Vol 2018, No 5 (2018)

The results of thermodynamic simulation of the desulfurization of a medium-carbon steel by slags of the CaO–SiO₂–MgO–Al₂O₃–B₂O₃ system are presented. The HSC Chemistry 6.12 software package is used for the simulation. The thermodynamic simulation is performed for 20 various chemical compositions of slags with various B₂O₃ contents (1–4%)¹ and basicities ((CaO)/(SiO₂) = 2–5). The computations are performed using the Equilibrium Compositions module in the temperature range from 1500 to 1700°C with an increment of 50°C at a gas phase pressure of 0.1 MPa. The main results of the calculations are presented as the dependences of the change in the sulfur content in steel [S] on the temperature, the content of B₂O₃, and the slag basicity. An increase in the temperature of metal desulfurization from 1500 to 1700°C exerts a favorable effect on the sulfur content for the studied range of slag basicities. In particular, the sulfur content in steel decreases from 0.012 to 0.009% when steel is processed with the slag having 3% B₂O₃ and a basicity (CaO)/(SiO₂) = 2. A positive effect of an increase in the slag basicity from 2 to 5 on metal desulfurization is observed: the degree of desulfurization increases from 61.1 to 97.2% at 1600°C and 3% B₂O₃ content in the slag. As the B₂O₃ content in a slag increases from 1 to 4%, its refining properties decrease significantly in the range of basicity not higher than 2. In the range of high slag basicities (3–4), the negative effect of acidic oxide B₂O₃ on the refining properties of the slag decreases, providing low sulfur contents (which do not exceed [S] = 0.003–0.004% at 4% B₂O₃). At a slag basicity of 5, the sulfur content in steel decreases to 0.001%, all other things being equal. The simulation results can be used for the calculation of steel desulfurization processed by slags containing B₂O₃.

In diffusion brazing, a brazing alloy layer thickness introduced into the gap between brazed parts is very small, which hinders the study of the isothermal solidification process. In this work, the isothermal solidification of an Al–Zn alloy is investigated at large volume and mass of the initial liquid that takes part in isothermal solidification. Zinc cylinders are caulked in the holes bored in aluminum cubes. The samples thus assembled are held at 500 ± 10°C for different times. The volume fraction of isothermal solidified crystals has been determined, and the growth rate of isothermal crystals is shown to decrease upon holding. The crystals formed during isothermal solidification width are up to 380 μm and length more than 1 mm. They are observed in the samples that are held more than 2 days. The zinc content in the isothermal solidified crystals corresponds to its mean content in the aluminum solid solution at 490–510°C, according to the Al–Zn phase diagram. The composition of the former liquid that surrounded the crystals during isothermal solidification coincides with the equilibrium composition of the liquid in the Al–Zn system at a temperature of 490–510°C.

Thermogravimetry studies show that the oxidation of aluminum–rare-earth metal (R) melts obeys a parabolic law. The true oxidation rate of the melts is on the order of 10^–4–10^–3 kg/(m² s). In the Al–R systems, the minimum oxidation rate corresponds to the compositions of intermetallic compounds. The oxidation rate of a melt is shown to increase with temperature. It is found by IRS (infrared spectroscopy) and XRD (X-ray diffraction) that the melt oxidation products consist of γ-Al₂O₃, R₂O₃ (R = La, Ce, Pr, Nd, Y, Sc), CeO₂, and rare-earth metal monoaluminates RAlO₃ (CeAlO₃, LaAlO₃, NdAlO₃).

The saturated vapor pressures of lead, silver, and antimony are calculated for Pb–Ag and Pb–Sb alloys at temperatures of 1073–1773 and 823–1073 K, respectively. High ratios (p_Sb*/p_Pb*) × 10³ = 15.0–1.8 and p_Pb*/p_Ag* = 2.9 × 10³–74.0 create theoretical possibilities for sequential selective separation of these metals by vacuum distillation, during which the vapor is enriched in antimony and then lead and the liquid is enriched in silver. For vapor–liquid equilibrium (VLE) diagram, the lever rule (the rule of line segments) can be used to predict the amounts of substance, residue, and sublimate at a given temperature. Calculations of the ternary-alloy parameters can be performed by the Wilson equation using parameters obtained for the binary systems. The fractional Gibbs free energy (–ΔG_Pb/Sb/Ag = (2.1–22.4)/(1.9–25.5)/(18.1–50.0)), the enthalpy (ΔH_Pb/Sb/Ag = ±(0.2–16.9)/–(0.2–1.8)/(105–140) J/(K mol)), and the entropy (ΔS_Pb/Sb/Ag = (2.4–13.4)/(2.2–15.2)/(20.8–30.0) J/(K mol)) of the components of the Pb–Sb–Ag melts are calculated. As the fractions of metals in a starting alloy increase, the thermodynamic parameters decrease. The negative and positive values of the enthalpy indicate exothermic and endothermic processes in the melt during distillation of components, respectively. The calculated and experimental thermodynamic parameters are shown to agree satisfactorily: the standard relative deviation is 1.9% and the root-mean square deviation is 0.1 kJ/mol.

A model is developed to calculate the Hall–Petch relation parameters for the submicrocrystalline (SMC) metals fabricated by severe plastic deformation (SPD) methods. The model is based on the assumption that the flow stress in SMC metals includes both conventional contributions (caused by lattice dislocations, impurity atoms, etc.) and a contribution related to the long-range internal stress fields created by the SPD-induced defects distributed over grain boundaries. Equations are derived to calculate the Hall–Petch relation parameters as functions of the strain and the strain rate. The results calculated by the derived equations agree well with the experimental data. The low resistance of grain boundaries to the motion of grain boundaries in SMC materials (see part I of this work) is found to be related to a violation of the Hall–Petch relation in SMC metals.