 at 1773 K and 1.0 at 1873 K.     

MgO solubility in BOF slag equilibrated with ambient air

The MgO solubility in the CaO‐MgO‐Fe₂O₃‐FeO‐SiO₂‐(MnO)‐(Al₂O₃) slag was measured under the condition of equilibrium with the ambient air at 1873 K as a fundamental study for precise slag coating control in BOF operation. The CaO/SiO₂ mass ratios of the main slag were 1, 1.5, 2, 3 and 4, and total iron content was in the range of 10 to 35 %. Moreover, 1 to 13 % of MnO and 2 to 12 % of Al₂O₃ were added to the melt to evaluate their effects on the MgO solubility. The effect of slag composition on the MgO solubility was discussed and quantified by means of a newly developed formula. As the basicity in slag increases, the MgO solubility decreases. The effect of iron oxide content is observed to be dependent on the basicity of slag. An increase in iron oxide content makes the MgO solubility higher for basic slag but lower for acidic slag. It is revealed that the MgO solubility in steelmaking slag is controlled by the complex anion formation reaction of iron oxide. Both Al₂O₃ and P₂O₅ increase the MgO solubility by diluting the basic oxides as SiO₂ does, while manganese oxide affects the MgO solubility in a similar manner as iron oxide. The MgO solubility can be described as a function of slag composition, X = (%CaO) + 0.45(%Fe₂O₃+ %FeO) + 0.55(%MnO), in the equation of (%MgO) = 0.00816X^2‐1.404X + 62.31. Based on the results, the guidance for addition of MgO‐containing material could be suggested for best slag coating practice.     

Dissolution behaviour of manganese ore in basic oxygen furnace type slag

In order to improve manganese yield during the reduction process of manganese ore in blowing practices employing less slag at BOF, the dissolution behaviour of manganese ore in slag has been studied in an experimental scale. The effect of temperature, slag composition, addition of CaF₂, and pre-treatment of manganese ore was examined for the dissolution behaviour of manganese ore into BOF type slags. The precipitation of (Fe,Mn)O phase in slag was observed during the addition of manganese ore. The dissolution rate of manganese ore into molten slag increased with temperature, and also increased with the initial contents of FeO, MgO and MnO. However, the effect of slag basicity was not evident on the dissolution rate of manganese ore into slag. The addition of CaF₂ and pre-treatment of Mn ore were very effective to promote the dissolution of manganese ore into slag.     

Reduction of MnO from molten slags with liquid steel of high carbon content

This work estimated the reduction of MnO in slags of the CaO‐SiO₂‐FeO‐CaF₂‐MnO system and liquid steel with the initial composition (mass contents) 0.75 %Mn, 0.16 % Si and 0.5 to 2.0 % C, as an alternative to introducing Mn to the steel melt. The slag basicities (CaO/SiO₂) In the experiments were 2 and 3. MnO was obtained from manganese ore. The experiments were carried out in an open 10 kg induction furnace using Al₂O₃‐based refractory at 1873 K. The oxygen potential was measured throughout the experiments with a galvanic cell (ZrO₂‐solid electrolyte with a Cr/Cr₂O₃ reference electrode). The MnO reaction mechanism was analysed in terms of the slag basicity, the silicon and the initial carbon contents in the melt. The rate and the degree of MnO reduction were found to increase with the increasing of initial carbon content; however, the effect of slag basicity was less important. A kinetic analysis of the process was performed using a coupled reaction model.     

Study on the foaming of CaO-SiO2-FeO slags: Part I. Foaming parameters and experimental results

In order to understand the effect of slag composition on foaming in iron and steelmaking processes, slag foaming was quantitatively studied for CaO-SiO₂-FeO slags in the temperature range of 1250 °C to 1400 °C. It was found that slag foaming could be characterized by a foaming index (Σ), which is equal to the retention or traveling time of the gas in the slag, and the average foam life ( τ). The effects of P₂O₅, S, MgO, and CaF₂ on foaming were studied. As expected, slag foaming increased with increasing viscosity and decreasing surface tension. It was found that suspended second-phase solid particles such as CaO, 2CaO SiO₂, and MgO stabilized the foam and had a larger effect on foaming than changes in viscosity and surface tension for the slags studied. Kimihisa Ito, Research Associate, formerly with the Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

