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Slag fuming process is used to extract zinc from the lead blast furnace slags and recently for the extraction of multiple elements from the complex primary and recycling feed streams, making the thermochemistry of the process challenging. To meet new challenges, computer models with predictive powers outside of the range of normal process conditions are necessary. These models cannot rely exclusively on sets of existing process data and must have a foundation in thermodynamics combined with reasonable kinetic factors. The accuracy of predictions largely depends on the quality of thermodynamic data, including phase equilibria, elemental distributions, and calorimetry measurements. Present study demonstrates the recent developments of the self-consistent thermodynamic model for the gas/slag/matte/metal/speiss/solid phases within the Cu-Pb-Zn-Fe-Ca-Si-O-S-Al-Mg-As-Sb system, applied to zinc fuming, with attention to the phase equilibria and partitioning of minor elements in the process. As a demonstration of calculations far outside of normal operations, the use of ammonia as an alternative to coal is investigated. It was shown that from the thermodynamic point of view the process can reach the same final concentration of zinc and the heat balance of the reactor in the same amount of time when coal is replaced in the process by ammonia.

The combined effects of Al2O3, CaO and MgO slagging components on phase equilibria and thermodynamics in the basic Cu–Fe–O–S–Si system have been evaluated at 1473 K (1200 ºC) and p(SO2) = 0.25 atm for a range of oxygen partial pressures and matte compositions. The experimental technique included high-temperature equilibration of the samples on a spinel substrate under controlled gas atmosphere (CO/CO2/SO2/Ar), followed by rapid quenching and subsequent measurement of the equilibrium phase compositions using Electron Probe X-ray Microanalysis (EPMA). The experimental data have been compared with the results of thermodynamic calculations undertaken using FactSage software and an internal thermodynamic database. Both the experimental results and the calculations results revealed that the presence of Al2O3, CaO and MgO reduced both the sulphur and copper concentrations in the slag phase for a given set of process conditions. The data have been used for further optimisation of the parameters of the thermodynamic database describing multicomponent metallurgical systems. The resulting thermodynamic database is capable of predicting, with high accuracy, the phase equilibria and the distribution of all elements between the phases in the Cu–Fe–O–S–Si–(Al, Ca, Mg) system. Graphical Abstract

The experimental study of the phase equilibria between calcium ferrite slag, metallic copper, spinel and/or dicalcium ferrite in the Cu2O-FeO x -CaO system has been carried out. Effects of temperature, oxygen partial pressure and Fe/CaO ratio on phase assemblages and compositions have been estimated. The advanced experimental technique including high-temperature equilibration on primary phase substrates, rapid quenching of the samples and quantitative measurements of equilibrated phase compositions using electron probe X-ray microanalysis has been applied. Spinel and dicalcium ferrite substrates have been specially designed to study phase equilibria at certain primary phase fields. Obtained experimental results have been compared with thermodynamic assessment of the Cu2O-FeO x -CaO system and available literature data.

Magnesium oxide-based refractory materials are used industrially to contain the chemically aggressive slags present in lead smelting systems. In the present study an integrated experimental and thermodynamic modeling approach was taken to provide fundamental information on the chemical reactions taking place in these systems. New experimental phase equilibria and liquidus data were obtained for the PbO–MgO–SiO2 system in air in the temperature range 750 °C to 1740 °C. In the MgO–SiO2 binary, new experimental results were obtained at 1550 °C to 1740 °C and compared to the available thermodynamic data in the literature. The experiments were carried out using the high-temperature equilibration of oxide powder mixtures followed by rapid quenching of the samples. Electron probe X-ray microanalysis (EPMA) was used to determine the compositions of the solid and liquid phases present at equilibrium conditions. Phase equilibria and liquidus isotherms in the cristobalite and tridymite (SiO2), pyroxene (protoenstatite MgSiO3), olivine (forsterite Mg2SiO4), barysilite (Pb8MgSi6O21), massicot (PbO) and periclase (MgO) primary phase fields were measured, and the extent of the high-silica two-liquid immiscibility gap in equilibrium with cristobalite was determined. The experimental results were used to optimize the parameters in a thermodynamic database that was subsequently used to describe this multi-component, multi-phase system and predict the liquidus for the PbO–MgO–SiO2 system. The new data were used to characterize the chemical interactions of magnesia-based refractory with PbO–MgO–SiO2 slags.

