Thermodynamics of nitrogen in CaO-SiO2-AI2O3 slags and its reaction with Fe-Csat. melts

The solubility of nitrogen as the nitride ion in CaO-SiO₂-Al₂O₃ slags in equilibrium with N₂-CO gas mixtures and carbon was measured at 1823 K. The nitride capacity (C _N3-) was calculated to compare the nitrogen contents measured under different nitrogen and oxygen potentials.C _N3- decreased with increasing basicity and by replacing SiO₂ with A1₂O₃. The nitrogen partition ratio between carbon saturated iron and the slag was measured in CO gas at one atmosphere at 1823 K. By comparing the partition ratios with the corresponding nitride capacities measured by the gas-slag experiments, it was concluded that the oxygen partial pressure at the slag-metal interface was controlled by the Fe-FeO reaction. A new definition of nitride capacity was proposed based on the reaction between nitrogen and the network former,i.e., SiO₂ or A1₂O₃. This capacity could consistently explain the experimental results. Empirical equations were derived to estimate the activity coefficients of silicon and aluminum nitrides in the slags. On leave of absence from the Research Institute of Mineral Dressing and Metallurgy, Tohoku University, Sendai, Japan.     

Viscosity of CaO-SiO2-Al2O3-MgO-B2O3 slags

The viscosity of CaO-SiO₂-Al₂O₃ slags with 8% MgO and 4% B₂O₃ is investigated over a broad range of composition, by means of a simplex-lattice experiment design. For slag of basicity 6–8 in the upper left region of the local simplex, with 15–25% Al₂O₃, 8% MgO, and 4% B₂O₃, the viscosity is high: 9.4–26.4 P over the range 1500–1530°C. Displacement of the slags of basicity 5–8 to the lower region of the local simplex ensures high fluidity in the given range of Al₂O₃ concentration: the viscosity is 1.5–6.1 P over the range 1500–1530°C.     

The thermodynamic behavior of sulfur in BaO-BaF2 slags

A gas-slag-metal equilibration technique was used to determine the sulfide capacity of the BaO-BaF₂ system at 1473 and 1573 K. The dependence of carbonate capacity on the slag composition was also measured at these temperatures. It was found that the BaO-BaF₂ system has the highest sulfide capacities among the fluxes which are of metallurgical interest. The dependence of sulfide and carbonate capacities on the partial pressure of O₂ and CO₂ was also investigated. The partial pressure of CO₂ proved to have a strong effect on these values at the investigated temperatures. The influence of temperature on the sulfide and carbonate capacities was studied in the temperature range between 1423 and 1623 K. The data for sulfide and carbonate capacities were correlated in order to check if the carbonate capacity can be used as a measure of basicity of slags. It was found that the carbonate capacity can be used as a representative measure of the slag basicity at low contents of BaO and at temperatures higher than 1623 K when the carbonate dissolution into the slag is low and the ratio of the activity coefficient of a sulfide ion to that of a carbonate ion is independent of slag composition. on leave from the Department of Metallurgy, Higher Institute of Chemical Technology, Sofia, Bulgaria     

