Experimental Studies on the Sulfide Capacities of CaO-SiO<Subscript>2</Subscript>-CrO<Subscript>x</Subscript> Slags

To understand the desulfurization process during the refining of Cr-containing steel grades, this work was initiated to study the reactions between Cr-sulfur and chromium-containing slags. The sulfide capacities of CaO-SiO₂-CrO_x pseudo-ternary slags were measured using the traditional gas-slag equilibration technique between 1823 K and 1923 K. Sixteen different slag compositions were examined, and two different equilibrium oxygen partial pressures were used to understand the impact of the varying valence of Cr on the sulfide capacities. The results showed that log₁₀ Cs varied linearly with the reciprocal T, and the slope was higher than the corresponding value reported for the binary CaO-SiO₂ of corresponding composition. It was difficult to isolate the relative effects of the bi- and trivalent Cr in the slags because the Cr²⁺/Cr³⁺ ratio was influenced by the basicity of the slag. By using the equation developed by these authors earlier that related Cr²⁺/Cr³⁺ with basicity, oxygen partial pressure, and temperature, it was possible to obtain an approximate trend of the CrO effect on the sulfide capacities; viz. the sulfide shows a decreasing trend as Cr²⁺ replaces Ca²⁺ in the slag. With a continued increase of Cr²⁺ content, indications of the occurrence of a minimum point were observed; beyond which the sulfide capacities showed a slight increasing trend. The latter was attributed, based on slag-structure analysis by Gaskell et al., to the increasing extent of the polymerization reaction releasing oxygen ions for sulfide reactions.     

Activity of Chromium Oxide in CaO‐SiO2 based Slags at 1873 K

Thermodynamic properties of chromium oxides in molten slags are very important for optimization of stainless steel refining processes as well as reduction processes of chromium ores. The solubility of chromite into molten slags has been found to vary drastically with oxygen partial pressure and slag composition in the former studies by the authors. In the present study, activity data and redox equilibria of chromium oxides measured under moderately reducing conditions, P_O2= 6.95×10^?11 atm, at 1873 K are summarized. For the CaO‐SiO₂‐CrO_x system, the activity coefficient of chromium oxide increased with increasing basicity and the optimized slag composition for stainless steel refining is assessed as that saturated with CaCr₂O₄ and Cr₂O₃ using the phase relations determined. On the other hand, the presence of MgO and Al₂O₃ brings about different behaviour of chromium oxide activity and redox equilibria and the 44 mass per cent CaO ‐ 39 mass per cent SiO₂ ‐11 mass per cent Al₂O₃ ‐ 6 mass per cent MgO slag is recommended to reduce the chromium oxidation loss in the practical stainless steel refining process at 1873 K.     

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.     

SHS Metallurgy of Cr<Subscript>2</Subscript>AlC MAX Phase-Based Cast Materials

A review of publications on the structure, properties, fabrication methods, and application fields of materials based on the Cr₂AlC MAX phase is given. It is noted that the most promising method of formation of such materials is self-propagating high-temperature synthesis (SHS), one of the directions of which is SHS metallurgy. A powder mixture of chromium III and chromium VI oxides of the analytical grade, aluminum of ASD-1 grade, and carbon is used as the base charge in investigations. The adiabatic combustion temperature and composition of final products is calculated using the THERMO special program. Experiments were performed in an SHS reactor with volume V = 3 dm³ under the initial pressure of inert gas (Ar) P₀ = 5 MPa. The influence of the ratio of initial reagents on SHS parameters (the combustion rate, pressure increment, and yield of the target product), composition, and microstructure of target products is investigated experimentally. A scientific approach of the formation of cast materials in the Cr–Al–C system consisting of the Cr₂AlC MAX phase and phases Cr₃C₂ and Cr₅Al₈ by the SHS metallurgy method is developed. The structural-phase states of target products are studied. It is established experimentally that, varying the content of initial reagents (aluminum and carbon) in the charge, it is possible to substantially affect the synthesis regularities, composition, and microstructure of final products. An increase in the content of the Cr₂AlC MAX phase in the final product and a decrease in the Cr₅Al₈ content occur with an increase in the carbon content (above stoichiometric) in the initial mixture. An increase in the aluminum content (above stoichiometric) in the initial mixture leads to an increase in the content of the Cr₂AlC MAX phase in the final product and a decrease in the content of the Cr₃C₂ phase.     

Monte Carlo and Molecular Dynamics Simulation of Disorder in the Ag<Superscript>+</Superscript> Fast Ion Conductors Pearceite and Polybasite

The pearceite-polybasite group of minerals (i.e., pearceite, antimonpearceite, arsenpolybasite, and polybasite) of general stoichiometry [M₆^IT₂^IIIS₇][Ag₉^ICu^IS₄], with M = Ag⁺, Cu⁺ and T = As³⁺, Sb³⁺, occur relatively commonly in nature. All have recently been shown to exhibit Ag ⁺ fast ion conduction at rather low temperatures (only slightly above or below room temperature[1]). The average crystal structure determination of these materials shows the positions of the Ag⁺ ions to be smeared out or delocalized within sheets in an ordered framework structure comprised of the other ions. At the same time, strong and highly structured diffuse scattering has been observed, which contains diffuse peaks that are incommensurate with the diffraction peaks of the framework structure. In order to try to understand the origins of the fast ion conduction properties of these materials, we have used computer simulation of a model system (Monte Carlo and molecular dynamics (MD)) to analyze this observed diffuse scattering.     