Present society challenges, including metal scarcity, recycling, and environmental restrictions, resulted in the increased complexity and variability of metallurgical feed streams. Metallurgical processes involving complex lead and copper-containing slag and matte phases are now commonly used in response. Optimization of existing and development of new metallurgical processes require fundamental information on slag–matte phase equilibrium. Development of the experimental methodology for the characterization of slag–matte phase equilibrium is presented in the paper. Following a detailed analysis of the potential reaction pathways, experimental techniques have been developed that enable accurate measurement of slag–matte phase equilibrium in the Pb-Fe-O-S-Si system. The application of the techniques has been demonstrated for two important sets of conditions: (i) Condensed phase equilibrium for the slag–matte–metal–tridymite subsystem; and (ii) Gas–slag–matte–tridymite equilibrium at fixed oxygen and sulfur partial pressures. The experimental methodology involves high-temperature equilibration of synthetic samples, fast quenching, and microanalysis of the compositions of phases using electron probe X-ray microanalysis (EPMA). The experimental results are not affected by the changes in the bulk composition of samples during equilibration; this helps to overcome the significant barriers previously encountered in undertaking accurate measurement and characterization of these systems.

An experimental study has been carried out to determine the compositions of the slag/matte/metal/tridymite phases in equilibrium in the Cu-Fe-O-S-Si system at 1200℃. The measurements covered the full range of matte compositions from copper-free mattes to white metal, i.e. from 0 to 80 wt% of copper in matte. The research methodology involved high-temperature equilibration, quenching of the samples and accurate measurement of the phase compositions by electron probe X-ray microanalysis. The oxygen concentrations in mattes were directly measured using the EPMA. A comprehensive set of experimental equilibrium data has been obtained for coexisting matte, slag, Cu-Fe metal alloy and Fe-Cu metal alloy phases. It has been shown that solid iron-copper alloys were present at matte grades below 56 wt% Cu, while liquid copper-iron alloys were formed for matte grades higher than 56 wt% Cu. The experimental measurements have been compared with data reported in the literature and the trends calculated using the thermodynamic model descriptions of the system.

Phase equilibria of the PbO-“FeO”-SiO2 and PbO-“FeO”-CaO-SiO2 slags with liquid Pb metal, solid or liquid Fe metal and solid oxides [cristobalite and tridymite SiO2, wustite (Fe,Ca)O1+x, olivine (Fe,Ca)2SiO4, dicalcium silicate (Ca,Fe)2SiO4, wollastonite (Ca,Fe)SiO3 and lime (Ca,Fe)O] were investigated at 1100-1689 °C. These conditions correspond to the minimum solubility of PbO in slag in presence of Pb and Fe metals at reducing conditions and represent the limit of lead smelting and slag cleaning process. High-temperature equilibration on silica or iron foil substrates, followed by quenching and direct measurement of Pb, Fe, Ca, and Si concentrations in the phases with the electron probe x-ray microanalysis (EPMA) was used to accurately characterize the system. Present results provide important basis for improvement of the thermodynamic models for all phases in this system.

The CaO·3(Al,Fe)2O3, (C(A,F)3), phase forms a solid solution in the FeO-Fe2O3-CaO-Al2O3 system and is an end member of the SFCA (Silico-Ferrite of Calcium and Aluminum) suite of solid solutions observed in industrial iron ore sinters. SFCA acts as a bonding phase in these sinter materials so an accurate description of the phase equilibria and thermodynamic properties of this phase can be used to assist in the design and operation of Fe-sintering and Fe-making processes. New experimental data are reported on the liquidus and sub-liquidus phase equilibria in the iron-rich region of the FeO-Fe2O3-CaO-Al2O3 system in air. The study was undertaken using equilibration/quenching and microanalysis techniques enabling the compositions of the liquid and solid phases in equilibrium at high temperature to be directly and accurately measured. The compositional limits of the C(A,F)3 phase and associations with the primary phase fields of CA [CaO·(Al,Fe)2O3], CA2 [CaO·2(Al,Fe)2O3], CA6 [CaO·6(Al,Fe)2O3], Hematite [(Fe,Al)2O3], Spinel [(Fe,Ca)O·(Fe,Al)2O3)], C2F [2CaO·(Fe,Al)2O3], C2F3A (2CaO·3Fe2O3·Al2O3), CF [CaO·(Fe,Al)2O3], and CF2 [CaO·2(Fe,Al)2O3] have been determined in the high-iron, low-melting temperature region of the system. The C(A,F)3 is found to be stable over a wide range of temperatures (1213 °C to 1400 °C) and alumina compositions (3.3 to 33.6 mol pct AlO1.5). The solid-phase C2F3A (2CaO·3Fe2O3·Al2O3), which is isostructural to SFCA-I indicated by previous researchers, has been found to be stable up to 1225 °C in the FeO-Fe2O3-CaO-Al2O3 system in air.

