Distribution of Bi Between Slags and Liquid Copper

The distribution of Bi between liquid copper and calcium ferrite slag containing 24 wt pct CaO, iron silicate slag with 25 wt pct SiO₂, and calcium iron silicate slags was measured at 1573 K (1300 °C) under controlled CO-CO₂ atmosphere. The experimental results showed that bismuth distribution is affected by the oxygen partial pressure, and bismuth is likely to exist in slags in the 2+ oxidation state, i.e., as BiO. The distribution ratio between calcium ferrite slag and metal was found to be close to that of iron silicate slag. The Bi distribution ratio was found to decrease with increasing SiO₂ and Al₂O₃ content in slag. Increasing temperature was found to decrease the Bi distribution ratio between slag and metal. Using the measured equilibrium data on Bi content of the metal and slag and composition dependence of the activity of Bi in liquid copper, the activity and hence activity coefficient of BiO in the slag was calculated. The close value of activity coefficient of BiO in both slags at the same oxygen partial pressure indicates that the CaO-BiO and SiO₂-BiO interactions are likely to be at the same level, or the FeO _x -BiO interaction is the predominant interaction for BiO in the slag. Therefore at a constant FeO _x content in the slag, the CaO-BiO and SiO₂-BiO interactions doesn’t affect \( \gamma_{\text{BiO}} \) significantly.     

Phase equilibrium and minor-element distribution between Ni3S2-FeS matte and calcium ferrite slag under high partial pressures of SO2

Calcium ferrite slag has been successfully used in the copper smelting process, but no attempt has been made to use it in the nickel smelting process. The phase equilibrium and the distribution of minor elements between the Ni₃S₂-FeS matte and the CaO-FeO_x-based slag (containing about 2 wt pct MgO) in a magnesia crucible were investigated at 1523 K under controlled partial pressures of S₂, O₂, and SO₂ of 10.1, 50.7, and 101.3 kPa, respectively. The results were compared with those for the iron-silicate-based slag, and the following conclusions were obtained: (1) there is no significant difference in the solubility of nickel between both slags in the high-matte-grade range, (2) the dissolution of cobalt in the calcium ferrite slag is clearly smaller than that in the iron silicate slag, (3) detrimental arsenic, antimony, and bismuth are preferentially collected and fixed in the calcium ferrite slag rather than in the iron silicate slag, and (4) it is considered, with regard to technical feasibility, that the use of the calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel converting stage.     

Lead solubility in FeO x -CaO-SiO2 slags at iron saturation

Experiments have been carried out to determine the equilibria between FeO _x -CaO-SiO₂ slag and lead metal in iron crucibles at temperatures ranging from 1473 to 1573 K. It has been found that the highest lead solubilities are observed in the silica-saturated iron silicate slags, while the lowest solubilities are observed in the CaO-saturated calcium ferrite slags. The activity coefficient of PbO varies from 0.15 to 3, depending on the slag composition. Changes in temperature do not have a significant impact on the activity coefficient. The activity of FeO and pct Fe³⁺/pct Fe²⁺ ratios have been determined as a function of slag composition. These new experimental data have been incorporated into an optimized thermodynamic slag model using the computer package FACT.     

The solubility of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> in calcium ferrite slags at 1573 K

Continuous converting of copper matte based on calcium ferrite slag has many attractions for the copper smelting industry. However, a serious drawback is that this slag leads to shorter furnace campaigns because it is aggressive toward the magnesia-chromia refractories that form the furnace lining. As part of an investigation into the causes of this aggressiveness with a view to devising strategies to mitigate it, the solubility of Cr₂O₃ in calcium ferrite slag has been determined. The standard drop-quench experimental technique was employed at a temperature of 1573 K and a relatively high oxygen partial pressure of 3.7×10⁻⁴ atm, conditions similar to those used in continuous converting. It was found that approximately 2 wt pct of Cr₂O₃ can dissolve in calcium ferrite slag under these conditions. The Cr₂O₃ solubility was found to be unaffected by the Cu₂O content of the slag, but may decrease as CaO content decreases. The implications of these findings on the mechanism of attack of magnesia-chromia refractories by calcium ferrite slag are discussed.     

