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At least 37 records · Page 2

Efficient Recovery of Copper and Cobalt from the Matte–Slag Mixture of ISA Furnace by Injection of Coke and Pyrite

During ISA copper smelting process, ISASMELT furnace discharges a large amount of matte and slag mixture and the separation of them has an important influence on the recovery of valuable metals. This paper presented a reduction-sulfurization sedimentation process for recovering copper and cobalt from the matte–slag mixture of ISA furnace. Firstly, matte–slag mixture and traditional static sedimentation slag are characterized to determine their mineral composition and occurrence state. It indicates that Cu is primarily lost in slag in the form of sulfide, while Co is mostly lost in the form of oxide. With coke and pyrite as the reducing agent and vulcanizing agent, an orthogonal laboratory experiment was conducted to determine the effects of the smelting temperature and additive dosage on the recovery process. The optimum slag cleaning conditions were found to be: a coke dosage of 2 pct, a pyrite dosage of 2 pct, and a smelting temperature of 1260 °C lasting for 2 hours. In order to improve on the low utilization ratio of additives associated with the industrial sedimentation process, an innovative additive introducing method was put forward which enables the additives to mix and react with slag more adequately. A powder injection device was purpose-made to inject additives into molten slag in dispersion state, and a laboratory experiment was carried out to simulate this process. By injecting 2 pct coke and 2 pct pyrite, the contents of Cu and Co in cleaned slag decreased to 0.46 and 0.01 pct, respectively. It proves that the injection of additives into molten slag is an effective method to recover Cu and Co from the matte–slag mixture of ISA furnace.

36 MATERIALS SCIENCE↗

Wetting and Erosion of ZrO{sub 2}-Graphite Refractory by CaO-SiO{sub 2} and CaO-Al{sub 2}O{sub 3}-Based Mold Slags for Submerged Entry Nozzle

To moderate the erosion in a slag-line zone and extend the service life of a submerged entry nozzle during continuous casting of high-Mn and high-Al steel, the current study developed a low-reaction CaO-Al{sub 2}O{sub 3}-based slag with lower SiO{sub 2} and higher Al{sub 2}O{sub 3} contents than that of conventional CaO-SiO{sub 2}-based slag. The static sessile drop technique and dynamic rotating cylinder method were utilized to investigate the erosion behavior of ZrO{sub 2}-graphite refractory by the above slags. The main results indicated that silicate-based slag could wet the ZrO{sub 2}-graphite substrate completely, while the aluminate-based slag spread rapidly in the first 20 minutes, and then a slag drop with an unchanged profile formed on the substrate. The equilibrium contact angles with the substrate at 1623 K were 0 and 79 deg for the CaO-SiO{sub 2} and CaO-Al{sub 2}O{sub 3} based slags, respectively. The comparison of the influences of the rotating speed and the temperature revealed that the decrease of erosion rate could be realized by the developed slag. An examination of ZrO{sub 2}-saturation limit also indicated that the low-reaction slag could dissolve much more ZrO{sub 2} oxidation, accompanied by a less-negative effect on the viscosity of the molten slag.

36 MATERIALS SCIENCE↗

In situ high-temperature Raman spectroscopy for online EAF slag analysis

Real-time monitoring of slag chemistry is critical for optimizing Electric Arc Furnace (EAF) steelmaking operations, where dynamic variations in slag composition directly influence slag foaming, refractory degradation, and thermal efficiency. Conventional techniques such as X-ray fluorescence (XRF), Fourier-transform infrared (FTIR), and scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDS) are commonly used to analyze slag composition, but their offline nature and equipment constraints limit their applicability for online monitoring in harsh industrial environments. To address this challenge, we present an in situ, high-temperature analytical approach that integrates Raman spectroscopy with a custom designed fiber-optic probe for real-time slag characterization at 1550 °C. The system enables non destructive spectral acquisition from molten slags, providing molecular-level insights into silicate polymerization and iron oxidation states. Eight synthetic slag samples were evaluated, and key Raman features—such as Q n silicate units and FeO₄/FeO₆ coordination environments—were identified and quantitatively correlated with slag basicity and Fe₂O₃ content. The results demonstrate agreement between Raman spectral ratios and bulk slag chemistry, validating the method’s capability to track compositional and structural changes under molten temperature. This work establishes the feasibility of deploying fiber-optic Raman probe for online EAF slag monitoring and highlights their potential to support closed-loop control strategies, thereby enhancing process stability, refractory protection, and steel quality in industrial steelmaking applications.

