Fig. 1. XRD and SAED patterns for (a) as-cast, (b) HPT deformed state after 10 revolutions, and (c) sub-Tg annealed state at 533 K for 360 min. All HPT deformation and sub-Tg annealing treatments were performed on the as-cast state in this work.

Fig. 2. Temperature dependence of the shear modulus for Pd40Ni40P20 MG samples in different states. The heating rate was 3 K/min for all measurements. The convergence of the curves above Tg for different glassy samples indicates the reliable accuracy of the measurement.

Fig. 3. Calculated interstitial-type defect concentrations and their temperature dependencies upon isochronous heating based on the corresponding shear modulus data using Eq. (1)) for as-cast, AC_N03, AC_N10, AC_473 K/30 min and AC_533 K/360 min samples. The shear susceptibility β amounts to 21 for the Pd40Ni40P20 metallic glass [56].

Fig. 4. Total heat flow (HF), reversible heat flow (Rev HF) and nonreversible heat flow (Nonrev HF) measured by MDSC (endotherm upwards) for the as-cast, AC_N10, AC_473 K/30 min and AC_533 K/360 min samples. The heating rate was 5 K/min.

Fig. 5. (a) DSC measurements (endotherm upwards) of the AC_473 K/30 min sample at different heating rates. (b) Kissinger plots of the peak temperature versus heating rate for the shadow glass transition and glass transition overshoot.

Fig. 6. Calculated heat flow (dotted lines) based on the shear moduli using Eq. (5) and the corresponding experimental heat flow (solid lines) for as-cast, AC_N10 and AC_473 K/30 min samples (endotherm upwards). The green arrow denotes that the hump part (in the green box) during the exothermic process of the as-cast sample shifts to be the shadow glass transition after annealing at 473 K for 30 min.

Fig. 7. (I) Atomic motions (from transparent spheres to corresponding solid spheres) during internal stress relaxation in the frozen state (blue spheres), resulting in the reduction of average atomic distance and the shrinkage of MGs. (II) Local cage-breaking processes and the generation of local supercooled liquids (orange spheres within the dashed circle), leading to β relaxation. (III) Massive cage-breaking processes and the generation of supercooled liquid on the global scale (red spheres), leading to α-relaxation. (IV) The evolution of the relaxation spectrum is shown by three typical states. The as-cast state contains significant internal stress relaxation (blue area), β-relaxation (orange area) and α-relaxation (red area). If the annealing 1 (Ann1) is applied, the relaxation spectrum will consist of internal stress relaxation (blue pattern), β-relaxation (orange pattern) and α-relaxation (red area). If the annealing 2 (Ann2) is applied, β-relaxation is reduced to be a weak shoulder of α-relaxation, and α-relaxation (red pattern) is significantly enhanced. Internal stress relaxation is undetectable.