Effects of the Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Content on the Viscosity of CaO-SiO<Subscript>2</Subscript>-10 Pct Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> Quaternary Slag

The present study experimentally investigates the effect of Cr₂O₃ on the viscosity of molten slags. The viscosities of CaO-SiO₂-10 pct Al₂O₃-Cr₂O₃ quaternary slags with two different binary basicities (R, basic slag with R = 1.2 and acidic slag with R = 0.8) were measured by the rotating cylindrical method from 1813 K to 1953 K (1540 °C to 1680 °C). The results showed that the viscosity of both types of slag decreased as the Cr₂O₃ content increased, but the viscosity of acidic slags exhibited a greater decrease. The slags showed good Newtonian behavior at such high temperatures. Cr₂O₃ could act as a network modifier to simplify the Si-O-Si tetrahedral structure, as verified by the Raman spectral analysis, which was consistent with the decreasing trend of viscosity. The activation energy of viscous flow decreased slightly with increasing Cr₂O₃, but increasing the basicity seemed to be more effective in decreasing the viscosity than adding Cr₂O₃.     

Solid Phase Equilibrium Relations in the CaO-SiO<Subscript>2</Subscript>-Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>-La<Subscript>2</Subscript>O<Subscript>3</Subscript> System at 1273 K

Silicate slag system with additions Nb and RE formed in the utilization of REE-Nb-Fe ore deposit resources in China has industrial uses as a metallurgical slag system. The lack of a phase diagram, theoretical, and thermodynamic information for the multi-component system restrict the comprehensive utilization process. In the current work, solid phase equilibrium relations in the CaO-SiO₂-Nb₂O₅-La₂O₃ quaternary system at 1273 K (1000 °C) were investigated experimentally by the high-temperature equilibrium experiment followed by X-ray diffraction, scanning electron microscope, and energy dispersive spectrometer. Six spatial independent tetrahedron fields in the CaO-SiO₂-Nb₂O₅-La₂O₃ system phase diagram were determined by the Gibbs Phase Rule. The current work combines the mass fraction of equilibrium phase and corresponding geometric relation. A determinant method was deduced to calculate the mass fraction of equilibrium phase in quaternary system according to the Mass Conservation Law, the Gibbs Phase Rule, the Lever’s Rule, and the Cramer Law.     

Effects of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and CaO/SiO<Subscript>2</Subscript> Ratio on Phase Equilbria in the ZnO-“FeO”-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-SiO<Subscript>2</Subscript> System in Equilibrium with Metallic Iron

The phase equilibria and liquidus temperatures in the ZnO-“FeO”-Al₂O₃-CaO-SiO₂ system in equilibrium with metallic iron have been determined experimentally in the temperature range 1383 K to 1573 K (1150 °C to 1300 °C). The experimental conditions were selected to characterize lead blast furnace and imperial smelting furnace slags. The results are presented in a form of pseudoternary sections ZnO-“FeO”-(Al₂O₃ + CaO + SiO₂) with fixed CaO/SiO₂ and (CaO + SiO₂)/Al₂O₃ ratios. It was found that wustite and spinel are the major primary phases in the composition range investigated. Effects of Al₂O₃ concentration as well as the CaO/SiO₂ ratio on the primary phase field, the liquidus temperature, and the partitioning of ZnO between liquid and solid phases have been discussed for zinc-containing slags.     

Thermodynamic Modeling of Metal Desulfurization with Boron-Containing Slags of the CaO–SiO<Subscript>2</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> System

In thermodynamic modeling of the desulfurization of steel by CaO–SiO₂–MgO–Al₂O₃–B₂O₃ slag on the basis of HSC 6.12 Chemistry software (Outokumpu), the influence of the temperature (1500–1700°C), the slag basicity (2–5), and the B₂O₃ content (1–4%)1 on the desulfurization is analyzed. It is found that the sulfur content is reduced with increase in the temperature from 1500 to 1700°C, within the given range of slag basicity. At 1600°C, the sulfur content in the metal is 0.0052% for slag of basicity 2; at 1650°C, by contrast, its content is 0.0048%. Increase in slag basicity from 2 to 5 improves the desulfurization, which increases from 80.7 to 98.7% at 1600°C. If the B₂O₃ content in the slag rises, desulfurization is impaired. At 1600°C, the sulfur content in the metal may be reduced to 0.0052 and 0.0098% when using slag of basicity 2 with 1 and 4% B₂O₃, respectively; in the same conditions but with slag of basicity 5, the corresponding values are 0.00036 and 0.00088%, respectively. Note that desulfurization is better for slag without B₂O₃. According to thermodynamic modeling, metal with 0.0039 and 0.00019% S is obtained at 1600°C when using slag of basicity 2 and 5, respectively, that contains no B₂O₃. The results obtained by thermodynamic modeling for the desulfurization of metal by CaO–SiO₂–MgO–Al₂O₃–B₂O₃ slag of basicity 2–5 in the range 1500–1700°C are consistent with experimental data and may be used in improving the desulfurization of steel by slag that contains boron.     

