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By H F. Yu, S Ueda, J Diao, W F. Gu, Y Sasaki, H Qin

The main reason for the underutilisation of steelmaking slags is their instability, which is influenced by their complex phase structure. Recycling and sustainable steelmaking slag face challenges due to the presence of magnesium oxide (MgO), a crucial component in steelmaking slag. This study investigates the phase evolution of steelmaking slag during the cooling process with different MgO contents, using high-temperature experiments and FactSage™ software, ver 8.1, (by Thermfact/CRCT and GTT-Technologies) thermodynamic equilibrium calculations. X-ray diffraction (XRD) and scanning electron microscope - energy dispersive x-ray spectroscopy (SEM-EDS) analyses identified main phases in steelmaking slag, including Ca2SiO4 (C2S), RO (MgO-FeO solid solution), Ca2Fe2O5 (C2F), and Ca3SiO5 (C3S). The study reveals that RO phase increases as the MgO content increases. C3S precipitates from steelmaking slag with a 12 mass per cent MgO content at a reduced temperature of 1400°C. It is important to note that C3S remains in the steelmaking slag even after slow cooling. This may be due to the substitution of Ca2+ in C3S by Fe2+ and Mg2+ ions. Intriguingly, the precipitation of f-CaO in steelmaking slag with 10 mass per cent of MgO content occurred after one year, while there was no manifestation of f-CaO precipitation in the steelmaking slag with 12 mass per cent of MgO content even after one year. This discrepancy suggests a potential stabilising effect of an appropriate amount of MgO in steelmaking slag. However, it is crucial to emphasise that this inference lacks supporting data, necessitating further research to validate this hypothesis. The significance of this work is in uncovering the complexities of steelmaking slag behaviour, providing essential insights for optimising recycling processes. The research sheds light on the factors that influence the phase composition and stability of steelmaking slag, contributing to the utilisation of steelmaking slags, promoting environmental sustainability, and enhancing the overall efficiency of metallurgical processes in the current industrial landscape.

Jun 19, 2024

By S Khadhraoui, T Yusuf, C Kirmse, E Hecker, R Degel, A Akouch, N Borowski, M Reuter

For an optimal design and control of metallurgical processes, a deep understanding of the thermodynamics of the governing reactions is required. Modelling the thermochemical behaviour of those reactions is complex, as it involves multi-component and multi-phase systems. For this purpose, thermodynamic computing systems such as FactSage™ (Bale et al, 2016), which combine Gibbs energy minimisation routines with large databases of optimised thermodynamic data of solutions and compounds, have been used within the SMS group GmbH. Recently, the successful integration of those thermodynamic computing systems into the digital platforms of SMS has been achieved through ChemApp, which made running complex thermochemical calculations in Python-integrated development environments possible. ChemApp is a programmer’s package for thermochemistry and incorporates the Gibbs energy minimiser of FactSage™ as reported by Petersen and Hack (2007) as well as by Zietsman and Petersen (2018). The digital platforms link the fundamental and the industrial aspects together and can be applied as a process advisor, or for the evaluation of the environmental footprint and the economic implications of different process routes, as discussed by Reuter (2023). Two examples illustrating the progress of the developments in this regard will be introduced: 1. The Tilting Refining Furnace (TRF) for copper scrap recycling and refining to anode copper (the BlueControlApp). 2. Dephosphorisation control for the oxygen steelmaking process (Basic Oxygen Furnace (BOF)).

