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By Mustafa Kumral, Mehmet Balci

Strategic mine planning focuses on cutoff grade selection, capacity planning and block sequencing. Despite significant knowledge accumulated, potential value can be added to mineral sourcing by addressing various aspects. A case study on a metallic deposit with a lognormal grade distribution examines if grade/metal distribution influences cutoff grade selection. Six data sets with different shape and scale factors, but the same ore tonnage and metal quantity, are analyzed. Results indicate deposits with lower shape and scale factors are more sensitive to metal price and discount rate changes. The study also investigates the effect of economies of scale (EoS) on project value, focusing on the ratio of variable cost to total cost (capacity factor). Two regression analyses are conducted for optimal capacity planning and cutoff grade selection. The first shows capacity planning is highly sensitive to the EoS of mining and mineral-processing costs, with grade variability and metal distribution being negligible. In the second analysis, grade variability and EoS of mineral processing costs are vital for cutoff grade selection.

Sep 1, 2024

By M A. Rhamdhani, R Z. Mukhlis

Removing the ledge formation in the Hall-Heroult cell during the electrolysis process may significantly reduce the energy requirement of the aluminium production process. In the absence of the ledge, however, the sidewall-material types become heavily restricted since the cryolite is very corrosive at the electrolysis temperatures. This paper study the corrosion behaviour of sintered nickel ferrite, nickel aluminate, and magnesium aluminate refractories (as possible candidates for sidewall material) in molten aluminium and cryolite melts with various alumina content at 980°C. Immersion tests of refractories with various porosity were conducted to assess the suitability of the refractories in the corrosive environment of the electrolysis cells. Microstructural change of the refractory after immersion were analysed using secondary scanning electron microscopy (SEM). Sampling of the melts were taken at 0, 10 min, 30 min, and each hour up to 6 hrs, and subsequently analysed by Inductively Coupled Plasma (ICP) spectroscopy. Based on the projected concentration of the refractories constituents in the melts, it was predicted that the corrosion rate of NiFe2O4, NiAl2O4 and MgAl2O4 in cryolite with 11 wt per cent Al2O3 were 461 × 103, 1.03 × 103, and 798 × 103 cm/a, respectively. Much lower corrosion rate of 2.3 cm/a for NiFe2O4, 2.6 cm/a for NiAl2O4 and 0.3 cm/a for MgAl2O4 were predicted if the refractories in contact with aluminium melts. Erosion played an important role in the corrosion as the concentration of the refractory constituents in the melts were beyond its solubility limit. It is therefore crucial to increase the densities of the refractory and improve its wetting characteristics.

Aug 21, 2024

By R G. Reddy, A Yahya

The sulfur distribution ratio (Ls) is an expression of the amount of sulfur in slag to the amount of sulfur in molten metal. The sulfide capacities calculated from Reddy-Blander (RB) model were used to calculate the sulfur distribution ratio (Ls). A new Reddy model for sulfur distribution ratio (Ls) was developed for modelling Ls for ironmaking, steelmaking, and secondary steelmaking conditions. Besides calcium oxide, the major component in the ladle furnace (LF) slags is alumina. The Ls was calculated for typical LF slags as a function of temperature and composition. The model calculated Ls values are in good agreement with the experimental and industrial slags data. The extremely low oxygen potential in these furnaces after fully-killed steel is favourable for desulfurisation. For any given slag’s composition and temperature, its sulfide capacity can be calculated a priori. The equilibrium sulfur distribution ratio between this slag and liquid metal in a particular vessel can also be calculated a priori. The Ls for ladle furnace (LF) slags is about twice those for blast furnaces (BF) slags and ten times those of basic oxygen furnace (BOF) slags. The desulfurisation of pig iron in BF and desulfurisation of steel in LF during secondary steelmaking are recommended. Steel desulfurisation in steelmaking furnaces is not effective. Since the model used to calculate the sulfur distribution ratio (Ls) is a priori, it is a useful tool for the iron and steel makers in improving the product quality and optimisation of the industrial furnace operations.

