Constitutional Segregation of Al2O3 in Mold Slag and Its Impact on Steel Cleanliness During Continuous Casting

The alumina pickup in a range of mold fluxes used for continuous casting of aluminum (Al)-killed ultralow carbon, low carbon, and peritectic steel have been measured. The Al₂O₃ pickup in slag varies approximately from 7 to 12 pct and depends on the slag basicity. Significantly higher Al₂O₃ pickup reported in basic slags and polynomial relationship exists between them. The effect of chemical composition on microstructure evolution and Al₂O₃ partitioning during crystallization was identified in all three types of mold slags. The microsegregation of Al₂O₃ inclusions in the constituent phase of CaO-SiO₂-Al₂O₃ based slag film is presented. Constitutional segregation of Al₂O₃ inclusion in slag was found to affect the Al₂O₃ pickup phenomena during continuous casting. Segregation of alkalis like Na and K was also observed in an Si-rich interdendritic matrix, whereas F was retained in the dendrites of all the slags studied. The Al₂O₃ inclusion partitioning and interdendritic segregation in the mold slag is studied with metallographic evidence.     

Amphoteric behavior of alumina in viscous flow and structure of CaO-SiO<Subscript>2</Subscript> (-MgO)-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags

The viscosity of CaO-SiO₂ (-MgO)-Al₂O₃ slags was measured to clarify the effects of Al₂O₃ and MgO on the structure and viscous flow of molten slags at high temperatures. Furthermore, the infrared spectra of the quenched slags were analyzed to understand the structural role of Al₂O₃ in the polymerization or depolymerization of silicate network. The Al₂O₃ behaves as an amphoteric oxide with the composition of slags; that is, the alumina behaves as a network former up to about 10 mass pct Al₂O₃, while it acts as a network modifier, in parts, in the composition greater than 10 mass pct Al₂O₃. This amphoteric role of Al₂O₃ in the viscous flow of molten slags at the Newtonian flow region was diminished by the coexistence of MgO. The effect of Al₂O₃ on the viscosity increase can be understood based on an increase in the degree of polymerization (DOP) by the incorporation of the [AlO₄]-tetrahedra into the [SiO₄]-tetrahedral units, and this was confirmed by the infrared (IR) spectra of the quenched slags. The influence of alumina on the viscosity decrease can be explained on the basis of a decrease in the DOP by the increase in the relative fraction of the [AlO₆]-octahedral units. The relative intensity of the IR bands for the [SiO₄]-tetrahedra with low NBO/Si decreased, while that of the IR bands for [SiO₄]-tetrahedra with high NBO/Si increased with increasing Al₂O₃ content greater than the critical point, i.e., about 10 mass pct in the present systems. The variations of the activity coefficient of slag components with composition indirectly supported those of viscosity and structure of the aluminosilicate melts.     

Crystallization Characteristics of CaO-Al2O3-Based Mold Flux and Their Effects on In-Mold Performance during High-Aluminum TRIP Steels Continuous Casting

Crystallization behaviors of the newly developed lime-alumina-based mold fluxes for high-aluminum transformation induced plasticity (TRIP) steels casting were experimentally studied, and compared with those of lime-silica-based mold fluxes. The effects of mold flux crystallization characteristics on heat transfer and lubrication performance in casting high-Al TRIP steels were also evaluated. The results show that the crystallization temperatures of lime-alumina-based mold fluxes are much lower than those of lime-silica-based mold fluxes. Increasing B₂O₃ addition suppresses the crystallization of lime-alumina-based mold fluxes, while Na₂O exhibits an opposite effect. In continuous cooling of lime-alumina-based mold fluxes with high B₂O₃ contents and a CaO/Al₂O₃ ratio of 3.3, faceted cuspidine precipitates first, followed by needle-like CaO·B₂O₃ or 9CaO·3B₂O₃·CaF₂. In lime-alumina-based mold flux with low B₂O₃ content (5.4 mass pct) and a CaO/Al₂O₃ ratio of 1.2, the formation of fine CaF₂ takes place first, followed by blocky interconnected CaO·2Al₂O₃ as the dominant crystalline phase, and rod-like 2CaO·B₂O₃ precipitates at lower temperature during continuous cooling of the mold flux. In B₂O₃-free mold flux, blocky interconnected 3CaO·Al₂O₃ precipitates after CaF₂ and 3CaO·2SiO₂ formation, and takes up almost the whole crystalline fraction. The casting trials show that the mold heat transfer rate significantly decreases near the meniscus during the continuous casting using lime-alumina-mold fluxes with higher crystallinity, which brings a great reduction of surface depressions on cast slabs. However, excessive crystallinity of mold flux causes poor lubrication between mold and solidifying steel shell, which induces various defects such as drag marks on cast slab. Among the studied mold fluxes, lime-alumina-based mold fluxes with higher B₂O₃ contents and a CaO/Al₂O₃ ratio of 3.3 show comparatively improved performance.     

