Study on the foaming of CaO-SiO2-FeO slags: Part II. Dimensional analysis and foaming in iron and steelmaking processes

An empirical equation for the foaming index Σ of a CaO-SiO₂-FeO slag was obtained by dimensional analysis. The effect of second-phase particles on slag foaming was well described by calculating the viscosity of the mixture using the modified Einstein equation. The anticipated foaming in basic oxygen furnace (BOF), electric arc furnace (EAF), and bath-smelting processes was estimated using the parameter Σ for various operating conditions and slag compositions. For BOF operations, it is predicted that foaming is most extreme in the middle of the blow, and a stable foam in EAF is achieved with less basic slags with low FeO contents. For bath smelting, foam heights of 5 m are possible, and a higher degree of prereduction prior to smelting will reduce foaming (because of smaller gas evolution) and possibly increase production rates. Running the process at a higher pressure will also reduce foam heights, because the volume of gas generated is less. Kimihisa Ito, Research Associate, formerly with the Department of Metallurgical Engineering and Materials Science, Carnegie Mellon University     

Electrical and electronic conductivity of CaO-SiO2-FeO x slags at various oxygen potentials: Part I. Experimental results

The oxygen potential dependences of total electrical and partial electronic/ionic conductivities for ‘FeO’-CaO-SiO₂ slags have been studied both experimentally and theoretically in the present work. In the first part of this two-part article, the experimental results are presented for slags with 30 wt pct ‘FeO’ and CaO/SiO₂ wt ratios of 0.5, 1.0, and 2.0. For each slag composition, measurements of total electrical conductivity and electronic transference were made over a range of oxygen potentials and temperatures. The results were used to calculate the partial conductivities. A maximum was achieved in total and electronic conductances as a function of equilibrium CO₂/CO. The CO₂/CO corresponding to the maximum was shifted to lower values with increasing slag basicity (CaO/SiO₂ ratio). The other effect of basicity was increasing total and partial conductivities, with a magnitude that depends on oxygen potential and temperature. The activation energies for ionic and electronic conductances were in similar ranges and decreased with the basicity.     

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.     

Thermal Conductivity of the Molten CaO-SiO2-FeO x System

Thermal conductivity measurements were carried out on synthetic steelmaking slag using the hot-wire method. Furthermore, local structure analysis in the melts was carried out in order to investigate the relationship with the composition dependence. The thermal conductivity of the CaO-SiO₂-FeO _x melts significantly decreased as the content of FeO _x increases, particularly at lower basicity. Both chemical analysis and the observation show that the amount of Fe²⁺ increases when CaO/SiO₂ is smaller, implying more basic behavior of FeO than FeO_1.5. According to further analyses by M?ssbauer spectroscopy, the degree of basicity of FeO_1.5 remains virtually unchanged in the composition range of interest. From the experimental results, it could be concluded that the thermal conductivity of the silicate melt containing iron oxide is highly dependent on the valence of the Fe ion and comparatively independent of the amphoteric behavior of FeO_1.5.     

Electrical and electronic conductivity of CaO-SiO2-FeOx slags at various oxygen potentials: Part II. Mechanism and a model of electronic conduction

The experimental results obtained for ionic and electronic conductivity of ‘FeO’-CaO-SiO₂ melts have been analyzed considering the mechanism of each conduction process. The Nernst-Einstein equation was employed to calculate diffusion coefficients of Fe²⁺ and Ca²⁺ cations from ionic conductance. A “diffusion-assisted charge transfer” model was developed to explain the dependence of the electronic conductivity on the oxidation state of iron in the slag. The model considers the electronic conduction as a two-step process: in one step, ferrous ions diffuse from their initial position to a proper distance from ferric ions; in the next step, an electron is transferred between Fe²⁺ and Fe³⁺. The optimum distance of the iron ions for electron hopping was found to be approximately 4 Å, in great consistency with the values reported for electron transfer between Fe²⁺ and Fe³⁺ in aqueous solutions and solid glasses.     

Evaluation of the activity and molecular form of bi in cu smelting slags: Part I. ternary silicate slags

The thermodynamic behavior of bismuth in the chemical systems associated with copper processing is not well understood. This study was designed to further the understanding of the physical chemistry of bismuth in slags that have similar compositions to those found in copper extractive metallurgical processing. The silicate system investigated was the FeO-Fe₂O₃-SiO₂ ternary system in which bismuth was dissolved using an isopiestic experimental technique. Bismuth vapor pressures of 1 • 10⁻⁵ atm and 7.5 • 10⁻⁴ atm were used, and the silicates were equilibrated with this vapor at temperatures of 1458 K and 1523 K. In these experiments, the slag composition was varied such thatP _{O 2} ranged from 10⁻¹² to 10⁻⁸ atm. Bismuth was found to enter the silicate slag in both neutral and oxidic molecular forms. The oxidic form identified was that of BiO. The data suggest that the activity coefficient of neutral bismuth, γ_Bi, is dependent on the solubility of that species in slag, even at the low concentrations observed in this study. It has been hypothesized, based on the large diameter of neutral Bi, that only a limited number of sites are available to accommodate neutral Bi, and that as the limit is approached γ_Bi increases significantly. That hypothesis is shown to be consistent with the experimental results obtained in the present work as well as the results obtained by other investigators.     

