Effect of Li<Subscript>2</Subscript>O on the Behavior of Melting,Crystallization, and Structure for CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Based Mold Fluxes

The effect of Li₂O content on the behavior of melting, crystallization, and molten structure for CaO-Al₂O₃-based mold fluxes was investigated in this article, through use of single hot thermocouple technology (SHTT), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray diffraction (XRD). The SHTT results showed that the melting temperature range of the designed mold fluxes decreases and the crystallization of mold fluxes is inhibited first and then becomes enhanced when the Li₂O content increases from 1 to 6 mass pct. The FTIR and Raman spectroscopy results suggested that Li₂O could release O^2? ions to break the complex Al-O-Al structural unit into Al-O^? structure. Meanwhile, Li₂O could also stabilize the structural unit of Si-O-Al by link aluminate and Q ₀ ^Si structure through providing Li⁺ ions to merge into the network and compensate for the charges between Al³⁺ and Si⁴⁺. Besides, the XRD results indicated that the precipitation of LiAlO₂ in molten slag would enhance the crystallization behavior of mold flux when Li₂O content is over 4.5 mass pct.     

Effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Concentration on Density and Structure of (CaO-SiO<Subscript>2</Subscript>)-xAl<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The effect of Al₂O₃ concentration on the density and structure of CaO-SiO₂-Al₂O₃ slag was investigated at multiple Al₂O₃ mole percentages and at a fixed CaO/SiO₂ ratio of 1. The experiments were conducted in the temperature range of 2154 K to 2423 K (1881 °C to 2150 °C) using the aerodynamic levitation technique. In order to understand the relationship between density and structure, structural analysis of the silicate melts was carried out using Raman spectroscopy. The density of each slag sample investigated in this study decreased linearly with increasing temperature. When the Al₂O₃ content was less than 15 mole pct, density decreased with increasing Al₂O₃ content due to the coupling of Si (Al), whereas above 20 mole pct density of the slag increased due to the role of Al³⁺ ion as a network modifier.     

The Thermodynamic Behavior of Copper in the CaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> and BaO-B<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag System

The Cu solubility was measured in the CaO-B₂O₃ and BaO-B₂O₃ slag systems to understand the dissolution mechanism of Cu in the slags. The Cu solubility had a linear relationship with oxygen partial pressure in the CaO-B₂O₃ slag system, which corresponds with previous studies. Also, the Cu solubilities in slag decreased with increasing the slag basicity, which value of slope was close to –0.5 in logarithmic form. From the results of experiment, the Cu dissolution mechanism established as follows:

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.     

Effect of Slag Composition on the Crystallization Kinetics of Synthetic CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags

The crystallization kinetics of CaO-SiO₂-Al₂O₃-MgO (CSAM) slags was studied with the aid of single hot thermocouple technique (SHTT). Kinetic parameters such as the Avrami exponent (n), rate coefficient (K), and effective activation energy of crystallization (E _A ) were obtained by kinetic analysis of data obtained from in situ observation of glassy to crystalline transformation and image analysis. Also, the dependence of nucleation and growth rates of crystalline phases were quantified as a function of time, temperature, and slag basicity. Together with the observations of crystallization front, they facilitated establishing the dominant mechanisms of crystallization. In an attempt to predict crystallization rate under non-isothermal conditions, a mathematical model was developed that employs the rate data of isothermal transformation. The model was validated by reproducing an experimental continuous cooling transformation diagram purely from isothermal data.     

The solubility of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> in calcium ferrite slags at 1573 K

Continuous converting of copper matte based on calcium ferrite slag has many attractions for the copper smelting industry. However, a serious drawback is that this slag leads to shorter furnace campaigns because it is aggressive toward the magnesia-chromia refractories that form the furnace lining. As part of an investigation into the causes of this aggressiveness with a view to devising strategies to mitigate it, the solubility of Cr₂O₃ in calcium ferrite slag has been determined. The standard drop-quench experimental technique was employed at a temperature of 1573 K and a relatively high oxygen partial pressure of 3.7×10⁻⁴ atm, conditions similar to those used in continuous converting. It was found that approximately 2 wt pct of Cr₂O₃ can dissolve in calcium ferrite slag under these conditions. The Cr₂O₃ solubility was found to be unaffected by the Cu₂O content of the slag, but may decrease as CaO content decreases. The implications of these findings on the mechanism of attack of magnesia-chromia refractories by calcium ferrite slag are discussed.     