The sulphide capacity of CaO-SiO2-Al2O3-MgO(-FeO) smelting reduction slags

The effects of MgO and FeO contents on the sulphide capacity of Corex slags were investigated at 1773 K using gas/slag equilibrium technique as a fundamental study for stabilising Corex operational conditions. The gradual substitution of MgO for CaO at a fixed basicity [B = {(%CaO)+(%MgO)}/(%SiO₂)] decreased the sulphide capacities of CaO-SiO₂-Al₂C₃-MgO slags. The addition of FeO into the CaO-SiO₂-Al₂O₃-MgO slags at the fixed (%CaO)/(%SiO₂) ratio, MgO and Al₂O₃ contents significantly increased the sulphide capacities. The sulphide capacity decreased according to the increasing Al₂O₃ content at the fixed (%CaO)/(%SiO₂) ratio, MgO and FeO content. Based on the previously reported and present values of sulphide capacities, the sulphide capacity as a function of slag composition on the mole fraction base at 1773 K was expressed by the formula of log C_S = X_CaO – 3.89 X_SiO2 – 3.18 X_Al2O₃ – 0.55 X_MgO + 2.43 X_FeO – 2.61. In addition, the relationship between the sulphide capacity and optical basicity could be represented as the formula of log C_S = 12.51 A – 12.24 and the theoretical optical basicity of FeO was found be 0.94 from the correlation. The effect of FeO on the sulphur distribution ratio was estimated using the present sulphide capacity values and the oxygen activity in liquid iron, which could be determined with the help of Fe/FeO equilibrium. FeO activity in slag was well described by the quadratic formalism based on the regular solution model. The sulphur distribution ratio according to FeO content varies in an opposite way, compared with that of the sulphide capacity.     

Silicon-Oxygen equilibrium and nitrogen distribution between CaO-SiO2 slags and liquid iron

Silicon-oxygen equilibria in an Fe-0.003 ~ 27 mass pct Si alloy in equilibrium with the CaO-SiO₂ slags were studied in the temperature range of 1823 to 1923 K using a lime crucible. At the same time, nitrogen distribution ratios, L_N, between slag and metal were measured, and from these results and the reported values for activities of SiO₂, nitride capacities, , defined by (mass pct N). were evaluated. It was found that the values for L_N decreased, whereas those for increased with an increase in temperature. Activities of SiO₂ were determined using the values for L_N and obtained in previous gas-slag experiments. These values were compared with the previous results.     

The effect of CaF2 on the viscosities and structures of CaO-SiO2(-MgO)-CaF2 slags

The viscosities of CaO-SiO₂(-MgO)-CaF₂ slags were measured to clarify the effect of CaF₂ on the viscous flow of molten slags at high temperatures and the solidification behavior of slags. Furthermore, the infrared (IR) spectra of the quenched slags were analyzed to understand the structural role of CaF₂ in the modification of slag structure. The CaF₂ affects the critical temperature (T _CR) of the slags; that is, the higher the content of CaF₂, the lower the T _CR of the slags. It is suggested that some extent of undercooling as a driving force is needed for the precipitation of solid particles in the melt. In the composition of B (≡(mass pct CaO)/(mass pct SiO₂)) = 1.0, the T _CR was decreased about 150 to 200 K by addition of 10 mass pct MgO, while the T _CR was increased about 100 K by MgO addition at B = 1.3. The effect of CaF₂ on the viscous flow of molten slags can be understood based on a decrease in the degree of polymerization by F⁻ as well as by O²⁻ ions and this was confirmed by the IR spectra of the quenched slags. The relative intensity of the IR bands for [SiO₄]-tetrahedra with low NBO/Si decreased, while that of the IR bands for [SiO₄]-tetrahedra with high NBO/Si increased with increasing CaF₂ content. The decrease in viscosity of the CaO-SiO₂-MgO-CaF₂ (B = 1.0) system by CaF₂ addition was negligible, while the effect of CaF₂ on the viscosity was significant in the more basic system (B = 1.3).     

Activities in CaO-SiO2-Al2O3 slags and deoxidation equilibria of Si and Al

By using the data in previous and present slag-metal equilibrium experiments, the activities of SiO₂ along the liquidus lines in CaO-SiO₂-Al₂O₃ slags were determined at 1823 and 1873 K from the reaction Si+2O=SiO₂ (s), in which the oxygen activities were estimated from the measured oxygen contents or from the combination of nitrogen distribution ratios (L _N) and nitride capacities (C _N). The activities of Al₂O₃ were also determined from the reaction 2Al+3O=Al₂O₃ (s), in which the oxygen activities were estimated from the values for L _N and C _N, or from the reaction 3SiO₂ (s)+4Al=2Al₂O₃ (s)+3Si, in which the activities of SiO₂ and the contents of Al and Si along with the respective interaction coefficients were used. The activities of Al₂O₃ and CaO in the entire liquid region were estimated from the Rein and Chipman’s activities of SiO₂ by using the method of Schuhmann. On the basis of these activities, the deoxidation equilibria of Si and Al in steels were discussed.     