Jun 19, 2024

By S J. Kim, S W. Kim, L Tomas da Rocha, S Jung

Al2O3 has been regarded as a harmful gangue component in iron ore, especially causing reduction degradation in industrial sintering of iron ore. The current study aimed to utilise low-grade iron ore containing high Al2O3 content in sintering process. In order to counteract the adverse effect of Al2O3 on reduction behaviour of iron ore sinter, mill-scale and calcined dolomite were chosen as FeO- and MgO-bearing materials. Firstly, mill-scale was added to high Al2O3 sinter and addition was optimised as 10 wt per cent, then calcined dolomite was added further. Magnetite and magnesio-ferrite were identified as the major phases in iron ore sinter when adding mill-scale and calcined dolomite. As the dosage of calcined dolomite increased beyond 4 wt per cent of in sinter mix, unreacted MgO particles were observed, which is ascribed to the limitation of MgO dissolution into magnetite matrix. Both mill-scale and calcined dolomite were effective in improving compressive load and Reduction Disintegration Index (RDI) of iron ore sinter although its reduction degree was highly decreased. The addition of both FeO and MgO-bearing materials to high Al2O3 sinter has a potential to improve the sinter quality, also contribute to the recycling of industrial by-product. However, the amount should be optimised in views of phase development and deterioration of reducibility.

Jun 19, 2024

By A Kondratiev, A E. Moiseev

Viscosity of oxide melts is one of the fundamental physicochemical properties that plays a crucial role in important technological and natural processes like slag flow, slag/metal separation, volcano eruptions etc. However, many oxides melt at extremely high temperatures and are highly corrosive in the liquid state, which makes experimental measurement of melt viscosity by traditional experimental techniques a difficult and expensive, if not unachievable, task. In this case it might be useful to employ other methods of viscosity determination such as modelling or simulation. In the present paper the shear viscosity coefficients of selected pure refractory oxides (CaO, MgO, Al2O3 and others) have been simulated at temperatures above their melting points via the classical molecular dynamics and compared to the available viscosity data (eg experimental viscosities, other model predictions) collected by the authors. The simulation has been carried out using the noncommercial molecular dynamics simulation package LAMMPS and the Born-Mayer-Huggins potential, which parameters for the selected oxides were taken from the literature. Several viscosity calculation techniques (the Stokes-Einstein and Green-Kubo equations, the so called Einstein relations, and the non-equilibrium molecular dynamics methods) have been applied to ensure a more reliable viscosity calculation. It has been demonstrated that the simulated viscosity of the selected melts agrees with the available experimental data. It has also been shown that the simulated viscosity of a number of the oxide melts investigated is close to that calculated by phenomenological viscosity models, which supports viscosity extrapolation from the corresponding binaries and ternaries, if no experimental data is present for unary systems. In general, it has been demonstrated that the molecular dynamics simulation could provide a reasonable estimation of viscosity if no other viscosity data is available.

Jun 19, 2024

By G Stovpchenko, G Jianjun, L Medovar

Electroslag remelting (ESR) today and into the future, will still be the main process for producing high-quality ingots by suppressing segregation, not just refining chemical composition from impurities. This paper analyses state-of-the-art electroslag refining with a focus on ESR with consumable electrodes, and recent technology with liquid metal supply (ESR LM) in view of their refining abilities and development trends, taking into consideration that the size of the ingots required by industry continues to grow, and the composition of new materials sophisticates to withstand increasingly higher mechanical and temperature loads . The yield of suitable metal in large ingots produced by conventional casting is low due to problems of element segregation by height and crosssection. For example, conventional ingots for nuclear powerplant rotors today reach nearly 700 t in weight. Attempts to directly replace such giant ingots with big-diameter ESR ingots weighing approximately 400 t were also unsuccessful because of growing segregation. Modern ESR equipment and technologies produce 200–250 t of ingots of satisfactory quality, reaching 2.5 m in diameter, implementing the change of consumable electrodes during remelting to increase ingot length. Another way to mitigate segregation is to enlarge the smaller diameter ESR ingot by a 500– 800 mm coaxial layer to the desirable diameter by ESR in the current-supplying mould (CSM). Modelling and experiments prove that refining from impurities and non-metallic inclusions at ESR most effectively occurs at the slag bath and liquid metal pool interface because the ESR LM has provided the same desulfurisation. ESR’s special refining capabilities in CSM come from the much longer time of LM residence shown at titanium purification from hard-melting nitride inclusions that are unremovable in vacuum arc remelting (VAR) and electron beam melting (EBM). Implementation of ESR technologies in CSM, especially with LM supply, is prospective to produce heavy enlarged and hollow forging ingots with prevented development of segregation due to dividing cross-section and reducing overheat of solidifying metal.

