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Thermodynamic driving forces and growth rates in rapid solidification are analysed. Taking into account the relaxation time of the solute diffusion flux in the model equations, the present theory uses, in a first case, the deviation from local chemical equilibrium, and ergodicity breaking. The second case of ergodicity breaking may exist in crystal growth kinetics of rapidly solidifying glass-forming metals and alloys. In this case, a theoretical analysis of dendritic solidification is given for congruently melting alloys in which chemical segregation does not occur. Within this theory, a deviation from thermodynamic equilibrium is introduced for high undercoolings via gradient flow relaxation of the phase field. A comparison of the present derivations with previously verified theoretical predictions and experimental data is given. This article is part of the theme issue ‘Heterogeneous materials: metastable and non- ergodic internal structures’.

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