Aug 21, 2024

By A Nigam, K Biswas, R Sarkar

Because of the problems with 1st and 2nd generations of Advanced High-Strength Steels (AHSS), a 3rd generation of AHSS steels has become prominent and these steels have properties in between the 1st and 2nd generations of AHSS. However, although the 3rd generation of AHSS is a promising candidate as a replacement for its predecessors, there remain some challenges in processing these steels which are essentially medium Mn (Mn content ~ 5–7 wt per cent) and high Al (Al content ~ 1– 3 wt per cent) steels. The use of conventional casting powders based on the CaO-SiO2 system is unsuitable for high and medium Mn/Al steels. This work investigates the development of CaO-Al2O3- based mold fluxes for casting third-generation AHSS steel. Mold fluxes, with otherwise similar compositions but different C/A ratios, are tested and their crystallisation behaviour is examined using differential scanning calorimetry (DSC). A calcium aluminate phase having a composition Ca12Al14O33 was found to be the main crystalline phase in the mold fluxes. A decrease in crystallisation temperature was observed as the CaO/Al2O3 ratio increased from 1.00 to 1.33. The effective crystallisation rate constant exhibited an increase with decreasing crystallisation temperature, indicating a potential influence of nucleation rate on the overall crystallisation rate and suggesting an anti-Arrhenius behaviour in the crystallisation process of these mold fluxes.

Aug 21, 2024

By Z Li, Z Yan, T Htet, S Zhang

During the pyrometallurgical processes, a substantial quantity of high-temperature ironmaking and steelmaking slags, generated at temperatures ranging from 1400 to 1600°C, is wasted, as the heat contained in these slags is released into the environment during the tapping process without effective utilisation. On the other hand, a significant amount of energy is required to reheat the cold materials for the manufacturing of glass and mineral-wool, often necessitating the addition of high-silica materials to facilitate the production process. In this study, an innovative approach is presented to harness the heat present in molten metallurgical slags to directly produce new raw materials for glass and mineral-wool manufacturing while simultaneously reducing energy consumption and mitigating CO2 emissions. The theoretical amount of waste glass that can be effectively added in the process has been estimated via thermodynamic calculation. Experimental assessments were conducted to examine the impact of high-silica waste materials on the dissolution, melting and fluidity. Potential recipes for glass and mineral-wool manufacturing were suggested and an assessment of the energy savings, and reduction in CO2 emissions with manufacturing of glass and mineral-wool using this innovative approach were included. It was determined that the processes could lead to a reduction of over 26 kg of CO2 emissions per 100 kg of new material used, primarily due to the utilisation of heat from slag and the accelerated smelting process.

Aug 21, 2024

By D Stepanenko, G Stovpchenko, L Lisova, D Togobitskaya, L Medovar

Classical electroslag remelting of consumable electrodes is a drop-by-drop melt feeding through a slag layer into a renewing molten metal bath, slowly solidifying into a homogeneous, dense, defectfree ingot in a copper water-cooled mould. The new look at the additive nature of the electroslag remelting (ESR) process in a protective atmosphere allowed us to formulate the principles of a comprehensive thermodynamic-based model that can predict dynamic changes in slag and metal composition at certain ingot remelting. The model considers drastically different slag-to-metal mass ratios at the beginning and end of remelting and predicts gas, slag and metal composition in a chain of thermodynamic subsystems. Despite consisting of calcium fluoride and stable oxides, the ESR slag can oxidise main and active elements from steel and alloys (primarily aluminium, titanium and silicon) due to chemical reactions between slag and metal. ESR is not an electrochemical process in its nature. However, slags are ionic melts and deviation in their composition causes a change in their properties, affecting both operation mode and ingot quality. Another important understanding derived from the modern metallurgy technological route is that the ability to refine metal from impurities is not a priority for the ESR because consumable electrode has already passed all stages of refining and deep degassing at ladle treatment that changes ESR slags engineering principles. The critical importance became slag’s ability to generate process heat and keep the melting composition in the metal bath unchanged (except for non-metallic inclusions assimilation). Slag engineering for ESR required a compromise between chemical inertness to a metal composition and desired physical properties deriving from technological reasons. The Directed Chemical Bonds Concept (DCBC) in a multicomponent oxide system was used to build predictive models of electric conductivity and the melting temperature of fluoride-oxide slag based on their chemical composition. Both models help to design a customised composition of effective slags for steel and alloy groups or individual grades, and they are significant steps in the development of a comprehensive model of electroslag remelting.