Dissolution Behavior of Chromite Ore in CaO-SiO2 System

Numerous investigations proposed that the dissolution of chromite ore is the rate-controlling step for the smelting reduction of chromite ore. The mechanism of chromite ore dissolution in the binary CaO-SiO₂ system is presented. The effect of basicity, temperature, and reducing conditions on chromite ore dissolution is elaborated. The solubility of chromite ore increases considerably when the basicity increases from 0.56 to 0.65. However, the solubility of chromite ore decreases when the basicity further increases from 0.65 to 0.74. The positive effect of reducing conditions on the solubility of chromite ore is evident. The maximum dissolved Cr₂O₃ in slag under reducing conditions by using a graphite crucible reaches 2.6 wt% after 15 min of dissolution. The element diffusion behavior at the chromite/slag interface is elaborated through SEM-EDS technology. The analysis suggests that the rate-controlling step in the early stage is the interface dissolution reaction. After a certain time, the rate-controlling step becomes the mass transfer of Cr₂O₃ from the chromite ore to the chromite/slag interface. The activation energy of the dissolution reaction is $E_{\mathrm{r}}$ = 285.29 kJ mol⁻¹.     

Sulfide capacity of high alumina blast furnace slags

Sulfide capacities of high alumina blast furnace slags were experimentally determined using the gas-slag equilibration technique. Two different slag systems were considered for the current study, namely, CaO-SiO₂-MgO-Al₂O₃ quaternary and CaO-SiO₂-MgO-Al₂O₃-TiO₂ quinary system. The liquid slag was equilibrated with the Ar-CO-CO₂-SO₂ gas mixture. Experiments were conducted in the temperature range of 1773 to 1873 K. The effects of temperature, basicity, and the MgO and TiO₂ contents of slags on sulfide capacity were studied. As expected, sulfide capacity was found to increase with the increase in temperature and basicity. At the higher experimental temperature, titania decreases the sulfide capacity of slag. However, at the lower temperature, there was no significant effect of titania on the sulfide capacity of slag. Sulfide capacity increases with the increase in MgO content of slag if the MgO content is more than 5 pct.     

Study on refining slags targeting high cleanliness and lower melting temperature inclusions in Al killed steel

Abstract

Three high basicity slags (A, B and C) were used in laboratory to refine Al killed steel to target high oxide cleanliness and low melting temperature inclusions. Inclusions were of CaO–MgO–Al₂O₃–SiO₂ system after 90 min reaction, parts of which were MgO based. Total oxygen were in the range of 0·0007–0·0010 and 0·0005–0·0010% respectively when slag A (CaO/SiO₂, 6–8; Al₂O₃, ～40%) and slag B (CaO/SiO₂, 6–8; Al₂O₃, ～30%) were applied, with inclusions all in spherical shape and mainly <5 μm. Inclusion composition concentrated in or around the lower melting point region (<1500°C) under slag A, while it became more scattered under slag B. Total oxygen varied between 0·0008 and 0·0011% under slag C (CaO/SiO₂, 3–4; Al₂O₃, about 20–25%). Many of the inclusions were in larger size, irregular morphology and located far away from the lower melting point region. Formation of MgO based inclusions closely related to solubility behaviour of MgO in the slag.     

The solubility of water vapour in CaO‐SiO2‐Al2O3‐MgO slag system

The solubility of water vapour in the CaO‐SiO₂‐Al₂O₃‐MgO quaternary slag system was measured using an inert gas fusion technique with thermal conductivity detection. The slags were equilibrated with argon‐water vapour mixture corresponding to 0.157 bar of water vapour pressure at 1873 K. The slag solubility of water vapour is proportional to the square root of vapour pressure. Since the hydroxyl capacity of slag, C_OH shows an independence on the relative amount of CaO or MgO in slag, the contributions of CaO and MgO on the hydroxyl capacity are equivalent on a molar basis. Whereas, Al₂O₃ shows a better effect on the hydroxyl capacity than SiO₂. A linear relationship between hydroxyl capacity and slag basicity in logarithmic scale was obtained with the slope of 1/2, confirming the water vapour dissolution reaction into a basic slag as (O^2‐) + H₂O(g) = 2(OH^?). The correlation between hydroxyl capacity and slag components was derived in terms of their contributing weight factors. The measured values of C^'_OH agree well with the calculated ones using the interaction energies of α_H‐Al = ?38300 and α_H‐Mg = ?22700 J determined with the aid of the regular solution model. In addition, the correlation between hydroxyl capacity and sulphide capacity was empirically derived as a formula of logC_OH = 1/2logC_S + (4.38 ± 0.25) through the thermodynamic expression of both capacities by virtue of the common oxygen ion activity.