Thermodynamic behaviour of Cu in molten Fe‐C‐S alloys at high temperatures

The activity of Cu in molten Fe‐C‐S alloys at high temperatures was measured by a thermochemical equilibration technique. The effects of the contents of Cu, C, and S in the molten alloy as well as temperature on the activity coefficient of Cu in pure and carbon‐saturated iron were determined by measuring the distribution ratio of Cu between molten silver and Fe‐C‐S alloy melts. In molten pure iron and carbon‐saturated iron, the activity coefficient of Cu under infinite dilution, was measured as 11.0 and 28.5, respectively, at 1823K. The interaction parameters between Cu and Cu, S, C in the molten iron at 1823K were estimated: . The dependence of in molten Fe‐C alloy on temperature was determined as follows: pure iron: , carbon‐saturated iron: . Combining the effects of temperature and those of alloying components, the activity coefficient of Cu in the molten Fe‐C‐S alloy could be estimated as follows: .     

Thermodynamic Behaviour of Chlorine in CaO‐SiO2‐MgO‐Al2O3(‐CaF2) Slags

The solubility of chlorine in CaO‐SiO₂‐Al₂O₃‐MgO(‐CaF₂) slag was measured at 1673 ‐1823 K. By estimating the chloride capacity of slags, thermodynamic behaviour of chlorine in the molten slag was investigated. Chloride capacity increased with increasing CaO / SiO₂ ratio (C/S). An increase in MgO content decreased chloride capacity at C/S≥1.0 because it lowered the activity of Ca²⁺ which seemed to have strong affinity with Cl^? in molten slag. Also, the chloride capacity decreased with increasing Al₂O₃ content. The affinity between the Ca²⁺ and Cl^? ions was confirmed by measuring the infrared spectra of slags. The dissolution reaction of chlorine into slag was exothermic and its molar enthalpy was evaluated from the experimental results at 1673 ‐ 1823 K. Based on the result obtained in the present study, the quantitative prediction of chlorine distribution during the blast furnace process was performed. It was estimated that almost all chlorine in the blast furnace would be absorbed into molten slag even if the PCI ratio was increased or low quality coal with chlorine content less than 1.0 mass% was injected.     

The Thermodynamic Properties of Fe‐Mn‐C Melt at Reduced Pressure

The solubility of carbon in the Fe‐Mn‐C system was measured under reduced pressure of 1 Pa at 1573 K and 1673 K, respectively. The carbon solubility in terms of mole fraction in the iron based solution was found varying with manganese mole fraction in the solution and with temperature, as x_C= 0.1819 + 0.2531 x_Mn at 1573 K and x_C = 0.1981 + 0.2515x_Mn at 1673K. Manganese has a stronger influence on the carbon solubility at lower pressure than it has at higher pressure. The pressure was found to have an insignificant effect on the carbon solubility when manganese in the melt was absent. The activity interaction parameters between manganese and carbon in the alloy were determined from carbon solubilities at 1573 and 1673 K. Analysis of the experimental results showed that under vacuum conditions, the activity interaction parameter of manganese with carbon is higher than that at atmospheric pressure.     

Thermodynamic properties of La2C3 and Gd2C3 at high temperatures

The enthalpies of lanthanum and gadolinium sesquicarbides were determined in the range 400–1900 K by the method of mixtures. The temperature dependences of the basic thermodynamic properties were calculated and tabulated. The temperatures, enthalpies, and entropies of the peritectic reactions were determined. Institute for Meterials Science Problems, Ukrainian Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 7–8, pp. 59–63, July–August, 1997.     

Influence of alumina and magnesia on phase equilibria in the system Fe‐CaO‐FeOn‐SiO2 at 1600 °C

The phase relations in the systems CaO‐FeO_n‐SiO₂‐Al₂O₃ and CaO‐FeO_n‐SiO₂‐MgO at 1600 °C saturated with liquid iron are described. The phase conditions in the quaternary system with aluminium oxide are so far rather unknown. An addition of aluminium oxide makes the calciumsilicates and lime saturation areas move towards the CaO corner thus enlarging the homogeneous liquidus space accordingly. Aluminium oxide can be considered as a flux in this case. The fields of different solid solutions in the system CaO‐FeO_n‐SiO₂‐MgO were taken into account. Some additional (2 to 4)‐phase areas occur with increasing MgO content. This causes the precipitation of magnesiowustite which dominates the system accordingly. The changed phase relations strongly influence the direction of tie‐lines and their length. Therewith, the correlation between liquid phase and solid phase, calculated via lever rule, is influenced, too.     