Reactions of dense MgO with calcium ferrite-based slags at 1573 K

The drop-quench technique was used to investigate the solubility of dense MgO in calcium ferrite-based slags (CaO 20 wt pct) under oxygen potentials from 10⁻⁸ to 10⁻⁴ atm at 1573 K. The effect of copper oxide in the slag on the solubility of MgO was also examined in a CO₂ atmosphere. The results showed that MgO solubility in copper-free calcium ferrite slags was generally less than 2 wt pct and it increased with the addition of Cu₂O (up to 28.5 wt pct). It was found that magnesiowustite or magnesioferrite may form at the slag-refractory interface depending on the prevailing oxygen potential. The activity of MgO was estimated through equilibrium between the slag and the solid solution phases. The activity coefficient of MgO was found to be essentially independent of the oxygen potential within the range studied and to decrease from approximately 15 for the copper-free slag to 7 for slags with 28.5 wt pct Cu₂O.     

Influence of CaF<Subscript>2</Subscript> and Li<Subscript>2</Subscript>O on the Viscous Behavior of Calcium Silicate Melts Containing 12 wt pct Na<Subscript>2</Subscript>O

Understanding the viscous behavior of silica-based molten fluxes is essential in maintaining the reliability of steel casting operations and in preventing breakouts. In particular, high concentrations of aluminum in recently developed transformation induced plasticity (TRIP) and twinning induced plasticity (TWIP) steels tend to promote reduction of silica in the mold fluxes that result in the formation of alumina, which in turn increases the viscosity. To counteract this effect, significant amounts of fluidizers such as CaF₂ and Li₂O are required to ensure that mold fluxes have acceptable lubrication and heat transfer characteristics. The viscous behavior of the slag system based on CaO-SiO₂-12 wt pct Na₂O with various concentrations of CaF₂ and Li₂O has been studied using the rotating spindle method to understand the effects on the viscosity with these additives. CaF₂ additions up to 8 wt pct were effective in decreasing the viscosity by breaking the network structure of molten fluxes, but CaF₂ concentrations above this level had a negligible effect on viscosity. Li₂O additions up to 2 wt pct were also effective in decreasing the viscosity, but the effect was comparatively negligible above 2 wt pct. Using Fourier transform infrared (FTIR) analysis of as-quenched slag samples, it was concluded that the viscosity was controlled more effectively by changing the larger complex silicate structures of rings and chains than by changing the amounts of simpler dimers and monomers.     

A thermodynamic study on cobalt containing calcium ferrite and calcium iron silicate slags at 1573 K

Redox equilibria, activities of cobalt, iron and their oxides in calcium ferrite and calcium ironsilicate slags, were measured through metal-slag-gas equilibrium experiments under controlled oxygen potentials (10⁻⁷ to 3 × 10⁻⁷ atm) at 1573 K. Results on the redox equilibria show that addition of CoO to calcium ferrite slag increases the equilibrium Fe³⁺/Fe²⁺ ratio in these melts. Measured activities of CoO and FeO showed positive deviations from ideal behavior, while that of Fe₂O₃ showed negative deviation. Partial substitution of CaO by SiO₂, by up to 4 wt pct SiO₂ in the calcium ferrite based melts, resulted in increases in the activity coefficients of CoO and Fe₂O₃. Phase equilibria studies on the cobalt containing CaO-FeO-Fe₂O₃-SiO₂ slags were also carried out using the drop-quench technique. Good agreement between the activity data and the liquidus temperature with respect to magnetite solid solution containing CoO was observed.     

Confocal Scanning Laser Microscopy Studies of Crystal Growth During Oxidation of a Liquid FeO-CaO-SiO<Subscript>2</Subscript> Slag

The oxidation of FeO in 30 wt pct FeO-35 wt pct CaO-35 wt pct SiO₂ slag was investigated as part of a wider study on the recovery of Fe units through magnetic separation. A confocal scanning laser microscopy (CSLM) technique was used to visualize the oxidation of FeO in the liquid slag. The formation event was observed in situ under the CSLM and the onset of precipitation on a surface of the slag liquid was recorded at various temperatures in an oxidizing atmosphere. A Time-Temperature-Transformation (TTT) diagram was constructed based on the CSLM results. Samples obtained from the CSLM heating chamber were analyzed by a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS).     

Experimental Study of Ferrous Calcium Silicate Slags: Phase Equilibria at {\text{P}}_{{{\text{O}}_{2} }} Between 10?5?atm and 10?7?atm

Ferrous calcium silicate slags, whose principal components are “FeO _x ”-CaO-SiO₂, are widely used in copper smelting and converting operations. In the current study, high-temperature equilibration and rapid quenching techniques were used to study the phase equilibria of the ferrous calcium silicate slags. The compositions of phases in the slags were measured accurately using electron probe X-ray microanalysis (EPMA). The phase equilibria of the system have been characterized at oxygen partial pressures between 10⁻⁵ atm and 10⁻⁷ atm at selected temperatures between 1473 K and 1623 K (1200 °C and 1350 °C). The effects of oxygen partial pressure and temperature on the compositions of phases in the slags are presented.     

