Thermodynamic Optimization of the Ternary Ga-Sn-Te System Using Modified Quasichemical Model

Thermoelectric (TE) materials are of great interest to many researchers because they directly convert electric and thermal energy in a solid state. Various materials such as chalcogenides, clathrates, skutterudites, eutectic alloys, and intermetallic alloys have been explored for TE applications. The Ga-Sn-Te system exhibits promising potential as an alternative to the lead telluride (PbTe) based alloys, which are harmful to environments because of Pb toxicity. Therefore, in this study, thermodynamic optimization and critical evaluation of binary Ga-Sn, binary Sn-Te, and ternary Ga-Sn-Te systems have been carried out over the whole composition range from room temperature to above liquidus temperature using the CALPHAD method. It is observed that Sn-Te and Ga-Te liquids show the strong negative deviation from the ideal solution behavior. In contrast, the Ga-Sn liquid solution has a positive mixing enthalpy. These different thermodynamic properties of liquid solution were explicitly described using Modified Quasichemical Model (MQM) in the pair approximation. The asymmetry of ternary liquid solution in the Ga-Sn-Te system was considered by adopting the toop-like interpolation method based on the intrinsic property of each binary. The solid phase of SnTe was optimized using Compound Energy Formalism (CEF) to explain the high temperature homogeneity range, whereas solid solution, Body-Centered Tetragonal (BCT) was optimized using a regular solution model. Thermodynamic properties and phase diagram in the Ga-Sn-Te and its sub-systems were reproduced successfully by the optimized model parameters. Using the developed database, we also suggested several ternary eutectic compositions for designing TE alloy with improved properties.

Developing Practical Models of Complex Salts for Molten Salt Reactors

olten salt reactors (MSRs) utilize salts as coolant or as the fuel and coolant together with fissile isotopes dissolved in the salt. It is necessary to therefore understand the behavior of the salts to effectively design, operate, and regulate such reactors, and thus there is a need for thermodynamic models for the salt systems. Molten salts, however, are difficult to represent as they exhibit short range order that is dependent on both composition and temperature. A widely useful approach is the modified quasichemical model in the quadruplet approximation that provides for consideration of first and second nearest neighbor coordination and interactions. Its use in the CALPHAD ap-proach to system modeling requires fitting parameters using standard thermodynamic data such as phase equilibria, heat capacity, and others. Shortcoming of the model is its inability to directly vary coordination numbers with composition or temperature. Another issue is the difficulty in fitting model parameters using regression methods without already having very good initial values. The proposed paper will discuss these issues and note some practical methods for the effective genera-tion of useful models.

Thermodynamic Assessment of Liquid Fe-Ni-C Alloy Using Modified Quasichemical Model

The liquid solution properties in the Fe-Ni and Fe-Ni-C systems have been thermodynamically assessed using the modified quasichemical model in the pair approximation. The asymmetry of the Fe-Ni and Fe-Ni-C alloy melts was verified by measuring the melting points of Fe-Ni binary alloys on the Ni-rich side, and the C solubility limit in Fe-Ni melt over the entire concentration range at 1500°C and 1600°C. The solubility minimum of C and the maximum partial enthalpy of mixing of C in the ternary Fe-Ni-C system occurred at near the maximum short-range ordering composition of the binary Fe-Ni liquid solution. The extrema of the partial properties of C in the ternary Fe-Ni-C system were successfully reproduced with only one constant adjustable ternary parameter.

Thermodynamic Modeling of Ni-C, Co-C, and Ni-Co-C Liquid Alloys Using the Modified Quasichemical Model

The strong interactions between the metallic elements and C in liquid Ni, Co, and Ni-Co alloys have been thermodynamically analyzed. The liquid solution properties in Ni-C and Co-C systems showed significant asymmetry because of the short-range ordering of C exhibited in the liquid solution. Using the modified quasichemical model in the pair approximation, the Ni-C and Co-C systems were re-optimized to simultaneously reproduce the present experimental results of the C solubility and the reported thermodynamic properties in the liquid phases. In particular, the partial enthalpy data of C in liquid Ni and Co alloys were considered for the first time on the thermodynamic assessment of Ni-C and Co-C liquid solutions. The asymmetric interpolation method was introduced to evaluate the Gibbs free energy in the ternary system based on the binary Gibbs free energies in the Ni-C and Co-C systems. The C solubility data measured in the ternary Ni-Co-C alloy melt over a wide Co concentration range were successfully reproduced without any additional ternary model parameter by considering the short-range ordering of C.

Theory of Inhomogeneous Short Range Order and Calphad Modeling. Part 2. Quasichemical Theory

The equations of the Quasichemical Theory are deduced directly from the equations of the Theory of Inhomogeneous Short Range, establishing TISR as the rigid generalization of the Quasichemical Theory.Methodological advantages of TISR are demonstrated.The Modified Quasichemical Model is critically discussed as other generalization of the same Quasichemical Theory.Multiple comparative examples are provided.