Thermodynamics Calculation and Experimental Study on Separation of Bismuth from a Bismuth Glance Concentrate Through a Low-Temperature Molten Salt Smelting Process

The main purpose of this study is to characterize and separate bismuth from a bismuth glance concentrate through a low-temperature, sulfur-fixing smelting process. This article reports on a study conducted on the optimization of process parameters, such as Na₂CO₃ and zinc oxide wt pct in charging, smelting temperature, smelting duration on the bismuth yield, resultant crude bismuth grade, and sulfur-fixing rate. A maximum bismuth recovery of 97.31 pct, crude bismuth grade of 96.93 pct, and 98.23 pct sulfur-fixing rate are obtained when a charge (containing 63.50 wt pct of Na₂CO₃ and 22.50 wt pct of bismuth glance, as well as 5 pct in excess of the stoichiometric requirement of zinc oxide dosage) is smelted at 1000 K (727 °C) for 150 minutes. This smelting operation is free from atmospheric pollution because zinc oxide is used as the sulfur-fixing agent, which can capture sulfur from bismuth sulfide and form the more thermodynamic-stable compound, zinc sulfide. The solid residue is subjected to a mineral dressing operation to obtain suspension, which is filtered to produce a cake, representing the solid particles of zinc sulfide. Based on the results of the chemical content analysis of the as-resultant zinc sulfide, more than 93 pct zinc sulfide can be recovered, and the recovered zinc sulfide grade can reach 60.20 pct. This material can be sold as zinc sulfide concentrate or roasted to be regenerated as zinc oxide.     

Diffusion of Au in the Intermetallic Compound Ti<Subscript>3</Subscript>Al

The Au diffusion in the Ti₃Al compound was investigated at six compositions from 25 to 35 at. pct Al by using the diffusion couples (Ti-X at. pct Al/Ti-X at. pct Al-2 at. pct Au; X = 25, 27, 29, 31, 32, and 35) at 1273 to 1423 K. The diffusion coefficients of Au in Ti₃Al ( D_\textAu^{\textTi₃ \textAl} ) \left( {D_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} } \right) are relatively close to those of Ti. The D_\textAu^{\textTi₃ \textAl} \texts {D}_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}} slightly increase with Al concentration within the same order of magnitude. The activation energies of Au diffusion, Q_\textAu^{\textTi₃ \textAl} \texts, Q_{\text{Au}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}, evaluated from the Arrhenius plots were relatively close to those of Ti diffusion, Q_\textTi^{\textTi₃ \textAl} \texts, Q_{\text{Ti}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}, rather than those of Al diffusion, Q_\textAl^{\textTi₃ \textAl} \texts; {Q}_{\text{Al}}^{{{\text{Ti}}_{3} {\text{Al}}}} {\text{s}}; therefore, it was suggested that Au atoms diffuse by the sublattice diffusion mechanism in which Au atoms substitute for Ti sites preferentially in Ti₃Al and diffuse by vacancy mechanism on Ti sublattice. The influence of the D0₁₉ ordered structure (hcp base) of Ti₃Al on diffusion of Au and other elements is discussed by comparing the diffusivities in Ti₃Al and α-Ti.     

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

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     

Solubilities of Chlorine in CaO-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-MgO Slags: Correlation Between Sulfide and Chloride Capacities

To derive a correlation between sulfide and chloride capacities through our own systematic experimental studies by using a gas equilibrium technique involving Ar-H₂-H₂O-HCl gas mixtures, the solubilities of chlorine were determined for CaO-SiO₂-MgO-Al₂O₃ slags at temperatures between 1673 K and 1823 K (1400 °C and 1550 °C). As a formula to correlate sulfide and chloride capacities, the following equation that is the function of temperature only was obtainable;

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:

Effects of Zr Additions on the Microstructure and Impression Creep Behavior of AZ91 Magnesium Alloy

The effects of 0.2, 0.6, and 1.0 wt pct Zr additions on the microstructure and creep behavior of AZ91 Mg alloy were investigated by impression tests carried out under constant punching stress (σ _imp) in the range 100 to 650 MPa, corresponding to the modulus-compensated stress levels of 0.007 ￡ s_\textimp \mathord

Effect of Nitrogen Content on the Microstructure and Mechanical Properties of Ti-Mo-N Coating Films