Comparison of Ferrous Calcium Silicate Slag and Calcium Ferrite Slag Interactions with Magnesia-Chrome Refractories

The cost of maintaining and eventually replacing refractories as a result of slag attack is a significant cost component in the copper industry. Converting matte to blister copper takes place in reactors lined with direct-bonded magnesia-chrome refractories, and several continuous converting operations use calcium ferrite slag. Unfortunately, the low viscosity of calcium ferrite slag makes it aggressive toward the refractories. Ferrous calcium silicate (FCS) slag has been proposed as a replacement; however, the effect of this slag on magnesia-chrome refractories has not been studied. In this work, the interactions between FCS slag and magnesia-chrome refractory at 1573 K (1300 °C) with an oxygen partial pressure of 10⁻⁶ atm were studied and compared with that experienced with calcium ferrite slag under the same conditions. Both slags penetrated the pores in the refractory and caused compositional change in the chromite spinel intergranular bonding phase through cation interdiffusion, which resulted in cracking and debonding of periclase grains. It was observed that the refractory was penetrated much more deeply by calcium ferrite slag than FCS slag because of the higher surface tension and lower viscosity of calcium ferrite slag. As a result, the refractory was attacked less by FCS slag than it was by calcium ferrite slag. It is concluded that the use of FCS slag in continuous copper converting is likely to extend refractory life.     

Distribution of nickel between copper-nickel and alumina saturated iron silicate slags

The solubility of nickel in slag was determined by equilibrating copper-nickel alloys with alumina-saturated iron silicate slags in an alumina crucible at 1573 K. The experiments were carried out under controlled oxygen partial pressures in the range of 10^-10 to 10^-8 atm by use of suitable CO-CO₂ gas mixtures, and at Fe/SiO₂ ratio 1.34. The results showed that nickel dissolves in slag both as Ni²⁺ (nickel oxide) and Ni‡ (nickel metal), and the relation obtained was: (Wt pct Ni in slag) = (ie33-01) The activity coefficient of nickel oxide (γ^dgNio) and distribution coefficient of nickel (A_Ni) is calculated to be 0.375 and 233.3, respectively. γ^dgNio and A_Ni are found to be independent of oxygen partial pressures. The presence of alumina increases the solubility of nickel in slags.     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature     

The activity coefficient of cobalt oxide in silica-saturated iron silicate slags

The solubility of cobalt oxide in silica-saturated iron silicate slags (1.16 to 10.00 wt pct) in equilibrium with cobalt-gold-iron alloys (1.10 to 6.52 wt pct cobalt) and oxygen pressures of 10₋₉ to 10₋₁₀ atm (1 atm = 1.013 x 105 Pa) has been investigated at 1573 K. The activity coefficient of cobalt oxide, γ_CoO, has been calculated relative to pure solid cobalt oxide as standard, namely, γ_CoO = 0.91 ± 0.09 and a relationship derived between weight percent cobalt in slag, Co (wt pct), oxygen pressure, pO₂, and activity of cobalt relative to liquid cobalt,aCo, namely, Co (wt pct) = 1.32 x 10⁶ pO ₂ ^1/2 a_Co ± 10 pct Both errors are calculated at the 95 pct confidence level. Formerly Senior Lecturer in Pyrometallurgy, Murdoch University, Murdoch, Western Australia Formerly Postgraduate Student, Murdoch University, Murdoch, Western Australia     

Kinetics of CO-CO<Subscript>2</Subscript> reaction with CaO-SiO<Subscript>2</Subscript>-FeOx melts

Measurements of the rate of interfacial reaction between CO₂-CO mixtures and CaO-SiO₂-FeOx slags have been made using the ¹³CO₂-CO isotope exchange technique. Ranges of slag compositions from 0 to 100 wt pct ‘FeO’ and CaO/SiO₂ between 0.3 and 2.0 were examined in the experiments. For each slag, the dependence of the apparent rate constant on temperature and equilibrium oxygen potential was studied. The relationship between the rate constant and oxygen potential was found to be in the form k _a=k _a ^o (a_o)^-α. The parameter a, with values between 0.5 and 0.9, was dependent on the slag composition. The activation energy of the reaction was independent of iron oxide content and dependent on slag basicity.     

