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.     

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.     

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.     

Effects of oxygen atmosphere,FeOx and basicity on mineralogical phases of CaO–SiO2–MgO–Al2O3–FetO–P2O5 steelmaking slag

ABSTRACT

The mineralogical phase of slag after crystallisation is essential to utilisation of steelmaking slag. The mineralogical phases of cooled multicomponent CaO–SiO₂–MgO–Al₂O₃–Fe_tO–P₂O₅ slag with different iron oxide contents and basicities (defined as the ratio of mass percentage of CaO to mass percentage of SiO₂ (w(CaO)/w(SiO₂))) in different atmospheres were investigated in the present work by scanning electronic microscopy and energy dispersed spectroscopy analysis and X-ray diffraction. The mineralogical phases in steelmaking slag cooled in argon are mainly nCa₂SiO₄-Ca₃(PO₄)₂ (thereafter nC₂S-C₃P) solid solution, (Fe, Mn, Mg)O (RO) phase. Some CaMgSiO₄ phases could be found in slag with lower basicity. The mineralogical phases in steelmaking slag cooled in air are mainly nC₂S-C₃P solid solution, spinel phase. The overall crystallisation of slag cooled in both argon and air was enhanced with increasing basicity. However, the crystal sizes become smaller in sample with high basicity. The Fe-enriched phases were transformed from non-faceted RO phase in sample cooled in argon to faceted spinel phases in sample cooled in air. The crystallisation of slag cooled in both argon and air was promoted with increasing FeO_x content. The phosphorus content in solid solution was elevated with decreasing basicity and increasing FeO_x content. It was implied by the present work that appropriate basicity and air oxidation would be beneficial to magnetic separation and phosphorus utilisation.     

Inclusion composition control in tyre cord steel by top slag refining

Abstract

In order to improve the inclusion type and composition in tyre cord steel, ladle furnace refining has been simulated by laboratory experiments and thermodynamic calculation. It was found that slag metal reaction time and top slag composition have an important influence on the inclusion compositions in the final steel. To produce the desired low melting point ductile inclusions the optimum conditions were: reaction time 60 min, basicity (CaO/SiO₂) of top slag in the range of 1·0–1·2 and Al₂O₃ content of slag in the range of 3–9 mass-%. These were then confirmed in industrial trials.     

Thermodynamic Simulation of the Influence of the Temperature and the Basicity of a Boron-Containing Slag on Steel Desulfurization

The results of thermodynamic simulation of the desulfurization of a medium-carbon steel by slags of the CaO–SiO₂–MgO–Al₂O₃–B₂O₃ system are presented. The HSC Chemistry 6.12 software package is used for the simulation. The thermodynamic simulation is performed for 20 various chemical compositions of slags with various B₂O₃ contents (1–4%)¹ and basicities ((CaO)/(SiO₂) = 2–5). The computations are performed using the Equilibrium Compositions module in the temperature range from 1500 to 1700°C with an increment of 50°C at a gas phase pressure of 0.1 MPa. The main results of the calculations are presented as the dependences of the change in the sulfur content in steel [S] on the temperature, the content of B₂O₃, and the slag basicity. An increase in the temperature of metal desulfurization from 1500 to 1700°C exerts a favorable effect on the sulfur content for the studied range of slag basicities. In particular, the sulfur content in steel decreases from 0.012 to 0.009% when steel is processed with the slag having 3% B₂O₃ and a basicity (CaO)/(SiO₂) = 2. A positive effect of an increase in the slag basicity from 2 to 5 on metal desulfurization is observed: the degree of desulfurization increases from 61.1 to 97.2% at 1600°C and 3% B₂O₃ content in the slag. As the B₂O₃ content in a slag increases from 1 to 4%, its refining properties decrease significantly in the range of basicity not higher than 2. In the range of high slag basicities (3–4), the negative effect of acidic oxide B₂O₃ on the refining properties of the slag decreases, providing low sulfur contents (which do not exceed [S] = 0.003–0.004% at 4% B₂O₃). At a slag basicity of 5, the sulfur content in steel decreases to 0.001%, all other things being equal. The simulation results can be used for the calculation of steel desulfurization processed by slags containing B₂O₃.     