SiO_2-CaO-Al_2O_3-MgO-FeO熔渣的电解还原行为

电解含有铁氧化物的熔渣是一个潜在的减少甚至消除CO2排放的钢铁冶炼短流程新工艺.本文采用MgO或Y2O3稳定的氧化锆管内装碳饱和铁熔体做阳极,构建可控氧流电池:铁棒|Fe+FeO(slag)|ZrO2(MgO或Y2O3)|[O](Fe+C饱和)|石墨棒.在1723 K高温下通过测定电池开路电压-时间曲线、线性扫描伏安曲线、恒电压电解曲线研究了SiO2-CaO-Al2O3-MgO-FeO熔渣的电解还原行为,并借助扫描电镜与能谱分析了残样的显微结构与成分.结果表明:在本实验条件下,测定获得SiO2-Ca O-Al2O3-MgO-FeO熔渣中FeO的分解电压约为-0.25 V,测定结果位于Fact Sage热力学软件理论计算值范围内,表明采用本实验装置测定熔渣中FeO分解电压是可行的.在外加电压条件下可以从SiO2-CaO-Al2O3-MgO-FeO熔渣中电解还原获得金属铁(或铁合金).可控氧流电解还原电流的大小及FeO还原效果与外加电压、ZrO2稳定剂的种类和ZrO2管(阳极)插入熔渣中的深度等因素有关.     

Photon conductivity of metallurgical slags of the three component system CaO-SiO2-Al2O3

The measuring method proposed by Keene and Quinn has been further developed to investigate 3-component slags of the system CaO-SiO₂-Al₂O₃ at temperatures of 800–1600°C in the wavelength range of 550 to 850 nm. The results are presented with the aid of the complex refraction index, which embodies all information on the optical properties of the slags investigated, including photon conductivity and thermal emissivity. Comparison of the photon conductivities determined shows good agreement with the corresponding values of various types of glass cited in literature. The discontinuous pattern of the phonon conductivity curve in the melting range of 40% CaO-40% SiO₂-20% Al₂O₃ slag, as already found by Gammal and Li, is also evident from the data of the present investigation.     

CaO-SiO2-MgO-Al2O3-Cr2O3渣系黏度结构分析及Iida模型应用

 为了实现冶炼铬铁合金过程中含铬渣系黏度的精准控制,从微观结构方面研究了碱度及Cr2O3质量分数变化对铬铁冶炼渣系黏度的影响并优化了Iida黏度预测模型。通过转筒法测量CaO-SiO2-MgO-Al2O3-Cr2O3渣系黏度,结合拉曼光谱从熔渣微观结构方面阐述了Cr2O3质量分数及碱度变化对CaO-SiO2-MgO-Al2O3-Cr2O3渣系黏度的影响。结果表明,熔渣黏度与其表征聚合度的BO参数值均随Cr2O3质量分数的增加而升高,随二元碱度值的增大而降低,熔渣黏度与渣系聚合度变化趋势相一致。根据测量得到的含Cr2O3熔渣黏度数据,进一步优化了Iida黏度预测模型。经过优化后的模型计算黏度值与实际测值吻合较好,利用Iida黏度模型可在较大的温度与成分范围内进行含铬渣黏度的预测。     

The equilibrium partitioning of titanium between Ti3+ and Ti4+ valency states in CaO-SiO2-TiO x slags

