Vitrification decoupling from α-relaxation in a metallic glass

Understanding how glasses form, the so-called vitrification, remains a major challenge in materials science. Here, we study vitrification kinetics, in terms of the limiting fictive temperature, and atomic mobility related to the α-relaxation of an Au-based bulk metallic glass former by fast scanning calorimetry. We show that the time scale of the α-relaxation exhibits super-Arrhenius temperature dependence typical of fragile liquids. In contrast, vitrification kinetics displays milder temperature dependence at moderate undercooling, and thereby, vitrification takes place at temperatures lower than those associated to the α-relaxation. This finding challenges the paradigmatic view based on a one-to-one correlation between vitrification, leading to the glass transition, and the α-relaxation. We provide arguments that at moderate to deep undercooling, other atomic motions, which are not involved in the α-relaxation and that originate from the heterogeneous dynamics in metallic glasses, contribute to vitrification. Implications from the viewpoint of glasses fundamental properties are discussed.