Aug 21, 2024

By A Vickerfält, J Huss, J Martinsson

The European Union has listed vanadium (V) as one of the critical raw materials for the transition to a future green society, as stated in the Critical Raw Material Act, written by Grohol and Veeh (2023). In the steelmaking industry based on V-containing iron ore, V is a possible by-product from the slag. A requirement for slags to be suitable for V extraction is a V content preferably above 8 wt per cent as V2O3 and a phosphorus (P) content below 0.1 wt per cent as P2O5. Hence, it is important to keep V in the slag phase while the P is moved to the metal phase during the steelmaking process.

Aug 21, 2024

By A Kamaraj, M Mohanasundaram, R Kumar, P Tikare

This study presents a comprehensive thermodynamic optimisation and sustainability analysis of the secondary copper smelting process for Waste Printed Circuit Board (WPCB) recycling. The study investigates various scenarios with different proportions of WPCB in the input stream, ranging from 0 per cent to 100 per cent. Through thermodynamic modelling using FactSage™ version 8.1, the optimisation process is conducted in three stages. The results of the thermodynamic modelling indicate that the best-case scenario for WPCB recycling is achieved with a 40 per cent proportion of WPCB in the input stream. This case exhibits a maximum copper recovery of 99.93 per cent while minimising the formation of other waste. In addition to the thermodynamic analyses, environmental factors such as the carbon emission index and resource utilisation efficiency are studied. The 40 per cent WPCB recycling case exhibits a resource utilisation efficiency of 93.055 per cent and a carbon emission rate of 0.133. The present investigation highlights the significant benefits of a 40 per cent WPCB recycling scenario through a secondary copper smelting process in terms of base metal recovery and energy efficiency, thus emphasising its potential for sustainable PCB waste management and resource utilisation.

Aug 21, 2024

By H Zhang, S Li, J Song, Z Lv

In this paper, a method for extracting and refining metallic molybdenum using low-temperature ZnCl2- NaCl-KCl molten salt was proposed. The electrochemical behaviour of molybdenum ions in ZnCl2- NaCl-KCl molten salt was investigated in detail, and pure metallic molybdenum was collected on the cathode. The reduction and diffusion processes of Mo(V) ions in ZnCl2-NaCl-KCl molten salt were determined through a series of electrochemical methods. The diffusion coefficients and nucleation modes of Mo(V) ions were also studied, and electrolysis was conducted for a prolonged period at a constant current density. The results indicated that the electrode reduction of Mo(V) ions in ZnCl2- NaCl-KCl molten salt proceeds through a three-step reaction: Mo(V) → Mo(IV) → Mo(III) → Mo at 250°C. The Mo(V) → Mo(IV) reaction was reversible and diffusion-controlled, with a Mo(V) diffusion coefficient of 6.02 × 10-6 cm2 s-1. Additionally, the nucleation mode of Mo(V) ions was instantaneous nucleation. The products electro-deposited were confirmed of metallic molybdenum with a particle size of less than 1 μm.

Aug 21, 2024

By R G. Reddy, Z Zhang

Viscosities of CaO-aluminosilicate ternary melts were estimated using a structure-based model. The model considers depolymerisation effects and related breakdown of the silicate network structure on the addition of metal oxides to the melts. The predicted values are in good agreement with the experimental values over the whole temperature and composition range.