Jun 19, 2024

By M Zhu, G Tranell, N Simkhada, K Jakovljevic, M Wallin

Silicon is a vital element in many products today, such as electronic components, solar devices, high-quality alloys, and many others. The growing global demand highlights the need for the development of sustainable production methods to meet this demand as an alternative to the current carbothermic reduction, submerged arc furnace (SAF) based process. An alternative to this is the aluminothermic reduction of quartz in a CaO-SiO2 slag, which not only reduces direct carbon dioxide emissions but also promotes the utilisation of secondary raw materials such as quartz fines, aluminium dross and scrap as well as secondary alumina (SA) from dross recycling. In the current study, the effects of SA and CaF2 additions to slag on the resulting metal composition and metal yield were explored. Results were compared with thermodynamic simulations using FactSage™ 8.1. Experimental results show that, in agreement with thermodynamic simulations, the silicon content of the alloy is increased, while the Ca is decreased for starting slags where CaO-SiO2 is partly replaced by CaF2. Similarly, the addition of SA to the initial slag results in an alloy with a higher silicon content.

Jun 19, 2024

By V Shrotri L Muhmood, P Gandhre

The current work deals with the measurement of some thermophysical properties of Ca(NO3)2 based ternary nitrate molten salts as HTF (heat transfer fluid) / TES (Thermal Energy Storage) material for CSP (Concentrating solar power) plants. The density and viscosity of different compositions of the ternary salt mixture containing Ca(NO3)2, NaNO3 and KNO3 close to the liquidus has been experimentally measured. An attempt has also been made to measure the melting point of the salt using the cooling curve technique as well as Differential Scanning Calorimetry (DSC). Thermogravimetric analysis has also been performed to estimate the peak operating temperature of the salt. Compatibility of suitable pipe material (SS304) with molten salt has also been discussed. The salt mixture proves to be a viable alternative to the already existing HTFs like Therminol VP-1 (organic oil) or Solar Salt® in regards to its lower melting point, wider operating range, low cost, nontoxicity, sufficiently high density and comparable viscosity.

Jun 19, 2024

By X Yang, T Zhang, Z Li, Z Yan, M A. Williams, S Qin, P Wilson

Continuous development of complex new steel grades to meet the ever-increasing demand of high performance causes recurrent issues in steel continuous casting such as surface quality defects (eg cracks, depressions, deep oscillation marks) and productivity challenges (eg faster casting, near-net shape casting). Continuous casting of steel is a highly successful metallurgical process. Much of this success can be attributed to the performance of the casting powder that is added to the top of the mould, creates a liquid slag pool as it is heated, and forms a slag film between the watercooled copper mould and steel shell during its passage down the mould. Mould powder selection is a compromise between the conflicting requirements of heat transfer and lubrication. In an EU RFCS (Research Fund for Coal and Steel)-funded project, various techniques are developed to offer the opportunity to adapt the slag film to meet the conflicting needs in different parts of the mould such that mild cooling can be generated in the meniscus, mid-broad face or corner areas whilst maintaining lubrication and offering higher cooling rates in other areas of mould. This has significant potential to address the industrial issues in product quality and productivity of continuous casting. This paper reports, as part of the EU RFCS project, the determination of crystallinity and porosity in slag films for casting challenging and innovative steel grades using new methods. In comparison with the methods such as X-ray powder diffraction (XRD) analysis and optical microscopy / scanning electron microscopy (OM/SEM) analysis that are currently adopted by the industries, EBSD (electron backscatter diffraction) has been employed to determine the crystallinity of the slag films taken from industry casters. X-ray computed tomography (XCT) plus 3D image reconstruction has been used to determine the slag film % porosity with pore volume, pore size distribution, and pore location, which can be linked with the performance of the slag films during casting different steel grades.