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.     

Dissolution of Lime in Synthetic ‘FeO’‐SiO2 and CaO‐‘FeO’‐SiO2 Slags

Dissolution of different CaO samples into molten synthetic ‘FeO’‐SiO₂ and ‘FeO’‐SiO₂‐CaO slags was carried out in a closed tube furnace at 1873 K. The slag was kept stagnant. It was found that the dissolution rate was very fast when CaO rod was dipped into ‘FeO’‐SiO₂ slag. In the case of ‘FeO’‐SiO₂‐CaO slag, the dissolution of CaO rod in the stagnant slag was retarded after the initial period (2 minutes). Only less than 16 percent CaO reacted with the slag, irrespective of the type of lime. Three phase‐regions were identified in the reacted part of the lime rod by SEM‐EDS analysis. The formation of these regions was explained thermodynamically. A dense layer of 2CaO · SiO₂ was found to be responsible for the total stop of the dissolution. It could be concluded that constant removal of the 2CaO · SiO₂ layer would be of essence to obtain a high dissolution rate of lime. In this connection, it was found necessary to study the dissolution of lime in moving slag to reach a reliable conclusion regarding the relevance of the reactivity obtained by water ATSM test to the real reactivity of lime in high temperature slag.     

Reoxidation of Al‐Killed Steel by Ca(OH)2 in the High Basicity Slag

In the present work, reoxidation of Al‐killed steel by Ca(OH)₂ in high basicity slag was investigated by using laboratory experiments at 1873 K in MgO crucibles with various amount of Ca(OH)₂ addition into slag. The CaO–SiO₂–Al₂O₃–MgO–Ca(OH)₂ slags were used to study the effect of Ca(OH)₂ on total oxygen content, aluminum loss, and FeO content in the slag. It was shown that total oxygen content decreased with the time when no Ca(OH)₂ was added into the slag, but it first increased and then decreased with the time when the addition of Ca(OH)₂ was made. Moreover, aluminum loss and FeO content in the slag increased with increasing Ca(OH)₂ content.     

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.     

Reduction of iron oxides from liquid slags using a graphite rotating disc

Research work has been carried out on the reduction of FeO from liquid slags of the CaO‐FeO‐SiO₂ ternary system using a graphite rotating disc technique. The investigations were conducted on slags with a basicity of CaO/SiO₂ = 1.27 and FeO contents of 20 and 60%, at temperatures of 1350 and 1420°C. The calculated viscosity range for these slags is within 2.53 – 0.43 dPa·s. It has been found that the factor controlling the reduction process is diffusion of FeO towards the disc surface, both in the case of the reduction from the slag with 20% FeO and in the case of the reduction from the slag with 60% FeO fraction. The diffusion coefficient of FeO at the reduction temperature of 1350°C is of the order of magnitudes of 10^?7 cm²/s, while at 1420°C it reaches the order of 10^?6 cm²/s. The calculated thickness values for the limiting diffusion layers range from 8.54·10^?3 to 0.70·10^?3 cm. It has been found that with increasing reduction rate also Boudouard's reaction starts to be important to the overall reduction rate. The limiting reduction rate at which Boudouard's reaction starts to be important to the entire process is dependent on temperature, being approximately 10.0·10^?6 mol FeO/cm² s at 1350°C, and approximately 15.0·10^?6 mol FeO/cm² s at 1420°C.     

Thermodynamics of manganese distribution between liquid iron and the CaO–Al2O3–SiO2–FeO–MnO system

The thermodynamics of distribution of constituents between liquid iron and the CaO–Al₂O₃–SiO₂–FeO–MnO system at 1600°C was studied using electrochemical indication of the equilibrium partial pressure of oxygen in both phases. The results show that oxidation potential of the Fe(l)–CaO–Al₂O₃–SiO₂–FeO–MnO system, expressed in terms of log p(O₂), is directly proportional to log (x(MnO) · x(FeO)/w| Mn |). Manganese distribution coefficient, L'_mn, in intersection CaO/Al₂O₃ = 1 decreases with increasing slag basicity expressed in terms of activity a(CaO) or 1/γ(MnO). Experimentally determined equilibrium constant K_Mn/Fe is equal to 2.7 for 1600°C. The number of exchanged electrons between Fe-O-Mn-Si electrode and the slag approaches the theoretical value.     