Aug 21, 2024

By S Karosiya, A Sharma, M Jain, N N. Viswanathan, M M. Pande, D Kumar, S Kumar

Desulfurisation of steel during ladle refining is governed by both thermodynamics and kinetics. For effective desulfurisation, thermodynamically, a low partial pressure of oxygen at the steel-slag interface and highly basic slag which possess a large sulfide capacity are desired. Kinetically, the mass transfer coefficient of sulfur in the liquid steel and in the slag determines the rate of desulfurisation. A fast desulfurisation rate is achieved by maintaining sufficiently strong argon stirring of the melt. In the present work, sulfur mass balance for steel and slag was performed after the desulfurisation treatment for several industrial heats. The decrease in the sulfur quantity of the liquid steel was more than the increase in the sulfur quantity of the slag. The discrepancy in the sulfur mass balance suggests that the sulfur could be transferred to: (a) the gas (via slag) phase; or to (b) the refractory (crucible) phase. The preliminary investigation of the refractory samples taken at slag-refractory and steel-refractory interface showed no interaction of sulfur with the refractory. Therefore, the possibility of sulfur transfer to the gas phase was verified by carrying out melting experiments of sulfur containing slag in an argon/air atmosphere. Sulfur containing slag was initially melted in an MgO-C crucible under an argon atmosphere followed by creating the air atmosphere just above the melt. Careful sampling and analysis from the cold spots of the crucible, much above the melt surface, revealed formation of a fibrous structure. Scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS) analysis of these fibrous deposits confirmed the presence of oxides and sulfides. Oxidation of sulfur containing slag under air atmosphere was also performed using a thermogravimetric analysis (TGA) set-up. It showed a constant sulfur loss in the range of 1300– 1500°C. Thermodynamic calculations carried out using FactSage™ ver 8.3 for these experimental conditions are in good agreement with the observed results.

Aug 21, 2024

By G Sartor, A Rich, D Grimsey, R Forzatti, M White

An in-depth process model was developed for the pyrometallurgical, off-gas systems and water balance of the Kalgoorlie Nickel Smelter. This model was used to assess plant capacity with changing concentrate grades, increased throughput and tighter environmental emissions under a range of potential future operating conditions. Comparison of modelled results allowed for flow sheet optimisation across a range of metrics including sustainability, processing capacity and costs. Process modelling software, METSIM® (ver 2020.06 by METSIM International), was used to simulate the flash furnace, integrated electric slag cleaning furnace, Pierce-Smith converters, matte granulation, waste heat boiler, hot gas handling equipment, wet gas cleaning plant and acid plant. The METSIM® model was divided into three separate, yet interconnected models: metals, off-gas and water balancing. This allowed for improved modelling efficiency and traceability while minimising manual error. The METSIM® model was supported by inputs from other specialised software. Chemical thermodynamics software, FactSage™ (ver 8.2 by GTT Technologies), was used to establish relationships for the flash furnace fluxing strategy and determine the operating temperature. Arena® (ver 16.0 by Rockwell Automation), a discrete event modelling software, was used to simulate material movements within the aisle as well as Pierce-Smith converter operation, allowing for integration with upstream and downstream systems. A dynamic data exchange (DDE) was used to connect the results of each software package, interfacing through Excel® (version 4203 by Microsoft). The integration between models provided a streamlined approach to test capacity, bottlenecks, water consumption and emissions under a range of operating conditions, enabling a more robust process. Further downstream modelling techniques were used to assess mechanical equipment. METSIM® outputs provided key parameters for combustion assessments using computational fluid dynamics and finite element analysis for the furnace mechanical design.