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.     

Activity Coefficient of SiO2 in SiO2-Al2O3-CaO Slags with Low SiO2-Content at 1873 K (1600 °C)

The activity coefficient of SiO₂ in SiO₂-Al₂O₃-CaO slags with limited Al₂O₃ content was measured by equilibrating Fe-C-Si melt and slags at 1873 K (1600 °C). When the Al₂O₃ content was between 48 and 54 wt pct, the results show that $ \gamma_{{{\text{SiO}}_{ 2} }} $ rapidly decreases as the amount of SiO₂ in the slag decreases. The equilibrium amounts of Si and Al in a Fe melt in equilibrium with SiO₂-Al₂O₃-CaO slags were calculated based on the result of this study.     

Solubilities of carbon in CaO-Al2O3-SiO2 slags saturated with liquid iron

By equilibrating the CaO-Al₂O₃-SiO₂ slags with Fe - 0.0003～0.07% Al - 0.002～3.5% Si - 0.9～2.0% C alloys (mass contents in %) at 1873 K, the solubilities of carbon were measured as a function of Si contents in metal, using an alumina or lime crucible. The distribution ratios of carbon as a C^2- -ion were found to be linearly related to Si contents with a slope of 1/2 at a given slag composition. The carbide capacity, , defined by (% C) , increased with increasing SiO₂ contents at a given CaO/AlO_1.5 molar ratio in the CaO-AlO_1.5SiO₂ system.     

Study on Mold Slag with High Al2O3 Content for High Aluminum Steel

The slag-steel equilibrium reaction between the newly developed mold slag ND-MSL and 20Mn23AlV steel has been studied at high temperatures in the laboratory. The crystal morphology, microanalysis, and phase analysis of the original and final ND-MSL slags were studied by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). Results show that, in the final ND-MSL slag, the constitution of SiO₂ decreased by 0.7 wt pct and Al₂O₃ increased by 6.46 wt pct, while the melting temperature, viscosity, and crystallization rate increased by 62 K, 0.66 dPa s, and 15 pct, respectively. NaAlSi₃O₈ and CaAl₂Si₂O₈ were found to be precipitated in the final ND-MSL slag. Both the original and final ND-MSL slags have a small amount of LiF crystal and good glass form. The ND-MSL slag has little change in the composition and properties compared with the two currently used mold slags.     

Thermodynamics of iron oxide in FexO‐dilute CaO + Al2O3 + SiO2 + FexO slags at 1873 K

The ferrous and ferric ion capacities, and , for the slag of CaO + Al₂O₃ + SiO₂ are determined at 1873 K by means of the distribution equilibrium of iron between Fe_xO dilute slags of the system and Pt + Fe alloys under a controlled atmosphere. Compared with the values of for CaO + Al₂O₃ binary slag at a constant ratio of Al₂O₃ to decreases with an increase in SiO₂ content. Nearly linear relationships are observed between the logarithm of the ferrous and ferric ion capacities and the optical basicity. Applying these capacities, the relationship between (%Fe^T) and PO₂ under iron saturation, as well as the iron redox equilibrium in slag in relation to the optical basicity were discussed.     

