Thermodynamic modeling of the Fe-Sn system including an experimental re-assessment of the liquid miscibility gap

Abstract

The usage of low-grade ferrous scrap has increased over decades to decrease CO₂ emissions and to produce steel products at a low cost. A serious problem in melting post-consumer scrap material is the accumulation of tramp elements, e.g., Cu and Sn, in the liquid steel. These tramp elements are difficult to remove during conventional steelmaking processes. Sn is considered as one of the most harmful tramp elements because, together with Cu, it sometimes induces the liquid metal embrittlement in high-temperature ferrous processing, e.g., continuous casting and hot rolling. Furthermore, the chemical interaction between Fe and Sn plays an important role in the Sn smelting process. The raw material used in the Sn smelting process is SnO₂ (cassiterite), in which Fe₃O₄ is a gangue in the Sn ore. In the process, the reduction of Fe₃O₄ is unavoidable, which results in forming a Fe-Sn alloy (hardhead). The recirculation of the hardhead decreases the furnace capacity and increases the energy consumption in the smelting. The need to efficiently recover Sn from secondary resources is therefore inevitable. The CALculation of PHAse Diagrams (CALPHAD) approach helps to predict the equilibrium state of the multicomponent system. Previously reported studies of the Fe-Sn system show inconsistencies in the calculations and the experimental results. Mainly the miscibility gap in the liquid phase was under debate, as experimental data of the phase boundary are scattered. Experimental study and re-optimization of model parameters were carried out with emphasis on the correct shape of the miscibility gap. Three different experimental techniques were employed: differential scanning calorimetry, electromagnetic levitation, and contact angle measurement. The present thermodynamic model has higher accuracy in predicting the solubility of Sn in the body-centered cubic (bcc), compared to previous assessments. This is achieved by re-evaluating the Gibbs energies of the FeSn and FeSn₂ compounds and the peritectic reaction related to Fe₅Sn₃. Also, the inconsistencies related to the miscibility gap around X_Sn = 0.31-0.81 were resolved. The database developed in the present study can contribute to the development of a large CALPHAD database containing tramp elements.

Keywords

Fe-Sn / thermodynamics / CALPHAD / miscibility gap / contact angle measurement / DSC

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