Effects of nitrogen content on the microstructure, hardness, and friction coefficient of Ti-Mo-N coating films were investigated. Ti-Mo-N films were deposited onto an AISI304 stainless steel substrate by reactive r.f. sputtering in the mixture of argon and nitrogen gases with various gas flow rates. The hardness and friction coefficients were measured by nanoindentation and ball-on-disk testing systems, respectively. The hardness of the Ti-Mo-N films increased with increasing a nitrogen gas flow rate ( f_\textN2 ) \left( {f_{{{\text{N}}_{2} }} } \right) and showed a maximum hardness of about 30 GPa at a f_\textN2 = 0.3 \textccm f_{{{\text{N}}_{2} }} = 0.3\,{\text{ccm}} . On the one hand, the films deposited at f_\textN2 3 1.0  \textccm f_{{{\text{N}}_{2} }} \ge 1.0\;{\text{ccm}} showed a constant hardness value of approximately 25 GPa. On the other hand, the friction coefficient of the Ti-Mo-N film decreased with increasing N content and was 0.44 in the film deposited at f_\textN2 = 2.0  \textccm. f_{{{\text{N}}_{2} }} = 2.0\;{\text{ccm}}.     

Thermodynamic Measurement of Di-calcium Phosphate

The thermodynamic properties of the CaO-P₂O₅ system are important to develop an effective refining process in the iron and steel industry. In this study, the thermodynamic properties of (CaO)₂P₂O₅ were investigated because the properties are necessary to develop a new dephosphorization process. The vapor of gaseous phosphorus and phosphorus oxide in equilibrium with a mixture of (CaO)₂P₂O₅ and (CaO)₃P₂O₅ at 1373 K to 1498 K (1100 °C to 1225 °C) were detected directly as an ion current by double Knudsen cell mass spectrometry. Comparing the ion currents with those from a mixture of Al₂O₃P₂O₅ and Al₂O₃, which is used as a reference mixture in this study, the Gibbs energy change of the following reaction was calculated:

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:

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

     

Dissolution Behavior of Indium in CaO-SiO2-Al2O3 Slag

The solubility of indium in a molten CaO-SiO₂-Al₂O₃ system was measured at 1773 K (1500 °C) to establish the dissolution mechanism of indium under a highly reducing atmosphere. The solubility of indium increases with increasing oxygen potential, whereas it decreases with increased activity of basic oxide. Therefore, a dissolution mechanism of indium can be constructed according to the following equation:

Oxidation and Condensation of Zinc Fume From Zn-CO<Subscript>2</Subscript>-CO-H<Subscript>2</Subscript>O Streams Relevant to Steelmaking Off-Gas Systems

The objective of this research was to study the condensation of zinc vapor to metallic zinc and zinc oxide solid under varying environments to investigate the feasibility of in-process separation of zinc from steelmaking off-gas dusts. Water vapor content, temperature, degree of cooling, gas composition, and initial zinc partial pressure were varied to simulate the possible conditions that can occur within steelmaking off-gas systems, limited to Zn-CO₂-CO-H₂O gas compositions. The temperature of deposition and the effect of rapidly quenching the gas were specifically studied. A homogeneous nucleation model for applicable experiments was applied to the analysis of the experimental data. It was determined that under the experimental conditions, oxidation of zinc vapor by H₂O or CO₂ does not occur above 1108 K (835 °C) even for highly oxidizing streams (CO₂/CO = 40/7). Rate expressions that correlate CO₂ and H₂O oxidation rates to gas composition, partial pressure of water vapor, temperature, and zinc partial pressure were determined to be as follows:

$$ {\text{Rate}}\left( {\frac{\text{mol}}{{{\text{m}}^{2} {\text{s}}}}} \right) = 406 \exp \left( {\frac{{ - 50.2 \,{\text{kJ}}/{\text{mol}}}}{RT}} \right)\left( {p_{\text{Zn}} p_{{{\text{CO}}_{2} }} - p_{\text{CO}} /K_{{{\text{eq}},{\text{CO}}_{2} }} } \right)\,\frac{\text{mol}}{{{\text{m}}^{2} \times {\text{s}}}} $$

$$ {\text{Rate}}\left( {\frac{\text{mol}}{{{\text{m}}^{2} {\text{s}}}}} \right) = 32.9 \exp \left( {\frac{{ - 13.7\, {\text{kJ}}/{\text{mol}}}}{RT}} \right)\left( {p_{\text{Zn}} p_{{{\text{H}}_{2} {\text{O}}}} - p_{{{\text{H}}_{2} }} /K_{{{\text{eq}},{\text{H}}_{2} {\text{O}}}} } \right)\,\frac{\text{mol}}{{{\text{m}}^{2} \times {\text{s}}}} $$

It was proven that a rapid cooling rate (500 K/s) significantly increases the ratio of metallic zinc to zinc oxide as opposed to a slow cooling rate (250 K/s). SEM analysis found evidence of heterogeneous growth of ZnO as well as of homogeneous formation of metallic zinc. The homogeneous nucleation model fit well with experiments where only metallic zinc deposited. An expanded model with rates of oxidation by CO₂ and H₂O as shown was combined with the homogenous nucleation model and then compared with experimental data. The calculated results based on the model gave a reasonable fit to the measured data. For the conditions used in this study, the rate equations for the oxidation of zinc by carbon dioxide and water vapor as well as the homogeneous nucleation model of metallic zinc were applicable for various temperatures, zinc partial pressures, CO₂:CO ratios, and H₂O partial pressures.