Effect of MgO on Liquidus Temperatures in the ZnO-“FeO”-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-SiO<Subscript>2</Subscript>-MgO System in Equilibrium with Metallic Iron

The phase equilibria in the ZnO-“FeO”-Al₂O₃-CaO-SiO₂-MgO system have been determined experimentally in equilibrium with metallic iron. Synthetic slags were equilibrated at a high temperature, quenched, and then the compositions of the phases in equilibrium were measured using electron probe X-ray microanalysis. Pseudoternary sections of the form ZnO-“FeO”-(Al₂O₃ + CaO + SiO₂) for CaO/SiO₂ = 0.71, (CaO + SiO₂)/Al₂O₃ = 5 and fixed MgO concentrations of 2, 4, and 6 wt pct have been constructed. Wustite (Fe²⁺,Mg,Zn)O and spinel (Fe²⁺,Mg,Zn)O·(Al,Fe³⁺)₂O₃ are the major primary phases in the temperature and composition ranges investigated. The liquidus temperatures are increased by 140 K in the wustite primary phase field and by 70 K in the spinel primary phase field with the addition of 6 wt pct MgO in the slag. The partitioning of MgO and ZnO between the solid and liquid phases has been discussed.     

A Sulfide Capacity Prediction Model of CaO-SiO2-MgO-FeO-MnO-Al2O3 Slags during the LF Refining Process Based on the Ion and Molecule Coexistence Theory

A sulfide capacity prediction model of CaO-SiO₂-MgO-FeO-MnO-Al₂O₃ ladle furnace (LF) refining slags has been developed based on the ion and molecule coexistence theory (IMCT). The predicted sulfide capacity of the LF refining slags has better accuracy than the measured sulfide capacity of the slags at the middle and final stages during the LF refining process. Increasing slag binary basicity, optical basicity, and the Mannesmann index can lead to an increase of the predicted sulfide capacity for the LF refining slags as well as to an increase of the sulfur distribution ratio between the slags and molten steel at the middle and final stages during the LF refining process. The calculated equilibrium mole numbers, mass action concentrations of structural units or ion couples, rather than mass percentages of components, are recommended to represent the slag composition for correlating with the sulfide capacity of the slags. The developed sulfide capacity IMCT model can calculate not only the total sulfide capacity of the slags but also the respective sulfide capacity of free CaO, MgO, FeO, and MnO in the slags. The comprehensive contribution of the combined ion couples (Ca²⁺ + O²⁻) and (Mn²⁺ + O²⁻) on the desulfurization reactions accounts for 96.23 pct; meanwhile, the average contribution of the ion couple (Fe²⁺ + O²⁻) and (Mg²⁺ + O²⁻) only has a negligible contribution as 3.13 pct and 0.25 pct during the LF refining process, respectively. The oxygen activity of bulk molten steel in LF is controlled by the [Al]–[O] equilibrium, and the oxygen activity of molten steel at the slag–metal interface is controlled by the (FeO)–[O] equilibrium. The ratio of the oxygen activity of molten steel at the slag–metal interface to the oxygen activity of bulk molten steel will decrease from 37 to 5 at the initial stage, and further decrease from 28 to 4 at the middle stage, but will maintain at a reliable constant as 5 to 14 at the final stage during the LF refining process. The proposed high-oxygen potential layer of molten steel beneath the slag–metal interface can be quantitatively verified.     

Liquidus Temperatures in the “Cu<Subscript>2</Subscript>O”-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO System at Molten Metallic Copper Saturation

Calcium ferrite slags, which are represented by the “Cu₂O”-FeO-Fe₂O₃-CaO system at copper saturation, have been applied successfully to existing copper-converting processes. Because of the industrial importance of this system, the characterization of the effects of oxygen partial pressure and silica on the phase equilibria is necessary to improve the control of process parameters, which include fluxing and operating temperatures. In the current study, experimental methods, which use the equilibration/quenching/electron probe X-ray microanalysis (EPMA) techniques with primary phase substrate support, were subsequently developed to incorporate fixed oxygen partial pressure experiments. Experiments were carried out at 1200 °C and 1250 °C both with and without silica additions; both liquidus and solidus data were reported for the primary phase field of spinel and dicalcium ferrite between the oxygen partial pressures of 10^−5.0 and 10^−6.5 atm. The analyzed compositions of the liquid and solid phases are used to construct the phase diagram of the pseudoternary “Cu₂O”-“Fe₂O₃”-CaO system in equilibrium with metallic copper at fixed oxygen partial pressures and with additions of silica. The maximum solubility of silica within the liquid slag phase, prior to dicalcium silicate precipitation, was measured at specific conditions. Two empirical equations used for the calculation of the copper oxide concentration in calcium ferrite slag are evaluated with the new experimental data defined in the current study.