A combined experimental and thermodynamic study has been carried out to determine the CaO effect on the equilibria between slag/matte/metal (Fe or Cu)/tridymite phases in the Cu-Fe-O-S-Si-Ca system at 1473 K (1200 °C). The experimental methodology included equilibration of the mixtures at high temperatures on substrates made from the primary phase, followed by rapid quenching of the samples and direct measurement of the condensed phase compositions using the Electron Probe X-ray Microanalysis (EPMA) technique. New experimental results have been obtained for fixed concentrations of CaO in slag phase (1.5, 6, 9, and 18 wt pct). All results have been plotted as functions of the copper concentration in the matte phase and provides information about the effect of CaO on the oxygen and sulfur concentration in the matte phase; the Fe/SiO2 ratio in slag; and dissolved copper and sulfur in slag. The experimental research is part of integrated experimental and thermodynamic study aimed to development and optimisation a thermodynamic database for copper-containing systems of non-ferrous metallurgy.

Experimental measurements have been undertaken of the gas-matte-spinel and gas-slag-matte-spinel equilibria in the Cu–Fe–O–S–Si system at 1200°C and pSO2 of 0.1 and 0.6 bar. The technique involved ...

Rising concentrations of impurities are expected at copper fire-refining stage due to lower availability of high-quality copper concentrates and due to increasing recycling of electronics and other secondary materials in primary copper smelting. Extra steps involving the removal of impurities from copper into the slag phase may provide a solution, but better understanding of thermochemistry is needed to evaluate the feasibility of changes in the process. In the present study, the distribution coefficients of Pb, Bi, and Ag between the fayalite or calcium ferrite slags and copper-based metal at 1250 °C were measured experimentally, using high-temperature equilibration, rapid quenching, and electron probe X-ray microanalysis (EPMA). The experiments were undertaken in a closed system using a modified substrate support technique, at relatively high oxidizing conditions typical for copper refining. The improved substrate technique enables the measurement of distributions coefficients for slags in equilibrium with solid spinel (Fe3O4) or dicalcium ferrite (Ca2Fe2O5). Experimental results of the present study and the literature data were analyzed together using thermodynamic modeling. As a result, thermodynamic database has been developed and used to predict the effects of oxygen partial pressure, wt% Cu in slag, temperature, and Fe/SiO2 and Fe/CaO in slags on the distribution coefficients of Pb, Bi, and Ag for the fayalite and calcium ferrite slag systems.

New experimental measurements have been made to determine liquidus isotherms, univariant and invariant equilibria in the FeO-Fe2O3-CaO-SiO2, CaO-SiO2 and FeO-Fe2O3-SiO2 systems in air at temperatures between 1190 °C and 1730 °C. The study was undertaken using equilibration/quenching and microanalysis techniques, enabling the compositions of the liquid and solid phases in equilibrium at temperature to be accurately measured. The data have been used to define liquidus in the primary phase fields of hematite (Fe2O3), spinel [(Fe,Ca)O·Fe2O3], lime (CaO), tridymite or cristobalite (SiO2), dicalcium ferrite (2CaO·Fe2O3, C2F), pseudo-wollastonite (CaO·SiO2, CS), rankinite (3CaO·2SiO2, C3S2), dicalcium silicate (2CaO·SiO2, C2S), tricalcium silicate (3CaO·SiO2, C3S) and the two liquids miscibility gap. These data obtained in the present study provide a more complete and more accurate description of the multi-component Fe-Ca-Si-O-Al-Mg-Cu-S system directly relevant to applications in the cement, the ferrous and non-ferrous metallurgical industries.

The distributions of arsenic, lead, tin and zinc between iron silicate slag and copper in equilibrium with tridymite in the Cu–Fe–O–Si system have been experimentally determined at selected oxygen partial pressures (P(O2)) at temperatures of 1 523 K and 1 573 K. The experimental technique involved high temperature equilibration in a sealed silica ampoule to minimize the vaporization of minor elements, rapid quenching of the condensed phases, and the direct composition measurements of the condensed phases using microanalysis techniques. The effective P(O2)s of the samples were determined based on the measured Cu2O concentrations in slag. The new experimental data resolve discrepancies found in previous studies and have been used in the development of a new thermodynamic database of the Cu–Fe–O–Si system containing minor elements.

A combination of high-temperature experiments and thermodynamic modeling in the CaO–Cu2O–FeO–Fe2O3–SiO2 system provides the fundamental information necessary to design and improve processes such as WEEE recycling through black copper route, continuous converting of copper matte, copper dross smelting, slag cleaning, and valorization of copper slag. In the experiments, samples were equilibrated on a primary phase substrate or Fe metal foil, then rapidly quenched and studied using the Electron Probe X-ray Microanalysis. The FactSage software was used for calculations, combined with custom developed thermodynamic database. A systematic analysis is provided to select the fluxing strategy and increase the copper recovery in industrial processes. Slag liquidus and concentration of copper in slag were assessed as functions of oxygen partial pressure, temperature, Fe/SiO2 in slag, and wt% CaO in slag.

