Nitrogen solubility in CaO-CaF2-SiO2 melts

The preceding paper^[5] demonstrated that nitrogen dissolves in silicate melts either as a free ion or complex anion, being incorporated into silicate networks. In the present study, the influence of CaF₂ addition to CaO-SiO₂ melts on the nitrogen solubility was investigated along the liquidus at 1573 K and within the liquidus at 1723 K at constant CaF₂ levels. In the latter case, as the SiO₂ content increases from CaO saturation, the total nitrogen content decreases to reach the minimum and then starts to increase up to the SiO₂ saturation. This is in accord with the abovementioned mechanism of nitrogen dissolution, which is supported by the changing behavior of free and incorporated nitrogen contents with the slag composition. The role of CaF₂ is complicated through the formation of fluorosilicates. The CaF₂ seems not to function simply as a diluent but to enhance the dissolution of nitrogen by releasing oxygen from silicate networks, promoting the formation of free nitride ions. Formerly Graduate Student, Department of Metallurgy, The University of Tokyo.     

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.     

The Effects of CaF2, Basicity, and Atmospheric Conditions on the Solubility of Carbon and Nitrogen in the CaO-SiO2-Al2O3-Based Slag System

The solubility of carbon and nitrogen in the CaF₂-CaO-SiO₂-Al₂O₃ slag system was studied. The effects of the CaF₂, extended basicity (CaO/(SiO₂ + Al₂O₃)), and atmospheric conditions on the dissolution behavior of the carbon and nitrogen, as well as the correlations of the behaviors with the slag structure observed at 1773 K (1500 °C), are presented. Increases in the extended basicity and the CaF₂ increased the solubility of carbon in the slag. In the case of nitrogen dissolution, a characteristic parabolic curve with an identifiable minimum was observed for the slag. This curve shape correlated with a change in the dominant mechanism of dissolution from an incorporated to a free nitride. The solubility of carbon in the mixture of CO with N₂ was significantly higher than that of carbon in the mixture of CO with Ar and is likely due to the formation of cyanide. Thus, when carbon is present in significant quantities in the slag, the solubility of nitrogen in the slag increases. The degree of depolymerization of the slag with increased content of CaO/(SiO₂ + Al₂O₃) and CaF₂ was verified using Fourier transform infrared and Raman spectroscopy.     

Modeling Viscosities of CaO-MgO-FeO-MnO-SiO2 Molten Slags

A model for estimating the viscosity of silicate melts is proposed in this article. The structural characteristics of a silicate slag can be described by the numbers of the bridging oxygen, nonbridging oxygen, and free oxygen present in the slag. A method of calculating the numbers of the different types of oxygen ions is presented in this article, which involves a simple approximation of “complete bridge breaking.” With just a few parameters, the model provides both the temperature and composition dependencies of viscosity for the pure component: SiO₂; the binary systems: MgO-SiO₂, CaO-SiO₂, FeO-SiO₂, and MnO-SiO₂; the ternary systems: CaO-MgO-SiO₂, CaO-FeO-SiO₂, MgO-FeO-SiO₂, and CaO-MnO-SiO₂; and the quaternary systems: CaO-MgO-MnO-SiO₂ and CaO-FeO-MnO-SiO₂. It was found that the ability of different basic metal oxides to decrease viscosity varies and is in the following hierarchy: FeO > MnO > CaO > MgO. Two factors influence the viscosity: The first is related to the mutual interaction among different ions, and the stronger the interaction, the higher the viscosity. The second factor is the size (radius) of basic oxide cation, with viscous flow becoming increasingly more difficult (i.e., viscosity increases) as the cation size increases. However, there is a paradox in the effect of cation radius (of the basic oxide) on the two factors. Thus, varying cation size causes competitive effects; smaller cationic radii give stronger interactions among ions but less hindrance to viscous flow (and vice versa for large cation radii).     

