Search Documents

By N Kado, T Iwama, R Inoue, S Ueda

Steelmaking slags are usually used as roadbed and civil engineering materials. However, the expansion phenomenon, which is caused by the volume expansion during hydration of free CaO and free MgO contained in steelmaking slag, is indispensable. Since the hydration of free MgO in steelmaking slag is much slower than that of free CaO, it is qualitatively considered that free MgO contributes to the hydration expansion of steelmaking slag over a long period of time. Similar to free CaO, free MgO consists of undissolved MgO and crystallised MgO in steelmaking slag. The latter precipitates during slag cooling. When divalent metal oxides (FeO, MnO, CaO) are dissolved in the crystallised MgO to form a MgO-based solid solution, it is expected to inhibit the hydration reaction similar to precipitated CaO. From the previous hydration test of Magnesioferrite, which was calcined after mixing MgO and Fe2O3 reagents, it was found that the higher the Fe2O3 concentration, the slower the hydration reaction progressed. In this study, by clarifying the influence of calcination conditions of MgO-FeO and MgO-FeO-MnO solid solutions, which were prepared by the calcination of mixture of MgO, FeO and MnO reagents, on their hydration reactivity, the effect of composition and thermal treatment on the formation of free MgO that is not hydrated (or easily hydrated) were discussed. To investigate the influence of MgO grain size, coarse MgO particles, which were obtained by crushing MgO crucible, were also used for heat treatment. With increasing the amount of FeO and MnO in the MgO-FeO-MnO solid solution, the hydration reaction became more suppressed. The expansion suppression effect was higher with solid-solved FeO than with solidsolved MnO. When the calcination temperature of the MgO-FeO solid solution was increased, the Fe3+/Fe2+ concentration ratio increased, resulting in a higher hydration rate.

Jun 19, 2024

By C Samuelsson, Q Shu, A Lennartsson, F Gyakwaa, A Andersson, J Isaksson

The physico-chemical property, viscosity, is essential for pyrometallurgical processes and influences the settling rate of valuable metal droplets in slag, affecting the metal recovery. The copper slag from smelting furnaces typically contains between 1 and 2 wt per cent Cu, which equals to or is higher than in most sulfidic copper ores mined today, meaning the slag is a valuable resource for copper extraction. A low viscosity is desirable for slag-cleaning through a settling furnace where entrained droplets settle under gravity. One approach to control the viscosity is through the slag composition. The literature has limited data on the correlation between viscosity, slag structure, and optical basicity of iron silicate slag with FeO/SiO2, CaO, and Al2O3 as factors. Therefore, the present study evaluated the influence of these factors on viscosity and correlations with slag structure and optical basicity. The FeO/SiO2 ratio (at%/at%) and the CaO and Al2O3 content were altered in two levels, resulting in a two-level full factorial design with three factors. The study was done by synthesising FeO–SiO2–Al2O3–CaO–MgO–Cr2O3 melts, followed by water granulation. The melt structure of the samples was analysed with the help of Raman Spectroscopy. The viscosity was then estimated with a high-temperature rheometer using a Mo spindle and crucible. The results showed a correlation between the optical basicity, FeO/SiO2 ratio, and viscosity, where a high optical basicity and FeO/SiO2 ratio were beneficial for achieving a low melt viscosity.

Jun 19, 2024

By S Basu, S L. A Gowravaram

CaF2 has been a common constituent in a wide variety of welding fluxes, including those used for submerged arc welding (SAW). The widespread use of CaF2 stems from its role in lowering the liquidus temperature as well as the viscosity of the molten slag that covers the weld pool. However, the harmful effect of fluoride evaporation from molten flux, on the environment as well as the health of the users is becoming increasingly evident over the years. This has led to increasing attention towards reducing the CaF2 concentration in the fluxes. The fluoride-free formulations face the challenging requirement to maintain the thermo-physical properties (viscosity, liquidus temperature etc) like those observed in fluoride-containing fluxes. In the present work, three fluxes with compositions in the CaO-MnO-SiO2-Al2O3 system have been identified as promising alternatives to the CaF2-rich fluxes. However, the thermo-physical properties of any such flux need to be comparable to CaF2-based commercial SAW fluxes before it can be adopted for regular use. The single hot thermocouple technique (SHTT) has been used by several researchers in the past as a tool for observing the melting and solidification characteristics of fluxes. This device has been developed in the present work and is used to characterise the melting behaviour of the fluxes. The measured solidus and liquidus temperatures from SHTT were compared with the results from differential thermal analysis (DTA) and simulations using the FactSage™ software for a comprehensive understanding. In spite of having a slight deviation in the measured values from the multiple techniques, the results obtained from these multiple methods show that the selected compositions could be potential CaF2 free alternative welding fluxes.