47 OTHER INSTRUMENTATION↗

New Slag for Nickel Matte Smelting Process and Subsequent Fe Extraction

Large quantities of residual slag with high Fe content are left behind in pyrometallurgical nickel processing. How to separate and recover iron from the high fayalite residue is still a problem because iron mainly exists as iron-magnesium silicate in slag. This article suggests that the slag for nickel smelting is adjusted by increasing the amount of lime, partly instead of quartz, to form liable reduction compounds for subsequent Fe extraction. Based on the thermodynamic analysis and phase diagram of the FeO-SiO{sub 2}-CaO-MgO slag system, the new slag composition was chosen, the suitable melting point of relevant slags was measured, and the phase change was observed. The new slag with a composition of 7 to 9 pct MgO, 10 to 15 pct CaO and 1.5 to 1.8 Fe/SiO{sub 2} was found to work well for nickel matte smelting. With the increase of CaO and decrease of SiO{sub 2} content in slag, Ca(Fe, Mg)Si{sub 2}O{sub 6} and Mg(Ca)Fe{sub 2}O{sub 4} are the main existing phases instead of (Fe, Mg){sub 2}SiO{sub 4} in the residual smelting slag. More than 50 pct of Fe-containing phases are in the form of MgFe{sub 2}O{sub 4} when 15 pct CaO is added, which is what we want because the MgFe{sub 2}O{sub 4} is much better for magnetic separation and reduction than the original (Fe, Mg){sub 2}SiO{sub 4}. In this way, Fe can be much more easily extracted from residual slag and have multipurpose benefits.

36 MATERIALS SCIENCE↗

Study of Non-Newtonian Behavior of CaO-SiO{sub 2}-Based Mold Slag and Its Effect on Lubrication in Continuous Casting of Steel

To understand the effect of the non-Newtonian behavior of mold slag on lubrication during continuous casting of steel, the current study investigated the rheology of CaO-SiO{sub 2}-based mold slag using a rotational viscometer with variable rotating speed. The constitutive equations at different temperatures were determined. Subsequently, the obtained viscosity as a function of temperature and shear rate was incorporated into a validated mathematical model. The main results demonstrated that slag viscosity decreased dramatically with increased shear rate as the experimental temperature approached the break temperature of mold slag, meaning that the mold slag had a property of shear thinning. The predicted evolution of slag viscosity during mold oscillation was consistent with the shear thinning as the shear rate exerted on the slag channel varied. The calculated slag consumption was higher than that for slag treated as a Newtonian fluid, which agreed well with measurements using a miniature continuous caster. This study finds that the consideration of the non-Newtonian behavior of mold slag is significant to understand the lubrication mechanism and optimize related parameters via simulation.

36 MATERIALS SCIENCE↗

Effect of Slag-Steel Reaction on the Initial Solidification of Molten Steel during Continuous Casting

With the mold simulator technique, the effect of slag-steel reaction on the initial shell solidification as well as the heat transfer and lubrication behavior of the infiltrated mold/shell slag film was studied in this article. The results showed that the Al{sub 2}O{sub 3} content, the CaO/SiO{sub 2} ratio, and the viscosity of mold flux were increased with the progress of the slag-steel reaction during casting. The slag-steel reaction has two major effects on the initial shell solidification: one is increasing the mold heat flux and shell thickness by the decrease of slag film thickness. The other is the reduction of mold heat flux by the increase of crystal fraction in slag film. Mold flux with a lower basicity, viscosity, and crystallization temperature would result in a larger liquid slag consumption and the uneven infiltration of slag into the mold and shell gap that eventually leads to the irregular solidification of initial shell with a poor surface quality, such as slag entrapment and depressions as well as glaciation marks. Conversely, mold flux with a higher viscosity, basicity, and crystallization temperature would result in a smaller liquid slag consumption, which would cause the poor mold lubrication, the longitudinal shell surface defects, and drag marks.