Thermal diffusivity measurements of some synthetic CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> slags

In an attempt to systematize the knowledge of the heat conduction of liquid silicates, the effective thermal diffusivities of some synthetic slags containing CaO, Al₂O₃, and SiO₂ have been measured, using the three-layer laser-flash method on a differential scheme in the temperature range of 1625 to 1825 K. The effective thermal diffusivities measured, which are a combination of the phononic and photonic heat-transfer mechanisms, were found to increase with increasing temperature for all the presently investigated slags. The slag compositions were chosen in such a way that the changes in the effective thermal diffusivities would reflect the changes in the structure of the slags. It was observed that, at a CaO/Al₂O₃ molar ratio of 4.42, an increase of the SiO₂ content had very little effect on the effective thermal diffusivity values. On the other hand, addition of SiO₂ to a slag with the CaO/Al₂O₃ molar ratio of 2.59 resulted in a significant increase in the effective thermal diffusivity. The addition of Al₂O₃ to slags with a constant CaO/SiO₂ molar ratio resulted in a marked increase in the effective thermal diffusivity. Both these trends indicate that there might be an influence of the network formation in silicate melts on the effective thermal diffusivity.     

Thermodynamics of Boron Removal from Silicon Using CaO-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> Slags

Slag refining is one of few metallurgical methods for removal of boron from silicon. It is important to know the thermodynamic properties of boron in slags to understand the refining process. The relation of the distribution coefficient of boron to the activity of silica, partial pressure of oxygen, and capacity of slags for boron oxide was investigated. The link between these parameters explains why the distribution coefficient of boron does not change much with changing slag composition. In addition, the thermodynamic properties of dilute boron oxide in CaO-MgO-Al₂O₃-SiO₂ slags was determined. The ratio of the activity coefficient of boron oxide and silica was found to be the most important parameter for understanding changes in the distribution coefficient of boron for different slags. Finally, the relation between the activity coefficient of boron oxide and slag structure was investigated. It was found that the structure can explain how the distribution coefficient of boron changes depending on slag composition.     

A quasi-chemical viscosity model for fully liquid slags in the Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-‘FeO’-SiO<Subscript>2</Subscript> system

A structurally based viscosity model for fully liquid silicate slags has been proposed and applied to the Al₂O₃-CaO-‘FeO’-SiO₂ system at metallic iron saturation. The model links the slag viscosity to the internal structure of melts through the concentrations of various anion/cation structural units (SUs). The concentrations of structural units are equivalent to the second nearest neighbor bond concentrations calculated by the quasi-chemical thermodynamic model. This viscosity model describes experimental data over the entire temperature and composition range within the Al₂O₃-CaO-‘FeO’-SiO₂ system at metallic iron saturation and can be extended to other industrial slag systems.     

Amphoteric behavior of alumina in viscous flow and structure of CaO-SiO<Subscript>2</Subscript> (-MgO)-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> slags

The viscosity of CaO-SiO₂ (-MgO)-Al₂O₃ slags was measured to clarify the effects of Al₂O₃ and MgO on the structure and viscous flow of molten slags at high temperatures. Furthermore, the infrared spectra of the quenched slags were analyzed to understand the structural role of Al₂O₃ in the polymerization or depolymerization of silicate network. The Al₂O₃ behaves as an amphoteric oxide with the composition of slags; that is, the alumina behaves as a network former up to about 10 mass pct Al₂O₃, while it acts as a network modifier, in parts, in the composition greater than 10 mass pct Al₂O₃. This amphoteric role of Al₂O₃ in the viscous flow of molten slags at the Newtonian flow region was diminished by the coexistence of MgO. The effect of Al₂O₃ on the viscosity increase can be understood based on an increase in the degree of polymerization (DOP) by the incorporation of the [AlO₄]-tetrahedra into the [SiO₄]-tetrahedral units, and this was confirmed by the infrared (IR) spectra of the quenched slags. The influence of alumina on the viscosity decrease can be explained on the basis of a decrease in the DOP by the increase in the relative fraction of the [AlO₆]-octahedral units. The relative intensity of the IR bands for the [SiO₄]-tetrahedra with low NBO/Si decreased, while that of the IR bands for [SiO₄]-tetrahedra with high NBO/Si increased with increasing Al₂O₃ content greater than the critical point, i.e., about 10 mass pct in the present systems. The variations of the activity coefficient of slag components with composition indirectly supported those of viscosity and structure of the aluminosilicate melts.     

