Thermodynamic approach for the understanding of the kinetics of heat effects induced by structural relaxation of metallic glasses

We present a novel approach to the understanding of heat effects induced by structural relaxation of metallic glasses. The key idea consists in the application of a general thermodynamic equation for the entropy change due to the evolution of a non-equilibrium part of a complex system. This non-equilibrium part is considered as a defect subsystem of glass and its evolution is governed by local thermoactivated rearrangements with a Gibbs free energy barrier proportional to the high-frequency shear modulus. The only assumption on the nature of the defects is that they should provide a reduction of the shear modulus-a diaelastic effect. This approach allows to determine glass entropy change upon relaxation. On this basis, the kinetics of the heat effects controlled by defect-induced structural relaxation is calculated. A very good agreement between the calculation and specially performed calorimetric and shear modulus measurements on three metallic glasses is found.