Nitrogen solubilities in CaO—CaF2 melts

Nitrogen solubilities in the CaO—CaF₂ system were determined under controlled oxygen partial pressures as well as at carbon saturation. Nitrogen contents (as N^3?) were shown to strongly depend on oxygen partial pressure from 10^?11 to 10^?13 atm. At carbon saturation both nitride and cyanide contents are also dependent on oxygen partial pressure, i.e. CO partial pressure. The dependence of nitride and cyanide contents on nitrogen partial pressure was found to be compatible with the theory and is described by the equations proposed in this paper. The results are also discussed in terms of nitride and cyanide capacities for a better understanding of the dissolution of nitrogen in slags of different composition. The temperature dependence of nitride content showed an increase in nitride content with increasing temperature.     

Dissolution of Lime in Synthetic ‘FeO’‐SiO2 and CaO‐‘FeO’‐SiO2 Slags

Dissolution of different CaO samples into molten synthetic ‘FeO’‐SiO₂ and ‘FeO’‐SiO₂‐CaO slags was carried out in a closed tube furnace at 1873 K. The slag was kept stagnant. It was found that the dissolution rate was very fast when CaO rod was dipped into ‘FeO’‐SiO₂ slag. In the case of ‘FeO’‐SiO₂‐CaO slag, the dissolution of CaO rod in the stagnant slag was retarded after the initial period (2 minutes). Only less than 16 percent CaO reacted with the slag, irrespective of the type of lime. Three phase‐regions were identified in the reacted part of the lime rod by SEM‐EDS analysis. The formation of these regions was explained thermodynamically. A dense layer of 2CaO · SiO₂ was found to be responsible for the total stop of the dissolution. It could be concluded that constant removal of the 2CaO · SiO₂ layer would be of essence to obtain a high dissolution rate of lime. In this connection, it was found necessary to study the dissolution of lime in moving slag to reach a reliable conclusion regarding the relevance of the reactivity obtained by water ATSM test to the real reactivity of lime in high temperature slag.     

Thermodynamics of lead and bismuth in CaO–CaF2 melts

In order to understand a new refining process for removing tramp elements from alloy steels under strongly reducing conditions, the authors previously reported the thermodynamic behaviour of P, Sn, Sb, As and Cu in CaO–CaF₂ melts. In this investigation, the thermodynamic behaviour of Pb and Bi in CaO–CaF₂ melts under oxygen partial pressures from 10^?16 to 10^?20 atm was studied at temperatures ranging from 1360 to 1550°C, using a similar technique. It was shown that Pb and Bi exist in slag mainly as Ca₂Pb and Ca_1.5Bi, respectively, under very low oxygen partial pressure although a part of Pb is soluble in slags as metal. The obtained results were extrapolated to lower oxygen partial pressures to investigate the possibility of removing these tramp elements from molten iron, causing Bi to be removed from molten iron below an oxygen partial pressure of 10^?23 atm, whereas Pb is removed under higher oxygen partial pressures.     