Jun 19, 2024

By J H. Heo, J H. Park, M J. Lee

In this paper, the challenging points regarding the high temperature physical chemistry of slags to achieve the improved and stable electric arc furnace (EAF) or electric smelting furnace (ESF) technology on the way to green steel will be reviewed, and the recent experimental and modelling research will be discussed. For example, the initial melting phenomena of hot briquetted iron (HBI) and the slag formation behaviour was observed using a high-frequency induction furnace. Main component of gangue oxides in HBI was SiO2, Al2O3, and CaO in conjunction with unreduced iron oxide. To increase the dephosphorisation efficiency, the distribution ratio of phosphorus between metal and slag was calculated using FactSage™ software, version 8.2 (CRCT ThermFact, Inc., Montreal, Canada) and was compared to the measured results. The optimisation of slag chemistry is required not only for maximum dephosphorisation efficiency with good slag foamability but also for minimum slag volume with less refractory corrosion in EAF process. The slag chemistry is also one of key parameters affecting the operation efficiency in ESF in view of FeO reduction behaviour, viscosity, sulfide capacity, etc.

Jun 19, 2024

By X Hu, J Björkvall, L Sundqvist Ökvist

The metal production industry is a significant contributor to global CO2 emissions due to the use of fossil fuels such as coal and coke. To mitigate these emissions and meet climate goals, innovative and sustainable technologies are required. Molten salt electrolysis is a promising technology that directly produces metals from their precursor sulfides or oxides using electricity. When combined with renewable electricity and an inert anode, the electrolysis process can be carbon neutral. This paper presents the results of two pilot-scale studies on the electrolytic reduction of metal oxides and sulfides in molten salts. The first study focuses on the electrolytic reduction of chalcopyrite in molten NaCl-KCl salt. The results demonstrate that in situ separation of copper, iron, and sulfur is possible, enabling the extraction of all valuable elements without CO2 emissions. Furthermore, the findings underscore the capability to eliminate impurities like zinc, antimony, arsenic, and mercury from the electrolysis product. The second study investigates the electrolytic reduction of pure/synthetic chemicals of wüstite, hematite, and magnetite, as well as a magnetite-type iron ore in molten NaOH salt. The findings reveal a stepwise reduction of iron oxides from high valence to low valence, ultimately leading to the production of metallic iron electrolytically. Notably, this study underscores the challenges associated with the selection of an economically viable and durable inert anode material for efficient oxygen generation. These results indicate that molten salt electrolysis provides a sustainable and green route for base metal production. The use of this technology has the potential to significantly reduce CO2 emissions in the metal production industry, contributing to achieving climate goals.

Jun 19, 2024

By S Basu, P M. Midhun

Electro-Slag Remelting (ESR) is a process capable of producing ingots with much lower centre-line segregation and better internal soundness than conventional ingot casting processes, as well as lower inclusion and sulfur concentrations. This process is commonly used for alloyed steels intended for critical applications like components of marine turbines, supercritical powerplants and rocket motor casings. It involves melting a metal electrode using electrical resistive heating in a slag pool and re-solidification of the resulting metal droplets beneath the slag layer, forming an ingot. Conventional ESR fluxes consist primarily of CaF2, Al2O3 and CaO, along with minor concentrations of SiO2, MgO etc. The emission of fluoride vapour from the molten slag causes several environmental and health problems, triggering a need to develop and reduce the fluoride content in the ESR flux. The present study aims to develop low-CaF2 alternatives to commercial ESR fluxes without compromising on productivity and the surface quality of the refined ingot. Thus, the modification in chemical composition needs to satisfy properties like electrical resistivity, viscosity and liquidus temperature, essential for efficient ESR operation. Since electrical resistivity and viscosity are highly dependent on the ionic structure of the molten slag, it is important to understand the effect of compositional modification on the structure of the flux. The present study employs Fourier-transform infrared spectroscopy (FT-IR) and Raman spectroscopy to investigate the structural variations in the modified fluxes, especially the effect of changing SiO2 concentration, in comparison with conventional CaF2-rich fluxes. Additionally, thermal analysis (Differential Thermal Analysis (DTA) and Thermogravimetric Analysis (TGA)) has been carried out to characterise the melting behaviour of the fluxes. The findings are compared with simulations carried out using the FactSage™ software, ver 8.3 (GTT Technologies, Aachen, Germany). Simultaneous analysis of liquidus temperature and the structure is expected to help in identifying the practical suitability of modified ESR flux compositions for industrial implementation.