The redox behavior of titanium in CaO-SiO₂-TiO _x melts was investigated using a slag-gas equilibrium technique. Titanium partitioning between Ti³⁺ and Ti⁴⁺ valency states and the ratio of activity coefficients of TiO_1.5 and TiO₂ were determined as functions of oxygen partial pressure, temperature, and slag composition. The equilibrium experiments were carried out at temperatures between 1783 and 1903 K under CO-CO₂-Ar gas atmosphere with oxygen partial pressure ranging from 10⁻¹² to 10⁻⁷ atm (1.01×10⁻¹⁰ kPa to 1.01×10⁻⁵ kPa). The slags had CaO/SiO₂ ratios between 0.55 and 1.35 and total titanium oxide concentrations from 7 to 50 mass pct. Experimental results showed that the Ti³⁺/Ti⁴⁺ ratio in CaO-SiO₂-TiO _x slags, containing up to 50 mass pct TiO _x , increased with decreasing oxygen partial pressure and decreased with increasing CaO/SiO₂ ratio and decreasing temperature. Measured variation of the redox ratio Ti³⁺/Ti⁴⁺ with oxygen partial pressure closely followed the ideal behavior. Increasing the CaO/SiO₂ ratio increased the ratio of activity coefficients of TiO_1.5 and TiO₂. The effect of total titania content on this ratio was more complex and in accord with Raman spectroscopy data.     

Distribution of metal droplets in top slags during ladle treatment

Abstract

The investigation focused on the mixing of the metal and slag phases during ladle refining from the point of tapping the EAF to casting. Steel droplet distributions were determined for slag samples taken at different stages in the ladle refining process at two different steel plants in Sweden. The droplet distributions were determined using light optical microscopy and classification according to the standard SS111116. Sample analysis results showed the slag samples taken before vacuum degassing to contain the greatest concentration of steel droplets. The total interfacial area between the steel droplets and slag was determined to be 3–14 times larger than the projected flat interfacial area between the steel and slag. The effects of slag viscosity and reactions between steel and slag on metal droplet formation in slag were also considered.     

Determination of sulfide capacities of CaO-SiO2 slags containing CaF2 and B2O3 by an encapsulation method

The sulfide capacities of CaO-SiO₂ melts containing CaF₂ and B₂O₃ have been measured by simultaneous equilibration of samples within quartz capsules at 1503°C. In this method, the compositions of both the condensed phases and the static gas environment adjust to es-tablish a mutual equilibrium. Although the sulfurizing potential,P _{S 2}/P _{O 2}, is neither preset nor directly measured, the sulfide capacities,C _s, of all samples within the capsule are related by the following equation:C _S(j)=(pct S)j/(pct S)i · C_S(i)· Hence, the sulfide capacities of all samples may be calculated from the measurement of the final sulfur content of each sample and the inclusion of a “reference” slag sample for which C_S is known from previous measurements. In the present study, quartz capsules containing as many as fifty slag samples including several reference samples have been equilibrated. With considerable difficulty the encapsulation-equilibration method atl503°C has been developed into an acceptable procedure. The influences of CaF₂ and B₂O₃ on the sulfide capacities of several CaO-SiO₂ melts have been measured. The results may be summarized as follows: 1) for melts of fixed CaO/SiO₂ ratio, the addition of CaF₂ increases sulfide capacity and the addition of B₂O₃ decreases sulfide capacity, 2) the substitution of CaF₂ for CaO does not alter sulfide capacity significantly, and 3) the substitution of B₂O₃ for SiO₂ increases sulfide capacity slightly. These results have been obtained for melts with CaO/SiO₂ mass ratios ranging from 1.00 to 1.28 and with flux additions up to 10 wt pct.     

The sulfur partition ratio with Fe-CSAT melts and the sulfide capacity of CaO-SiO2-Na2O- (Ai2O3) slags

The sulfur partition ratio between slag and carbon saturated iron and the sulfide capacity of CaO-Na₂O-SiO₂ slags and a 48 pet CaO-45 pet Al₂O₃-7 pet SiO₂-(Na₂O) slag have been mea-sured at 1400 °C. The addition of Na₂O to a CaO-SiO₂ slag increases the sulfur partition ratio and the sulfide capacity; however, Na₂O at low concentrations has no measurable effect on the sulfide capacity of a CaO-Al₂O₃-SiO₂ slag. To convert the sulfur partition ratio to the sulfide capacity, the oxygen potential was calculated assuming equilibrium between iron in the alloy and FeO in the slag with the activity of FeO calculated via a regular solution model. The optical basicity may be used to correlate the data, but at high Na₂O contents the data do not adhere to the correlation previously developed for CaO-based slags. Formerly Graduate Student at Carnegie Mellon University     