Crystallization Behaviors of CaO-SiO2-Al2O3-Na2O-CaF2-(Li2O-B2O3) Mold Fluxes

The effects of basicity (CaO/SiO₂), B₂O₃, and Li₂O addition on the crystallization behaviors of lime-silica-based mold fluxes have been investigated by non-isothermal differential scanning calorimetry (DSC), field emission scanning electron microscopy, X-ray diffraction (XRD), and single hot thermocouple technique. It was found that the crystallization temperature of cuspidine increased with increasing the basicity of mold fluxes. The crystallization of wollastonite was suppressed with increasing the mold flux basicity due to the enhancement of cuspidine crystallization. The addition of B₂O₃ suppresses the crystallization of mold flux. The crystallization temperature of mold flux decreases with Li₂O addition. The size of cuspidine increases, while the number of cuspidine decreases with increasing mold flux basicity. The morphology of cuspidine in mold fluxes with lower basicity is largely dendritic. The dendritic cuspidine in mold fluxes is composed of many fine cuspidine crystals. On the contrary, in mold fluxes with higher basicity, the cuspidine crystals are larger in size with mainly faceted morphology. The crystalline phase evolution was also calculated using a thermodynamic database, and compared with the experimental results determined by DSC and XRD. The results of thermodynamic calculation of crystalline phase formation are in accordance with the results determined by DSC and XRD.     

Fluorine‐Free Mould Powders for Slab Casting: Crystallization Control in the CaO–SiO2–TiO2–Na2O–Al2O3 System

The main problem related to the development of fluorine‐free mould powders for slab casting is effectively controlling the heat transfer between the steel shell and mould. In commercial mould powders crystallization of cuspidine (Ca₄Si₂O₇F₂) from mould slag has a great effect on heat‐transfer control. In industrial process the crystallization rate for a fluorine‐free mould slag should be similar to the crystallization rate of cuspidine. To evaluate the crystallization rate for slags time‐temperature‐transformation (TTT) diagrams can be constructed using the Single Hot Thermocouple Technique by in situ observation. In the present work, fundamental information related to crystallization control in the CaO–SiO₂–TiO₂–Na₂O–Al₂O₃ system was obtained. It was observed that the addition of Na₂O in CaO–SiO₂–TiO₂ slags dramatically shortens the crystals' incubation times in TTT diagrams to the range of seconds. It is possible to control the crystallization kinetics in CaO–SiO₂–TiO₂ slags by changing the Na₂O content. Some observations for the crystals' morphology are reported.     

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.     

Activities of FetO in CaO-Al2O3-SiO2-FetO (<5 pct) slags saturated with liquid iron

The activity coefficients of Fe_tO in CaO-Al₂O₃ and CaO-Al₂O₃-SiO₂ slags with 0.01 to 5 mass pct Fe_tO were determined at 1873 K from the data obtained in the present and previous slag-metal experiments, using an alumina or lime crucible. It was found that the activity coefficients of Fe_tO obeyed a dilute solution law and increased with increasing the content of SiO₂. Based on the findings pertaining to the activity coefficient, the values for the activities of SiO₂ and Al₂O₃ in CaO-Al₂O₃-SiO₂ slags were assessed.     

The Viscous Behavior of FeO<Subscript>t</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Copper Smelting Slags

Understanding the viscous behavior of copper smelting slags is essential in increasing the process efficiency and obtaining the discrete separation between the matte and the slag. The viscosity of the FeO_t-SiO₂-Al₂O₃ copper smelting slags was measured in the current study using the rotating spindle method. The viscosity at a fixed Al₂O₃ concentration decreased with increasing Fe/SiO₂ ratio because of the depolymerization of the molten slag by the network-modifying free oxygen ions (O²⁻) supplied by FeO. The Fourier transform infrared (FTIR) analyses of the slag samples with increasing Fe/SiO₂ ratio revealed that the amount of large silicate sheets decreased, whereas the amount of simpler silicate structures increased. Al₂O₃ additions to the ternary FeO_t-SiO₂-Al₂O₃ slag system at a fixed Fe/SiO₂ ratio showed a characteristic V-shaped pattern, where initial additions decreased the viscosity, reached a minimum, and increased subsequently with higher Al₂O₃ content. The effect of Al₂O₃ was considered to be related to the amphoteric behavior of Al₂O₃, where Al₂O₃ initially behaves as a basic oxide and changes to an acidic oxide with variation in slag composition. Furthermore, Al₂O₃ additions also resulted in the high temperature phase change between fayalite/hercynite and the modification of the liquidus temperature with Al₂O₃ additions affecting the viscosity of the copper smelting slag.     

