Viscosities of the Quaternary Al2O3‐CaO‐MgO‐SiO2 Slags

Viscosities of some quaternary slags in the Al₂O₃‐CaO‐MgO‐SiO₂ system were measured using the rotating cylinder method. Eight different slag compositions were selected. These slag compositions ranging in the high basicity region were directly related to the secondary steel making operations. The measurements were carried out in the temperature range of 1720 to 1910 K. 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 iso‐viscosity contours in the Al₂O₃‐CaO‐MgO‐SiO₂ system relevant to ladle slags were calculated at 1823 K and 1873 K for 5 mass% MgO and 10 mass% MgO sections. The predicted results showed good agreement with experimental values and the literature data.     

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.     

The slag-metal equilibrium in tin smelting

An equilibrium study was undertaken to investigate the effect of the CaO/SiO₂ and Fe/SiO₂ ratios and the SnO and Al₂O₃ contents of slags on the distribution of Fe and Sn between slag and metal in tin smelting. The experiments were performed at 1200 °C by equilibrating Sn-Fe alloys with silicate slags under reducing conditions in closed crucibles. The slag and metal analyses were used to calculate the γ_SnO/γ_FeO ratio in the slags and a multiple-linear regression on these values indicated that, in the range of slag compositions investigated, γ_SnO/γ_FeO is a function only of the CaO/SiO₂ ratio. At 1200 °C, γ_SnO/γ_FeO varies from about 1.1 for CaO-free slags to 3.6 for slags in which the CaO/SiO₂ ratio is 1.0. In practical applications, the slag-metal equilibrium in tin smelting is usually discussed in terms of the variation of the distribution coefficient,k, with the Fe content of the metal, wherek is defined ask = [pct Sn]/[pct Fe] · (pct Fe)/(pct Sn). An equation fork was derived in terms of the atom fraction of iron in the metal, the γ_SnO/γ_FeO in the slag, and the temperature. This equation was used to construct graphs ofk as a function of the iron content over the slag compositions and at temperatures which cover the range of tin smelting practice.     

Influence of SiO2 Addition on the Properties of Al2O3‐CaO‐CaF2 Slag

The Al₂O₃‐CaO‐CaF₂ slag system is used in making special quality steels by the electro‐slag re‐melting process (ESR). The purpose of our investigation was to analyse ESR slag that contained SiO₂. The slag samples with different SiO₂ fractions (0 ‐ 20 mass %) were examined by chemical analysis, differential thermal analysis, simultaneous thermal analysis, X‐ray diffraction, electron microscopy and wetting angle measurement. With addition of SiO₂ the polymerization of slags was increased due to the formation of new silicate complex compounds that influenced their melting points and wetting angles.     

Immobilization of Chromium in Slags using MgO and Al2O3

Chromium containing slags from stainless steelmaking may be leached by acidic environments, therefore they should be treated before being stockpiled or land filled. In this work, synthetic slags were prepared and the effect of CaO/SiO₂, Cr₂O₃, MgO and Al₂O₃ contents on the stability of the mineralogical species formed was analysed. The morphology and composition of the slags were determined by XRD and SEM‐EDS, whilst their chemical stability was evaluated by leaching with an aqueous acetic acid solution. It was found that CaCr₂O₄ and CaCrO₄ are present in slags prepared with neither MgO nor Al₂O₃. The Al₂O₃‐based slags mainly produced Ca₂Al₂SiO₇ and the Cr(VI)‐containing oxide complex Ca₄Al₆CrO₁₆, whilst MgO‐based slags produced Mg Cr₂O₄ as main mineralogical species. Additionally, Eh‐pH diagrams for the Ca‐Cr‐H₂O and Mg‐Cr‐H₂O systems at 25°C were constructed. The results showed that the lowest chromium concentration levels in the leaching liquors corresponded to MgO‐based slags owing to the stable binding of chromium in spinel with MgO. It was also observed in the Al₂O₃‐based slags that when increasing the slag basicity from 1 to 2, the leachability of the slags was notably increased.     