Effects of FeO and CaO/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ratio in Slag on the Cleanliness of Al-Killed Steel

The slag composition plays a critical role in the formation of inclusions and the cleanliness of steel. In this study, the effects of FeO content and the C/A (CaO/Al₂O₃) ratio in the slag on the formation of inclusions were investigated based on a 10-minute slag–steel reaction in a MgO crucible. The FeO content in the top slag was shown to have a significant effect on the formation of MgO·Al₂O₃ spinel inclusions, and critical content exists; when the initial FeO content in the slag was less than 2 pct, MgO·Al₂O₃ spinel inclusions formed, and the T.O (total oxygen) was 20 ppm; when the initial FeO content in the slag was more than 4 pct, only Al₂O₃ inclusions were observed and the T.O was 50 ppm. It was clarified that the main source of Mg for the MgO·Al₂O₃ spinel inclusion formation was the top slag rather than the MgO crucible. In addition, the cleanliness of the steel increased as the initial FeO content in the top slag decreased. As regards the effects of the C/A ratio, the MgO amount in the observed inclusions gradually increased, whereas the T.O content decreased gradually with the increasing C/A ratio. Slag with a composition close to the CaO-saturated region had the best effect on the inclusion absorption.     

Evaluating the Diffusion Coefficient of Sulfur in Low-Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slag

The chemical diffusion coefficient of sulfur in the ternary slag of composition 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was measured at 1680 K, 1700 K, and 1723 K (1403 °C, 1427 °C, and 1450 °C) using the experimental method proposed earlier by the authors. The P_\textS2 P_{{{\text{S}}_{2} }} and P_\textO2 P_{{{\text{O}}_{2} }} pressures were calculated from the Gibbs energy of the equilibrium reaction between CaO in the slag and solid CaS. The density of the slag was obtained from earlier experiments. Initially, the order of magnitude for the diffusion coefficient was taken from the works of Saito and Kawai but later was modified so that the concentration curve for sulfur obtained from the program was in good fit with the experimental results. The diffusion coefficient of sulfur in 51.5 pct CaO-9.6 pct SiO₂-38.9 pct Al₂O₃ slag was estimated to be in the range 3.98 to 4.14 × 10⁻⁶ cm²/s for the temperature range 1680 K to 1723 K (1403 °C to 1450 °C), which is in good agreement with the results available in literature     

Distribution Ratios of Phosphorus Between CaO-FeO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/Na<Subscript>2</Subscript>O/TiO<Subscript>2</Subscript> Slags and Carbon-Saturated Iron

In order to effectively enhance the efficiency of dephosphorization, the distribution ratios of phosphorus between CaO-FeO-SiO₂-Al₂O₃/Na₂O/TiO₂ slags and carbon-saturated iron (\( L_{\text{P}}^{\text{Fe-C}} \)) were examined through laboratory experiments in this study, along with the effects of different influencing factors such as the temperature and concentrations of the various slag components. Thermodynamic simulations showed that, with the addition of Na₂O and Al₂O₃, the liquid areas of the CaO-FeO-SiO₂ slag are enlarged significantly, with Al₂O₃ and Na₂O acting as fluxes when added to the slag in the appropriate concentrations. The experimental data suggested that \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the binary basicity of the slag, with the basicity having a greater effect than the temperature and FeO content; \( L_{\text{P}}^{\text{Fe-C}} \) increases with an increase in the Na₂O content and decrease in the Al₂O₃ content. In contrast to the case for the dephosphorization of molten steel, for the hot-metal dephosphorization process investigated in this study, the FeO content of the slag had a smaller effect on \( L_{\text{P}}^{\text{Fe-C}} \) than did the other factors such as the temperature and slag basicity. Based on the experimental data, by using regression analysis, \( \log L_{\text{P}}^{\text{Fe-C}} \) could be expressed as a function of the temperature and the slag component concentrations as follows:

