Thermodynamic modelling of crystalline unary phases



Progress in materials science through thermodynamic modelling may rest crucially on access to a database, such as that developed by Scientific Group Thermodata Europe (SGTE) around 1990. It gives the Gibbs energy math formula of the elements in the form of series as a function of temperature, i.e. essentially a curve fitting to experimental data. In the light of progress in theoretical understanding and first-principles calculation methods, the possibility for an improved database description of the thermodynamics of the elements has become evident. It is the purpose of this paper to provide a framework for such work. Lattice vibrations, which usually give the major contribution to math formula, are treated in some detail with a discussion of neutron scattering studies of anharmonicity in aluminium, first-principles calculations including ab initio molecular dynamics (AIMD), and the strength and weakness of analytic model representations of data. Similarly, electronic contributions to math formula are treated on the basis of the density of states math formula for metals, with emphasis on effects at high T. Further, we consider math formula below 300 K, which is not covered by SGTE. Other parts in the paper discuss metastable and dynamically unstable lattices, math formula in the region of superheated solids and the requirement on a database in the calculation of phase diagrams.