Influence of refining slag composition on cleanness and fatigue life of 60Si2MnA spring steel

The influence of basicity and Al₂O₃ content of LF refining slag on T.[O] (total oxygen) as well as type, number and size of non-metallic inclusions in Al killed 60Si2MnA spring steel was investigated. The results showed that with the increase of slag basicity R(CaO/SiO₂) or the decrease of Al₂O₃ content in slag, the T.[O], number and size of non-metallic inclusions decreased significantly. On the one hand, as the slag basicity increased, inclusions in steel were transformed from Al₂O₃–SiO₂–CaO–MgO quaternary system to Al₂O₃–SiO₂–CaO–MgO–CaS quinary system, which made the formation of voids between inclusions and steel matrix to decrease. Furthermore, thermodynamic calculations showed that CaS could only form in steel (R?≥?3.4). Al₂O₃–SiO₂–CaO–MgO came close to the compositions of the low melting point area, while Al₂O₃–SiO₂–CaO–MgO–CaS deviated from this. On the other hand, as the Al₂O₃ content in slag increased, Al₂O₃–SiO₂–CaO–MgO–CaS came close to the compositions of the low melting point area. In conclusion, the cleanness and fatigue life of 60Si2MnA spring steel had been improved by the increase of slag basicity or the decrease of Al₂O₃ content in slag.     

Influence of calcium treatment on cleanness and fatigue life of 60Si2MnA spring steel

Contrasting experiments of Al killed 60Si2MnA spring steel were carried out between using and excluding calcium treatment under LF refining slags with low and high basicity ratios (R: CaO/SiO₂?=?3.4, 5.0), respectively. Results showed the high basicity refining slag had a certain effect on controlling inclusions and improving the cleanness of spring steel similarly to calcium treatment. The T.[O] (total oxygen) content of steel without calcium treatment got to below 15?ppm and the fatigue life was long, up to 7.8?×?10⁶?cycles. But in order to reduce the T.[O] below 10?ppm, as well as inclusion number and size in spring steel further, meanwhile, the appropriate calcium treatment should still be used. Besides, as the [Ca] content in the steel with calcium treatment increased, inclusions transformed from Al₂O₃–SiO₂–CaO–MgO to Al₂O₃–SiO₂–CaO–MgO–CaS completely, which reduced the formations of voids between inclusions and steel matrix, and voids decreased with the increase of CaO/Al₂O₃ value and CaS content of inclusions. Finally, the fatigue life of spring steel with high basicity slag and calcium treatment increased to 9.1?×?10⁶ cycles.     

Electrical and electronic conductivity of CaO-SiO2-FeO x slags at various oxygen potentials: Part I. Experimental results

The oxygen potential dependences of total electrical and partial electronic/ionic conductivities for ‘FeO’-CaO-SiO₂ slags have been studied both experimentally and theoretically in the present work. In the first part of this two-part article, the experimental results are presented for slags with 30 wt pct ‘FeO’ and CaO/SiO₂ wt ratios of 0.5, 1.0, and 2.0. For each slag composition, measurements of total electrical conductivity and electronic transference were made over a range of oxygen potentials and temperatures. The results were used to calculate the partial conductivities. A maximum was achieved in total and electronic conductances as a function of equilibrium CO₂/CO. The CO₂/CO corresponding to the maximum was shifted to lower values with increasing slag basicity (CaO/SiO₂ ratio). The other effect of basicity was increasing total and partial conductivities, with a magnitude that depends on oxygen potential and temperature. The activation energies for ionic and electronic conductances were in similar ranges and decreased with the basicity.     

