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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

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 B J. Monaghan, P Zulli, X F. Dong

In the lower zone of blast furnace (BF), slag trickles down through a packed bed of carbonaceous particles in the form of films, rivulets or droplets. During its downward flow, there are significant interactions occurring between slag and other phases, ie gas and packing particles. In particular, the interaction between gas and slag is closely associated with the key flow phenomena such as loading, flooding or channelling in the lower zone of the BF. With gas introduced laterally through tuyeres and slag flowing downward from the cohesive zone to the hearth, this interaction varies throughout the lower zone and in the cohesive zone:  strong cross-flow of gas relative to the slag occurs in front of the raceway  counter-current flow of gas and slag occurs in the upper parts of the lower zone  both strong cross- and counter-current flow of gas and slag around and within the cohesive zone. These interactions can be linked to furnace irregularities, affecting smooth operation and limiting production. Therefore, understanding the gas-slag interaction and its influencing factors remains critical for BF process control. In the current review, the physical behaviour and key influencing factors of gas and slag flow are initially examined. Numerical models describing gas and slag flows in a packed bed at micro-, mesoand macro-scopic levels, are reviewed. Each simulation approach has its advantages and limitations, as well as unique assumptions when used in BF process modelling. Applications of these approaches to gas-slag flow in key identified functional zones will highlight the differences between approaches and modelling outcomes. As no single approach can fully address all aspects of gasslag interactions, an integration of different approaches is considered an effective and beneficial method in providing a more complete understanding of gas-slag flow in the BF process.

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

By F Diaz, G Hovestadt, B Friedrich, D Latacz, M Sommerfeld

The metallurgical sector significantly contributes to the global carbon footprint and encounters the challenge of developing more sustainable production methods. This study introduces novel approaches aimed at reducing CO2 emissions within the industrial sector, some of which have been developed up to the demonstration scale. In two case studies, urban waste from the agricultural sector (corn, olives, coconut etc) and waste electrical or electronic equipment (WEEE) recycling residues (shredder light fractions (SLF)) were subjected to thermal treatment. The resulting materials were then used as substitutes for conventional fossil-based reducing agents in both the copper and ferroalloy industries. Furthermore, hydrogen was employed at different scales to assess its efficacy as a reducing agent for recovering metal oxides from fayalitic copper slags. Our findings reveal promising prospects and defined specific challenges for the integration of these alternative reducing agents in the industry. The synergistic use of pyrolysed SLF, bio-coke, and hydrogen presents a viable pathway to significantly diminish CO2 emissions while simultaneously improving the sustainability of the metallurgical sector.

Jun 19, 2024

By M A. Rhamdhani, K Avarmaa, A Putera, J Chen, G Brooks

Silicon-based photovoltaic cells are currently the most dominant types applied to convert solar energy to electricity. In solar-grade silicon (SG-Si), the control of boron (B) and phosphorus (P) is very critical. Generally, these elements are difficult to remove into acceptable sub-ppm levels from lower grade Si. This study investigates slag treatment as a process for Si refining, focusing on the behaviour of P and B. The experiments were conducted by equilibrating Si-B-P alloys with 43 wt per cent SiO2 – 47 wt per cent CaO – 10 wt per cent Al2O3 slag under inert atmosphere at 1500°C. Different crucible materials were used (Al2O3, SiO2 and MgO), which determined the primary saturation phase for the system and modified the final slag composition accordingly. The samples were equilibrated and analysed with microanalysis techniques (EPMA (electron probe microanalysis) and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry)). New standards were prepared and applied in the LA-ICP-MS analyses. Experimental results show that silver is essentially fully dissolved in silicon, as well as most phosphorus with LP ( = wt per cent P in slag/wt per cent P in Si) between 0.1–0.3. The distribution coefficient of boron was measured to be between 1 and 2. The crucible material used had an influence on the phase compositions and slight influence on the distribution coefficients of boron and phosphorus. The experimental results provided new accurate data when considering applicability of slag treatment as a technique for Si refining and Si PV cell recycling.

