Thermodynamics of MnO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MnS Liquid Oxysulfide: Experimental and Thermodynamic Modeling

The activities of MnO and MnS in a MnO-SiO₂-Al₂O₃(or AlO_1.5)-MnS liquid oxysulfide solution were investigated by employing the gas/liquid/Pt-Mn alloy chemical equilibration technique under a controlled atmosphere at 1773 K (1500 °C). Also, the sulfide capacity, defined as C _S = (wt pct S)(pO₂/pS₂)^1/2, in MnO-SiO₂-Al₂O₃ slag with a dilute MnS concentration was obtained from the measured experimental data. As X _SiO2/(X _MnO + X _SiO2) in liquid oxysulfide increases, the activity coefficient of MnO decreases, while that of MnS first increases and then decreases. As X(AlO_1.5) in liquid oxysulfide increases, the activity coefficient of MnS increases, while no remarkable change is observed for the activity coefficient of MnO. The behavior of the activity coefficient of MnS was qualitatively analyzed by considering MnO + A _x S _y (SiS₂ or Al₂S₃) = MnS + A _x O _y (SiO₂ or Al₂O₃) reciprocal exchange reactions in the oxysulfide solution. The behavior was shown to be consistent with phase diagram data, namely, the MnS saturation boundary. Quantitative analysis of the activity coefficient of the oxysulfide solution was also carried out by employing the modified quasichemical model in the quadruplet approximation.     

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.     

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     

The Interface of TiB<Subscript>2</Subscript> and Al<Subscript>3</Subscript>Ti in Molten Aluminum

In the grain refinement of aluminum, Al₃Ti and TiB₂ particles are introduced to reduce the casting grain size down to 200 micrometer level, which makes cold working possible. The particles are brought in by the addition of Al-Ti-B-type master alloys. It is generally believed that TiB₂ particles are stable and nucleate α-Al grains in solidification in the presence of titanium in solution from the dissolution of Al₃Ti particles in the master alloys. The titanium in solution either forms Al₃Ti layers on the surface of TiB₂ particles to promote the nucleation of α-Al grains or remains as solute to restrict the growth of α-Al grains in solidification. However, a consensus on a grain refinement mechanism is still to be reached due to the lack of direct observation of the three phases in castings. This paper presents finding of the TiB₂/Al₃Ti interfaces in an Al-Ti-B master alloy. It demonstrates a strong epitaxial growth of Al₃Ti on the surface of TiB₂ particles, a sign of the formation of an Al₃Ti layer on the surface of TiB₂ particles in grain refinement practice. The Al₃Ti layer has a crystal coherency with α-Al and hence offers a substrate for heterogeneous nucleation of α-Al grains. However, the layer must be dynamic to avoid the formation of compounded Al₃Ti and TiB₂ particles leading to the loss of efficiency in grain refinement.     

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.     

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:

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.     

Synthesis and Non-isothermal Carbothermic Reduction of FeTiO<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> Solid Solution Systems

To investigate the carbothermic reduction behaviors of xFeTiO₃·(1 ? x)Fe₂O₃ solid solutions, the solid solutions with different x values were synthesized and used in the corresponding reactions. With an increase in x, the temperature pertaining to the onset of carbothermic reduction increased, while the rate of reduction of the solid solutions, α, decreased. The lattice parameters calculated from XRD patterns indicated that the solid solution with a higher x led to a larger lattice distortion. The non-isothermal kinetics were calculated, and an average activation energy E value of 3.0 × 10² kJ/mol was obtained.     

Effect of Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> on Structure,Viscosity, and Crystalline Phase of CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-Li<Subscript>2</Subscript>O-Ce<Subscript>2</Subscript>O<Subscript>3</Subscript> Slags

Aiming at devising new mold flux for Ce-bearing stainless steel, a fundamental investigation on the effect of Ce₂O₃ on properties of the CaO-Al₂O₃-Li₂O-Ce₂O₃ slag was provided by the present work. The results show that adding Ce₂O₃ could decrease the viscosity of the slag due to its effects on decreasing the polymerization of the slag. The crystalline process was restrained by increasing the content of Ce₂O₃, and the crystalline phases also can be influenced by the slag structure. The crystalline phases were transferred from LiAlO₂ and CaO to LiAlO₂ and CaCeAlO₄ with the addition of Ce₂O₃ to the slag, which could be well confirmed by the structure of the unit cell of the crystals.     

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:

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

     

Electrical conductivity of NaF-AlF<Subscript>3</Subscript>-CaF<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> melts

The electrical conductivity of NaF-AlF₃-Al₂O₃ melts with a CaF₂ concentration of 5 wt % is measured at a continuously varying cell constant when the molar cryolitic ratio CR = [NaF]/[AlF₃] changes from 1.2 to 2.0 [1, 2]. The experimental data are used to obtain a regression equation to describe the dependence of the electrical conductivity of the melts under study on CR, the alumina content, and temperature {χ] = f(CR, [Al₂O₃], T)}.     

The Ca(SO<Subscript>4</Subscript>)-Na<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)-Ca<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>)<Subscript>2</Subscript>-Na<Subscript>3</Subscript>(AsO<Subscript>4</Subscript>) phase diagram

The phase diagram of the CaSO₄-Na₂SO₄-Ca₃(AsO₄)₂-Na₃(AsO₄) system was measured by differential thermal analysis and by an equilibration and quenching technique. Thermodynamic models were developed giving the Gibbs energies of all phases as functions of temperature and composition. Optimized model parameters were obtained by assessment of all available thermodynamic and phase equilibrium data. The models, which reproduce all the data within experimental error limits, were used to calculate the liquidus surface of the system. The modified quasi-chemical model in the quadruplet approximation was used for the liquid solution. For the various solid solution phases, the modified quasi-chemical model, which accounts simultaneously for short-range-ordering among first-nearest-neighbor (FNN) and second-nearest-neighbor (SNN) pairs, was used for the first time within the framework of the compound energy formalism. The distinction between true model parameters and formalism parameters is made. Implications of the work for the potential use of sulfate fluxes for copper refining are discussed.     

Phase-equilibrium data and liquidus for the system “MnO”-CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> at Al<Subscript>2</Subscript>O<Subscript>3</Subscript>/SiO<Subscript>2</Subscript> of 0.55 and 0.65

Phase-equilibrium data and liquidus isotherms for the system “MnO”-CaO-(Al₂O₃+SiO₂) at silicomanganese alloy saturation have been determined in the temperature range of 1373 to 1723 K. The results are presented in the form of the pseudoternary sections “MnO”-CaO-(Al₂O₃+SiO₂) with Al₂O₃/SiO₂ weight ratios of 0.55 and 0.65. The primary-phase fields have been identified in this range of conditions.