$$ \begin{aligned} \log L_{\text{P}}^{\text{Fe-C}} & = 0.059({\text{pct}}\;{\text{CaO}}) + 1.583\log ({\text{TFe}}) - 0.052\left( {{\text{pct}}\;{\text{SiO}}_{2} } \right) - 0.014\left( {{\text{pct}}\;{\text{Al}}_{2} {\text{O}}_{3} } \right) \\ \, & \quad + 0.142\left( {{\text{pct}}\;{\text{Na}}_{2} {\text{O}}} \right) - 0.003\left( {{\text{pct}}\;{\text{TiO}}_{2} } \right) + 0.049\left( {{\text{pct}}\;{\text{P}}_{2} {\text{O}}_{5} } \right) + \frac{13{,}527}{T} - 9.87. \\ \end{aligned} $$

     

Experimental Investigation and Thermodynamic Modeling of the B<Subscript>2</Subscript>O<Subscript>3</Subscript>-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> System for Recycling of NdFeB Magnet Scrap

NdFeB magnet scrap is an alternative source of neodymium that could have a significantly lower impact on the environment than current mining and extraction processes. Neodymium can be readily oxidized in the presence of oxygen, which makes it easy to recover neodymium in oxide form. Thermochemical data and phase diagrams for neodymium oxide containing systems is, however, very limited. Thermodynamic modeling of the B₂O₃-FeO-Fe₂O₃-Nd₂O₃ system was hence performed to obtain accurate phase diagrams and thermochemical properties of the system. Key phase diagram experiments were also carried out for the FeO-Nd₂O₃ system in saturation with iron to improve the accuracy of the present modeling. The modified quasichemical model was used to describe the Gibbs energy of the liquid oxide phase. The Gibbs energy functions of the liquid phase and the solids were optimized to reproduce all available and reliable phase diagram data, and thermochemical properties of the system. Finally the optimized database was applied to calculate conditions for selective oxidation of neodymium from NdFeB magnet waste.     

Phase equilibrium and distribution of minor elements between Ni-S melt and Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-CaO-MgO Slag at 1873 K

Distribution of nickel and minor elements such as Au, Ag, Fe, Co, Cu, As, and Sb between the Ni-S alloy and the CaO-Al₂O₃ based slag phases in a magnesia crucible was studied at 1873 K. Partial pressure of SO₂ was controlled at 10.1 kPa, while partial pressures of O₂ and S₂ ranged between the point of NiO precipitation (po₂ of 10.1 Pa) and the point at which Ni₃S₂ is formed (ps₂ of 4.0 kPa). The nickel content in the slag and the sulfur and oxygen contents in the metal at a given po₂ or pso₂ decrease when the temperature is increased from 1773 to 1873 K. The distribution ratios of iron, cobalt, and copper, defined by (wt pct X in slag)/{wt pct X in alloy}, where X is the minor element in the slag, have larger values than that of nickel, while the values of Au, Ag, Sb, and As are lower than that of nickel. The distribution behavior of nickel and minor elements is discussed based on the concept of oxidic and sulfidic dissolution.     

Understanding the Relationship Between Structure and Thermophysical Properties of CaO-SiO<Subscript>2</Subscript>-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Molten Slags