Thermodynamics of Arsenic in FeOx-CaO-SiO<Subscript>2</Subscript> Slags

The distribution of arsenic between calcium ferrite slag and liquid silver (wt pct As in slag/ wt pct As in liquid silver) with 22 wt pct CaO and between iron silicate slag with 24 wt pct SiO₂ and calcium iron silicate slags was measured at 1573 K (1300 °C) under a controlled CO-CO₂-Ar atmosphere. For the calcium ferrite slags, a broad range of oxygen partial pressure (10^–11 to 0.21 atm) was covered, whereas for the silicate slags, the oxygen partial pressure was varied from 10^–9 to 3.1 × 10^–7 atm. The measured relations between the distribution ratio of As and the oxygen partial pressure indicates that the oxidation state of arsenic in these slags is predominantly As³⁺ or AsO_1.5. The measured distribution ratio of arsenic between the calcium ferrite slag and the liquid silver was about an order of magnitude higher than that of the iron silicate slag. In addition, an increasing concentration of SiO₂ in the calcium-ferrite-based melts resulted in decreases in the distribution of arsenic into the slag. Through the use of measured equilibrium data on the arsenic content of the metal and slag in conjunction with the composition dependent on the activity of arsenic in the metal, the activity of AsO_1.5 in the slags was deduced. These activity data on AsO_1.5 show a negative deviation from the ideal behavior in these slags.     

A thermodynamic study of dephosphorization using BaO-BaF2, CaO-CaF2, and BaO-CaO-CaF2 systems

Phosphorus partition ratios between BaO-BaF₂ fluxes and copper-phosphorus alloys have been measured as a function of slag composition at 1400 °C. A molybdenum sleeve has been used to avoid contact between the slag and the crucible in order to prevent the absorption of slag by the graphite crucible. The effects of additions of BaO to the CaO-CaF₂ system have been investigated by measuring the phosphorus partition ratios between these fluxes and Fe-C_sat-P alloy as a function of slag composition at 1400 °C. Also, the activity of BaO as a function of slag composition at 1400 °C has been determined by equilibrating a silver-barium alloy with the BaO-CaO-CaF₂ fluxes and CO in a graphite crucible. The results indicate that phosphorus partition ratios with carbon-saturated iron, L_P, for the BaO-BaF₂ system are relatively high, going up to 400, even for oxygen partial pressure as low as 7.8 × 10⁻¹⁶ atm. The phosphate capacity and the activity coefficient of PO_2.5 for this system were calculated from the experimental results using the available thermodynamic data. No effects of barium oxide addition in lime-based fluxes were observed for BaO contents less than 40 pct. One of the reasons for this phenomenon is that BaO activity in a lime-based flux is very small for BaO content less than 46 pct. However, for high BaO contents, increases significantly, as does the activity of BaO. Formerly Research Associate, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

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.     

Solubility of nitrogen in CaO-SiO2-CaF2 slag system

Equilibrium experiments between gas and slag were carried out to understand the thermodynamic behaviour of nitrogen in the CaO-SiO₂-CaF₂ slag system at 1600°C. The solubility of nitrogen in this slag system increased as the oxygen potential decreased and as the reaction temperature increased. The values of the nitride capacity have a minimum at about 2.0 slag basicity, having higher values in both more acidic and basic regions. This may be explained by two mechanisms for nitrogen dissolution; incorporated nitride ion and free nitride ion state. In slag with 2.0 basicity or less, MgO content increased the nitride capacity slightly. At higher slag basicity, however, nitride capacity decreased with MgO content. The effects of BaO to substitute CaO on nitride capacity showed similar behaviour as MgO. This complex relationship between basicity of slag and nitride capacity is explained by using optical basicity. It was found that nitride capacity and optical basicity had a close relationship even in the different basic oxide systems.     