Silico-ferrite of calcium and aluminum (SFCA) is the major bonding phase in iron ore sintering process and is critical to enhancing the sinter properties, such as reducibility and mechanical strength in subsequent blast furnace operations. The phase relations foundations of the alumina-free silico-ferrite of calcium (SFC) have been previously experimentally investigated in air by the authors (Chen et al. ISIJ Int 59:795–804, 2019, Cheng et al. Metall Mater Trans B 51:1587–1602, 2020) and in 1 atm CO2 (Chen et al. ISIJ Int, 59:805–809, 2019). Present investigation using equilibration and quenching followed by electron probe X-ray microanalysis (EPMA) technique, follows those previous works on the SFC, with the focus on the effects of: (i) Al2O3 (in the “Fe2O3”-CaO-Al2O3 and the “Fe2O3”-CaO-SiO2-Al2O3 system in air), and (ii) the effect of $$ p_{{{\text{O}}_{2} }} $$ (the “Fe2O3”-CaO-Al2O3 in 1 atm CO2 atmosphere), to investigate the thermodynamic stability of the C(A, F)3 [Ca(Al, Fe)6O10] solid solution in the “Fe2O3”-CaO-Al2O3 system in both air and pure CO2 atmospheres between 1150 °C and 1250 °C; and the silico-ferrite of calcium and aluminum (SFCA) solid solution with 1, 2 and 4 wt pct of Al2O3 in bulk compositions in the “Fe2O3”-CaO-SiO2-Al2O3 system at temperatures in the range between 1255 °C and 1340 °C. Present study shows that C(A, F)3 is stable over a wide range of Al2O3 concentration (8.8 to 26.7 wt pct Al2O3, or 12.5 to 34.8 mol pct AlO1.5). It also becomes less stable in terms of both the temperature and the compositional stability range as the oxygen partial pressure is reduced. The SFCA phase in the “Fe2O3”-CaO-SiO2-Al2O3 system is found to be present in the range of 1 to 4 wt pct Al2O3 bulk compositions selected in air. The relative stability of this phase increases with increased Al2O3 in the bulk material. Tie-lines joining the SFCA and the corresponding liquid and hematite phases are constructed over the range of composition investigated at sub-liquidus temperatures. The new experimental measurements show that the CaO/SiO2 ratio in the SFCA phase is almost identical to that in the liquid. The distribution ratio of Al2O3 between SFCA and liquid is in the range 2/1 to 3/1.

The individual effects of Al2O3, CaO and MgO on gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si-(Al, Ca, Mg) system at 1473 K (1200 °C) and p(SO2) = 0.25 atm. have been experimentally measured for a range of oxygen partial pressures and matte compositions. The experimental methodology has included the high temperature equilibration of individual samples on a spinel primary phase substrate under controlled gas atmospheres (CO/CO2/SO2/Ar), followed by rapid quenching of the equilibrium condensed phases and direct measurement of the phase compositions using electron probe x-ray microanalysis. The experimental results show that the presence of Al2O3, CaO and MgO reduce the iron, sulphur and copper concentrations in the slag phase. Present study is undertaken as part of an integrated approach involving thermodynamic modelling and experimental measurements. The experimental data are compared with predictions obtained using the current thermodynamic database for the Cu-Fe-O-S-Si-(Al, Ca, Mg) system in order to further improve thermodynamic parameters.

Due to the increasing complexity of materials processed in primary and secondary lead smelting, better control of impurity elements is required. In the present study, distributions of Cu, As, Sb and Sn between PbO–FeO–Fe2O3–SiO2 slag and Pb metal are characterized experimentally and analyzed using thermodynamic calculations. Experimental methodology involved closed-system equilibration of sample mixtures at high temperature followed by rapid quenching. The compositions of phases were measured using electron probe X-ray microanalysis and laser ablation inductively coupled plasma mass spectrometry. Thermodynamic calculations were performed using the FactSage software coupled with an internal thermodynamic database. Experimentally obtained distribution coefficients wt.% in slag/wt.% in metal at 1 200 °C (1 473 K) follow the sequence Sn >> Cu > As ≈ Sb at P(O2) < 10−9.5 atm and Sn >> As ≈ Sb > Cu at P(O2) > 10−8.5 atm. Model predictions are in good agreement with the experiment.

The solidification of liquids having bulk compositions in the high iron region of the ‘Fe2O3’-CaO-SiO2 system having selected CaO/SiO2 ratios has been investigated. The compositions investigated we...