36 MATERIALS SCIENCE↗

Study of the Mechanism of Liquid Slag Infiltration for Lubrication in Slab Continuous Casting

Consistent and uniform lubrication of the solidifying shell, especially in the meniscus, is crucial for the smooth continuous casting operation and production of strands free of surface defects. Thus, the current study established a coupled model to study the inflow behavior of liquid slag to the mold-strand channel, taking the solidification of steel and slag and the periodic oscillation of mold into account. The difficulties and solutions for the simulation were described in detail. The predicted profiles of the slag rim and initial shell were in good agreement with the reports. The main results indicated that liquid slag could be squeezed out and back into the slag pool in a negative strip period while a large amount of liquid slag could infiltrate into the mold-strand channel. Thus, the amount of slag consumed in the negative strip period was relatively small compared with that in the positive strip period. The predicted variation of slag consumption during mold oscillation was periodic, and the average value was 0.274 kg/m{sup 2}, which agreed well with the slag consumption in industrial practice. The current model can predict and optimize the oscillation parameters aiming at stable lubrication conditions.

36 MATERIALS SCIENCE↗

Effects of FeO and CaO/Al{sub 2}O{sub 3} Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al{sub 2}O{sub 3}) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al{sub 2}O{sub 3} spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al{sub 2}O{sub 3} spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al{sub 2}O{sub 3} inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al{sub 2}O{sub 3} spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.

36 MATERIALS SCIENCE↗

Lime Dissolution in Foaming BOF Slag

The paper describes the dissolution mechanisms of lime into liquid and foaming slags relevant to the BOF process. Two different master slags are employed, representing two different periods of the converter process: an early stage where the FeO content is fixed to 45 wt pct, and a later stage where the FeO content is fixed to 25 wt pct. For these master slags, the ratio between CaO/SiO{sub 2} is varied to examine the effect of basicity on lime dissolution. Calcium silicates are formed and peeled off, or partially peeled off, from the interface between the lime cube and the slag in all cases. The main difference for the dissolutions in pure liquid slag and foaming slag is the controlling step for dissolution. In liquid slag, the controlling mechanism is the removal of the calcium silicate layers, while in foaming slag, the controlling mechanism is the contact area between the lime and the liquid slag phase of the foam. The strong convection in the foam enhance the dissolution process, in some cases, the lime even dissociates into small pieces.

36 MATERIALS SCIENCE↗

Formation of Plastic Inclusions in U71Mnk High-Speed Heavy-Rail Steel Refined by CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO Slag

To precisely control the characteristics of nonmetallic inclusions with high plasticity in U71Mnk high-speed heavy-rail steel deoxidized by Si and Mn, the chemical composition of CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO slag in the ladle furnace (LF) refining process was optimized by thermodynamic calculations. Relationships among the refining slag, nonmetallic inclusions, and elemental concentrations in the steels were analyzed to obtain the conditions for determining the optimal composition of refining slag. The optimal compositions and the component activities of CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO refining slag were determined and discussed according to calculations using FactSage 7.0. Finally, ten industrial experiments were performed. Variations in the compositions of LF refining slag, inclusions, and steel, as well as the sizes of the inclusions, and metallographic classification assessment of the U71Mnk steel product, were investigated and discussed to verify the feasibility and effectiveness of the optimized LF refining slag. Kinetics of steel–slag and steel-inclusion reactions during LF refining was studied and compared. The results show that to obtain low [O], [Al], and [S] contents and inclusions with high plasticity in molten steel, the optimal composition of the LF refining slag should be CaO: 44.2 to 51.7 wt pct, SiO{sub 2}: 41.4 to 47.0 wt pct, Al{sub 2}O{sub 3}: 0 to 4.7 wt pct and MgO 5.0 to 7.0 wt pct, where the basicity R is above 1.00 and the C/A ratio is above 9.00. After the LF refining process, the contents of total oxygen (T.O.), [Al], and [S] gradually stabilized in the range of 0.0008 to 0.0012 wt pct, 0.002 to 0.0028 wt pct and 0.0026 to 0.0037 wt pct, respectively. The densities of the three kinds of typical inclusions (CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO, MnS, and CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO-MnS) also decreased and reached approximately 0.25/mm{sup 2}, and no inclusion larger than 6.0 μm was found. The composition of the inclusions gradually changed into the optimal range in the CaO-SiO{sub 2}-Al{sub 2}O{sub 3}-MgO slag system during the LF refining process.

