Advanced Study Group Ab Initio Based Modelling (ABM)
Thermodynamic properties of cementite (Fe3C)
B. Hallstedt, D. Djurovic, J. von Appen, R. Dronskowski, A. Dick, F. Körmann, T. Hickel, J. Neugebauer.
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry, 34, 129-133, (2010)
Cementite (Fe3C) is one of the most common phases in steel. In spite of its importance, thermodynamic investigations, either experimental or theoretical, of cementite are infrequent. In the present work, the thermodynamic properties of cementite are reevaluated and Gibbs energy functions valid from 0 K upwards presented. At high temperature (1000 K and above), the Gibbs energy is practically unchanged compared to previous evaluations. The energy of formation at 0 K was also calculated using density functional theory. This energy of formation (+8 kJ/mol at 0 K) is in reasonable agreement with the present thermodynamic evaluation (+23.5 kJ/mol at 0 K and +27.0 kJ/mol at 298.15 K) and with a solution calorimetric measurement of the enthalpy of formation (+18.8 kJ/mol at 298.15 K). In addition, the heat capacity was calculated theoretically using ab initio data combined with statistical concepts such as the quasiharmonic approximation. The theoretical calculation agrees equally well as the present evaluation with experimental data, but suggests a different weighting of the experimental data. In order to use it directly in the thermodynamic evaluation further modifications in the Fe–C system, primarily of the fcc phase, would be required in order to reproduce phase equilibrium data with sufficient accuracy.
Keyword(s): CALPHAD; ab initio calculations; cementite (Fe3C); iron-carbon