Thermodynamic behaviour of carbon in CaO-SiO2 slag system

In order to understand the thermodynamic behaviour of carbon in steelmaking slag at high temperature, the carbon dissolution into CaO-SiO₂ slag system has been investigated including the effects of temperature and slag components on the carbon dissolution reaction. It was found that carbide solubility in the CaO-SiO₂ slag decreased with increasing oxygen potential to confirm the theoretical relationship of ?1/2, which reflected the ionic exchange reaction mechanism between carbon and oxygen ions. Carbide solubility in slag as a function of slag basicity for various slag systems appeared to confirm this mechanism. This reaction mechanism implied that the carbide dissolution proceeded due to the reaction of solid carbon and oxygen ions supplied from (CaO) in slag. The oxygen ion appears to be the driving force as it is influenced by the slag components as well as the temperature as shown in the concept of the carbide capacity of slag. The solubility of carbide in the CaO-SiO₂ slag increased with the addition of CaF₂; the role of CaF₂ for carbide dissolution into slag could be speculated to have complex effects on indirect increase in basicity in spite of (CaO) dilution. Substitution of CaO by MgO decreased the solubility of carbide in the CaO-SiO₂-MgO slag, possibly caused by the relatively low electro-negativity of MgO.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

Influence of SiO2 Addition on the Properties of Al2O3‐CaO‐CaF2 Slag

The Al₂O₃‐CaO‐CaF₂ slag system is used in making special quality steels by the electro‐slag re‐melting process (ESR). The purpose of our investigation was to analyse ESR slag that contained SiO₂. The slag samples with different SiO₂ fractions (0 ‐ 20 mass %) were examined by chemical analysis, differential thermal analysis, simultaneous thermal analysis, X‐ray diffraction, electron microscopy and wetting angle measurement. With addition of SiO₂ the polymerization of slags was increased due to the formation of new silicate complex compounds that influenced their melting points and wetting angles.     

Thermodynamic behaviours of manganese and phosphorus between CaO‐MgOsat‐SiO2‐Al2O3‐FetO‐MnO‐P2O5 ladle slag and liquid iron

The thermodynamic equilibria of manganese and phosphorus between liquid iron and CaO‐MgO_Sat‐SiO₂‐Fe_tO‐MnO‐P₂O₅‐Al₂O₃ (0–33%) ladle slag have been investigated at 1873 K from the viewpoint of Mn and P yields for the production of high‐strength steels. The equilibrium distribution ratios of Mn and P were found to increase with increasing Fe_tO content; however, these ratios vary with basicity, but they do this the other way round. The addition of alumina into slag at a fixed basicity and Fe_tO content decreases both the equilibrium manganese and phosphorus distributions. The equilibrium distribution ratios were discussed in terms of the variation of activity coefficients of Fe_tO, MnO and PO_2.5, according to the slag basicity and Al₂O₃ content. The quantitative contributions of basicity and (%Fe_tO + %MnO) on L_Mn and L_P were empirically determined and their usefulness was discussed with the aid of plant data: To improve Mn and P yields in the practical RH operation, it is strongly recommended that Fe‐Mn and Fe‐P alloys be added after Al deoxidation treatment inducing relatively high Al₂O₃ in slag and maintaining low Fe_tO content. In addition, a ladle slag composition for the targeted Mn and P contents in liquid iron was substantially estimated using the empirical relationships.     

Thermodynamics of antimony,arsenic, and tin in CaO—CaF2 melts

In view of the importance of tramp element contamination of steel products through a large volume of scrap consumption in the near future, the thermodynamic behaviour of Sb, As, Sn and Cu in CaO—CaF₂ melts under reducing conditions was studied by examining the dependences of distribution of each element between Cu, Ag or Sn alloys and CaO—CaF₂ melts on the CaO activity, oxygen partial pressure and temperature around 1 500°C. As a result, the reaction products on treatment by Ca compounds were demonstrated to be Ca₃Sb₂, Ca₃As₂, Ca₂Sn and CaCu. Experimentally obtained distributions were extrapolated to lower oxygen partial pressures less than 10^?18 atm to estimate the feasibility of removing those tramp elements from molten iron. It is thermodynamically indicated that if the prevailing oxygen partial pressure of the environment is below 10^?23 atm, these impurities, except Cu, would be substantially removed from molten steel.     

