Thermodynamic aspects of the constitution, grain refining, and solidification enthalpies of Al-Ce-Si alloys

Abstract

The ternary Al-Ce-Si phase equilibria were investigated using X-ray diffraction (XRD) methods, metallography, scanning electron microscopy with energy-dispersive X-ray analysis (SEM/EDX) and wavelength-dispersive X-ray microanalysis, and differential thermal analysis (DTA). The focus was on the Al-rich corner and the phases in equilibrium with (Al). Key experiments were selected by preliminary thermodynamic calculations. A consistent thermodynamic description was developed using the Calphad method incorporating all experimental data. A thermodynamic assessment for the binary Ce-Si system was also performed. Two ternary phases, Ce(Si1−xAlx)2 (τ1) and AlCeSi2 (τ2), were confirmed. The phase Al2CeSi2 (τ4) was sporadically observed, but is apparently metastable. The earlier reported phase Al4Ce3Si6 could not be confirmed. In addition, the enthalpy of solidification of five Al-rich ternary alloys was measured in a differential scanning calorimetry (DSC) heat flux calorimeter. The agreement with the thermodynamic enthalpy calculations is acceptable. The fundamental intricacies involved in calculating a “latent” heat for alloys with a freezing range are pointed out. Various phase diagrams of the Al-Ce-Si system were calculated based on the thermodynamic description. They were used to quantitatively identify possible contributions to the grain refinement potential of Ce in Al-Si alloys due to the phase equilibria.