Aug 21, 2024

By X Yang

White phosphorus (P4) is a critical element in industry, but its current production from phosphate rock using the carbothermal reduction method raises significant environmental and health concerns. This pressing issue necessitates the development of new technologies that facilitate the sustainable production of P4. In response, my team is actively developing an innovative, coke-free approach for white phosphorus production. This method involves the dissolution of phosphate rock in molten CaCl2, followed by the extraction of P4 through electrochemistry at relatively low temperatures. Moreover, this approach has the potential to utilise phosphate-bearing solid wastes as raw materials, further enhancing its environmental benefits. By employing this cutting-edge technique, we aim to revolutionise the phosphorus chemical industry towards greener and more sustainable practices. This paper provides evidence of the feasibility and effectiveness of our proposed approach.

Aug 21, 2024

By M Zhu, J Safarian

Understanding the slag composition-structure-property relationship remains challenging due to the amorphous nature of slag melts and the difficulty of high-temperature experimental investigations. Since the CaO-Al2O3-SiO2 slag system is maybe the most important slag system for various hightemperature metallurgical process, the present research employed high-throughput molecular dynamics (MD) simulations on the entire composition region of the CaO-Al2O3-SiO2 slag system to determine physical properties like molar volume, density and diffusivity, structural properties such as distribution of different oxygen types for each simulated slag melt. The obtained slag properties result from the simulations displayed good consistency with experimental data, underscoring the reliability of the MD simulation as a novel tool to predict reasonable slag properties and to study slag behaviour from atomistic insight. The simulated results demonstrate a near-linear relationship between molar volume changes and composition, highlighting the predominant role of oxygen atoms, which is attributed to the significantly larger size of oxygen compared to other cations in the slag melts. This disparity in size leads to oxygen ions occupying most of the space in slags, thereby playing a major role in determining the overall molar volume. The simulation results of slag density revealed a decreasing trend with increased SiO2 content and identified a local minimum at constant SiO2 when Al2O3 content increases, also consistent with established slag density models. Furthermore, the simulated oxygen self-diffusion coefficients reveal a strong composition-structureproperty relationship, where an increase in CaO content enhances slag diffusivity, while a minimum in diffusivity is observed near a CaO/Al2O3 ratio of unity. The diffusivity minimum also corresponding to the local viscosity maxima, indicating effective simulation of charge compensation effects and dynamic characteristics of slag melts. The simulated distribution of oxygen types in slag — bridging oxygen (BOs), non-bridging oxygen (NBOs), free oxygen (FOs) and tricluster oxygen (TOs) — reveals a composition-dependent pattern: BOs peak near CaO/Al2O3 = 1, NBOs and FOs are abundant in CaO-rich areas with NBOs peaking near the Ca3SiO5 composition, FOs in the CaO corner, and TOs predominantly in the Al2O3 corner, highlighting the complex interplay of network formers and modifiers for the charge compensation effects on the slag’s structural properties. The successful application of MD simulations in this study paves the way for a powerful approach to explore the complex relationships in multicomponent slag systems and bridges the gap between mathematics modelling and experimental observations in high-temperature metallurgical processes.

Aug 21, 2024

By R G. Reddy

The complexity in treating environmentally harmful impurities such as As, Sb, Bi from the base metal matte or metal in the smelting stage are responsible for the high cost of the refining process. The impurity capacities (such as arsenic, antimony and bismuth) of slags were calculated a priori using Reddy-Blander (RB) model. The capacity predictions were for a wide range of matte and slag compositions in copper smelting conditions. The calculated impurities capacities and impurity distribution ratios results are in good agreement with the available experimental and industrial slags data. The a priori knowledge of impurities is useful for reduction of energy consumption and enhanced environmental control in the current and future non-ferrous metal processes.

