Thermodynamic description of metastable fcc/liquid phase equilibria and solidification kinetics in Al-Cu alloys

Philos Trans A Math Phys Eng Sci. 2022 Feb 21;380(2217):20200327. doi: 10.1098/rsta.2020.0327. Epub 2022 Jan 3.

Abstract

The thermodynamic description of the fcc phase in the Al-Cu system has been revised, allowing for the prediction of metastable fcc/liquid phase equilibria to undercoolings of ΔT = 421 K below the eutectic temperature. Hypoeutectic Al-Cu alloys that are prone to pronounced microsegregation were solidified containerlessly in electromagnetic levitation. Solidus and liquidus concentrations were experimentally determined from highly undercooled samples employing energy-dispersive X-ray analysis. Solid concentrations at a rapidly propagating solid/liquid interface were additionally calculated using a sharp interface model that considers all undercoolings and is based on solvability theory. Modelling results (front velocity versus undercooling) were also corroborated by in situ observation with a high-speed camera. A newly established thermodynamic description of the fcc phase in Al-Cu is compatible with existing CALPHAD-type databases. Inconsistencies of previous descriptions such as a miscibility gap between Al-fcc and Cu-fcc on the Al-rich side, an unrealistic curvature of the solidus line in the same composition range or an azeotropic point near the melting point of Cu, are amended in the new description. The procedure to establish the description of phase equilibria at high undercoolings can be transferred to other alloy systems and is of a general nature. This article is part of the theme issue 'Transport phenomena in complex systems (part 2)'.

Keywords: (highly) undercooled melt; calphad method; electromagnetic levitation; metastable extension of liquidus and solidus lines; rapid solidification; sharp interface model.