36 MATERIALS SCIENCE↗

Separation of Phosphorus and Manganese from Steelmaking Slag by Selective Reduction

Steelmaking slag contains considerable amount of manganese (Mn) and phosphorus (P), and recycling them is an important issue. Since Mn is an alloy added to enhance the steel quality, while P is a harmful impurity in the steel product, they need to be separated for recycling. We have already found the possibility of separating Mn and P from steelmaking slag by selectively reducing P{sub 2}O{sub 5} and FeO while suppressing the reduction of MnO. As a fundamental study for the selective reduction of P from steelmaking slag, in this study, we vary the slag basicity, graphite mixing ratio, temperature, and crucible type to find the optimum condition. Artificial steelmaking slag with various compositions is synthesized and mixed with graphite powder in an Al{sub 2}O{sub 3} or a MgO crucible. The reduction is conducted at 1673 K, 1773 K, and 1873 K for 20 to 80 minutes. As a result, carbon saturated metal is formed from the slag, and the reduced metal and slag were separated easily. We find that a decrease in slag basicity suppressed the reduction rate of Mn while enhancing that of P. The activation energy for the reduction rate constant of P is found to be close to that of the diffusion of P in slag.

36 MATERIALS SCIENCE↗

Carbonaceous Material Properties and Their Interactions with Slag During Electric Arc Furnace Steelmaking

The state of the interface between slag and carbon determines the slag foaming behavior and thus the effectiveness of carbon in electric arc furnace (EAF) steelmaking. This paper explores the interaction between synthetic slag and carbonaceous materials derived from various sources, including bio-char produced by two different technologies, graphite, coke, and char from tire pyrolysis. Different interfacial phenomena were found between slag and the carbonaceous materials examined. The interactions between bio-char and slag are found to be poor in comparison with other carbonaceous materials. Carbonaceous materials were characterized in terms of their chemical composition and the results obtained suggested that interfacial phenomena were not dominated by ash in the carbonaceous material. The effects of carbon crystalline structure on interaction with slag were evaluated by Raman spectroscopy and X-ray diffraction. Surface properties of the samples were evaluated using scanning electron microscopy, and surface morphology was identified as the principal factor affecting the interaction of slag on carbonaceous particles. The smooth surface of bio-char results in reduced slag foaming. This finding forms the basis for future research on the production of bio-char to be used as a slag foaming agent in EAF steelmaking.

36 MATERIALS SCIENCE↗

A deep insight on the coal ash-to-slag transformation behavior during the entrained flow gasification process

