Failure of Kissinger(-like) methods for determination of the activation energy of phase transformations in the vicinity of the equilibrium phase-transformation temperature

The activation energies of heterogeneous equilibrium phase transformations have been frequently determined by Kissinger(-like) analysis. This work demonstrates that the applicability of Kissinger(-like) method(s) to determine activation energies of heterogeneous phase transformations is justified if the phase transformation occurs far away from the equilibrium phase-transformation temperature but not if the phase transformation is investigated in the vicinity of the equilibrium phase-transformation temperature. Experimental results on the kinetics of the order–disorder transformation in Ni3Sn2, obtained both near the equilibrium phase-transformation temperature and considerably below it (using quenched samples), expose the non-validity and confirm the validity, respectively, of activation-energy values obtained by Kissinger(-like) analyses applied in the corresponding temperature ranges. Application of the Kissinger(-like) analysis in a temperature range close to the equilibrium phase-transformation temperature leads to erroneous, abnormally high values for the activation energy.