To address the increasing complexity of feed materials to pyrometallurgical processes, an integrated experimental and thermodynamic modeling research program is in progress to accurately characterize the multi-phase gas-slag-matte-speiss-metal-solids 17-component Cu/Pb-(Cu2O-PbO-ZnO-CaO-FeO-Fe2O3-SiO2)-(Al2O3-MgO)-S-(As-Bi-Sb-Sn-Ag-Au-Ni) system. New experimental data are used to continuously improve the thermodynamic database using FactSage. An example is provided on the slag-matte distributions of Bi, Pb, and Zn in equilibrium with tridymite in the Cu-Fe-O-S-Si system under copper smelting conditions. A closed system equilibration experimental technique with rapid quenching was used. Major element concentrations in phases were measured with electron probe x-ray microanalysis. A laser ablation inductively coupled plasma mass spectrum technique was used for determination of Bi, Pb, and Zn concentrations in slag. New experimental data contributed to the optimization of thermodynamic model parameters. Improved thermodynamic databases can be used to accurately predict the elemental distributions in multi-component systems; an example is given for the minor element distributions between slag and matte for industrial conditions.

The gas-slag-matte-tridymite equilibria in the Cu–Fe–O–S–Si system at 1200°C have been experimentally studied. An improved experimental technique was used, which includes high temperature equilibration of sulfide-oxide mixtures on silica substrates at p(SO) = 0.6 atm, preservation of the equilibrium phases by rapid quenching, and direct compositional analysis of the phases using microanalysis techniques. The new data have enabled the effects of sulfur dioxide partial pressure between 0.1 and 0.6 atm on the equilibria to be accurately determined. Whilst, for a given matte grade, the dissolved copper in slag is not sensitive to sulfur dioxide partial pressure, the Fe/SiO in slag in equilibrium with tridymite was found to increase with increasing p(SO). This latter observation has implications for fluxing practice in industrial copper smelting operations.

Experimental measurements have been made of the compositions of slag, matte and tridymite phases in chemical equilibrium in the Cu-Fe-O-S-Si system at 1300°C, p(SO) = 0.25 atm and selected oxygen partial pressures. The high temperature equilibration experiments were conducted using silica substrates under controlled CO-CO-SO-Ar gas atmospheres. The resulting phases obtained from the equilibrations were retained at room temperature through rapid quenching of the samples. The condensed phase compositions from the equilibrium experiments were measured by Electron Probe X-ray Microanalysis (EPMA). The data obtained in the present study, combined with those from previous studies, have enabled the liquidus slag temperature to be accurately described as a function of Fe/SiO ratio at p(SO) = 0.25 atm for temperatures between 1200 and 1300C and mattes containing from ∼44 to ∼ 78 wt pct Cu.

New experimental data are reported on the liquidus and sub-liquidus phase equilibria in the FeO-Fe2O3-CaO-SiO2 system in air. The study was undertaken using equilibration/quenching and microanalysis techniques enabling the compositions of the liquid and solid phases in equilibrium at temperature to be accurately measured. The limits of stability and associations of the primary phase fields of hematite (Fe2O3), dicalcium silicate (Ca2SiO4), silico-ferrite of calcium solid solution (SFC), dicalcium ferrite (Ca2Fe2O5), calcium ferrite (CaFe2O4), calcium diferrite (CaFe4O7) have been characterized in the high iron, high CaO/SiO2, low melting temperature region of the system. The full extent of the primary phase field of SFC has been determined, as have the conjugate lines joining the SFC and the corresponding liquid phase over the range of SFC compositions at sub-liquidus temperatures.

The cooling rate of the liquid oxide can be controlled in industrial sintering processes through the draft pressure and has the potential to influence microstructure formation. The solidification of a liquid within the hematite primary phase field in the ternary "FeO"-CaO-SiO system in air was undertaken at different cooling rates to determine the impact of cooling rate on the formation of product microstructures. Samples with a bulk composition of 72.7 wt% FeO and a CaO/SiO ratio of 3.46, were cooled from 1623 K (1350°C) at 2 K/s, 0.5 K/s, 0.1 K/s and 0.01 K/s and quenched at 5 K temperature intervals from 1533 K (1260°C) to 1453 K (1180°C). During cooling, four stages of phase assemblage formation were consistently observed at all cooling rates; in order of formation these are, Liquid +hematite (I), Liquid+hematite+dicalcium silicate(CS)(II), Liquid+CS+calcium diferrite (CF)(III) and CS+CF+calcium ferrite (CF)(IV). An intergrowth of silico-ferrite of calcium and aluminium-I (SFCA-I) and CaFeFeO was observed to form in some conditions in regions free of hematite, present in liquids solidifying at 0.5 K/s and 0.1 K/s. The sizes and shapes of microstructures were observed to systematically change with cooling rate, with a slower cooling rate typically resulting in coarser coupled microstructures and larger individual crystals. A larger proportion of coupled microstructures are observed at slower cooling rates, this appears to be related to the degree of undercooling prior to the nucleation of new phases. The equilibrium silico-ferrite of calcium (SFC) phase was not observed at any of the cooling rates investigated.