The Viscous Behavior of FeO<Subscript>t</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Copper Smelting Slags

Understanding the viscous behavior of copper smelting slags is essential in increasing the process efficiency and obtaining the discrete separation between the matte and the slag. The viscosity of the FeO_t-SiO₂-Al₂O₃ copper smelting slags was measured in the current study using the rotating spindle method. The viscosity at a fixed Al₂O₃ concentration decreased with increasing Fe/SiO₂ ratio because of the depolymerization of the molten slag by the network-modifying free oxygen ions (O²⁻) supplied by FeO. The Fourier transform infrared (FTIR) analyses of the slag samples with increasing Fe/SiO₂ ratio revealed that the amount of large silicate sheets decreased, whereas the amount of simpler silicate structures increased. Al₂O₃ additions to the ternary FeO_t-SiO₂-Al₂O₃ slag system at a fixed Fe/SiO₂ ratio showed a characteristic V-shaped pattern, where initial additions decreased the viscosity, reached a minimum, and increased subsequently with higher Al₂O₃ content. The effect of Al₂O₃ was considered to be related to the amphoteric behavior of Al₂O₃, where Al₂O₃ initially behaves as a basic oxide and changes to an acidic oxide with variation in slag composition. Furthermore, Al₂O₃ additions also resulted in the high temperature phase change between fayalite/hercynite and the modification of the liquidus temperature with Al₂O₃ additions affecting the viscosity of the copper smelting slag.     

Thermodynamics of chromium oxides in CaO-SiO2-CaF2 slag

The distribution ratio of chromium between a CaO-SiO₂-CaF₂ slag and liquid silver under the oxygen partial pressure used in practical hot-metal dephosphorization treatment was measured at 1623 K. The distribution ratio was minimal when the basicity index of a slag, wt pct CaO/wt pct SiO₂, was about 2. The redox equilibrium between CrO (Cr²⁺) and CrO_1.5 (Cr³⁺) in the slag was also measured as a function of slag composition. The calculated activity coefficient of CrO had a maximum value at wt pct CaO/wt pct SiO₂=2, whereas that of CrO_1.5 decreased monotonously with the increase in slag basicity.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the MnO-TiO2, MgO-TiO2, FeO-TiO2, Ti2O3-TiO2, Na2O-TiO2, and K2O-TiO2 systems

All available thermodynamic and phase diagram data have been critically assessed for all phases in the MnO-TiO₂, MgO-TiO₂, FeO-TiO₂, Ti₂O₃-TiO₂, Na₂O-TiO₂, and K₂O-TiO₂ systems at 1 bar pressure from 298 K to above the liquidus temperatures. All reliable thermodynamic and phase diagram data have been simultaneously optimized to obtain, for each system, one set of model equations for the Gibbs energy of the liquid slag as a function of composition and temperature and equations for the Gibbs energies of all compounds as functions of temperature. The modified quasichemical model was used for the molten slag phases.     

Effect of the Slag Composition and a Protective Atmosphere on Chemical Reactions and Non‐Metallic Inclusions during Electro‐Slag Remelting of a Hot‐Work Tool Steel

The remelting behavior of the hot‐work tool steel X37CrMoV5‐1 is investigated with several experimental melts on a lab‐scale ESR‐plant. The investigated parameters comprise a variation of the slag compositions and the use of a protective nitrogen atmosphere. Variations of the slag composition include slags with different contents of CaF₂, CaO, and Al₂O₃ as well as a variation of the SiO₂‐content in the slag. The remelted ingots are forged and analyzed regarding their chemical composition. The distribution and composition of the non‐metallic inclusions (NMI) is studied by an automated SEM‐EDX method. Additionally, the chemical composition of the slag after remelting is analyzed. The results show clearly an equilibrium reaction between Si and Al in the steel with SiO₂ and Al₂O₃ in the slag as well as the effect of oxygen in open ESR operation. A protective atmosphere reduces the Si‐losses during remelting, but has no major effect on the number or composition of NMI compared to open remelting. The content of NMI, especially the larger ones, is reduced significantly in all remelting experiments. The majority of the NMI are MA‐spinel type except for the CaO‐free slag, where alumina inclusions prevail. In general, remelting leads to an almost complete removal of sulfides, a reduction of oxisulfides, and a slight increase of oxides.     