The solubility of water vapour in CaO‐SiO2‐Al2O3‐MgO slag system

The solubility of water vapour in the CaO‐SiO₂‐Al₂O₃‐MgO quaternary slag system was measured using an inert gas fusion technique with thermal conductivity detection. The slags were equilibrated with argon‐water vapour mixture corresponding to 0.157 bar of water vapour pressure at 1873 K. The slag solubility of water vapour is proportional to the square root of vapour pressure. Since the hydroxyl capacity of slag, C_OH shows an independence on the relative amount of CaO or MgO in slag, the contributions of CaO and MgO on the hydroxyl capacity are equivalent on a molar basis. Whereas, Al₂O₃ shows a better effect on the hydroxyl capacity than SiO₂. A linear relationship between hydroxyl capacity and slag basicity in logarithmic scale was obtained with the slope of 1/2, confirming the water vapour dissolution reaction into a basic slag as (O^2‐) + H₂O(g) = 2(OH^?). The correlation between hydroxyl capacity and slag components was derived in terms of their contributing weight factors. The measured values of C^'_OH agree well with the calculated ones using the interaction energies of α_H‐Al = ?38300 and α_H‐Mg = ?22700 J determined with the aid of the regular solution model. In addition, the correlation between hydroxyl capacity and sulphide capacity was empirically derived as a formula of logC_OH = 1/2logC_S + (4.38 ± 0.25) through the thermodynamic expression of both capacities by virtue of the common oxygen ion activity.     

Chemical Potentials of Oxygen in Four‐Phase Assemblages of the System CaO‐P2O5‐CaF2‐FexO

In steelmaking processes, because of environmental requirements and health considerations, there is a strong incentive to reduce slag volume. The key to meet this requirement is the better understanding of phosphorus removal, which relies on the knowledge of the thermodynamic properties of slags and fluxes used for dephosphorization. In this study, the liquidus compositions of the four‐phase assemblages in the quaternary system CaO‐P₂O₅‐CaF₂‐Fe_xO were determined at 1573K by employing electron probe microanalysis. Measurements were also made on the Fe_xO activities at temperatures between 1523K and 1673K by employing an electrochemical technique involving stabilized zirconia electrolyte.     

Thermodynamic properties of lanthanum silicides at high temperatures

The enthalpies of five lanthanum silicides were determined over the temperature range 380–2225 K by the method of mixtures. Values of the basic thermodynamic functions of the materials were calculated and tabulated, as well as the temperatures, enthalpies, and entropies of fusion. The temperatures and enthalpies of fusion were related to the relative concentrations of silicon in the compounds.Institute of Materials Science Problems, Ukrainian National Academy of Sciences, Kiev. Translated from Poroshkovaya Metallurgiya, Nos. 3–4, pp. 48–53, April–May, 1994.     

Thermodynamic Activity of Chromium Oxide in CaO‐SiO2‐MgO‐Al2O3‐CrOx Melts

Thermodynamic activities of chromium oxide contained in CaO‐SiO₂‐MgO‐Al₂O₃ melts were measured in the present work using gas‐slag equilibrium technique. The oxygen partial pressure was varied (10^‐3, 10^‐4, 10^‐5 Pa). Gas mixture of CO, CO₂ and Ar were used and investigated at 1803, 1873 and 1923 K. The activities of CrO showed a strong positive deviation from ideality and a decrease with increasing temperature and oxygen partial pressure. A mathematical expression relating the amount of chromium oxide in the slag phase with the activity of Cr in the metal phase based on the present experimental results is presented.     

The oxygen pressure of dilute FexO‐CaO‐Al2O3 slag in equilibrium with liquid iron

The relationship between slag composition and oxygen partial pressure of dilute Fe_xO‐CaO‐Al₂O₃ slag in equilibrium with iron the activity of which is below 1 was extrapolated to give the oxygen partial pressure of a slag equilibrated with iron of the activity 1. In the process of extrapolation, the oxygen partial pressure and the activity of iron were unified to give a single thermodynamic quantity which is defined as: , where K(x) is the equilibrium constant for the formation reaction of Fe_xO and is considered to be a function of x. The dependence of on the slag composition was obtained experimentally. On the other hand, it was found that the plot of against log a_Fe has the slope ?1 as expected from the theoretical consideration. The relation has been employed to estimate the composition of slag in equilibrium with liquid iron. Thus, the obtained composition is used to calculate the values of and of the slag in equilibrium with liquid iron.