Jun 19, 2024

By J H. Park, M J. Lee

Because the environmental problems are occurred by greenhouse gases such as CO2, the industries have tried to increase electric motor efficiency to reduce CO2 emissions. A core material of electric motor is high-silicon electrical steel. The ferrosilicon (FeSi) alloy, a raw material for the production of electrical steel, affects the electric properties of silicon steel. The main impurities such as Ca, Al and Ti make inclusions or precipitates that causes core loss. The slag treatment has been widely used to remove impurity elements. Thermodynamic principles for the refining of several impurities, specifically Ca and Al, have been investigated, whereas thermodynamic behaviour of Ti has not been fully understood yet. Therefore, in the present study, the titanium distribution ratio () between ferrosilicon and CaO-SiO2-Al2O3 slag system at 1773 K was investigated. The results show that is influenced by both the basicity and stability of titanium ion in the slag. Specifically, exhibits a minimum value at about C/S=0.7 indicating a shift in the titanate structure unit from [TiO5]-square pyramid to [TiO4]-tetrahedron because of lack of Ca2+ ions in a C/S<0.8 region, contributing to an increase in titanate capacity and .

Jun 19, 2024

By L Klemettinen, A Jokilaakso, D Attah-Kyei, P Taskinen, M Tiljander, D Sukhomlinov, D Lindberg

In this study, the use of carbon neutral biochars as reducing agents in the pyrometallurgical treatment of nickel slag was investigated at 1400°C in order to recover valuable elements such as copper and nickel from the slag. A large amount of slag is generated during the nickel matte smelting. Nickel slag contains valuable elements such as copper, nickel and cobalt, which can be recovered. Disposal of this slag results in loss of resources and may cause pollution of the environment. It is important to retrieve these metals for environmental and economic reasons. In this study, the slag was reacted with non-fossil reducing agents (biochar) which were produced from hydrolysis lignin and black pellet biomass pyrolyzed at 600 and 1200°C and with metallurgical coke for comparison. The reduction experiments were done at 1400°C for 15, 30 and 60 mins under inert gas atmosphere. The samples were quickly quenched and analysed with Electron Probe X-ray Microanalysis (EPMA). The results showed that the use of biochar resulted in faster reaction kinetics in the reduction process compared to coke. The fast reaction kinetics is attributed to the relatively high content of volatiles in this biochar, leading to gas formation and thus mixing of the sample material. Moreover, thermodynamic modelling was also performed using FactSage™ to simulate equilibria with different amounts of biochar. The metal to slag distribution coefficient calculated from the results of thermodynamic modelling were consistent with experimental results. In addition, thermodynamic calculations confirmed that nickel is reduced rapidly and it deports to the metal alloy phase. As the reduction progresses or extra reductant is available for reactions, more iron is deported to the metal phase. The calculations also revealed that Zn vaporises into the gas phase.

Jun 19, 2024

By W Polkowski, M Tangstad, M Wallin, J Jiao

Fe-26Si-9B (wt per cent) alloy has been identified as a potential high-temperature phase change material (PCM) due to its attractive properties, such as its high latent heat of fusion and low volumetric change during solid/liquid transition. For the successful utilisation of this alloy into thermal energy storage (TES) systems, the development of a cost-effective production method is essential. Presently, the Fe-26Si-9B alloy is produced by mixing FeSi alloys with either pure boron element or FeB alloys. However, the use of pure boron is financially prohibitive, and the carbothermic reduction results in high greenhouse gas emissions and high energy consumption in the production of FeB alloys. In this regard, our study proposes a silicothermic reduction method to produce Fe-26Si-9B PCM by using FeSi alloys and B2O3-based oxides. Accordingly, the influence of various parameters on the production process was investigated, including operating temperature, holding time, B2O3 content in the added oxides, and initial Slag/Metal (S/M) ratio. Based on the experimental results, the optimal parameters for producing FeSiB alloys with over 9 wt per cent boron were determined. Consequently, it was documented that the FeSi alloys and the added oxides enriched with 50– 65 wt per cent B2O3 should be subjected to temperatures ranging from 1550–1650°C, maintain an initial S/M ratio exceeding 1, and ensure a holding duration beyond 1 hr. Moreover, the energy consumption of this process was estimated to be ~1.86 MWh/t metal and the mass loss was lower than 7 per cent. Therefore, silicothermic reduction offers a sustainable approach for producing FeSiB alloys with a boron content above 9 wt per cent.