     

Redox Equilibrium of Niobium in Calcium Silicate Base Melts

The oxidation state of niobium has been determined at 1873 K (1600 °C) in CaO-SiO₂-NbO _x melts with CaO/SiO₂ ratios (mass pct) of 0.66, 0.93 and 1.10, and 5.72 to 11.44 pct Nb₂O₅ (initial). The slag samples were equilibrated with gas phases of controlled oxygen pressure, then quenched to room temperature and analyzed chemically. The niobium is mainly pentavalent with small amounts in the tetravalent state. It was found that the Nb⁵⁺/Nb⁴⁺ ratio increases with oxygen pressure at a constant CaO/SiO₂ ratio and constant content of total niobium, closely according to the ideal law of mass action, which is proportional to \textp_\textO2 ^1/4 . {\text{p}}_{{{\text{O}}_{2} }}^{1/4} . The ratio also increases with total niobium content, and it seems to have a maximum at a basicity of about 0.93. The color of the solidified slag samples is described and is explained with the help of transmission spectra.     

Confocal Scanning Laser Microscopy Studies of Crystal Growth During Oxidation of a Liquid FeO-CaO-SiO<Subscript>2</Subscript> Slag

The oxidation of FeO in 30 wt pct FeO-35 wt pct CaO-35 wt pct SiO₂ slag was investigated as part of a wider study on the recovery of Fe units through magnetic separation. A confocal scanning laser microscopy (CSLM) technique was used to visualize the oxidation of FeO in the liquid slag. The formation event was observed in situ under the CSLM and the onset of precipitation on a surface of the slag liquid was recorded at various temperatures in an oxidizing atmosphere. A Time-Temperature-Transformation (TTT) diagram was constructed based on the CSLM results. Samples obtained from the CSLM heating chamber were analyzed by a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS).     

Microstructure Refinement After the Addition of Titanium Particles in AZ31 Magnesium Alloy Resistance Spot Welds

Microstructural evolution of AZ31 magnesium alloy welds without and with the addition of titanium powders during resistance spot welding was studied using optical microscopy, scanning electron microscopy, and transmission electron microscopy (TEM). The fusion zone of AZ31 magnesium alloy welds could be divided into columnar dendritic zone (CDZ) and equiaxed dendritic zone (EDZ). The well-developed CDZ in the vicinity of the fusion boundary was clearly restricted and the coarse EDZ in the central region was efficiently refined by adding titanium powders into the molten pool, compared with the as-received alloy welds. A microstructural analysis showed that these titanium particles of approximately 8 μm diameter acted as inoculants and promoted the nucleation of α-Mg grains and the formation of equiaxed dendritic grains during resistance spot welding. Tensile-shear testing was applied to evaluate the effect of titanium addition on the mechanical properties of welds. It was found that both strength and ductility of magnesium alloy welds were increased after the titanium addition. A TEM examination showed the existence of an orientation matching relationship between the added Ti particles and Mg matrix, i.e., [ 0 1[`1]0 ]<sub>\textMg</sub> //  [ 1[`2] 1[`3] ]<sub>\textTi</sub>  \textand ( 000 2 )<sub>\textMg</sub> //  ( 10[`1]0)_\textTi \left[ {0 1\bar{1}0} \right]_{\text{Mg}} // \, \left[ { 1\bar{2} 1\bar{3}} \right]_{\text{Ti}} \,{\text{and}}\,\left( {000 2} \right)_{\text{Mg}} // \, ( 10\bar{1}0)_{\text{Ti}} in some grains of Ti polycrystal particles. This local crystallographic matching could promote heterogeneous nucleation of the Mg matrix during welding. The diameter of the added Ti inoculant should be larger than 1.8 μm to make it a potent inoculant.     

Experimental Determination of Mg Activities in Fe-Mg Solutions

The thermodynamics of magnesium in liquid iron was determined at 1823 K (1550 °C). For this purpose, liquid iron was equilibrated with Ag-Mg alloys in a semienclosed molybdenum vessel. From the partition of magnesium between iron and silver, the activity coefficient of Mg and the self-interaction parameter e_\textMg^\textMg \varepsilon_{\text{Mg}}^{\text{Mg}} were determined.