Jun 19, 2024

By B J. Monaghan, R J. Longbottom, D J. Pinson, S J. Chew

Recycling steel plant by-products is a critical issue for achieving both environmental and economic sustainability of integrated steel plants. A key steel plant by-product stream is dust from basic oxygen steelmaking (BOS), which can be recycled back to the BOS vessel as iron units and to aid slag formation. The major limitations for its recycling are zinc and the uncertainty in zinc speciation of the dust. This uncertainty affects the amount of dust recycled and how it interacts with the slag during processing. BOS dust in stockpiles can undergo self-sintering reactions that oxidise the iron-bearing components. As this occurs, zinc (or oxide) may combine with iron oxides to form a zinc-iron spinel solid solution phase. Knowing which zinc-bearing species are present in the BOS dust is a key aspect in understanding and developing an efficient recycling process for the dust. To overcome difficulties associated with phase identification in the BOS dust (both fresh and selfsintered), particularly the magnetite-zinc ferrite spinel solid solution using X-ray diffraction (XRD) / scanning electron microscopy (SEM) / energy dispersive spectroscopy (EDS), high end characterisation tools, transmission electron microscopy (TEM) and Mössbauer spectroscopy, were also used. Such an approach allowed improved phase identification of key zinc- and iron-bearing phases that were not previously resolvable. The zinc in fresh BOS dust was mostly present as extremely fine separate particles of zinc oxide, attached to the iron particles. These extremely fine particles were <10 nm in size. Additionally, a small amount of zinc ferrite was also identified within the sample (most likely contained within a magnetite-zinc ferrite spinel solid solution). However, the zinc in the self-sintered BOS dust, was found to be present entirely in a magnetite-zinc ferrite spinel solid solution. While this spinel phase had been previously identified by XRD, it was not clear that it contained zinc. The Mössbauer results provided definitive evidence of zinc within the spinel phase.

Jun 19, 2024

By E Jak, P Hayes, J Chen, M Shevchenko, E Nekhoroshev, D Shishin

Recent decades have seen significant advancements in analytical and experimental techniques, thermodynamic theory, and computational capabilities in high temperature research which are particularly timely to address the challenges of increasingly complex and variable feedstocks in both primary and secondary pyrometallurgical processes, the need to optimise and improve them. Currently a research program is in progress on the development of the 20-component multi-phase thermodynamic database for pyrometallurgical smelting, refining and recycling systems describing thermodynamics and phase equilibria of molten slag, matte, speiss, salts, alloys and associated solids. The integrated experimental and modelling program has been supported for nearly two decades by several consortia of 14 major international companies with over 30 operations around the world, integrates many components, incorporates many in-house developments, and brings together many different groups of professionals of different levels from junior and mid-career to senior from both industry and university sectors. The aims of the paper are:  to outline the many components and issues of the overall program including analytical, experimental and thermodynamic modelling research as well as implementation of the results in industrial practice, professional education, planning and organisation issues.  to highlight the opportunities, challenges, and possible solutions.  to present these to all different groups of professionals involved in the current program.  and thus, importantly, to facilitate possible future further developments and collaborations in the field of phase equilibria and thermodynamics of complex high-temperature systems.

Jun 19, 2024

By J Zhang, L Klemettinen, A Jokilaakso, J Biswas, J Partinen, H O’Brien, A Klemettinen

Waste lithium-ion batteries (LIBs) are important secondary sources of many valuable materials, including Critical Raw Materials (CRMs) defined by the European Union (EU): lithium, cobalt, manganese, and graphite. Additionally, LIBs typically contain nickel and copper, which are classified as Strategic Raw Materials for EU since 2023. In recent years, great effort has been made to develop efficient recycling processes for waste LIBs. Pyrometallurgical processes have been essential in industrial production of metals for many decades. These technologies are relatively mature, with high adaptability for different raw materials. Pyrometallurgical treatment in LIB recycling typically involves the use of smelting processes, in which waste batteries are heated above their melting points and metals are separated through a reduction reaction in the liquid phase. Through this recycling route, cobalt, copper, and nickel can be efficiently recovered in the form of a metal alloy, whereas lithium and manganese are lost in the slag phase. The goal of this work was to increase the recoveries of valuable battery metals through a combination of hydro- and pyrometallurgical unit operations. First, industrial Li-ion battery scrap underwent a selective sulfation roasting stage, where the aim was to transform LiCoO2 and Mn-oxides into Li, Co and Mn sulfates. After roasting, the battery scrap was leached in distilled water with a solid to liquid ratio of 100 g/L at 60°C and recovered 95 per cent of Li, 61 per cent of Mn and 35 per cent of Co. After leaching, the solid leach residue was mixed with industrial Ni-slag and biochar, followed by reduction at 1350°C in argon atmosphere. The high-temperature smelting experiments were conducted as a function of time (5–60 mins) to investigate the reduction behaviour of battery metals. The results show that Co and Ni from the slag and leach residue can be efficiently recovered in the slag cleaning stage.