Jun 19, 2024

By G H. Park, Y J. Jun, J H. Park

The carbon solubility of the CaO-Al2O3-FeO-SiO2-MgO slag, the main system formed in the Ruhrstahl-Heraeus (RH) vacuum degasser, was measured at 1873 K to understand the effect of slag compositions on the carbon contamination in the ultra-low carbon (ULC) steels. The stable form of carbon was demonstrated to be carbonate by plotting the log [(wt%C)/aC] ratio against the log p(O2) which ranged -11 < log p(O2,atm) < -9. The carbon solubility of the CaO-Al2O3-FeO-SiO2-MgO slag can be estimated using thermodynamic model. The distribution ratio of carbon increased with increasing concentration of FeO due to the FeO reduction reaction and increased basicity of slag. The carbonate capacity of the CaO-Al2O3-FeO-SiO2-MgO slag can be expressed as a linear function of the activity of lime and the optical basicity.

Jun 19, 2024

By L Scheunis, A Van den Bulck, E Jak, K Verbeken, M Shevchenko, R Starykh, I Bellemans, P-J Boeykens

As a result of the globally increasing consumer use of electronic devices, it is expected that pressure will increase on the supply chain of precious metals. Hence, recycling of these electronics becomes increasingly important, as well as optimising the current processes. One major issue in metallurgical processes is the amount of metal that is lost into the slag. This metal loss is inherent to the production process and therefore, additional processing steps such as slag cleaning may be required. Slag cleaning can be done in electrical resistance furnaces where heat is produced using the Joule effect, making the slag’s electrical conductivity an important operating parameter. Since slags are ionic liquids, the electrical conduction happens via the movement of ions which is called ionic conductivity. However, within the presence of transition metal oxides, a second mechanism of conductivity occurs as electrons are able to hop from one transition state to another, which is known as electronic conductivity. As ‘FeO’ is a common slag component in the non-ferrous pyrometallurgical industry, both mechanisms are present, but their proportions vary with the respective amounts of the two forms of the multi-valent ions and hence, with the oxygen partial pressure. The goal of the present study is to develop an experimental set-up and methodology for measuring the electrical conductivity of synthetic SiO2 – CaO – AlO1.5 – ‘FeO’ slags at various oxygen partial pressures.

Jun 19, 2024

By S-C Shim, H-R Lee, Y Kang, H Shin

Since iron oxide and silicon oxide are major gangue components in various types of ore, FeO-SiO2 base slag, ie fayalite slag, has been often encountered in pyrometallurgical processes of non-ferrous metals. During most matte production processes such as the smelting of Cu, Pb, and Ni, the FeOSiO2 based slag is inevitably formed and plays an important role in refining crude metal as well as engineering aspects. Recently, similar pyrometallurgical approaches have been attempted in the recovery of valuable metals (Ni, Co, Cr) from wasted secondary batteries. Thus, the viscosity of the FeO-SiO2 based slag has great significance in properly controlling smelting processes. However, when molten metal or matte does not coexist with the slag during the measurement, there has been a serious difficulty in maintaining Fe valance and consequently, the slag composition. In the present research, the viscosity of molten FeO-SiO2 slag was measured in 1573~1673 K using a rotational viscometer. In order to keep the state of iron oxides, the oxygen partial pressure was controlled using CO/CO2 gas mixture. The optimised ratio of CO/CO2 could be calculated using Fe/Fe2+ and Fe2+/Fe3+ equilibria at each temperature. The composition of the slag, particularly Fe valance, after the measurement was analysed with the aid of an inductively coupled plasma – optical emission spectroscopy (ICP-OES) and an automatic potentiometric titrator. The measurement showed that the FeO-SiO2 slag has considerably low viscosity values in the molten state, and it sharply increases as the temperature decreases. In spite of the careful oxygen partial pressure control, a part of Fe2+ was found to be oxidised to Fe3+, with a maximal case reaching about 20 per cent. The increase in viscosity of FeO-SiO2 at low temperatures can be attributed to the composition change due to an unavoidable Fe2+ oxidation. In addition, the relationship between the change in the viscosity and the liquidus temperature of FeO-SiO2 based slag was discussed to understand the composition dependence of viscosity.