Formation of complex compounds of univalent copper at the Cu<Superscript>0</Superscript>-Cu<Superscript>2+</Superscript> interphase boundary in chloride solutions

Kinetics and a mechanism of formation of compounds of univalent copper at the interphase boundary Cu⁰-Cu²⁺ in the solution containing excess chlorine anions are investigated by the spectrophotometry method. It is shown that the [CuCl₂]^? and [CuCl₃]^2? complex anions are formed during the contact of metal copper with the Cu²⁺ ions. The former ones are characterized by the appearance of the band in the region of 233 nm in the spectra of electron absorption, and the latters ones—in the region of 273 nm. The dependence of intensity of absorption bands on the contact time of the Cu²⁺ ions with copper is used to estimate the kinetic parameters of formation and oxidation of the [CuCl₂]^? and [CuCl₃]^2? ions. A thickness of the reaction layer, in which they are formed, is determined. The formation of the Cu(I) compounds during the contact interaction of copper with the Cu²⁺ ions is confirmed by the results of electrochemical investigations. The mechanism of cathode reduction of copper-containing compounds on a copper electrode is suggested.     

Solid-phase reduction of Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> under chemical catalytic conditions

The kinetics of the solid-phase reduction of Cr₂O₃ with carbon under chemical catalytic action on the reacting system is studied. A significant intensification of the process in the presence of small amounts of potassium and sodium salts is established. The concepts of the catalyst action mechanism are considered and experimentally substantiated. Manufacture of iron–chromium master alloys with a restricted content of carbon can be organized at low temperatures, and they can be used in steelmaking.     

The Thermodynamics of Some Transition Metals in Molten Slags

In the present paper, the thermodynamic behaviour of transition metals, such as Cr, Ti, Nb and V in molten slags is systematically analysed based on a literature survey. These metals exist in molten slags with multi valences. Oxygen partial pressure, slag basicity, total content of each transition metal, content of each component in slag, and temperature are the influential factors on their thermodynamic properties in molten slags. Higher basicity and strong oxidative atmosphere are generally favourable for the stable existence of transition‐metal ions with higher oxidation states. Temperature is a factor that is less influential than the above‐mentioned ones. For a transition metal in molten slag, the concentration ratio of ions of different valences depends on the activity coefficient ratio of their oxides. The present paper summarizes the activity studies regarding the transition metal oxides in various molten slags. For chromium and titanium oxides, information on CaO? SiO₂ based systems is involved. For titanium oxides, its thermodynamic behaviour in MnO? SiO₂ based slags is introduced. For niobium and vanadium, the information in Na₂O? SiO₂, CaO? CaF₂? SiO₂ systems is provided. Thermodynamic studies are described for Nb₂O₅? MnO? SiO₂ molten slag equilibrated with liquid iron at 1828 K.     

Oxidation state and activities of chromium oxides in CaO-SiO2-CrOx slag system

The activities of chromium oxides in a CaO-SiO₂-CrO _x slag system were determined with the electromotive force (EMF) method by equilibrating with metallic chromium at 1873 K. The effect of slag basicity on the activity coefficients of CrO and CrO_1.5 was analyzed. The results showed that increasing the slag basicity increased the activity coefficient of CrO; however, the effect on that of CrO_1.5 was not significant. The oxidation state of chromium in CaO-SiO₂-CrO _x slags was systematically investigated at both 1873 and 1863 K. It was found that divalent and trivalent chromium coexists in the slags. Divalent chromium oxide is favored, instead of trivalent chromium oxide, because of low slag basicity and low oxygen potential. It was concluded that the oxidation state of chromium in the slag system varied greatly from almost pure “CrO” to a composition corresponding to Cr₃O₄. In addition, the thermodynamic data in the slag system were assessed based on the regular solution model to mathematically describe the activities of chromium oxides in the slags. A group of model parameters were obtained. The calculated activities of chromium oxides were comparable to the measured data.     

Investigation of behavior of elemental sulfur in H<Subscript>2</Subscript>O-OH<Superscript>−</Superscript>-CN<Superscript>−</Superscript> solutions

The processes of dissolution of elemental sulfur in S-H₂O-OH⁻-CN⁻ systems are investigated. These processes simulate the technological processes of cyanidation and the sorption leaching of Au from the biocakes of gold recovery plants in the range of concentrations of the CN⁻ ions of 0–0.02 mol/dm³ and the range of concentrations of the OH⁻ ions of 0–0.1 mol/dm³. Using the simple-lattice planning method of the experiment, mathematical models and “solvent composition-amount of dissolved sulfur” diagrams are constructed for temperatures of 20, 30, and 40°C. It is established that, at t = 20°C, the strongest effect on the solubility of S in the mentioned solvents exerts the concentration of cyanides, while, at t = 30 and 40°C, the larger contribution to an increase in transfer of S into the solution gives the OH⁻ content. The role of hydrolysis that the CN⁻ ion plays in increasing the solubility of sulfur in the studied systems is shown.