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.     

Kinetic studies on the dissolution of nitrogen in CaO-Al2O3, CaO-SiO2, and CaO-CaF2 melts

The rate of nitrogen dissolution in CaO-Al₂O₃, CaO-SiO₂, and CaO-CaF₂ melts was measured by ¹⁴N-¹⁵N isotope exchange reaction. The rate constant of nitrogen dissolution in CaO-based oxide melts, which is defined as first order with respect to nitrogen partial pressure, was found to be much smaller than that in molten iron-based alloys investigated in our previous work. The activation energies for nitrogen dissolution in 40 mass pct CaO-60 Al₂O₃ and 50 CaO-50 SiO₂ melts are 224 and 581 kJ/mol, respectively. For CaO-Al₂O₃ and CaO-SiO₂, dependence of the rate constant on composition is very similar to that of nitride capacities. Moreover, it was confirmed that the rate constant was not affected by oxygen or nitrogen partial pressure.     

Physicochemical Properties of CaO–SiO2–CaF2–NaF Slag system as a Mold Flux of Continuous Casting

The phase diagrams of CaO–SiO₂–CaF₂ and CaO–SiO₂–CaF₂–NaF systems were determined as a base system of mold fluxes. The commercial fluxes have the composition in which cuspidine first crystallizes. The thermodynamic stability of cuspidine was examined from the standard Gibbs energy of formation of cuspidine, which was measured, by two methods of the Galvanic cell method and the transpiration method. The effect of fluorine to silicate network was investigated. It is indicated that CaF₂ behaves as a neutral solvent for silicate slag. The crystallization in mold fluxes was measured by a high temperature XRD. Cuspidine predominantly appears because the construction of silicate glass with CaF₂ has CaF⁺ ion pair near non‐bridging oxygen. The over addition of Na₂O to mold flux prevents cuspidine from crystallizing.     

Critical evaluation and optimization of the thermodynamic properties and phase diagrams of the CaO-Al2O3, Al2O3-SiO2, and CaO-Al2O3-SiO2 systems

All available thermodynamic and phase diagram data have been critically assessed for all phases in the CaO-Al₂O₃, Al₂O₃-SiO₂, and CaO-Al₂O₃-SiO₂ systems at 1 bar pressure from 298 K to above the liquidus temperatures. All reliable data for the binary systems have been simultaneously optimized to obtain, for each system, one set of model equations for the Gibbs energy of the liquid slag and all solid phases as functions of composition and temperature. The modified quasichemical model was used for the slag. With these binary parameters and those from the optimization of the CaO-SiO₂ system reported previously, the quasichemical model was used to predict the thermodynamic properties of the ternary slag. Two additional small ternary parameters were required to reproduce the ternary phase diagram and ternary activity data to within experimental error limits. The calculated optimized phase diagram and thermodynamic properties are self-consistent and are the most reliable currently available estimates of the true values.     

Nitrogen solution in BaO-B2O3 and CaO-B2O3 slags

The nitrogen solubility and nitride capacity of the BaO-B₂O₃ and CaO-B₂O₃ systems were measured at 1698 and 1773 K, respectively, using a gas-liquid equilibration technique. These systems were chosen because they have wide liquidus regions at the temperature of interest and were expected to show two types of nitride solution behavior. The nitride capacities of both systems showed minimum values with changing composition. This was explained by considering that nitrogen can dissolve into slag as “free nitride” at high basicities and as “nitride incorporated” with the network for acidic slags. The change of the nitride capacity with optical basicity and the activity of the basic component followed the predicted behavior for the proposed solution mechanism. The nitride capacity of the BaO-B₂O₃ system is considerably greater than for the CaO-B₂O₃ system because BaO is a more basic oxide than CaO. The activity of BaO in the BaO-B₂O₃ system was also measured by equilibration with liquid silver, at known oxygen potentials, and the activities show large negative deviations from ideal behavior.     