Recent research provided deep insight on the coal ash-to-slag transformation characterization during the entrained flow gasification process, with experimentation on a 40 kg/hr (dry basis) coal-fed opposed multi-burner (OMB) entrained flow gasifier and simulation via FactSage™ software. A general mechanism is presented to relate the gasifier design temperature, ash fluid temperature, and operating temperature with the degree of the slag polymerization. The change of the high temperature zone, the corresponding particle residence time in the high temperature zone, and syngas composition have obvious effects on the slag mineral transformation behavior. Mineral types formed on the wall of the gasifier chamber were mainly anorthite (CaAl 2 Si 2 O 8 ), aluminum oxide (Al 2 O 3 ), and calcium sulfide (CaS). These minerals transformed to anorthite and diopside (CaMgSi 2 O 6 ) at the slag hole zone, while the minerals at the lock hopper were anorthite, orthoclase (KAlSi 3 O 8 ), quartz (SiO 2 ), gypsum (CaSO 4 ), calcite (CaCO 3 ), and halite (NaCl). FactSage™ predicted minerals as anorthite, diopside, orthoclase, and albite (NaAlSi 3 O 8 ), etc., where the slag temperature was below the ash fluid temperature and when the ratios of CO/CO 2 and (CO + H 2 )/CO 2 were lower than 1.0 and 2.0, respectively. By simulation, residual carbon was found to be the dominant factor over syngas composition to cause mineral transformation, and this was verified experimentally. The Ca-based crystals, typically anorthite, was shifted to diopside, near the slag hole zone, and a linear relationship was found between the content ratios of diopside/(anorthite + diopside), CaO/SiO 2 , and (CaO + MgO)/SiO 2 . A dimensionless number, θ, was defined to characterize the changing chemical composition and the degree of slag polymerization, with temperature deviation from the design condition. Three zones of θ were identified and related to the deviation between the actual gasification condition from the design condition. Finally, a low slag polymerization degree corresponded with a higher temperature deviation between the actual condition and design condition, and this proved that increased residual carbon content and changing iron valence state increased the mineral types when the slag temperature was below the ash fluid temperature.

01 COAL, LIGNITE, AND PEAT↗

Kinetics Analysis of Boron Removal from Silicon through Reactions with CaO-SiO{sub 2} and CaO-SiO{sub 2}-Al{sub 2}O{sub 3} Slags

Different types of slags have been used to refine silicon, particularly for removing boron impurity from metallurgical grade (MG) silicon. Although a number of slags have been used for silicon refining, there is limited information about boron removal kinetics, particularly during the refining reaction with CaO-SiO{sub 2}-Al{sub 2}O{sub 3} slags. This article investigates the boron removal kinetics using the CaO-SiO{sub 2}-Al{sub 2}O{sub 3} slag systems in the temperature range 1773 K to 1873 K (1500 °C to 1600 °C). All the results obtained in the present study provide a strong indication that the rate limiting step of the slag-silicon reaction kinetics was mass transport in the liquid slag. It was also shown in the study that as the reaction temperature is increased, the mass transfer coefficient is also increased. At any particular reaction temperature, adding alumina in the CaO-SiO{sub 2} slag was shown to decrease the mass transfer coefficient, which is consistent with the substantially higher viscosity of the alumina bearing slags over the CaO-SiO{sub 2} slag. The mass transfer coefficients were determined to be between 1.23 × 10{sup −6} and 2.82 × 10{sup −6} ms{sup −1}, with activation energies between 64 and 109 kJ/mol, respectively.

36 MATERIALS SCIENCE↗

Characteristics of Slag Infiltration in High-Mn Steel Castings

To determine the composition difference between the solid and liquid films in plant practice for high-Mn steel castings, a reaction experiment was carried out to investigate the composition profile of MnO and SiO{sub 2} in the slag layer. Based on the experimental results, a mathematical model of the mold slag for high-Mn steel was developed to describe the nonuniform infiltration behavior of mold slag during oscillation cycles. Moreover, the effects of uneven slag films on slab lubrication and heat transfer in the mold are discussed. The results show that the concentrations of MnO and SiO{sub 2} over the flux layer have an opposite stair-step distribution, which consists of a reaction layer and nonreaction layer. When the reaction layer thickness is 5 mm, a thicker liquid film is formed between the slab and the mold. The inhomogeneity of the composition in the solid film causes large fluctuations in the heat flux in the mold, resulting in irregular depressions on the shell surface. With a reacting thickness of 10 mm, the reacting slag fills in the gap to generate a thinner solid film, which increases the overall heat flux in the mold. Since mold oscillation combined with slag rim enhances the pressure flow in the vicinity of the meniscus, the liquid slag within 80 mm of the mold wall is mixed and consumed quickly. In contrast, the liquid slag beyond 80 mm from the mold wall with a low velocity stays longer in the liquid pool. The model predictions illuminate the characteristics of slag infiltration during high-Mn steel casting, showing good agreement with plant measurements.