The solidification of "FeO"-CaO-SiO liquids in air at a controlled cooling rate of 2.0 K/s for a range of FeO concentrations in the bulk has been investigated. The compositions investigated were selected such that the bulk compositions were within the hematite primary phase field and had a CaO/SiO ratio of 3.46 wt/wt. Non-equilibrium phase assemblages were formed for all bulk compositions investigated. Specifically, the silico ferrite of calcium (SFC) phase was not formed on cooling. The microstructures and proportions of the phase assemblages formed were found to vary with the FeO concentration in the bulk.

Thermodynamic modeling of the Pb-S and Cu-Pb-S systems is presented. All available experimental data in these systems are collected, assessed and used to optimize the model parameters. For the liquid phase, a solution (CuI, PbII, SII) is developed using the modified quasichemical model in pair approximation. Liquid copper, liquid lead metal, as well as matte phases are described using single solution with miscibility gaps. Earlier thermodynamic assessments available in the literature did not include all the data on the solubility of Cu and S in liquid Pb at low temperatures, 900 °C (1123 K), a significant discrepancy among different sets of literature data and existing thermodynamic assessments is revealed. Preliminary experiments are performed with the goal to understand the nature of the problem and to develop the methodology based on high-temperature equilibration, rapid quenching and electron probe x-ray microanalysis. The results of this study help to select accurate literature results in the optimization of model parameters. The resulting database is applicable to calculate slag/matte/metal distribution of lead in copper smelting and converting, as well as for predictions in the lead smelting and fire refining.

The effect of temperature, CaO, MgO and Al2O3 on important technological copper smelting parameters, such as the chemically dissolved copper in slag and the composition of the liquid phase in equilibrium with tridymite, are experimentally characterised as a function of copper concentration in matte. Two series of experiments for the gas/slag/matte/tridymite equilibria in the Cu-Fe-O-S-Si system at p(SO2) = 0.25 atm have been carried out. The effect of CaO at 1573 K (1300 °C), and the combined effect of Al2O3 + CaO + MgO at 1473 K (1200 °C) and 1573 K (1300 °C) have been measured in the first and second series of experiments respectively. The experimental methodology involves high temperature equilibration of samples on a substrate made from the primary phase under controlled gas atmosphere (CO/CO2/SO2/Ar), followed by rapid quenching of the equilibrium condensed phases and direct measurement of the phase compositions using the Electron Probe x-ray Microanalysis. The resulting data are used in the optimization of the thermodynamic database for the copper-containing systems.

Phase equilibria in the ZnO-“CuO0.5”-SiO2 system have been investigated at 1403-1948 K (1130-1675 °C) for oxide liquid in equilibrium with Cu-Zn metal (> 99% Cu) and solid oxide phases: (a) tridymite or cristobalite SiO2; (b) willemite Zn2SiO4; (c) zincite ZnO; and (d) cuprite Cu2O. Two-liquid immiscibility range in the high-SiO2 slags has also been studied. High-temperature equilibration on primary phase (SiO2, Cu2O), inert metal (platinum-iridium wire), or ceramic (Al2O3 for high-Cu2O slags) substrates, followed by quenching and direct measurement of Zn, Cu, Si and possible impurities (Al, Pt, Ir) concentrations in the phases with the electron probe x-ray microanalysis (EPMA) has been used to accurately characterize the system in equilibrium with metal. All results are projected onto the ZnO-“CuO0.5”-SiO2 plane for presentation purposes.

Experimental investigations have been undertaken to determine the effect of Al2O3in slag on the gas/slag/matte/tridymite equilibria in the multi-component Cu-Fe-O-S-Si-Al system at 1 200 8C, and P(SO2) = 0.25 atm. The experimental technique involves high temperature equilibration of synthetic samples on the open silica substrate in controlled gas atmospheres (CO/CO2/SO2/Ar), rapid quenching after a designated equilibration time followed by the compositional analysis of the condensed phases with electron probe X-ray microanalyzer. The experimental data of the present study provide information on the effect of alumina on the slag composition, such as the chemically dissolved copper, dissolved sulphur, and Fe/SiO2 ratio in slag at tridymite saturation at different Cu in matte. The new data have been used as inputs for the optimization of the thermodynamic databases for the copper-containing systems and can also be used to evaluate the fluxing strategy in the copper smelting operation.

Equilibria between gas/slag/matte/spinel phases in the Cu-Fe-O-S-Si system have been experimentally studied at 1523 K (1250 °C), P(SO2) = 0.25 atm, and a range of oxygen partial pressures. The experimental technique involved high temperature equilibration using spinel substrates in controlled gas atmospheres (CO/CO2/SO2/Ar), rapid quenching of the equilibrated phases, and direct measurement of phase compositions using Electron Probe X-ray Microanalysis. The influence of temperature on the gas/slag/matte/spinel equilibria has been analyzed. Comparisons with previous studies on the gas/slag/matte/tridymite equilibria and the most recent thermodynamic database have been provided. This is the first systematic study on the influence of temperature on the gas/slag/matte/spinel equilibria in the Cu-Fe-O-S-Si system at P(SO2) = 0.25 atm.