Viscosity of slags

The experimental determination of the viscosity of slags proves to be difficult. Therefore models for calculation have been developed. The Urbain‐III‐model is very often used for slags. In order to further improve its accuracy, the Forschungsgemeinschaft Eisenhüttenschlacken (FEhS) modified this model by adjusting the coefficients of Weymann's temperature relation in dependence of the CaO/SiO₂‐basicity of the slag: η = A.T.exp(10³.B/T) with A = f (C/S‐basicity); B = f (x_oxides). Viscosities calculated by means of this modified model fit well with measured values. It has been shown that the application of this model enables the optimisation of metallurgical reactions and processes. Furthermore it should be possible to optimise those properties of the solidified slag which are influenced by the viscosity of the liquid slag. Thus the production of construction materials could be further improved to fulfil the highest quality requirements.     

Distribution of Bi Between Slags and Liquid Copper

The distribution of Bi between liquid copper and calcium ferrite slag containing 24 wt pct CaO, iron silicate slag with 25 wt pct SiO₂, and calcium iron silicate slags was measured at 1573 K (1300 °C) under controlled CO-CO₂ atmosphere. The experimental results showed that bismuth distribution is affected by the oxygen partial pressure, and bismuth is likely to exist in slags in the 2+ oxidation state, i.e., as BiO. The distribution ratio between calcium ferrite slag and metal was found to be close to that of iron silicate slag. The Bi distribution ratio was found to decrease with increasing SiO₂ and Al₂O₃ content in slag. Increasing temperature was found to decrease the Bi distribution ratio between slag and metal. Using the measured equilibrium data on Bi content of the metal and slag and composition dependence of the activity of Bi in liquid copper, the activity and hence activity coefficient of BiO in the slag was calculated. The close value of activity coefficient of BiO in both slags at the same oxygen partial pressure indicates that the CaO-BiO and SiO₂-BiO interactions are likely to be at the same level, or the FeO _x -BiO interaction is the predominant interaction for BiO in the slag. Therefore at a constant FeO _x content in the slag, the CaO-BiO and SiO₂-BiO interactions doesn’t affect \( \gamma_{\text{BiO}} \) significantly.     

The Effect of Ladle Treatment on Inclusion Composition in Tool Steel Production

An in‐depth SEM‐investigation of the inclusion composition change in the ladle refining process during tool steel production was done. Plant trials were carried out at Uddeholm Tooling AB in Hagfors, Sweden. A series of samples was taken during ladle refining, from deslagging through vacuum treatment. The goal was evaluating the effects of the top slag and other process parameters on the inclusion composition during ladle refining. The main conclusion was that normal variations in the process have a large influence on inclusion composition. Furthermore, it was concluded that the MgO content in the top slag had a large influence on the inclusion composition throughout the whole ladle refining process. Also, the SiO₂ content in the ladle slag originating from the EAF‐slag, had a noticeable effect on the inclusions. The inclusions belonging to the system Al₂O₃‐CaO‐MgO‐SiO₂ 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.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

Thermodynamic Behaviour of Chlorine in CaO‐SiO2‐MgO‐Al2O3(‐CaF2) Slags

The solubility of chlorine in CaO‐SiO₂‐Al₂O₃‐MgO(‐CaF₂) slag was measured at 1673 ‐1823 K. By estimating the chloride capacity of slags, thermodynamic behaviour of chlorine in the molten slag was investigated. Chloride capacity increased with increasing CaO / SiO₂ ratio (C/S). An increase in MgO content decreased chloride capacity at C/S≥1.0 because it lowered the activity of Ca²⁺ which seemed to have strong affinity with Cl^? in molten slag. Also, the chloride capacity decreased with increasing Al₂O₃ content. The affinity between the Ca²⁺ and Cl^? ions was confirmed by measuring the infrared spectra of slags. The dissolution reaction of chlorine into slag was exothermic and its molar enthalpy was evaluated from the experimental results at 1673 ‐ 1823 K. Based on the result obtained in the present study, the quantitative prediction of chlorine distribution during the blast furnace process was performed. It was estimated that almost all chlorine in the blast furnace would be absorbed into molten slag even if the PCI ratio was increased or low quality coal with chlorine content less than 1.0 mass% was injected.     