Jun 19, 2024

By M I. Pownceby, M A. Rhamdhani, D M. Fellicia, S Palanisamy, R Z. Mukhlis

The trend of global copper production has prospectively increased over time. Based on typical mined ore grades, 1 t of copper ore generates approximately 6–10 kg of copper, which requires much energy, usually in the form of metallurgical coke. Copper production using carbon as a fuel and reductant contributes up to 0.3 per cent to global greenhouse gas (GHG) emissions. As a result, research into decarbonisation processes applicable to reducing low-grade copper sulfide ores, copper oxides, electronic wastes and other alternative complex Cu-rich materials has increased. Alternative fuels for reducing carbon-rich emissions in pyrometallurgical copper processing include methane, ammonia, biomass, solar and wind power, but in recent times increased focus has been on hydrogen as a potential fuel and reducing agent for materials such as oxidised copper scrap, Cu2O/CuO and Cu-rich slags/e-wastes. From a thermodynamic perspective, hydrogen exhibits a significantly more negative standard Gibbs free energy (ΔG°) than copper oxide making it a suitable reductant and the exothermic thermal effect from reaction between hydrogen and Cu2O/CuO may be used to control process parameters. These characteristics renders hydrogen an ideal gas for reducing copper oxides and copper-containing slags/e-wastes. This review article assesses previous research on utilising hydrogen for producing and refining copper from primary and secondary feed materials.

Jun 19, 2024

By J W. Dong, Y M. Li, J L. Tian, Z H. Jiang

Electroslag remelting is widely used to produce various special steels, mainly because of its ability to provide high cleanliness and excellent homogeneity of ingot. Undoubtedly an optimal slag plays a key role in removing inclusions and enhancing the mechanical properties of a specific special steel. In order to improve the metallurgical performance of the slag in electroslag refining of die steel, a variety of slags have already been developed using traditional trial-and-error methods. Nonetheless, these slags may not be inherently optimal for the specific requirements of actual die steel refining processes. In this work, we have designed a CaF2-CaO-Al2O3-SiO2-MgO quinary slag system using genetic algorithms method aiming to remove the existing large size inclusions (D and Ds type) in high quality die steel. The comprehensive effects of five components (CaF2, CaO, Al2O3, SiO2 and MgO) were studied based on existing fundamental theory. The slag composition was screened considering the parameters such as melting point, electrical conductivity, calcium ion concentration, and appropriate viscosity etc. Furthermore, the candidate optimal slag was applied in the industrial production of die steel by electroslag remelting method. The detection results indicate that majority large inclusions (D and Ds type) have been successfully removed, showing significant advantage to traditional slags. This result has demonstrated the genetic method to be efficient and reliable. In addition, depending on the personalised demand of other steel and alloys, this method allows for the adjustment of the screening frameworks and processes to develop the candidate optimal slags. This method has not been reported previously in the field of electroslag composition design, and compared with the traditional trial-and-error method, the new method will save a lot of time and experimental costs.

Jun 19, 2024

By E Jak, G Khartcyzov, M Shevchenko

The increasing complexity of ore resources and recycled materials in the feed of pyrometallurgical processes present a technical challenge to the metallurgical engineers working on maximising the recovery of the valuable elements and minimising the environmental impact of the processes. To address this challenge, the availability of computational tools that can predict the mass and energy balance in complex systems is required. Then the accurate description of phase equilibria in the complex multicomponent systems describing the chemistry of the pyrometallurgical processes becomes critical for the correct implementation of the indicated tools and facing the outlined industrial challenges. In the present study the distribution of selected elements (Pb, Zn, Fe, As, Sn, Sb, Bi and Ni) between oxide liquid and metal in the ‘CuO0.5’-CaO-AlO1.5 system in equilibrium with Cu metal at 1400°C (liquidus of CaAl2O4) was experimentally studied using the equilibration and quenching technique followed by the electron probe X-ray microanalysis of the resulted samples. The study covered a wide range of effective p(O2) over the system from 10-11 to 10-3.5 (corresponding to formation of immiscible CuO0.5-rich slag). To avoid loss of volatile elements (Pb, Zn, As, Sn, Sb and Bi), a correlation between ‘CuO0.5’ in oxide liquid and p(O2) in open system was obtained first, followed by studying the volatile elements distribution in closed conditions (Al2O3 crucible sealed in SiO2 ampoule), where ‘CuO0.5’ concentration was used as a marker to evaluate the effective p(O2) over the system. The experimental results were then used for the optimisation of the thermodynamic model parameters of the system as part of the integrated experimental and self-consisting thermodynamic modelling research program of phase equilibria in the Cu-Pb-Zn-Fe-Ca-Si-Al-Mg-O-S-(As, Sn, Sb, Bi, Ag, Au, Ni, Cr, Co and Na) gas/oxide liquid/matte/speiss/metal/solids system.