Aug 21, 2024

By S Wan, F Zhang, J You, K Tang, X Tang, C Bessada, A Canizarès, Q Zhang, L Lu

Microstructure of CaO-SiO2-based glassy samples with various Al2O3 contents were examined quantitatively by Raman spectroscopy and 27Al MAS NMR (magic-angle spinning nuclear magnetic resonance). Sequence of multiple cluster models of aluminosilicate system modified with Ca2+ and Na+ cations have been designed, and Raman spectra simulation were carried out after geometric optimisation by quantum chemistry (QC) ab initio calculation. The functional relationship between Raman scattering cross-section (RSCS) and stress index of silicon-oxygen tetrahedron (SIT) for aluminosilicates was established, which was applied to the calibration of experimental Raman spectra. Some five-fold coordinated aluminium (AlV, around 5 per cent) and less than 2 per cent sixfold coordinated aluminium (AlVI) were detected by 27Al MAS NMR, while most of aluminium remained in tetrahedral sites (AlIV). The hyperfine quantitative results of Raman spectroscopy and NMR showed a gradually production of AlIV with addition of Al2O3, along with the significant adjustment of Qi species distribution, in which Q1, Q2 reduced and fully polymerised Q4 increased while Q3 showed a non-monotonic variation and obtained the maximum at Al2O3 = 18 mol per cent. Furthermore, the effects of aluminium to bridging oxygen bond types (T-Ob, T = Si, Al) and the degree of polymerisation were also discussed in detail. The evolution of microstructure and its correlation with the viscosity of CaO-SiO2 based melts, incorporating various Al2O3 additives, have been investigated by employing in situ high temperature Raman spectroscopy at 1823 K and viscosity model. These structural features related to composition are essential theoretic foundation to understand their properties. The average Qi evolution culminates in an overall enhancement of the degree of polymerisation. Viscosity was determined utilising a rigorously selected viscosity model, elucidating a consistent upward trajectory as Al2O3 content is incrementally added. Furthermore, a quantitative analysis of the relationship between viscosity and structure was conducted based on the average number of non-bridging oxygen per network-forming tetrahedron (NBO/T). It provides valuable insights for examining and predicting viscosity behaviour of aluminosilicate systems.

Aug 21, 2024

By W Y. Kim, Y B. Kang, Y J. Park

The phase equilibria in the Al2O3–TiOx system were investigated in wide ranges of temperature and oxygen partial pressure: 1300~1600°C and 10-16.6~10-8 atm, respectively. The equilibrium phases and their compositions were identified using X-ray diffraction (XRD) and electron probe microanalysis (EPMA), respectively. Most noticeably, a wide range of pseudobrookite solid solution was found in equilibrium with almost pure alumina. At each temperature, the cationic ratio expressed as RTi = nTi/(nAl + nTi)) of the pseudobrookite solid solution showed a noteworthy dependency on the oxygen partial pressure. This resulted in the formation of a broad range of pseudobrookite solid solutions, ranging from Al2TiO5 (RTi = 1/3) to Ti3O5 (RTi = 1.0). Complete miscibility within the pseudobrookite solid solution was observed at 1600°C, with only a minor miscibility gap becoming evident below 1500°C. Based on the results obtained in the present study, the behaviours of Al2TiO5 pseudobrookite have implications in two key domains: (1) understanding changes in the physical properties of the materials, and (2) elucidating the evolution of Al–Ti complex oxide inclusions in liquid steel which can deteriorate the steel cleanliness.

Aug 21, 2024

By G M. Tranell, M Tangstad

The CO2 footprints in the production of Mn-ferroalloys and silicon/ferrosilicon are correlated with the fossil carbon consumption. The CO2 emissions may be reduced in the Mn-ferroalloy process by increasing the degree of prereduction and reduction of carbonate materials, while the silicon/ferrosilicon process is optimised based on silicon yield. By changing the fossil reductant into biogenic reductants, the global warming potential will be decreased even more. Even if the reductants are biogenic reductants, there will still be a global warming potential (GWP) in eg the electrode consumption and the CH4 emissions in the charcoal production. To reduce the use of fossil reductants there are also more disruptive technologies like the use of H2 that at least for the silicon production is on a very low technology readiness level (TRL). Using metallothermic processes will reduce the use of carbon but requires carbon neutral metal reductants. Electrowinning can have low CO2 emissions, and the electrowinning of pure Mn is a technology of high TRL. Salt and oxide electrolysis is under investigation for both Mn and Si production however the research is still on a low TRL. The use of CCS/CCU (carbon capture storage/utilisation) is a part of obtaining carbon neutral processes. Last, the energy mix used for these energy demanding processes is discussed.