Phase Equilibria in the System “FeO”-CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO at Different CaO/SiO<Subscript>2</Subscript> Ratios

The “FeO”-containing slags play an important role in the operation of an ironmaking blast furnace (BF), in particular the primary slags such as the system “FeO”-CaO-SiO₂-Al₂O₃-2 mass pct MgO with CaO/SiO₂ weight ratios of 1.3, 1.5, and 1.8 saturated with metallic iron. To investigate the characteristics of such a slag system and its behavior in BF, the phase equilibria and liquidus temperatures in the slag system have been experimentally determined using the high-temperature equilibration and quenching technique followed by an electron probe X-ray microanalysis (EPMA). Isotherms between 1553 K and 1603 K (1280 °C and 1330 °C) were determined in the primary phase fields of dicalcium silicate, melilite, spinel, and monoxide [(Mg,Fe²⁺)O]. Pseudo-ternary phase diagrams of (CaO + SiO₂)-Al₂O₃-“FeO” with a fixed MgO concentration at 2 mass pct and at CaO/SiO₂ ratios of 1.3, 1.5, and 1.8 have been discussed, respectively, simplifying the complexity of the slag system for easy understanding and applying in BF operation. It was found that the liquidus temperatures increase in melilite and spinel primary phase fields, but decrease in dicalcium silicate and monoxide primary phase fields with increasing Al₂O₃/(CaO + SiO₂) ratio. In addition, the liquidus temperatures decrease with increasing “FeO” concentration in dicalcium silicate and melilite primary phase fields, while showing an increasing trend in the spinel and monoxide primary phase fields. The data resulted from this study can be used to improve and optimize currently available database of thermodynamic models used in FactSage.     

A new experimental technique for determinations of the activities of P<Subscript>2</Subscript>O<Subscript>5</Subscript> and Fe<Subscript>x</Subscript>O—the system CaO-P<Subscript>2</Subscript>O<Subscript>5</Subscript>-Fe<Subscript>x</Subscript>O

An experimental technique was applied for simultaneous determinations of the activities of P₂O₅ and Fe_xO in slags. With this technique, phosphorus-containing liquid copper was heated inside an iron crucible at temperatures below 1600 K. When copper is melted, the iron crucible dissolves into liquid copper, to a small extent, to form ternary {Cu-Fe-P} liquid alloy, while 〈Cu-Fe-P〉 solid solutions are formed on the inner wall of the iron crucible. Slags containing tri-calcium phosphate were then brought into equilibrium with {Cu-Fe-P} liquid alloy. By measuring the equilibrium oxygen partial pressures with the aid of a zirconia electrolyte cell, activities of P₂O₅ and Fe_xO were obtainable. Between 1553 and 1593 K, the P₂O₅ activities could be expressed as

Construction of viscosity diagrams for CaO–SiO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–8% MgO–4% B<Subscript>2</Subscript>O<Subscript>3</Subscript> slags by the simplex lattice method

The simplex lattice method of planning experiments is used to study the viscosities of CaO–SiO₂–Al₂O₃–8% MgO–4% B₂O₃ slags in a wide chemical composition range. For each viscosity, we developed an adequate mathematical model in the form of a reduced third-order polynomial. The results of mathematical simulation are presented in composition–viscosity diagrams. Composition regions with a high fluidity of slags, the viscosities of which are 0.8–1.2 Pa s in the temperature range 1500–1600°C, are indicated in the diagrams.     

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.     

Interfacial Tension in the CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>-(MgO) Liquid Slag–Solid Oxide Systems

Interfacial phenomenon is critical in metal processing and refining. While it is known to be important, there are little data available for key oxide systems in the literature. In this study, the interfacial tension (σ _LS) of liquid slag on solid oxides (alumina, spinel, and calcium aluminate), for a range of slags in the CaO-Al₂O₃-SiO₂-(MgO) system at 1773 K (1500 °C), has been evaluated. The results show that basic ladle-type slags exhibit lower σ _LS with oxide phases examined compared to that of acid tundish-type slags. Also, within the slag types (acid and base), σ _LS was observed to decrease with increasing slag basicity. A correlation between σ _LS and slag structure was observed, i.e., σ _LS was found to decrease linearly with increasing of slag optical basicity (Λ) and decrease logarithmically with decreasing of slag viscosity from acid to base slags. This indicated a higher σ _LS as the ions in the slag become larger and more complex. Through a work of adhesion (W) analysis, it was shown that basic ladle slags with lower σ _LS result in a greater W, i.e., form a stronger bond with the solid oxide phases examined. This indicates that all other factors being equal, the efficiency of inclusion removal from steel of inclusions of similar phase to these solid oxides would be greater.     

