A model alloy, Mg 69Zn 27Yb 4, concurrently forms bulk metallic glass, metastable quasicrystals (QCs), and crystalline approximant phases from the melt. We demonstrate that a transient QC phase nucleates first from the melt and subsequently transforms into an equilibrium approximant phase. This nucleation path is likely to be a general mechanism in metastable QC-forming systems. We observed a metastable-to-stable phase transformation when we deployed fast differential scanning calorimetry using the experimental strategy of interrupted cooling after the onset of crystallization followed by heating at ultrafast rates to “up-quench” the previously frozen structure. This strategy can yield the discovery of hidden transient phases that are key to understanding the crystallization behavior in metallic systems, polymers, biological solutions, and pharmaceutical substances.
This study presents a unique Mg-based alloy composition in the Mg–Zn–Yb system which exhibits bulk metallic glass, metastable icosahedral quasicrystals (iQCs), and crystalline approximant phases in the as-cast condition. Microscopy revealed a smooth gradual transition from glass to QC. We also report the complete melting of a metastable eutectic phase mixture (including a QC phase), generated via suppression of the metastable-to-stable phase transition at high heating rates using fast differential scanning calorimetry (FDSC). The melting temperature and enthalpy of fusion of this phase mixture could be measured directly, which unambiguously proves its metastability in any temperature range. The kinetic pathway from liquid state to stable solid state (an approximant phase) minimizes the free-energy barrier for nucleation through an intermediate state (metastable QC phase) because of its low solid–liquid interfacial energy. At high undercooling of the liquid, where diffusion is limited, another approximant phase with near-liquid composition forms just above the glass-transition temperature. These experimental results shed light on the competition between metastable and stable crystals, and on glass formation via system frustration associated with the presence of several free-energy minima.