Studies have been undertaken to investigate the thermodynamic aspects of the reduction roasting of saprolite ores in the Caron Process. Reduction experiments have been conducted in controlled oxyge...

Laboratory studies have been undertaken to determine the mechanisms and kinetics of reactions occurring during the reduction roasting of saprolite ores with 1 wt% elemental sulphur addition. The reduction was undertaken using a 15%H/85%N gas mixture at temperatures between 400 and 800°C; nickel was recovered by subsequent leaching in an ammoniacial aqueous solution. The effect of sulphur on dehydroxylation, reduction and sintering was investigated. Improvements in nickel recoveries were obtained when 1 wt% S was added to the nickel-bearing serpentine ore prior to the reduction roasting. Characterisation of the reduced and leached ore samples indicated that this improved Ni recovery with S addition is due to the formation of a leachable nickel sulphide phase, and the suppression of sintering and recrystallisation of the olivine phase formed at high reduction temperatures.

Fundamental experimental investigations have been conducted to study the effect of Al2O3 on the equilibria between the gas phase (CO-CO2-SO2-Ar) and slag-matte-tridymite phases in the Cu-Fe-O-S-Si-Al system at 1573 K (1300 °C) and P(SO2) = 0.25 atm. The experimental technique used is based on equilibration, rapid quenching and electron probe x-ray microanalysis. New experimental data have been obtained for the four-phase gas-slag-matte-tridymite equilibria system for a range of alumina concentrations up to 20.4 mass% in the slag phase as a function of matte grade, including the concentrations of dissolved sulphur and copper in slag, and Fe/SiO2 ratios in slag. The results obtained for 1573 K (1300 °C) are also used to analyse the effect of temperature on phase equilibria in the range of conditions investigated to that of reported for 1473 K (1200 °C) in the literature. The results obtained show that the concentrations of sulphur, copper and “FeO” in slag decrease with increase of Al2O3 concentration in slag while it has no detectable effect on concentration of sulphur in matte for a given matte grade. The new data provided in the present study are of direct relevance to the pyrometallurgical processing of copper and will be used as an input for optimisation of the FactSage thermodynamic database for the copper-containing, multi-component multi-phase system.

Understanding the significance of magnesia as a common component in copper processing slags is essential for optimisation of the industrial copper production. Fundamental experimental studies have been undertaken to determine the effect of MgO on the equilibria between the gas phase (CO-CO2-SO2-Ar) and slag-matte-tridymite phases in the Cu-Fe-O-S-Si-Mg system at 1473 K (1200 °C) and 1573 K (1300 °C), and P(SO2) = 0.25 atm. The experimental methodology used was based on equilibration, quenching and microanalysis. New experimental data have been obtained for the four-phase gas–slag–matte–tridymite equilibria system for a range of MgO concentrations up to 3.1 wt pct in the slag phase as a function of matte grade, including the concentrations of dissolved sulphur and copper in slag, and Fe/SiO2 ratios in slag. The results are also used to analyse the effect of temperature on phase equilibria in the range investigated. The results obtained showed that dissolution of sulphur, copper and “FeO” in slag decreases with increase of MgO in slag while it has no detectable effect on concentration of sulphur in matte. Also, dissolved copper and sulphur in slag increases when temperature increases while the Fe/SiO2 ratio in slag is greater at 1473 K (1200 °C) than 1573 K (1300 °C). The new data provided in the present study are of direct relevance to the pyrometallurgical processing of copper and will be used as an input for optimization of the FactSage thermodynamic database for the copper-containing multi-component multi-phase system.

The present article continues the series reviewing the thermochemistry of complex multicomponent pyrometallurgical systems. The recovery of multiple metals through the Pb-based primary and recycling processes is an economic driving force for the circular economy of the future. In this study, equilibrium distributions of Ag, Au, Bi, and Zn between PbO–FeO–Fe2O3–SiO2 silica saturated slag and Pb metal phases were investigated experimentally, using high-temperature equilibration followed by rapid quenching. The measurement of phase compositions was done using microanalytical methods. Electron Probe X-ray Microanalysis (EPMA) was applied for those elements which present at relatively high concentrations. The Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) was used to measure very low concentrations of Ag and Au in slag. The starting mixtures of materials were planned using FactSage software and preliminary thermodynamic database to target specific proportions of phases and concentrations of Pb in slag after the achievement of equilibrium. Measured slag/metal distribution coefficients follow the sequence Zn ≫ Ag > Bi ≫ Au. Newly obtained results were critically assessed and used to improve the thermodynamic database. Integration between experiments and thermodynamic database development permits cross-analysis of distribution coefficients obtained in the present study with the parallel measurements of distribution in copper-based systems. The liquid slag phase was described using a two-sublattice Modified Quasichemical Model (MQM). Single sublattice MQM was applied for the liquid metal phase.