Kinetics of Transformation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> to MgO·Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Spinel Inclusions in Mg-Containing Steel

During ladle furnace refining, initial Al₂O₃ inclusions generally transform into MgO·Al₂O₃ spinel inclusions; these generated spinel inclusions consequently deteriorate the product quality. In this study, the transformation from Al₂O₃ to MgO·Al₂O₃ was investigated by immersing an Al₂O₃ rod into molten steel, which was in equilibrium with both MgO and MgO·Al₂O₃ spinel-saturated slag. A spinel layer, with a thickness of 4 μm, was generated on the Al₂O₃ rod surface just 10 s after its immersion at 1873 K (1600 °C). The thickness of the formed spinel layer increased with the immersion period and temperature. Moreover, the MgO content of the generated spinel layer also increased with the immersion period. In this study, the chemical reaction rate at 1873 K (1600 °C) was assumed to be sufficiently high, and only diffusion was considered as a rate-controlling step for this transformation. By evaluating the activation energy, MgO diffusion in the generated spinel layer was found to be the rate-controlling step. In addition, this estimation was confirmed by observing the Mg and Al concentration gradients in the generated spinel layer. The results of this study suggest that the MgO diffusion in the spinel inclusions plays a substantial role with regard to their formation kinetics.     

Quantum-Chemical Study of the Charge Transfer Mechanism in the MgTiF<Subscript>6</Subscript>–12MgCl<Subscript>2</Subscript> System

A quantum-chemical analysis of frontier molecular orbitals is used to propose a mechanism for the electrochemical electron transfer in the model system MgTiF₆ + 12MgCl₂. The geometric structure of the transient state is shown not to be intermediate between the initial and final states of the system. The contraction of the Ti–F bonds during totally symmetrical vibrations is found to be the most probable version providing electron transfer to the system.     

Resonance character of polymorphic transformations for the phase transition α′<Subscript><Emphasis Type="Italic">L</Emphasis></Subscript> → β-Ca<Subscript>2</Subscript>SiO<Subscript>4</Subscript>

Experimental results are presented showing that rapid cooling of dicalcium silicate is accompanied by delay of structural processes, which leads to a decreasing in temperature of the phase transition α′ _L → β-Ca₂SiO₄. As starting materials, nepheline ore and limestone were used. In preparing the charge, the dosage of starting components was calculated for obtaining a molar ratio of CaO/SiO₂ = 2.0. From the charge, the series of samples was prepared. Each of the samples was sintered to t = 1250°C with subsequent keeping of the material at this temperature for 30 min. Then the samples were subjected to rapid cooling in air to t = 750, 650, 550, 450, 350, 250, 150, and 25°C. By means of quantitative X-ray powder diffraction analysis using a DRON-3 setup, the content of α′ _L and β-Ca₂SiO₄ was determined in the samples. The data allow us to suppose the occurring polymorphic transformations in dicalcium silicate have a resonance character.     

Determination of gibbs energy of formation of cuspidine (3CaO · 2SiO<Subscript>2</Subscript> · CaF<Subscript>2</Subscript>) from the electromotive force method using CaF<Subscript>2</Subscript> as the solid electrolyte

The standard Gibbs energy change for the following reaction has been directly determined by electromotive force (EMF) measurement using CaF₂ as the solid electrolyte in the temperature range from 1313 to 1329 K.

Kinetics and High-Temperature Oxidation Mechanism of Ceramic Materials in the ZrB<Subscript>2</Subscript>–SiC–MoSi<Subscript>2</Subscript> System