Evaluation of the activity and molecular form of bi in cu smelting slags: Part I. ternary silicate slags

The thermodynamic behavior of bismuth in the chemical systems associated with copper processing is not well understood. This study was designed to further the understanding of the physical chemistry of bismuth in slags that have similar compositions to those found in copper extractive metallurgical processing. The silicate system investigated was the FeO-Fe₂O₃-SiO₂ ternary system in which bismuth was dissolved using an isopiestic experimental technique. Bismuth vapor pressures of 1 ? 10^?5 atm and 7.5 ? 10^?4 atm were used, and the silicates were equilibrated with this vapor at temperatures of 1458 K and 1523 K. In these experiments, the slag composition was varied such thatP _{O 2} ranged from 10^?12 to 10^?8 atm. Bismuth was found to enter the silicate slag in both neutral and oxidic molecular forms. The oxidic form identified was that of BiO. The data suggest that the activity coefficient of neutral bismuth, γ_Bi, is dependent on the solubility of that species in slag, even at the low concentrations observed in this study. It has been hypothesized, based on the large diameter of neutral Bi, that only a limited number of sites are available to accommodate neutral Bi, and that as the limit is approached γ_Bi increases significantly. That hypothesis is shown to be consistent with the experimental results obtained in the present work as well as the results obtained by other investigators.     

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).     

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.     

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.     

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.     

Influence of CaO-SiO2-Al2O3 Ternary Oxide System on the Reduction Behavior of Carbon Composite Pellet: Part I. Reaction Kinetics

The reduction behavior of composite pellets comprising of hematite, synthetic graphite, and several oxide binder systems was investigated in a laboratory-scale horizontal tube furnace. Three oxide binder systems using silica-rich, alumina-rich, and conventional blast furnace slag compositions were selected to examine the effect of oxide chemistry on the reduction behavior of pellets. Compositional differences in the CaO-SiO₂-Al₂O₃ ternary system were confirmed to influence the reactions occurring in composite pellets during the reduction of iron oxide. An in situ visualization approach was used to observe the oxide/iron/carbon interactions at high temperatures from 1623 K to 1773 K (1350 °C to 1500 °C). The off-gas composition was measured by means of an infrared analyzer to determine the pellet reaction rates. Changes in physical appearance during the in situ reaction experiments demonstrated a strong correlation between the oxide composition and internal reactions. Moreover, the mechanical properties of pellets were investigated by measuring compressive strength to understand the relationship between physical properties of pellets and the associated oxide binder systems selected for this study.     

低氧分压条件下CaO-SiO_2-P_2O_5(10%)-FeO体系热力学性质的研究

以促进2CaO·SiO_2-3CaO·P_2O_5固溶体生成的非均相脱磷工艺被视为未来实现转炉少渣冶炼的重要手段,但目前相关渣系热力学性质的研究较少,不能为合理解释非均相渣脱磷的机理提供理论依据.为此,本文利用FactSage热力学软件绘制了低氧分压(1mPa)条件下CaO-SiO_2-P_2O_5(10%)-FeO体系及其子体系的热力学相图,分析了不同温度下相平衡关系及液相线的变化规律.研究结果表明:升高温度可使体系中液相区及Ca_3(PO_4)_2初晶区的范围扩大,但会导致α'-Ca_2SiO_4的初晶区缩小以及Ca_2Fe_2O_5等物相的消失;降低氧分压可使体系的液相区缩小,并向高FeO的方向收缩;CaO-SiO_2-P_2O_5(10%)-FeO体系中存在较大的α'-Ca_2SiO_4与Ca_3(PO_4)_2共存区,尤其是α'-Ca_2SiO_4,Ca_3(PO_4)_2与Ca_2Fe_2O_5的三相共存区可极大地促进2CaO·SiO_2-3CaO·P_2O_5固溶体的生成.     

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。     

CaO-SiO2-FeOx及CaO-SiO2-P2O5-FeOx渣系热力学性质的研究

CaO-SiO2-FeOx三元渣系和CaO-SiO2-P2O5-FeOx四元渣系是转炉脱磷用渣的主要子渣系,研究这两种渣系的热力学性质可为脱磷渣的高效利用提供理论依据。利于相图软件FactSage分别绘制了这两种渣系的相图,并分析了温度和氧分压对体系相平衡关系和液相线的影响规律。分析结果表明:升高温度会使这两种渣系的液相区扩大,初晶相稳定区域显著减小;降低氧分压会导致尖晶石固溶体相的初晶区消失,磷石英(SiO2)、伪硅灰石(CaSiO3)、α’-Ca2SiO4固溶体相减小。     

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.     