Dephosphorization equilibria between pure molten iron and CaO-saturated FeOn–CaO–SiO2 and FeOn–CaO–Al2O3 slags

Metal-slag refining reactions have been investigated to determine dephosphorization equilibria in steelmaking using CaO-saturated slags, low in P₂O₅–content, based on the systems FeO_n–CaO–SiO₂ and FeO_n–CaO–Al₂O₃. Slag compositions have been optimized with respect to basicity and oxygen potential to achieve maximum partition ratios wt.%(P₂O₅)/wt.%[P] and minimum phosphorus contents in pure molten iron at 1550, 1600 and 1700°C. Both slag systems prove to be effective dephosphorizers. Optimal slag compositions are around 10 wt.% SiO₂ near the CaO–3CaO · SiO₂ double saturation in the case of FeO_n–CaO–SiO₂ slags and at Al₂O₃ contents tending to zero in the case of FeO_n–CaO–Al₂O₃ slags. Attempts were also made to present phosphate capacities C_PO4^3?, fractions of free oxygen ions x_O^2? and theoretical optical basicities Λ as a function of the FeO_n content of slags.     

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.     

Effect of Al2O3 and MgO on Interfacial Tension Between Calcium Silicate‐Based Melts and a Solid Steel Substrate

The effect of Al₂O₃ and MgO on the interfacial tension between the molten CaO–SiO₂‐based slag and solid steel at 1773 K was studied. The interfacial tension of molten slags slightly increased with increasing Al₂O₃, but no significant change of interfacial tension was observed with higher MgO. Fourier transform infrared (FTIR) of as‐quenched slag samples indicated the slag structure to polymerize with Al₂O₃ additions, but depolymerize with MgO additions. Further detailed studies of the slag surface using X‐ray photoelectron spectroscopy (XPS) showed the fraction of free oxygen ions to decrease with higher Al₂O₃ but remained constant at higher MgO. The results suggested that interfacial tension decreases not only with the depolymerization of the melt, but also with an increase in the free oxygen ions at the molten slag/solid steel interface.     

Evaluation of Secondary Steelmaking Slags and Their Relation with Steel Cleanliness

Based on data provided from an industrial plant and FactSage commercial software use, a study of secondary refining slags and inclusion cleanliness was performed. Six heats of two slag series, namely, A and B, with average chemical composition (wt pct) of 43.00CaO-25.90SiO₂-12.96Al₂O₃-18.13MgO for series A and 49.98CaO-23.88SiO₂-10.11Al₂O₃-11.99MgO-4.03CaF₂ for series B, were used for the study. Both series used DIN 38MnS6 modified steel. The effective viscosity, solid fraction, composition of the liquid fraction, and slag saturation degree in MgO (calculated through thermodynamic software) were related to the experimental results obtained for the inclusion cleanliness. The B slags showed lower effective viscosity than the A slags, due to their high liquid fraction. Regarding the capacity of slags in the inclusion removal, slag B5 resulted in the lowest inclusion density and was considered as the best choice among the slags studied. The inclusion species formed using B slags are constituted especially of CaO-Al₂O₃-SiO₂ and MgO-Al₂O₃ and are Al₂O₃ rich. The presence of sulfide-type inclusions (AlMnS and CaS) were more pronounced among A slags.     

Activity of Chromium Oxide in CaO‐SiO2 based Slags at 1873 K

Thermodynamic properties of chromium oxides in molten slags are very important for optimization of stainless steel refining processes as well as reduction processes of chromium ores. The solubility of chromite into molten slags has been found to vary drastically with oxygen partial pressure and slag composition in the former studies by the authors. In the present study, activity data and redox equilibria of chromium oxides measured under moderately reducing conditions, P_O2= 6.95×10^?11 atm, at 1873 K are summarized. For the CaO‐SiO₂‐CrO_x system, the activity coefficient of chromium oxide increased with increasing basicity and the optimized slag composition for stainless steel refining is assessed as that saturated with CaCr₂O₄ and Cr₂O₃ using the phase relations determined. On the other hand, the presence of MgO and Al₂O₃ brings about different behaviour of chromium oxide activity and redox equilibria and the 44 mass per cent CaO ‐ 39 mass per cent SiO₂ ‐11 mass per cent Al₂O₃ ‐ 6 mass per cent MgO slag is recommended to reduce the chromium oxidation loss in the practical stainless steel refining process at 1873 K.     