This study is devoted to the fabrication of the ZrB₂–SiC–(MoSi₂) compact ceramics according to hybrid technology (self-propagating high-temperature synthesis (SHS) + hot pressing), as well as to investigating its phase composition, structure, and high-temperature oxidation kinetics. Reaction mixtures are prepared according to the following scheme: mechanical activation (MA) of Si + C powders; wet admixing of Zr, B, and Si + C MA-mixture powders; and drying mixtures in a drying oven. The ZrB₂–SiC SHS composite powder is formed in a reactor in a combustion mode by elemental synthesis. Compact samples with a homogeneous structure and low residual porosity not exceeding 1.3% are formed by hot pressing the SHS powder. Two compositions are selected for testing, notably, the first one calculated for the formation of ZrB₂ + 25% SiC; the second composition is similar to the first one, but with the addition of 5% of the MoSi₂ commercial powder. The microstructure of the samples is presented by dispersed dark gray rounded SiC grains distributed among light faceted ZrB₂ grains. The sample with the MoSi₂ additive has a more finely dispersed structure. The high-temperature oxidation of the samples at 1200°C results in the formation of SiO₂?ZrB₂–(B₂O₃) complex oxide films on their surface with a thickness on the order of 20–30 μm, which serve as an efficient diffusion barrier and lower the oxidation rate. Their structure also contains ZrSiO₄ complex oxide after prolonged holding (longer than 10 h). In addition, an insignificant weight loss of the samples is observed after 10 h testing, which is caused by the volatilization of gaseous oxidation products (B₂O₂, CO/CO₂, MoO₃). The sample with the MoSi₂ additive shows better resistance to oxidation.     

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

The phase equilibria in the ZnO-“FeO”-Al₂O₃-CaO-SiO₂-S system have been determined experimentally in equilibrium with metallic iron. A pseudoternary section of the form ZnO-“FeO”-(Al₂O₃+CaO+SiO₂) for CaO/SiO₂ = 0.71 (weight), (CaO+SiO₂)/Al₂O₃ = 5.0 (weight), and fixed 2.0 wt pct S concentration has been constructed. It was found that the addition of 2.0 wt pct S to the liquid extends the spinel primary phase field significantly and decreases the size of the wustite primary phase field. The liquidus temperature in the wustite primary phase field is decreased by approximately 80 K and the liquidus temperature in the spinel primary phase field is decreased by approximately 10 K with addition of 2.0 wt pct S in the composition range investigated. It was also found that iron-zinc sulfides are present in some samples in the spinel primary phase field, which are matte appearing at low zinc concentrations and sphalerite (Zn,Fe)S at higher zinc concentrations. The presence of sulfur in the slag has a minor effect on the partitioning of ZnO between the wustite and liquid phases but no effect on the partitioning of ZnO between the spinel and liquid phases.     

Phase Equilibria Studies in the System ZnO-“FeO”-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-SiO<Subscript>2</Subscript> Relevant to Imperial Smelting Furnace Slags: Part I

The phase equilibria and the liquidus temperatures in the system ZnO-“FeO”-Al₂O₃-CaO-SiO₂ have been determined experimentally in equilibrium with metallic iron. Specifically, the effects of Al₂O₃ concentrations in Imperial Smelting Furnace slags are identified, and the results are presented in the form of pseudo-ternary sections ZnO-“FeO”-(Al₂O₃ + CaO + SiO₂) in which CaO/SiO₂ = 0.93 and (CaO + SiO₂)/Al₂O₃ = 5.0 and 3.5, respectively. It was found that, in the presence of Al₂O₃, the spinel phase is formed, the spinel primary phase field expands, and the wustite and melilite primary phase fields are reduced in size with an increasing Al₂O₃ concentration. The implications of the findings to industrial practice are discussed.     

Phase Equilibria Studies in the System ZnO-“FeO”-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-SiO<Subscript>2</Subscript> Relevant to Imperial Smelting Furnace Slags: Part II

The phase equilibria and the liquidus temperatures in the system ZnO-“FeO”-Al₂O₃-CaO-SiO₂ have been determined experimentally in equilibrium with metallic iron. Specifically, the effects of Al₂O₃ concentrations in Imperial Smelting Furnace slags are identified, and the results are presented in the form of pseudo-ternary sections ZnO-“FeO”-(Al₂O₃ + CaO + SiO₂) in which CaO/SiO₂ = 0.93 and (CaO + SiO₂)/Al₂O₃ = 5.0 and 3.5, respectively. It was found that, in the presence of Al₂O₃, the spinel phase is formed, the spinel primary phase field expands, and the wustite and melilite primary phase fields are reduced in size with an increasing Al₂O₃ concentration. The implications of the findings to industrial practice are discussed.     

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.     

Magnetic states in Fe<Subscript>65</Subscript>(Ni<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>35</Subscript> alloys

The ferromagnetic-antiferromagnetic concentration transition in Fe₆₅(Ni_{1 − x} Mn _x )₃₅ alloys is studied by neutron diffraction and small-angle magnetic neutron scattering (SMNS). The Curie and Néel temperatures are measured, and the antiferromagnetic moments and the cross sections of SMNS by magnetic heterogeneities are determined. The parameters of spin density fluctuations in the heterogeneities are obtained. A cluster mechanism of the nucleation of magnetic phases is revealed, and the spin-glass freezing temperatures are estimated. A low-temperature diagram is constructed for the magnetic states of the alloys.