Jun 19, 2024

By S Serp, M Duchateau, P Chevreux

Molten salt reactor (MSR) is a promising advanced reactor system aiming to the transmutation of minor actinides such as americium in order to reduce the inventory of ultimate nuclear waste. The fuel is a molten salt in which actinides are homogeneously dissolved in the liquid phase. A chloride salt may be retained for this concept, as it provides low melting point, high solubility of actinides, harder neutron spectrum. To avoid corrosion and precipitation issues, molten salt composition has to be carefully controlled with impurity content as low as possible. Obtaining pure actinide chlorides without contaminants such as oxide, oxychloride, hydroxide and water is still a challenge. To prepare actinide-bearing salt, the chlorination of actinides oxides was investigated in an unstirred reactor under flowing gas as solid-gas reaction. The carbochlorination of PuO2 were performed in the temperature range of 600 to 800°C with chlorine gas as a chlorinating agent and the presence of solid carbon. PuCl3 was successfully synthesised by this method and characterised by X-ray diffraction measurements but some impurities such as oxide phase remain inside the formed product. Refinements of anhydrous and hydrated PuCl3 phases by Le Bail method were also performed for crystalline materials definition. Conversion mainly depends on the chlorinating temperature and the contact between the oxide and the chlorinating agent. A conversion value of 70–80 per cent was achieved at 700°C from PuO2 with quite high specific surface area. The conversion rate was not improved with increasing the chlorination time. The volatilisation of Pu was observed during the carbochlorination experiments. To avoid a loss of Pu caused by sublimation, the chlorination temperature should be limited to 650°C despite that the conversion of PuO2 to PuCl3 was enhanced by increasing temperature. Both carbochlorination and hydrochlorination of AmO2 were also carried out leading to the formation of AmCl3. These first results suggest that americium oxide was chlorinated more readily than plutonium oxide. The purity of produced PuCl3 and AmCl3 still deserves further investigations.

Jun 19, 2024

By K Verbeken, D Seveno, A Maslov, I Bellemans

Recycling and decarbonisation current metallurgical processes is key for our planet’s future and in both cases, digital twinning will play an important role. However, the various modelling techniques being used for digital twinning require a lot of input values on variables such as viscosities, diffusion coefficients and surface energies that need to be known as a function of temperature, atmosphere and composition, but which are not widely available, such as in databases, for molten slag phases. The need for more accurate data on physical slag properties is clear and will be extremely relevant for making more realistic and quantitative simulations. Some of these properties are difficult to determine, which is inherent to the very high pyrometallurgical temperatures. Therefore, this work focuses on some aspects related to determining electrical conductivities, viscosities and surface tensions of slags via a combined experimental-modelling method. Besides experimental work, molecular dynamics (MD) simulations can be used to investigate oxidic slag physical properties. With MD simulations, one can follow the time evolution of a system (consisting of atoms or molecules) by integrating Newton’s equation of motion. The input for an MD simulation mainly consists of a force field as well as initial positions, velocities and mass of each atom. The determination of the transport properties in existing literature of MD simulations in oxidic systems, is typically based on incorrect assumptions. For example, to determine the ionic conductivity, the frequently-used Einstein-Stokes equation fails to take into account all ionic types and neglects correlated motion. Furthermore, the viscosity determination via the Einstein-Stokes formula also assumes independent motion of the different ions. This paper gives a brief overview of the opportunities and challenges related to the use of MD simulations for oxidic slag systems.

Jun 19, 2024