First-principles based calculation of binary and multicomponent phase diagrams for titanium carbonitride

Abstract

In this paper we have used a combined first principles and Calphad approach to calculate phase diagrams in the titanium–carbon–nitrogen system, with particular focus on the vacancy-induced ordering of the substoichiometric carbonitride phase, TiC x N y ( x + y ≤ 1 ). Results from earlier Monte Carlo simulations of the low-temperature binary phase diagrams are used in order to formulate sublattice models for TiC x N y within the compound energy formalism (CEF) that are capable of describing both the low temperature ordered and the high-temperature disordered state. We parameterize these models using first-principles calculations and then we demonstrate how they can be merged with thermodynamic descriptions of the remaining Ti–C–N phases that are derived within the Calphad method by fitting model parameters to experimental data. We also discuss structural and electronic properties of the ordered end-member compounds, as well as short range order effects in the TiC x N y phase.