Metallurgical fundamentals for vacuum refining of molten silicon and the behavior of different impurities in this process are studied. A novel mass transfer model for the removal of volatile impurities from silicon in vacuum induction refining is developed. The boundary conditions for vacuum refining system-the equilibrium partial pressures of the dissolved elements and their actual partial pressures under vacuum-are determined through thermodynamic and kinetic approaches. It is indicated that the vacuum removal kinetics of the impurities is different, and it is controlled by one, two, or all the three subsequent reaction mechanisms-mass transfer in a melt boundary layer, chemical evaporation on the melt surface, and mass transfer in the gas phase. Vacuum refining experimental results of this study and literature data are used to study the model validation. The model provides reliable results and shows correlation with the experimental data for many volatile elements. Kinetics of phosphorus removal, which is an important impurity in the production of solar grade silicon, is properly predicted by the model, and it is observed that phosphorus elimination from silicon is significantly increased with increasing process temperature.

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Abstract

Theories on the evaporation of pure substances are reviewed and applied to study vacuum evaporation of pure metals. It is shown that there is good agreement between different theories for weak evaporation, whereas there are differences under intensive evaporation conditions. For weak evaporation, the evaporation coefficient in Hertz-Knudsen equation is 1.66. Vapor velocity as a function of the pressure is calculated applying several theories. If a condensing surface is less than one collision length from the evaporating surface, the Hertz-Knudsen equation applies. For a case where the condensing surface is not close to the evaporating surface, a pressure criterion for intensive evaporation is introduced, called the effective vacuum pressure, p eff . It is a fraction of the vapor pressure of the pure metal. The vacuum evaporation rate should not be affected by pressure changes below p eff , so that in lower pressures below p eff , the evaporation flux is constant and equal to a fraction of the maximum evaporation flux given by Hertz-Knudsen equation as 0.844 _ n Max . Experimental data on the evaporation of liquid and solid metals are included.

Boron (B) is the most problematic impurity to be removed in the processes applied for the production of solar grade silicon. Boron removal from liquid silicon by sodium-silicate slags is experimentally studied and it is indicated that B can be rapidly removed within short reaction times. The B removal rate is higher at higher temperatures and higher Na 2 O concentrations in the slag. Based on the experimental results and thermodynamic calculations, it is proposed that B removal from silicon phase takes place through its oxidation at the slag/Si interfacial area by Na 2 O and that the oxidized B is further gasified from the slag through the formation of sodium metaborate (Na 2 B 2 O 4 ) at the slag/gas interfacial area. The overall rate of B removal is mainly controlled by these two chemical reactions. However, it is further proposed that the B removal rate from silicon depends on the mass transport of Na in the system. Sodium is transferred from slag to the molten silicon through the silicothermic reduction of Na 2 O at the slag/Si interface and it simultaneously evaporates at the Si/gas interfacial area. This causes a Na concentration rise in silicon and its further decline after reaching a maximum. A major part of the Na loss from the slag is due to its carbothermic reduction and formation of Na gas.

Thermodynamic knowledge about liquid silicon is crucial for the production of solar-grade silicon feedstock from molten silicon. In the current study, liquidus for silicon binary alloys is formulated using a previously developed method in which the liquidus curve is calculated using two constants. The liquidus measurements for the silicon portion of the silicon alloys with Al, Ca, Mg, Fe, Ti, Zn, Cu, Ag, Au, Pt, Sn, Pb, Bi, Sb, Ga, In, Ni, Pd, Mn, and Rh are reviewed, and the consistent data were used to determine the liquidus constants. The liquidus curves for silicon binary systems are calculated and plotted. It is indicated that the calculated liquidus curves fit well with the experimental data. A correlation between the determined liquidus constants is also observed, which can be used to gain a better understanding of the thermodynamics of the silicon binary melts.

The carbothermic reduction of 38.7 pct MnO-12.1 pct pct MgO-9.3 pct Al 2 O 3 -24.1 pct SiO 2 -10.4 pct FeO slag in Ar at 1600°C was studied using the sessile drop wettability technique. Pure graphite, coke, and charcoal were used as the carbon material substrates. The reduction rates were evaluated by sampling at different reduction times and by analyzing the chemical compositions of the reduced slag and the produced metal. The carbothermic FeO reduction from slag is initially fast followed by a much slower reduction rate. However, the rate of the MnO reduction is slow in the fast FeO reduction stage, and it starts to increase significantly during the slow FeO reduction stage. The kinetics of FeO and MnO reduction are affected by the type of carbonaceous materials. Moreover, the rate of the carbon dissolution/transfer into the produced metal phase and the amount of the transferred manganese to the metal phase depend on the type of carbon. Based on the experimental observations and the thermodynamic calculations, a mechanism for MnO reduction was proposed. According to this mechanism, MnO is mainly reduced through a metallothermic reduction by Fe and the rate of MnO reduction is controlled by the rate of the consumption of FeO from the slag, which takes place simultaneously. In contrast, the rate of FeO reduction in the fast initial reduction stage is controlled by the rate of the carbon dissolution/transfer into the metal phase. However, at the second slow FeO reduction stage, it is reduced mainly by the solid carbon.

Metallurgical grade alumina is produced worldwide through the well-known Bayer process, which unavoidably generates bauxite residue (BR, also known as red mud) in almost equal amounts to alumina. This study aims the valorization of BR through a smelting-reduction process to obtain calcium aluminate slags that can be a proper feed for alumina recovery via the Pedersen process. It investigates the thermodynamics and characteristics of the slags and pig iron produced from mixtures of BR, a bauxite beneficiation byproduct, and lime. In this context, the evolution of the different phases in the slags is studied with advanced analytical techniques and thermodynamic calculations. According to the results, a CaO/Al2O3 mass ratio within 1.3 to 1.4 in the slags can yield more Al2O3-containing leachable phases, such as CaO·Al2O3 and 12CaO·7Al2O3. The cooling dictates the amount and the characteristics of these phases, and the slower cooling rate yields improved slag characteristics. The distribution of the elements between the slag and metal phases shows that iron is separated, and the majority of the P, Cr, Ni, and V are distributed in the produced pig iron, while S, Ti, and Si are mostly concentrated in the slags.