36 MATERIALS SCIENCE↗

Enhancing CO 2 Mineralization Rate and Extent of Iron and Steel Slag via Grinding

Roughly 10% of the CO 2 emissions from iron and steel making are attributable to the direct release of CO 2 from the thermal decomposition of carbonates to produce flux, mainly CaO, used for impurity removal. Notably, these direct emissions remain even if carbon-based steelmaking is replaced by hydrogen-based steelmaking. After removing impurities from the molten metal, this flux becomes the solid waste product called ‘slag’, a primarily Ca-silicate material. The transformation of slag back into carbonates is thermodynamically spontaneous with negative ΔG in the ambient environment, meaning that ~10% of the CO 2 emissions from iron and steel making could be negated if equipment and methods were developed to support CO 2 mineralization. However, the rate of CO 2 mineralization using slag is slowed by several environmental, geometric, and processing factors. We leverage an experimentally verified model of CO 2 mineralization to determine how to efficiently accelerate the process. Increasing the crystallinity of slag, increasing the relative humidity, and reducing the grain size of slag particles provide the greatest increase in CO 2 mineralization rate at the lowest energy penalty. Increasing the concentration of CO 2 and the temperature provide only modest increases in the CO 2 mineralization rate while incurring a substantial energy penalty. For steelmaking slags, CO 2 mineralization represents low-hanging fruit as the current reuse pathways are low value. For ironmaking slag, replacing the production of amorphous slag for the cement industry with the production of crystalline slag for CO 2 mineralization becomes financially preferable when a carbon price/tax exceeds 67.40 USD/t-CO 2 .

42 ENGINEERING↗

Thermodynamics of Boron Removal from Silicon Using CaO-MgO-Al{sub 2}O{sub 3}-SiO{sub 2} Slags

Slag refining is one of few metallurgical methods for removal of boron from silicon. It is important to know the thermodynamic properties of boron in slags to understand the refining process. The relation of the distribution coefficient of boron to the activity of silica, partial pressure of oxygen, and capacity of slags for boron oxide was investigated. The link between these parameters explains why the distribution coefficient of boron does not change much with changing slag composition. In addition, the thermodynamic properties of dilute boron oxide in CaO-MgO-Al{sub 2}O{sub 3}-SiO{sub 2} slags was determined. The ratio of the activity coefficient of boron oxide and silica was found to be the most important parameter for understanding changes in the distribution coefficient of boron for different slags. Finally, the relation between the activity coefficient of boron oxide and slag structure was investigated. It was found that the structure can explain how the distribution coefficient of boron changes depending on slag composition.

36 MATERIALS SCIENCE↗

Modified DHTT Equipment for Crystallization Studies of Mold Slags

The double hot thermocouple technique (DHTT) enables simulations of the temperature gradient at near-service conditions during continuous casting of steel. With the equipment applied so far, a rectangular slag film of even thickness often cannot be achieved. Further, the minimum temperature frequently lies within the slag film. Modified equipment can avoid these disadvantages via the following design features. The entire furnace chamber is heated to the selected temperature of the cold wire, and the minimum temperature is not located within the slag film. Furthermore, the shape of the heating wire is improved, which enables mounting of a thin, rectangular slag film between four platinum wires. This modification allows for investigations on transparent and translucent slags. So far, the results from DHTT investigations were represented via snapshots of the samples at certain experimental times. Therefore, appropriate methods for the graphical representation of the results were suggested: the maximum crystallinity, the time related to certain crystallinities with a dependence on the position within the slag film, and the crystal growth rate. The CaO-MgO-Al{sub 2}O{sub 3}-SiO{sub 2} slag investigated with this equipment was mineralogically examined additionally, and based on thermodynamic calculations, the allocation of temperatures to certain positions within the crystallized slag film was possible.

36 MATERIALS SCIENCE↗