Fundamental studies have been undertaken to determine the microstructural and phase transformations occurring during the reduction roasting of saprolite ores. Laboratory studies have been undertaken to simulate the conditions occurring during the reduction roast step of the Caron Process. Selected serpentine samples have been treated at temperatures between 500°C and 800°C in H/N gas mixtures, and leaching tests on the reduced samples have been undertaken. Phase and microstructural changes have been characterised using X-ray Powder Diffraction (XRD), Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) techniques. A series of complex physical, microstructure and phase changes has been shown to occur during reduction roasting involving: (i) the dehydration of serpentine, (ii) the formation of a high-silica amorphous phase, (iii) the formation of Ni-Fe nanoparticles, and (iv) the nucleation, growth and recrystallisation of the forsterite (olivine) phase. The principal mechanism of removal of nickel from the reduced ore has been shown to occur through the selective leaching of the Ni-Fe alloy nano-particles from the surfaces in the product oxide.

Phase equilibria in the CaO-ZnO-Fe2O3 system have been investigated at 1483-1673 K (1210-1400 °C) for oxide liquid in equilibrium with air and solid oxide phases: (a) zincite (Zn,Fe,Ca)O1+x; (b) spinel (Zn,Fe,Ca)Fe2O4; (c) lime (Ca,Zn)O; (d) calcium ferrites dissolving zinc oxide: brownmillerite Ca2(Fe,Zn)2O5−x, and calcium diferrite (Ca,Zn)Fe4O7. High-temperature equilibration on inert metal (platinum) substrates, followed by quenching and direct measurement of the Ca, Zn and Fe concentrations in the phases with the electron probe x-ray microanalysis (EPMA) has been used to accurately characterize the system in equilibrium with air. All results are projected onto the CaO-ZnO-“FeO1.5” plane for presentation purposes. The present paper presents systematic characterization of liquidus over a wide range of compositions in this system in equilibrium with air.

The phases and the phase assemblages present in selected industrial iron ore sinters have been analysed. A new experimental laboratory-based procedure has been developed that enables sintering experiments to be undertaken under controlled temperature and gas conditions. The results indicate that the formation of the complex silico ferrite of calcia and alumina phase (SFCA) phase is strongly influenced by the sinter bulk composition. Within the range of compositions of interest to industrial iron ore sintering, an increase of CaO/SiO ratio facilitates the growth of the SFCA phase and the addition of AlO increases the stability of the SFCA at elevated temperatures. Decreasing the oxygen partial pressure not only decreases the liquidus temperature but also lowers the relative stability of the SFCA phase. These observations are consistent with results obtained from phase equilibria studies of these systems, and indicate clear links between phase equilibria, melt solidification processes and sinter product microstructures.

Assessment of literature data, experimental study and thermodynamic modeling of the Pb-As and Cu-Pb-As systems are presented. These chemical systems are of importance for metallic lead refining at 330-500 °C (603-773 K), and for separation of copper from lead in complex polymetallic processes at 1000-1150 °C (1273-1423 K). Few studies are available for the solubility of solid copper arsenide in lead at low temperature. At high temperature, significant discrepancies between available experimentally measured limits of two-liquid miscibility gap exist in the Cu-Pb-As system. Experimental investigation of the present study aimed to fill the gaps and resolve the discrepancies. It consists of equilibration, quenching and electron probe microanalysis. Thermodynamic modeling helped to analyze the results and provided a database of model parameters. Present study is a part of a larger research program aimed at characterization of phase equilibria, heat balance and distribution of elements during complex copper and lead smelting, refining and recycling.

Phase equilibria of the Pb-Cu-Si-O system have been investigated in the range 933-1938 K (660-1665 °C) for oxide liquid (slag) in equilibrium with solid Cu metal, liquid Pb-Cu alloy, or both solid and liquid metals, and solid oxide phases: (a) quartz, tridymite, cristobalite (SiO2); (b) cuprite (Cu2O); (c) lead silicates (PbSiO3, Pb2SiO4, Pb11Si3O17); (d) lead oxide (massicot, PbO); and (e) copper plumbite (Cu2PbO2). High-temperature equilibration on silica or copper substrates, followed by quenching and direct measurement of Pb, Cu and Si concentrations in the liquid and solid phases with the electron probe x-ray microanalysis (EPMA) has been used to accurately characterize the system in equilibrium with Cu or Pb-Cu metal. All results are projected onto the PbO-“CuO0.5”-SiO2 plane for presentation purposes. The present study is a continuation of the previous investigation of this system by the authors in a part of the silica and cuprite primary phase fields. Present data were later used to develop the thermodynamic models for all phases in this system.