Study on the foaming of CaO-SiO2-FeO slags: Part I. Foaming parameters and experimental results

In order to understand the effect of slag composition on foaming in iron and steelmaking processes, slag foaming was quantitatively studied for CaO-SiO₂-FeO slags in the temperature range of 1250 °C to 1400 °C. It was found that slag foaming could be characterized by a foaming index (Σ), which is equal to the retention or traveling time of the gas in the slag, and the average foam life ( τ). The effects of P₂O₅, S, MgO, and CaF₂ on foaming were studied. As expected, slag foaming increased with increasing viscosity and decreasing surface tension. It was found that suspended second-phase solid particles such as CaO, 2CaO SiO₂, and MgO stabilized the foam and had a larger effect on foaming than changes in viscosity and surface tension for the slags studied. Kimihisa Ito, Research Associate, formerly with the Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

CaO-SiO2-Al2O3-Fe2O3渣系脱磷行为

利用Factsage软件计算了Al2O3含量对CaO-SiO2-Al2O3-Fe2O3四元渣系熔点和黏度的影响,并通过实验研究了在1 400℃时,CaO-SiO2-Al2O3-Fe2O3四元渣系对高磷铁水脱磷行为的影响.结果表明:渣中Al2O3的质量分数在3％～6％之间时,随着A12O3含量的增加,渣系的熔化温度迅速降低,进一步增加渣中的A12O3含量,渣系的熔化温度逐渐增加;Al2O3对CaO-SiO2-Al2O3-Fe2O3渣系的黏度影响不大;渣中Al2O3的质量分数在3％～6％之间变化时,渣系脱磷能力变化不是很大,脱磷率维持在91％左右,进一步增加渣系中A12O3的量,脱磷率逐渐下降;Al2O3对脱磷率产生影响可能是其改变了炉渣中液相所占比例,进而影响磷从铁水中向液相渣的传质过程.     

Activities of SiO2 and Al2O3 and activity coefficients of FetO and MnO in CaO-SiO2-Al2O3-MgO slags

The activities of SiO₂ and Al₂O₃ in CaO-SiO₂-Al₂O₃-MgO slags were determined at 1873 K along the liquidus lines saturated with 2CaO · SiO₂, 2(Mg,Ca)O · SiO₂, MgO, and MgO · Al₂O₃ phases using a slag-metal equilibration technique. Based on these and previous results obtained in ternary and quaternary slags, the isoactivity lines of SiO₂ and Al₂O₃ over the liquid region on the 0, 10, 20, 30, and 40 mass pct Al₂O₃ planes and those on the 10 and 20 mass pct MgO planes were determined. The activity coefficients of Fe _t O and MnO, the phase boundary, and the solubility of MgO were also determined.     

基于转炉CaO-SiO2-FeO-10%MgO渣系脱磷行为

 基于CaO-SiO2-FeO-10%MgO渣系,从热力学角度对渣钢界面的脱磷行为进行分析,归纳出磷分配比与钢液温度、碳质量分数以及炉渣成分间的表达式,并在此基础上绘制出了CaO-SiO2-FeO-10%MgO渣系的等磷分配比线,同时分析了转炉终渣氧化性、碱度以及温度对磷分配比的影响情况。研究结果表明,转炉吹炼过程磷分配比是钢液温度、碳质量分数和炉渣成分的函数,通过与实际生产数据进行验证,发现其与实际结果吻合良好。基于该预测公式,在其他条件不变情况下,随着炉渣FeO质量分数增加,磷分配比[LP]先增加后减小,当终渣FeO质量分数为18%左右时达到最大值;随着终渣碱度的增加,渣钢间磷分配比增加,当终渣超过4.0时,磷分配比增加不再明显。