Jun 19, 2024

By P Hayes, D Fadhlurrahman

Molten slags, fluxes and salts play key roles in a wide range of the high temperature industrial process applications, including metals production, refining and recycling, metal manufacturing processes, electrochemical metal production cells, batteries, and efficient heat transfer media. Recognising the importance and significance of fundamental scientific knowledge of these systems, the International MOLTEN Conference series was established to provide a forum to bring together leading academic researchers and industrial engineers to present and discuss the latest scientific ideas and findings, and their application in their respective fields. This article presents an analysis of the research carried out in this field over time in terms of the number of journal articles, fields and slag systems studied and geographical origin of the research.

Jun 19, 2024

By S H. Li, H Z. Gu, A Huang

High aluminium steel is a promising advanced steel known for its exception properties and holds significant economic and strategic importance. However, the CaO-Al2O3-SiO2 based slag with high alumina content reacts vigorously with alumina refractories during the smelting process at high temperature, seriously affecting the safe and efficient production of furnaces and resulting in the formation of Al2O3-MgO non-metallic inclusions within the molten steel. This is a bottleneck problem for high-quality steel refining, and the key reaction path during the corrosion remains unclear. The dissolution reaction mechanism of alumina refractories in high alumina CaO-Al2O3-SiO2 slags under a weak static magnetic field was investigated in this work, using high temperature laser confocal microscopy and in situ radiation spectroscopy techniques. The results indicate that the interaction between the high alumina slags and the alumina refractories is governed by free radical reactions. The dissolution of alumina forms AlO and AlO2 radicals. The reaction rate increases with the C/S ratio of the slag due to its low polymerisation. The reaction between non-bridging oxygen and AlO2 free radicals accelerates the generation of AlO and O2ꞏ- radicals. The reaction layer composed of calcium aluminate is formed through the recombination of AlO, Caꞏ+ and O2ꞏ- radicals. The weak static magnetic field induces the Zeeman splitting of free radical pairs and intersystem crossing occurs, promoting the formation of triplet free radical pairs through the hyper-fine coupling effect. The reaction can be significantly inhibited as the triplet free radical pair does not meet Pauli’s incompatibility principle. This discovery perfects the structure theory of molten slags with radicals and provides supplement to the design of the highly slag-resistant refractories, and provides the theoretical basis for the development of external field protection technologies for high-quality steel refining.

Jun 19, 2024

By C Chen, T Kan

The distribution ratio of Pb (LPb s/m) between three types of slags (FeOx–SiO2, CaO–FeOx and FeOx– CaO–SiO2) and molten copper after equilibrium was measured at 1300°C and oxygen partial pressure (pO2) of 10-10–10-6 atm. Results showed that for FeOx–SiO2 slag, the LPb s/m increased from 0.024 to 2.57 with pO2 increased from 10-10 to 10-6 atm. The LPb s/m with CaO–FeOx slag was lower than the FeOx–SiO2 slag at the same pO2, ranging between 0.015 and 0.53. Using the FeOx–CaO– SiO2 slag generated LPb s/m values (0.02–1.6) in between. The oxygen partial pressure in the investigated range had no obvious effect on the activity coefficient of PbO (γPbO) which was averagely 0.44, 1.70 and 0.71 for FeOx–SiO2, CaO–FeOx and FeOx–CaO–SiO2 slags, respectively. The increases in the (CaO+MgO)/SiO2 mass ratio of the FeOx–CaO–SiO2 slag induced the decrease in the LPb s/m and the increase in the γPbO value. However, the variation in the Fe/SiO2 mass ratio didn’t exert obvious effects.

Jun 19, 2024