In the present work, the relationship between the microscopic structure and macroscopic thermophysical properties in a basic CaO-SiO₂-MgO-Al₂O₃ quaternary system was identified using Fourier transformation infrared, Raman and ²⁷Al magic angular spinning nuclear magnetic resonance (MAS-NMR) techniques. The Raman spectra quantitatively proved that with increasing Al₂O₃ content, the concentrations of the symmetric units of Q⁰(Si) and Q²(Si) decreased, while those of the asymmetric units of Q¹(Si) and Q³(Si) increased; consequently, the degree of polymerization of the networks increased, which resulted in an increase in slag viscosity. The ²⁷Al MAS-NMR spectra demonstrated that three structural units of Al atoms, namely, AlO₄, AlO₅, and AlO₆, mainly existed in the networks. With increasing Al₂O₃ content, the concentration of AlO₄ slightly decreased, while those of AlO₅ and AlO₆ increased; overall, Al₂O₃ acted as a network former in the present system. The increasing Al₂O₃ content led to additional AlO₆ and Si-NBO-Ca-NBO-Al frameworks, which replaced Si-NBO-Ca-NBO-Si in the networks (NBO: non-bridging oxygen) and induced a change in the primarily precipitated crystalline phase from Ca₂MgSi₂O₇ and Ca₂Al₂SiO₇ to MgAlO₄.     

Thermodynamic evaluation and optimization of the MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MnO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> systems and applications to inclusion engineering

All available thermodynamic and phase-diagram data have been critically evaluated and optimized for the liquid-slag phase and for all solid phases at 1 bar pressure from 298 K to above the liquidus temperatures for the systems MnO-Al₂O₃ and MnO-Al₂O₃-SiO₂, and a database of model parameters has been prepared. The modified quasichemical model was employed for the molten-slag phase. Calculations using the database were performed with applications to inclusion engineering for Mn/Si killed steel.     

Effect of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO slags on the formation of MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> inclusions in ferritic stainless steel

A thermodynamic equilibrium between the Fe-16Cr melts and the CaO-Al₂O₃-MgO slags at 1823 K as well as the morphology of inclusions was investigated to understand the formation behavior of the MgO-Al₂O₃ spinel-type inclusions in ferritic stainless steel. The calculated and observed activities of magnesium in Fe-16Cr melts are qualitatively in good agreement with each other, while those of aluminum in steel melts exhibit some discrepancies with scatters. In the composition of molten steel investigated in this study, the log (X _MgO/X _{Al 2}O₃) of the inclusions linearly increases by increasing the log [a _Mg/a _Al ² ·a _O ² ] with the slope close to unity. In addition, the relationship between the log (X _MgO/X _{Al 2}O₃) of the inclusions and the log (a _MgO/a _{Al 2}O₃) of the slags exhibits the linear correlation with the slope close to unity. The compositions of the inclusions are relatively close to those of the slags, viz. the MgO-rich magnesia-spinel solid solutions were formed in the steel melts equilibrated with the highly basic slags saturated by CaO or MgO. The spinel inclusions nearly saturated by MgO were observed in the steel melts equilibrated with the slags doubly saturated by MgO and MgAl₂O₄. The spinel and the Al₂O₃-rich alumina-spinel solid solutions were formed in the steel melts equilibrated with the slags saturated by MgAl₂O₄ and MgAl₂O₄-CaAl₂O₄ phases, respectively. The apparent modification reaction of MgO to the magnesium aluminate inclusions in steel melts equilibrated with the highly basic slags would be constituted by the following reaction steps: (1) diffusion of aluminum from bulk to the metal/MgO interface, (2) oxidation of the aluminum to the Al³⁺ ions at the metal/intermediate layer interface, (3) diffusion of Al³⁺ ions and electrons through the intermediate layer, and (4) magnesium aluminate (MgAl₂O₄ spinel, for example) formation by the ionic reaction.     

Density Measurements of Low Silica CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Slags

Density measurements of a low-silica CaO-SiO₂-Al₂O₃ system were carried out using the Archimedes principle. A Pt 30 pct Rh bob and wire arrangement was used for this purpose. The results obtained were in good agreement with those obtained from the model developed in the current group as well as with other results reported earlier. The density for the CaO-SiO₂ and the CaO-Al₂O₃ binary slag systems also was estimated from the ternary values. The extrapolation of density values for high-silica systems also showed good agreement with previous works. An estimation for the density value of CaO was made from the current experimental data. The density decrease at high temperatures was interpreted based on the silicate structure. As the mole percent of SiO₂ was below the 33 pct required for the orthosilicate composition, discrete \textSiO₄^{4 -} {\text{SiO}}_{4}^{4 - } tetrahedral units in the silicate melt would exist along with O^2– ions. The change in melt expansivity may be attributed to the ionic expansions in the order of