A Reaction Between High Mn-High Al Steel and CaO-SiO2-Type Molten Mold Flux: Part I. Composition Evolution in Molten Mold Flux

In order to elucidate the reaction mechanism between high Mn-high Al steel such as twin-induced plasticity steel and molten mold flux composed mainly of CaO-SiO₂ during continuous casting process, a series of laboratory-scale experiments were carried out in the present study. Molten steel and molten flux were brought to react in a refractory crucible in a temperature range between 1713 K to 1823 K (1440 °C to 1550 °C) and composition evolution in the steel and the flux was analyzed using inductively coupled plasma atomic emission spectroscopy, X-ray fluorescence, and electron probe microanalysis. The amount of SiO₂ in the flux was significantly reduced by Al in the steel; thus, Al₂O₃ was accumulated in the flux as a result of a chemical reaction, 4[Al] + 3(SiO₂) = 3[Si] + 2(Al₂O₃). In order to find a major factor which governs the reaction, a number of factors ((pct CaO/pct SiO₂), (pct Al₂O₃), [pct Al], [pct Si], and temperature) were varied in the experiments. It was found that the above chemical reaction was mostly governed by [pct Al] in the molten steel. Temperature had a mild effect on the reaction. On the other hand, (pct CaO/pct SiO₂), (pct Al₂O₃), and [pct Si] did not show any noticeable effect on the reaction. Apart from the above reaction, the following reactions are also thought to happen simultaneously: 2[Mn] + (SiO₂) = [Si] + 2(MnO) and 2[Fe] + (SiO₂) = [Si] + 2(FeO). These oxide components were subsequently reduced by Al in the molten steel. Na₂O in the molten flux was gradually decreased and the decrease was accelerated by increasing [pct Al] and temperature. Possible reactions affecting the Al₂O₃ accumulation are summarized.     

Open bite deformity in amelogenesis imperfecta. Part 2: Le Fort I osteotomies and treatment results

Functional conditions, skeletal and dento-alveolar stability and condylar changes in 15 patients with mandibular hypoplasia, anterior open bite (AOB) and amelogenesis imperfecta (AI), who had undergone a Le Fort I osteotomy, were analysed after a mean follow-up of 5 years. Two patients underwent a one-piece Le Fort I intrusion osteotomy and 13 patients a multi-segment Le Fort I osteotomy. In three of these patients, an additional bilateral sagittal split osteotomy was performed. Thirteen patients underwent a genioplasty. Surgery was followed by prosthetic rehabilitation in 10 patients. Skeletal and dento-alveolar stability were analysed on lateral cephalometric radiographs and condylar changes on orthopantomographic radiographs. Transverse stability of the dental arches was analysed on dental casts. The treatment results in this group were compared with patients with similar skeletal features but without amelogenesis imperfecta. The harmony of the long faces was restored and a reasonable vertical stability of the maxilla was achieved, however, a slight open bite and tongue interposition was still present. The transverse stability of dental arches (60%) was disappointing. Rigid internal fixation produced better transverse stability. Progressive condylar resorption was seen in two patients (13%). Less occlusal stability could be achieved in patients with AI, but resulted neither in less skeletal stability nor in more susceptibility to morphological condylar changes.     

Vacuum distillation of liquid metals: Part I. Theory and experimental study

The kinetics of vacuum distilling copper, tin, manganese, and sulfur from melted steel scrap have been measured. The experiments found that 70 to 90 pct of initial copper, 60 to 80 pct of initial tin, 80 to 100 pct of initial managanese, and 20 to 40 pct of initial sulfur can be eliminated in 30 minutes exposure to vacuum. Melt masses were in the range 10 to 60 kg, melt temperatures in the range 1850 to 2050 K, and chamber pressures in the range 3 to 400 pascals. Crucible diameter was 0.2m. Mass transport has been described in terms of Machlin's model for melt phase diffusion, Langmuir's model for evaporation, and convective bulk flow for gas phase mass transport. Two preliminary criteria are shown to demonstrate the suitability of vacuum distillation to any particular system and a third operational criterion is developed to define the range of vacuum required to eliminate gas phase mass transport resistance effectively. W.G. Davenport formerly with McGill University     

Vacuum evaporation of KCl-NaCl salts: Part II. vaporization-rate model and experimental results

A model based on the Hertz-Langmuir relation is used to describe how evaporation rates of the binary KCl-NaCl system change with time. The effective evaporation coefficient (α), which is a ratio of the actual evaporation rate to the theoretical maximum, was obtained for the KCl-NaCl system using this model. In the temperature range of 640 °C to 760 °C, the effective evaporation coefficient ranges from ～0.4 to 0.1 for evaporation experiments conducted at 0.13 Pa. At temperatures below the melting point, the lower evaporation coefficients are suggested to result from the more complex path that a molecule needs to follow before escaping to the gas phase. At the higher liquid temperatures, the decreasing evaporation coefficients result from a combination of the increasing vaporflow resistances and the heat-transfer effects at the evaporation surface and the condensate layer. The microanalysis of the condensate verified that composition of the condensate changes with time, consistent with the model calculation. The microstructural examination revealed that the vaporate may have condensed as a single solution phase, which upon cooling forms fine lamellar structures of the equilibrium KCl and NaCl phases. In conclusion, the optimum design of the evaporation process and equipment must take the mass and heat transfer factors and equipment materials issues into consideration.