Thermal Conductivity of the Molten CaO-SiO2-FeO x System

Thermal conductivity measurements were carried out on synthetic steelmaking slag using the hot-wire method. Furthermore, local structure analysis in the melts was carried out in order to investigate the relationship with the composition dependence. The thermal conductivity of the CaO-SiO₂-FeO _x melts significantly decreased as the content of FeO _x increases, particularly at lower basicity. Both chemical analysis and the observation show that the amount of Fe²⁺ increases when CaO/SiO₂ is smaller, implying more basic behavior of FeO than FeO_1.5. According to further analyses by M?ssbauer spectroscopy, the degree of basicity of FeO_1.5 remains virtually unchanged in the composition range of interest. From the experimental results, it could be concluded that the thermal conductivity of the silicate melt containing iron oxide is highly dependent on the valence of the Fe ion and comparatively independent of the amphoteric behavior of FeO_1.5.     

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.     

Thermodynamics of chromium oxides in CaO-SiO2-CaF2 slag

The distribution ratio of chromium between a CaO-SiO₂-CaF₂ slag and liquid silver under the oxygen partial pressure used in practical hot-metal dephosphorization treatment was measured at 1623 K. The distribution ratio was minimal when the basicity index of a slag, wt pct CaO/wt pct SiO₂, was about 2. The redox equilibrium between CrO (Cr²⁺) and CrO_1.5 (Cr³⁺) in the slag was also measured as a function of slag composition. The calculated activity coefficient of CrO had a maximum value at wt pct CaO/wt pct SiO₂=2, whereas that of CrO_1.5 decreased monotonously with the increase in slag basicity.     

Influence of MgO addition on mineralogy of iron ore sinter

The influence of MgO addition on sinter mineralogy was studied on sinters produced in a laboratory installation, with a wide range of MgO/CaO ratios at several basicity indices [B = (CaO + MgO)/ (SiO₂ + A1₂O₃)] between 0.7 to 1.9. The most striking influence of MgO is the suppression of hematite and Ca-ferrite phases and the increase in magnetite phase. In general, MgO favors the formation of glass and suppresses the precipitation of dicalcium silicates in favor of Ca-Fe-Mg olivines and pyroxenes. Microprobe studies revealed that most of the Mg was picked up by the magnetite phase to form mixed spinels of type (Fe, Mg)O · Fe₂O₃. At a constant basicity index, increased replacement of CaO by MgO also led to increased participation of FeO in the slag formation process, thus increasing the overall FeO content of sinter. A mechanism for the formation of mixed spinels has been proposed. The effect on various sinter properties resulting due to change in sinter mineralogy has been outlined. S. C. PANIGRAHY, with Department of Metallurgy and Metallography, State University of Ghent, Ghent, Belgium at the time the experiments were carried out     

Effect of CaO Addition on Iron Recovery from Copper Smelting Slags by Solid Carbon

We investigated the effect of flux (lime) addition on the reduction behavior of iron oxide in copper slag by solid carbon at 1773 K (1500 °C). In particular, we quantified the recovery of iron by performing typical kinetic analysis and considering slag foaming, which is strongly affected by the thermophysical properties of slags. The iron oxide in the copper slag was consistently reduced by solid carbon over time. In the kinetic analysis, we determined mass transfer coefficients with and without considering slag foaming using a gas holdup factor. The mass transfer of FeO was not significantly changed by CaO addition when slag foaming was ignored, whereas the mass transfer of FeO when slag foaming was considered was at a minimum in the 20 mass pct CaO system. Iron recovery, defined as the ratio of the amount of iron clearly transferred to the base metal ingot to the initial amount of iron in the slag phase before reduction, was maximal (about 90 pct) in the 20 mass pct CaO system. Various types of solid compounds, including Mg₂SiO₄ and Ca₂SiO₄, were precipitated in slags during the FeO reduction process, and these compounds strongly affected the reduction kinetics of FeO as well as iron recovery. Iron recovery was the greatest in the 20 mass pct CaO system because no solid compounds formed in this system, resulting in a highly fluid slag. This fluid slag allowed iron droplets to fall rapidly with high terminal velocity to the bottom of the crucible. A linear relationship between the mass transfer coefficient of FeO considering slag foaming and foam stability was obtained, from which we concluded that the mass transfer of FeO in slag was effectively promoted not only by gas evolution due to reduction reactions but also by foamy slag containing solid compounds. However, the reduced iron droplets were finely dispersed in foamy and viscous slags, making actual iron recovery a challenge.