Distribution behavior of cobalt, selenium, and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag

The distribution coefficients (D _X) of cobalt, selenium, and tellurium between nickel-copper-iron matte and silica-saturated iron silicate slag were determined as a function of matte and slag compositions, temperature, and the partial pressure of oxygen. The effect of slag additives, such as CaO, MgO, and Al₂O₃, on the distribution behavior of the minor elements was also investigated. Analysis of the data indicated that D _Co, D _Se, and D _Te were strongly dependent on the matte grade and slag additives. The effect of slag additives on the solubility of Co, Se, and Te in slag was discussed in terms of various experimental conditions. Cobalt distribution coefficients were found to decrease with increasing oxygen partial pressure, indicating the oxidic dissolution of cobalt in the slag. Based on the experimental results and available thermodynamic data, the activity coefficients of CoS in the nickel-copper-iron matte were estimated as a function of mole fraction of FeS in the matte at 1250 °C. Meanwhile, the distribution coefficients of both selenium and tellurium increased when raising the partial pressure of oxygen, implying that there was molecular dissolution of selenium and tellurium in the slag within the oxygen partial-pressure range investigated in this study.     

Phosphate capacity of CaO-AI2O3 slags containing CaF2, BaO,Li2O,or Na2O

Phosphorus partition ratios between CaO-Al₂O₃ and CaO-Al₂O₃-CaF₂ fluxes and Fe-C_sat-P alloys have been measured as a function of slag composition at 1500 °C. The effects of additions of BaO, Li₂O, and Na₂O to the CaO-Al₂O₃-CaF₂ system on the phosphorus partition ratios at 1400 °C and 1300 °C have been measured. From the partition ratio, and assuming that the oxygen potential is controlled by C-CO equilibrium, the phosphate capacities of the fluxes were calculated. Also, the activities of Li₂O and Na₂O were measured as a function of slag composition at 1300 °C by equilibrating the flux and the metal with Pb-Li or Pb-Na alloy and CO in a graphite crucible. The results indicate that phosphorus partition ratios with carbon-saturated iron and the phosphate capacities for additions of more basic oxides decrease in the following order: Na₂Oτ;Li₂Oτ;BaO. The activities of Li₂O and Na₂O in calcium aluminate fluxes have large negative deviations from ideal behavior; the activity coefficients at infinite dilution are on the order of 0.05 and 10^-5, respectively. Formerly Graduate Student, Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

Cryoscopic studies in fluoride-Oxide-Silica systems: Part II. systems containing Mg2+, Ca2+, Ba2+ and Pb2+

The depressions of the freezing temperatures of MgF₂, CaF₂, and BaF₂ by adding 2MO · SiO₂, 3MO · 2SiO₂, MO · SiO₂, 2MO · 3SiO₂, and MO · 2SiO₂ where M = Mg, Ca and Ba, have been measured, as have the depressions of the freezing temperature of PbF₂ resulting from additions of 2Pb · SiO₂, 3PbO · 2SiO₂ and PbO · SiO₂. The variations of the activities of the fluorides with liquidus composition have been calculated. These are shown to be in good agreement with a proposed theoretical model of the constitutions of these melts. In the alkaline earth systems with MO/SiO₂ > 1.5 linear chain silicate ions and free F⁻ ions are postulated and in melts of MO/SiO₂ < 1.5 reaction between F⁻ and silicate ions to form polyfluorosilicate anions is postulated. These conclusions are in agreement with those drawn from infrared absorption studies of CaF₂-CaO-SiO₂ glasses. The activity behavior in the reciprocal systems MF₂-M′O · SiO₂ and M′F₂-MO · SiO₂ is explained in terms of polymerization and preferred ionic association effects within the melts. In the lead fluoride-silicate systems fluorination of the silicate ions occurs at PbO/SiO₂ = 2 and, in contrast with the alkali and alkaline earth systems, it appears that polyfluorosilicate anions and free O²⁻ anions can coexist in lead fluorosilicate melts.