Shape Factor Effect on Inclusion Sedimentation in Aluminum Melts

Metallurgical and Materials Transactions B - The quality requirements of aluminum products are steadily increasing, and the presence of non-metallic inclusions have a large impact on the quality of...     

The equilibrium partitioning of titanium between Ti3+ and Ti4+ valency states in CaO-SiO2-TiO x slags

The redox behavior of titanium in CaO-SiO₂-TiO _x melts was investigated using a slag-gas equilibrium technique. Titanium partitioning between Ti³⁺ and Ti⁴⁺ valency states and the ratio of activity coefficients of TiO_1.5 and TiO₂ were determined as functions of oxygen partial pressure, temperature, and slag composition. The equilibrium experiments were carried out at temperatures between 1783 and 1903 K under CO-CO₂-Ar gas atmosphere with oxygen partial pressure ranging from 10⁻¹² to 10⁻⁷ atm (1.01×10⁻¹⁰ kPa to 1.01×10⁻⁵ kPa). The slags had CaO/SiO₂ ratios between 0.55 and 1.35 and total titanium oxide concentrations from 7 to 50 mass pct. Experimental results showed that the Ti³⁺/Ti⁴⁺ ratio in CaO-SiO₂-TiO _x slags, containing up to 50 mass pct TiO _x , increased with decreasing oxygen partial pressure and decreased with increasing CaO/SiO₂ ratio and decreasing temperature. Measured variation of the redox ratio Ti³⁺/Ti⁴⁺ with oxygen partial pressure closely followed the ideal behavior. Increasing the CaO/SiO₂ ratio increased the ratio of activity coefficients of TiO_1.5 and TiO₂. The effect of total titania content on this ratio was more complex and in accord with Raman spectroscopy data.     

Mechanisms and Kinetics of Liquid Silicon Oxidation During Industrial Refining

During oxidative ladle refining (OLR) of silicon, the metal surface is partly oxidized, resulting in the formation of a condensed silica fume (SiO₂). This fugitive emission of silica represents a potential health hazard to the workers in the silicon and ferrosilicon industry. In the current work, industrial measurement campaigns aimed at recording the fume generation during OLR were performed at the Elkem Salten plant in Norway. The measured amounts of silica produced were 2.5–5.1?kg/h, depending on the gas flow rate in the refining process. The rate of silica production correlates with the total flow rate and amount of air in the purge gas, and increases as the flow rate increases. The results of this work suggest that fume generation during OLR primarily results from oxidation of the exposed metal surface, with oxygen transport from the surrounding atmosphere to the metal surface being the limiting factor. Other identified mechanisms of SiO₂ formation were splashing of the metal and/or oxidation of SiO gas carried with the refining purge gas.     

Trace Elements in the Si Furnace-Part II: Analysis of Condensate in Carbothermal Reduction of Quartz

Silicon feedstock for production of solar-grade silicon should be as pure as possible to decrease the cost of manufacturing of solar cells. Impurities in quartz, carbonaceous materials, electrodes, and refractories are mostly present in the form of oxides. These oxides can be reduced to volatile gaseous compounds in presence of SiO(g) and CO(g) atmosphere and potentially leave the furnace or stay in the condensed reaction products, metal, and slag. This work investigates the conditions under which volatile impurities report to the gas phase in laboratory experiments with lumpy and pelletized mixtures of SiO₂, SiC, and Si at 1923 K and 2123 K (1650 °C and 1850 °C), respectively, were carried out. The volatile compounds were generated by the reduction of quartz and collected in the form of condensate. The effects of the reaction temperature, quartz type, charge composition, pellets, and lumps on the composition of the condensate were studied. The trace elements in the charge input, reacting charge, and condensate were analyzed using inductively coupled plasma (ICP)-mass spectroscopy (MS) and X-ray diffraction (XRD). CO(g) and SiO(g), which are the major components in reduction reactions, formed four types of condensate: white, brown, green, and orange. The condensate constituents were amorphous SiO₂, 3C:SiC, Si, and α-quartz. Each impurity present in the quartz charge entered the gas phase during quartz reduction and was detected in the condensate. Al and Fe show limited volatility. The volatility of Mn, P, and B depends on the charge mix: a higher P_CO enhances the concentration of these elements in the gas phase. Fluid inclusions, common in hydrothermal quartz, enhance the distribution of the contaminants to the gas phase. Industrial campaigns on Si and Fe-Si production confirm the experimental results.     

Control of grain size and -orientation in multi-crystalline silicon ingots

Two different cooling rates have been imposed during the early solidification of two multi-crystalline silicon ingots with 250mm diameter and 100mm height in a pilot scale directional solidification furnace. This has been done by opening a variable heat leak system below the crucible in order to achieve a high initial cooling rate in one of the ingots. The grain-structure and -orientation of these two ingots have been investigated by light microscopy (LM) and electron backscattered diffraction (EBSD), and their electrical properties by quasi-steady state photo-conductance (QSSPC) and surface photovoltage (SPV) method. The ingot with the high initial cooling rate shows predominantly grains which are significantly larger than what is usually found in mc-Si. The minority carrier diffusion lengths measured on the large grains in the ingot with high cooling rate show higher values than those measured on the ingot with smaller grains. These results indicate that principles of grain size and -orientation control in mc-Si ingots can be applied to a pilot scale furnace, and the potential for up-scaling to industrial ingots with improved electrical properties and, thus, higher solar cell conversion efficiency.     

