Challenges and limitations in development of large thermodynamic databases for multiple molten phases using the Modified Quasichemical Formalism

In the field of pyrometallurgy, the presence of multiple molten phases with distinct chemical compositions, such as slags, mattes, speiss liquids, metals and molten salts, is a well-known phenomenon. These phases exhibit strongly non-ideal solution behaviour and are mutually miscible to varying degrees. To describe these complex molten liquids, the Modified Quasichemical Model (MQM) has proven effective and has been applied to numerous binary, ternary and several higher-order multicomponent systems related to pyrometallurgy. In recent decades, the complexity of high-temperature processes has escalated due to increased impurity concentrations in primary ores, the incorporation of recycled consumer products and the integration of metallurgical plants through by-product and waste exchanges. To address these issues, PYROSEARCH laboratory has been developing large 20-component thermodynamic database using a generalised CALPHAD (CALculation of PHAse Diagrams) methodology integrated with experimental investigations. Over the past decade, strategic decisions were made balancing the ability to generate experimental data, prediction power, accuracy, stability of calculations, as well as computational time, which are discussed in the paper. Examples provided for issues of >3 liquid immiscibility, non-ionic behaviour and exaggerated ‘sharp’ enthalpies of mixing in silicate slags, dealing with multiple oxidation states, as well as comparative analysis of pair and quadruplet approximation in MQM.