Jun 19, 2024

By Y Cui, G Cao, H Zong, J Zheng, J Wang, S Yue, J Zhao, B Li

The iron (Fe) concentration in nickel slag is high, making its recovery and utilisation a hot and challenging topic. In the nickel smelting process, using CaO instead of SiO2 to adjust slag’s composition, and then directly reducing Fe from the output of molten slag is a more feasible method in practice for Fe recovery in nickel slag. The adjustment of slag’s composition in the nickel smelting process will have an impact on the distribution of impurity elements such as Pb, Zn, and As. In this paper, the slag adjustment of nickel smelting process was carried out with the oxygen-enriched topblowing system. The distribution of impurity elements in the smelting products with each composition slag was conducted by using thermodynamic software. Experimental verification was performed with rich oxygen top-blowing, and the distribution characteristics of impurity elements in the smelting products were characterised to explore the differences in mineral phases of impurity elements with each smelting conditions, elucidating the distribution patterns of Pb, Zn, and As in each phase. The results indicate that after slag adjustment, impurity elements are more easily to volatilisation and removal into the gas, reducing their total concentration in slag and matte. In the slag, the existence form of Pb, Zn is changed from silicate to ferrate, and As is changed from arsenate to low-valent arsenic oxide. It is easier to decompose the impurity-containing mineral phase and remove the impurity elements in the subsequent iron extraction process.

Jun 19, 2024

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 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 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 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 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

By S Jayakumari, E Ringdalen, V Canaguier

Silicomanganese (SiMn), containing approximately 16–30 per cent Si, is produced in submerged arc furnaces using various Mn sources and quartz as the primary raw materials, along with fluxes and reductants. In the high-temperature zone known as the coke bed, a silica-rich slag is formed. SiMn is produced through the reduction of SiO2 from the slag. Dissolution of quartz into slags with different compositions, the primary slag formed from the Mn sources and flux before any MnO reduction occurred, representing conditions at the top of the coke bed, and dissolution of quartz into a partially reduced slag to simulate conditions inside the coke bed has been investigated. Experimental investigations were carried out to study the dissolution of quartz particles of varying sizes, 5 mm and 25 mm in synthetic slags with different compositions at temperatures between 1400°C and 1600°C, with varying holding times. Observed results are compared with liquidus compositions and equilibrium phases for original and formed slags. Particle size has been shown to be of little importance for the dissolution. Quartz dissolved more easily in slag at top of the coke bed than slag in the coke bed. Complete dissolution was observed after 30 mins at 1600°C in all cases, but not after 0 mins.

Jun 19, 2024

By S Natsui, Y Goto, S Kawanishi, J Takahashi, H Nogami

The demand for copper increases yearly, and further improvements in copper smelting efficiency using flash furnaces are required. This study was conducted to understand and promote the interfacial reaction associated with the collision of silica flux and iron oxide particles, ie the formation reaction of fayalite slag, in the reaction shaft of the flash furnace. High-temperature microscopy was used to observe the reaction behaviour of a 2 mm granular SiO2 reagent in contact with micrometreorder- sized FeO reagents in situ. When the amount of FeO was lower than the stoichiometric amount with SiO2, the molten slag formed at the interface between FeO and SiO2 diffused into the SiO2 particle before dissolving the remaining FeO particles. It did not contribute to the subsequent reaction, and despite having the lowest amount of FeO among the samples in this study, many unreacted FeO particles remained on the surface of the samples after testing. On the other hand, under conditions with high FeO content and close to the eutectic composition of the FeO-SiO2 system, a liquid phase formed from low temperatures, gradually increasing in volume and eventually completely dissolving the 2 mm SiO2 grain. These results indicate that the early-stage slag is essential in increasing the interfacial area between FeO and SiO2 and facilitating the supply of FeO to SiO2. In other words, the FeO/SiO2 determines the amount of liquid phase and significantly influences the subsequent interfacial reaction rate between FeO and SiO2. Therefore, the local FeO/SiO2 of the particles falling down the reaction shaft should also be optimised to ensure early slag formation. Meanwhile, the time required for 2 mm SiO2 to complete the reaction for the temperature history employed in this study was significantly longer than the particle residence time in the reaction shaft. Further detailed investigation of the effects of silica flux particle size, composition, and reaction temperature on the reaction time will help find the conditions under which the reaction of silica flux can be completed in the reaction shaft. These kinetic approaches could contribute to future innovations in the copper smelting process using flash furnaces.