Thermodynamic and Kinetic Behavior of B and Na Through the Contact of B-Doped Silicon with Na2O-SiO2 Slags

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 Na₂O 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 Na₂O and that the oxidized B is further gasified from the slag through the formation of sodium metaborate (Na₂B₂O₄) 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 Na₂O 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.     

Active Oxidation of Liquid Silicon: Experimental Investigation of Kinetics

Small scale laboratory experiments on the oxidation of liquid silicon have reproduced important features of the industrial refining of liquid silicon: active oxidation led to the formation of amorphous silica spheres as a reaction product. The boundary condition for active oxidation in terms of maximum oxygen partial pressure in the bulk gas was found to lie between 2·10^?3 and 5·10^?3?atm at T?=?1,500?°C. The active oxidation of liquid silicon had linear kinetics, and the rate was proportional to bulk oxygen partial pressure and the square root of the linear gas flow rate, consistent with viscous flow mass transfer theory. Classical theory for unconstrained flow over a flat plate led to mass transfer rates for SiO_(g) which were 2–3 times slower than observed. However, computational fluid dynamic modeling to take into account the effects of reactor tube walls on flow patterns yielded satisfactory agreement with measured volatilization rates.     

Experimental Investigation and Thermodynamic Modeling of the B<Subscript>2</Subscript>O<Subscript>3</Subscript>-FeO-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Nd<Subscript>2</Subscript>O<Subscript>3</Subscript> System for Recycling of NdFeB Magnet Scrap

NdFeB magnet scrap is an alternative source of neodymium that could have a significantly lower impact on the environment than current mining and extraction processes. Neodymium can be readily oxidized in the presence of oxygen, which makes it easy to recover neodymium in oxide form. Thermochemical data and phase diagrams for neodymium oxide containing systems is, however, very limited. Thermodynamic modeling of the B₂O₃-FeO-Fe₂O₃-Nd₂O₃ system was hence performed to obtain accurate phase diagrams and thermochemical properties of the system. Key phase diagram experiments were also carried out for the FeO-Nd₂O₃ system in saturation with iron to improve the accuracy of the present modeling. The modified quasichemical model was used to describe the Gibbs energy of the liquid oxide phase. The Gibbs energy functions of the liquid phase and the solids were optimized to reproduce all available and reliable phase diagram data, and thermochemical properties of the system. Finally the optimized database was applied to calculate conditions for selective oxidation of neodymium from NdFeB magnet waste.     

Trace Elements in the Si Furnace. Part I: Behavior of Impurities in Quartz During Reduction

Quartz and carbonaceous materials, which are used in the production of silicon as well as electrodes and refractories in the silicon furnace, contain trace elements mostly in the form of oxides. These oxides can be reduced to gaseous compounds and leave the furnace or stay in the reaction products—metal and slag. This article examines the behavior of trace elements in hydrothermal quartz and quartzite in the reaction of SiO₂ with Si or SiC. Mixtures of SiO₂ (quartz or quartzite), SiC, and Si in forms of lumps or pellets were heated to 1923 K and 2123 K (1650°C and 1850°C) in high purity graphite crucibles under Argon gas flow. The gaseous compounds condensed in the inner lining of the tube attached to the crucible. The phases present in the reacted charge and the collected condensates were studied quantitatively by X-ray diffraction (XRD) and qualitatively by Electron Probe Micro Analyzer (EPMA). Contaminants in the charge materials, reacted charge and condensate were analyzed by Inductively Coupled Plasma-Mass Spectroscopy (ICP-MS). Muscovite in the mineral phase of quartz melted and formed two immiscible liquid phases: an Al-rich melt at the core of the mineral, and a SiO₂-rich melt at the mineral boundaries. B, Mn, and Pb in quartz were removed during heating in reducing atmosphere at temperature above 1923 K (1650°C). Mn, Fe, Al and B diffused from quartz into silicon. P concentration was under the detection limit. Quartzite and hydrothermal quartz had different initial impurity levels: quartzite remained more impure after reduction experiment but approached purity of hydrothermal quartz upon silica reduction.     

Critical assessment of the impurity diffusivities in solid and liquid silicon

The diffusion of impurities in solid and liquid silicon is critically reviewed and assessed in this paper. The activation energies and pre-exponential factors in theArrhenius equation have been evaluated using the least-squares analysis and semi-empirical correlations. Impurity diffusion coefficients for Ag, Al, As, Au, B, Bi, C, Co, Cr, Cu, Fe, Ga, In, Li, Mn, N, Ni, 0, P, S, Sb, Te, Ti, and Zn in both solid and liquid silicon have been obtained. The current assessed impurity diffusivities can be coupled with the assessed thermochemical properties for the simulation of diffusion phenomena in the production of solar grade cell silicon feedstock. The assessed diffusivities have been applied to simulate the impurity diffusion profiles and the denuded zone in the intrinsic gettering annealing.