Thermal Conductivity Measurements of Some Synthetic Al2O3-CaO-SiO2 Slags by Means of a Front-Heating and Front-Detection Laser-Flash Method

The thermal conductivities of some synthetic slags containing Al₂O₃, CaO, and SiO₂ have been determined in the temperature range between 1623?K (1350?°C) and 1823?K (1550?°C) by applying a front-heating front-detection laser-flash method. In this method, the temperature response curve is measured in the short initial time period immediately after irradiating a laser pulse. The resultant values obtained by this method are unaffected by the radiative heat transfer. The temperature dependence of the thermal conductivity values were found not to be significant for all slag samples currently investigated. The thermal conductivity (??) of samples is represented with standard deviation less than 2?pct of its value as a function of compositions as follows: $$ \lambda = - 0.48\left[ {{\text{Al}}_{ 2} {\text{O}}_{ 3} } \right] - 0.57\left[ {\text{CaO}} \right] - 0.55\left[ {{\text{SiO}}_{2} } \right] + 57.1{\text{ W m}}^{ - 1} {\text{ K}}^{ - 1} $$ where [Al₂O₃], [CaO], and [SiO₂] are molar percent of Al₂O₃, CaO and SiO₂, respectively. The equation is suggested to cover the region of the following compositions: 8.0?mol pct < Al₂O₃ <21.0?mol pct, 31.5?mol pct < CaO <41.5?mol pct and 43.0?mol pct < SiO₂ <58.1?mol pct. The addition of Al₂O₃ to slags with a constant CaO/SiO₂ molar ratio resulted in an increase in thermal conductivity. In contrast, the effects of addition of SiO₂ and CaO are found to be insignificant.     

A Thermodynamic Model for Prediction of Iron Oxide Activity in Some FeO‐Containing Slag Systems

A thermodynamic model for calculating the mass action concentrations of structural units in CaO–SiO₂–MgO–FeO–MnO–Al₂O₃–CaF₂ slags, i.e., the IMCT‐N_i model, has been developed based on the ion and molecule coexistence theory (IMCT). The calculated comprehensive mass action concentration of iron oxides $N_{{\rm Fe}_{t} {\rm O}} $ has been compared with the reported activity of iron oxide $a_{{\rm Fe}_{t} {\rm O}} $ in 14 FeO‐containing slag systems from literatures. The good agreement between the calculated $N_{{\rm Fe}_{t} {\rm O}} $ and reported $a_{{\rm Fe}_{t} {\rm O}} $ indicates that the developed IMCT‐N_i model can be successfully applied to predict the activity of iron oxide $a_{{\rm Fe}_{t} {\rm O}} $ as well as the slag oxidation ability of CaO–FeO (s1), SiO₂–FeO (s2), CaO–SiO₂–FeO (s3), CaO–FeO–Al₂O₃ (s4), SiO₂–MgO–FeO (s5), SiO₂–FeO–Al₂O₃ (s6), CaO–SiO₂–FeO–Al₂O₃ (s7), CaO–SiO₂–MgO–FeO–Al₂O₃ (s8), SiO₂–FeO–MnO (s9), SiO₂–FeO–MnO–Al₂O₃ (s10), FeO–MnO (s11), FeO–MnO–Al₂O₃ (s12), CaO–FeO–CaF₂ (s13), and CaO–SiO₂–FeO–CaF₂ slags (s14) in a temperature range of 1473–1973 K.     

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.     

Experimental and Theoretical Studies on the Viscosity–Structure Correlation for High Alumina-Silicate Melts

Blast furnaces are encountering high Alumina (Al₂O₃ > 25 pct) in the final slag due to the charging of low-grade ores. To study the viscosity behavior of such high alumina slags, synthetic slags are prepared in the laboratory scale by maintaining a chemical composition of Al₂O₃ (25 to 30 wt pct) CaO/SiO₂ ratio (0.8 to 1.6) and MgO (8 to 16 wt pct). A chemical thermodynamic software FactSage 7.0 is used to predict liquidus temperature and viscosity of the above slags. Experimental viscosity measurements are performed above the liquidus temperature in the range of 1748 K to 1848 K (1475 °C to 1575 °C). The viscosity values obtained from FactSage closely fit with the experimental values. The viscosity and the slag structure properties are intent by Fourier Transform Infrared (FTIR) and Raman spectroscopy. It is observed that increase in CaO/SiO₂ ratio and MgO content in the slag depolymerizes the silicate structure. This leads to decrease in viscosity and activation energy (167 to 149 kJ/mol) of the slag. Also, an addition of Al₂O₃ content increases the viscosity of slag by polymerization of alumino-silicate structure and activation energy from 154 to 161 kJ/mol. It is witnessed that the activation energy values obtained from experiment closely fit with the Shankar model based on Arrhenius equation.     