Jun 19, 2024

By L Klemettinen, J Biswas, W Malan, D Sukhomlinov, D Lindberg

In order to mitigate the effects of climate change, our society must be able to drastically reduce its CO2 emissions. As the metallurgical industry is a considerable contributor to these emissions, new greener technologies must be invented and developed. One option could be the direct production of metals from oxides using renewable electricity. The aim of this study was to investigate the possibility of using high-temperature molten oxide electrolysis (MOE) for iron and ferrochrome production. FactSage™, ver 8.2 (by Thermfact Ltd and GTT-Technologies) was utilised for estimating a feasible equilibrium electrolyte composition, and the experiments were conducted at 1550–1580°C in conical alumina crucibles with iridium wire as the cathode and platinum wire as the anode. The sources of iron and chromium were either pure FeO powder or industrial chromite pellets. Voltage was applied to the electrolysis cell for 6 hrs and the resulting current was measured, along with oxygen concentration in the off-gas line. The electrolyte comprised of SiO2, Al2O3, MgO and CaO. First, the effect of FeO concentration on iron reduction efficiency was investigated using only pure oxide powders as starting materials. The results indicated that 10 wt per cent FeO mixed with the electrolyte resulted in more efficient iron reduction compared to 20 wt per cent. In further experiments, industrial chromite pellets were ground and mixed with the CaO-free electrolyte. Iron and chromium reduction efficiencies were higher when approximately 19 wt per cent of the total sample mass consisted of pellets compared to increasing the pellet amount to 37 wt per cent. Generally, the chromium solubility in the liquid electrolyte was relatively low, and most of the chromium was confined to the spinel solid solution, from where its dissolution to the liquid electrolyte was very slow, resulting in slow reduction kinetics. For larger scale applications, economically more viable electrode materials should be investigated.

Jun 19, 2024

By G Brooks

The control of phosphorus in steelmaking is one of the famous challenges of pyrometallurgy. It is well established that highly basic slags, the presence of FeO in the slag and lower temperatures (less than 1650°C) are favourable for phosphorous removal. The thermodynamics of this reaction have been extensively studied under laboratory conditions and the general trends confirmed through industrial trials. However, in general, phosphorus slag/metal distributions measured in industry are far from equilibrium and quite specific to the oxygen steelmaking technology being used. This variability was quantified by Urban, Weinberg and Cappel (2015), who found that the phosphorus partition ratio measured in plants varied with blowing practice, stirring intensity and even converter life. Some recent kinetic studies by Gu, Dogan and Coley (2017) have shown how the kinetics of these reactions vary with FeO content and dissolved sulfur at the droplet scale. A global kinetic model by Rout et al (2018) provides meaningful predictions of where dephosphorisation occurs in an industrial basic oxygen furnace (BOF) and some recent heat transfer modelling by Madhavan et al (2021, 2022) implies that temperature difference between droplets and slag has a role to play in explaining why equilibrium is not achieved. This paper will review the current state of knowledge and provide suggestions on predicting phosphorous removal for industrial operations and how greater removal could be achieved.

Jun 19, 2024

By H Fukaya T Miki, J Gamutan

Molybdenum disilicide (MoSi2) is a promising material for thermal applications due to its excellent heat and oxidation resistance. It can operate at temperatures of up to 1800°C as furnace heating elements and protect refractory metals such as molybdenum from rapidly reacting with air to form volatile molybdenum oxides at elevated temperature. In this work, the feasibility of forming MoSi2 on a molybdenum substrate by hot dipping in a silicon-saturated molten metal bath was investigated. This method is simple, predictable and can be used to coat large components and complex parts. It was found that tetragonal MoSi2 can be successfully synthesised on the surface of the substrate after dipping for 15 mins at 1000°C using molten tin (Sn), bismuth (Bi) and copper (Cu) baths. The growth of the MoSi2 layer was fast within the first 15 mins and then gradually slowed down with time. After dipping for 60 mins at 1000°C, the thickness of the MoSi2 layer were measured as 441.5, 19.5 and 13.1 μm for the copper, tin, and bismuth baths, respectively. The MoSi2 coating synthesised in this study provided oxidation resistance at 1150°C by forming a protective SiO2 layer on the surface. The SiO2 layer prevented the sample from rapidly oxidising by inhibiting direct contact between the molybdenum substrate and oxygen in the atmosphere. Compared to conventional methods, the proposed hot dipping method produces a MoSi2 layer more rapidly and at much lower operating temperatures. This makes it a more attractive option for coating large and complex components, with the potential to enable the use of MoSi2 in a wider range of applications.

Jun 19, 2024