Aug 21, 2024

By M Suzuki

Although several models for the surface tension of molten oxide slag have been proposed, suitably accurate predictions of this property are not yet possible. The surface tension, or surface excess free energy, of molten oxides is largely determined by the ionic coordination induced by surface relaxation. However, the associated mechanism of surface structural relaxation for molten oxide mixtures such as slag is complex and not yet fully understood. To allow a better evaluation of surface relaxation characteristics, the present work analysed the ionic coordination associated with the surface-relaxed states of several oxide mixtures. This work especially focused on calcium aluminate slags because these materials exhibit complex relationships between composition and surface tension. The effects of incorporating low concentrations of SiO2 as a surface active component on the surface ionic coordination were also examined. X-ray absorption techniques were used to assess oxygen and cationic elements in glassy samples after surface relaxation treatments, and molecular dynamics simulations based on a polarisable ion model of molten slag with vacuum/melt interfaces were also performed. The X-ray absorption techniques provided data related to electron yields (which are primarily associated with surface features) and fluorescence yields (which evaluate the bulk material). Thus, the ionic coordination characteristics of both regions were investigated. The results of molecular dynamics calculations allowed statistical analysis of the distributions of Al- or Sicentred polymorphs as well as the bond angles between cations and oxygen anions in the vacuumexposed and bulk regions in the equilibrated melt. The results indicated that bridging oxygen ions were preferentially distributed in the relaxed surface region rather than non-bridging oxygens. These bridging oxygen ions represented vertex connections between AlO4 or SiO4 tetrahedra. In the case of the calcium aluminate slags, the addition of one Ca2+ ion as charge compensation for two Al3+ ions was found to be necessary to form two AlO4 tetrahedra. This specific feature of surface ionic coordination could be responsible for the complex trends observed in surface tension data. The incorporation of low concentrations of SiO2 reduced the proportion of tetrahedrally-coordinated Al ions such that higher coordination states become dominant in the bulk of the material, whereas AlO4 tetrahedra were preferentially distributed in the surface region. SiO4 tetrahedra were the preferred Si-centred polymorph and were likely connected to one another to form bridging oxygen ions at the surface. On the basis of these results, a model to predict slag surface tension was proposed, and the energy of the formation of the ionic clusters resulting from surface relaxation was taken into account.

Aug 21, 2024

By E Jak, M Shevchenko, E Nekhoroshev, D Shishin

In the field of pyrometallurgy, the presence of multiple molten phases with distinct chemical compositions, such as slags, mattes, speiss liquids, metals and molten salts, is a well-known phenomenon. These phases exhibit strongly non-ideal solution behaviour and are mutually miscible to varying degrees. To describe these complex molten liquids, the Modified Quasichemical Model (MQM) has proven effective and has been applied to numerous binary, ternary and several higher-order multicomponent systems related to pyrometallurgy. In recent decades, the complexity of high-temperature processes has escalated due to increased impurity concentrations in primary ores, the incorporation of recycled consumer products and the integration of metallurgical plants through by-product and waste exchanges. To address these issues, PYROSEARCH laboratory has been developing large 20-component thermodynamic database using a generalised CALPHAD (CALculation of PHAse Diagrams) methodology integrated with experimental investigations. Over the past decade, strategic decisions were made balancing the ability to generate experimental data, prediction power, accuracy, stability of calculations, as well as computational time, which are discussed in the paper. Examples provided for issues of >3 liquid immiscibility, non-ionic behaviour and exaggerated ‘sharp’ enthalpies of mixing in silicate slags, dealing with multiple oxidation states, as well as comparative analysis of pair and quadruplet approximation in MQM.

Aug 21, 2024