Dissolution of water vapour in ESR-slags of the systems CaO–Al2O3 and CaF2–CaO–Al2O3 by application of Fourier-Transform-Infrared-Spectroscopy

In CaO–Al₂O₃- and CaF₂–CaO–Al₂O₃-slags the soluted water vapour was quantitatively determined with Fourier-Transform-lnfrared-(FT-IR-)spectroscopy. The slags were equilibrated at 1500 and 1600 °C with definite H₂O- and H₂O/HF-partial pressures, respectively. The liquid slags were quenched in liquid D₂O. They solidified glassily. Water vapour exists in the slags soluted as OH^?-ion. For all slags investigated a linear dependence of the integral extinction upon the square root of the H₂O-partial pressure, respectively upon HF-partial pressure, was determined. The values of the integral extinction (CaF₂–CaO–Al₂O₃-slags) are calibrated by a H₂O-doping-technique. The solution enthalpy of H₂O in CaO–Al₂O₃-slags was estimated: endothermal reactions. Interpretation of the vibrational range yielded in a mainly tetrahedral coordination of Al³⁺ with O^2?- and F^? -ions in the glassy state. By heating the glassily solidified CaO–Al₂O₃-slags were transformed into their crystalline products: shifting of IR-peaks. The CaO–Al₂O₃- and CaF₂–CaO-slags were compared with a CaO–SiO₂–Al₂O₃-slag. The FT-IR-method is quick. The water content can be estimated with an uncertainty of less than ± 5% and is, therefore, suitable for process control of metallurgical procedures.     

Activities of SiO2 and Al2O3 and activity coefficients of FetO and MnO in CaO-SiO2-Al2O3-MgO slags

The activities of SiO₂ and Al₂O₃ in CaO-SiO₂-Al₂O₃-MgO slags were determined at 1873 K along the liquidus lines saturated with 2CaO · SiO₂, 2(Mg,Ca)O · SiO₂, MgO, and MgO · Al₂O₃ phases using a slag-metal equilibration technique. Based on these and previous results obtained in ternary and quaternary slags, the isoactivity lines of SiO₂ and Al₂O₃ over the liquid region on the 0, 10, 20, 30, and 40 mass pct Al₂O₃ planes and those on the 10 and 20 mass pct MgO planes were determined. The activity coefficients of Fe _t O and MnO, the phase boundary, and the solubility of MgO were also determined.     

Effect of FeO and Al2O3 on the MgO Solubility in CaO–SiO2–FeO–Al2O3–MgO Slag System at 1823 K

The MgO solubility in CaO–SiO₂–FeO–Al₂O₃–MgO quinary slag system at 1823 K was measured to evaluate the effect of FeO and Al₂O₃ on the MgO solubility. It was found that the MgO solubility was decreased with higher optical basicity, FeO concentration, and increased with higher Al₂O₃ concentration. The MgO solubility was affected by activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ). Increase of the activity coefficient of Mg²⁺ ($\gamma _{{\rm Mg}_{{\rm 2 + }} } $ ) with higher FeO or lower Al₂O₃ decreased the MgO solubility. The increment in MgO solubility is remarkably reduced beyond a critical $X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } /(X_{{\rm Al}_{2} {\rm O}_{{\rm 3}} } + X_{{\rm FeO}} )$ ratio. The significant decrease of the increment of MgO solubility is caused by the change of the molten slag structure. The excess stability function of Al₂O₃ and the Fourier transform infrared (FT‐IR) analysis were applied to indirectly verify the existence of the spinel structure in the CaO–SiO₂–FeO–Al₂O₃–MgO slag system.