Evaluation of Sulfur Addition to the High Basicity Slag on the Sulfur,Aluminum, and Cleanliness of High Sulfur Al‐Killed Molten Steel

In the present work, the influence of sulfur addition to the high basicity slag on the Al‐killed molten steel with high sulfur content was investigated by using a vacuum induction furnace at 1873 K in MgO crucibles. CaO–SiO₂–Al₂O₃–MgO–CaS slags were used to study the effect of high basicity slags with different CaS contents on sulfur loss, aluminum loss, and total oxygen content in the molten steel. It is shown that the sulfur content in the molten steel decreased with the time, and the addition of CaS into the slag can reduce the sulfur loss in the molten steel. Moreover, there was a decreasing tendency of the aluminum content in the molten steel with the time, and the addition of CaS into the slag can reduce the aluminum loss in the molten steel. Total oxygen content in the molten steel first increased and then decreased with the time when no CaS was added into the slag. However, it decreased monotonically with the time when the addition of CaS was made into the slag.     

Effect of composition on the crystallisation behaviour of blast furnace slag using single hot thermocouple technique

When the content of glass in blast furnace slag is over 95%, it can be used as a raw material in the manufacture of cement. The critical cooling rate required for the formation of glassy slag is one of the important characteristics for molten BF slag. The crystallisation behaviour of molten BF slag has been studied by in situ observation with the single hot thermocouple technique. The isothermal and non-isothermal experiments were performed to construct time–temperature-transformation and continuous-cooling-transformation diagrams. The effect of MgO, Al₂O₃ and binary basicity (CaO/SiO₂) on the critical cooling rate of the CaO–SiO₂–MgO–Al₂O₃ slags were studied under conditions of CaO/SiO₂?=?1.1–1.4, 6–12?mass% MgO and 10–16?mass% Al₂O₃. The following finding are reported in the present paper: (i) Higher MgO content increased the critical cooling rate; higher Al₂O₃ content decreased the critical cooling rate; higher CaO/SiO₂ increased the critical cooling rate. (ii) The crystallisation temperature of molten BF slag lowers as the cooling rate increases, the slag have larger critical cooling rate, higher crystallisation temperature. The results could be used to design proper cooling path of molten BF slag for the formation of glassy.     

Effects of basicity,MgO and MnO on mineralogical phases of CaO–FeOx–SiO2–P2O5 slag

The selective separation phosphorous rich phase from steel slag could be an effective way to utilise the steel slag. The mineralogical phase after cooling of steel slag is essential to selective separation of steel slag. In the present work, the mineralogical phases of CaO–FeO_x–SiO₂–P₂O₅ slag after controlled cooling were investigated by X-ray diffraction and scanning electronic microscopy and energy dispersed spectroscopy technique. It was found that the heat treatment at 1573?K would lead to the precipitation of Ca₂SiO₄–Ca₃P₂O₈ (C2S-C3P) solid solution for all samples. The heat treatment at 1273?K would lead to the precipitation of C2S-C3P, CaSiO₃ and Fe₂O₃. The increase of basicity would promote the crystallisation of CaO–FeO_x–SiO₂–P₂O₅ slag. The Effects of additions of MgO and MnO on phase formations of CaO–FeO_x–SiO₂–P₂O₅ slag were also studied. Fe₂O₃ gradually transformed into MgFe₂O₄ and MnFe₂O₄ in slag after crystallisation with addition of MgO and MnO, respectively. The sizes of MgFe₂O₄ and MnFe₂O₄ crystals increased with increases of MgO and MnO content. The increase of MgO and MnO content would promote the precipitation of MgFe₂O₄ phase and MnFe₂O_4, respectively. The precipitation of crystals from slag during cooling was interpreted by the kinetic and thermodynamic factors. It was proposed that addition of MgO and MnO in slag would be beneficial to magnetic separation of steel slag.     

A Viscosity Estimation Model for Molten Slags in Al2O3‐CaO‐MgO‐SiO2 System

A model for viscosity estimation of molten slags in the Al₂O₂‐CaO‐MgO‐SiO₂ system is presented in this work. The model is an extension to the viscosity estimation model of molten slags in the CaO‐FeO‐MgO‐MnO‐SiO₂ system developed before by the present author. The present model has explicitly taken charge compensation into consideration. It is postulated that Al exists in a structural unit MAl₂O₄ when MO/ Al₂O₃ >1 for the Al₂O₃‐MO‐SiO₂ system (MO=CaO, MgO). MAl₂O₄ has a similar behaviour as SiO₂, i.e. it can form an Al‐O‐Al network and be depolymerised by network modifying oxides (CaO, MgO). The present model is applied in viscosity estimation of some slags within the Al₂O₃‐CaO‐MgO‐SiO₂ system. A mean deviation of less than 25% is achieved for the present model.