Resolving heterogeneous particle mobility in deeply quenched liquid iron: an ultra-fast assembly-free two-step nucleation mechanism

Despite intensive research, little is known about the intermediate state of phase transforming materials, which may form the missing link between e.g. liquids and solids on the nanoscale. The unraveling of the nanoscale interplay between the structure and dynamics of the intermediate state of phase transformations (through which e.g. crystal nucleation proceeds) is one of the biggest challenges and unsolved problems of materials science. Here we show using unbiased molecular dynamics simulations and spatially resolved atomic displacement maps (d-maps) that upon deep quenching the solidification of undercooled liquid iron proceeds through the formation of metastable pre-nucleation clusters (PNCs). We also reveal that the hitherto hidden PNCs are nearly immobile (dynamically arrested) and the related heterogeneity in atomic mobilities becomes clearly visible on atomic displacement-maps (d-maps) when atomic jumps are referenced to the final crystalline positions. However, this is in contrast to PNCs found in molecular solutions, in which PNCs tend to aggregate, move and crystallize via an activated process. Coordination filtered d-maps resolved in real space directly demonstrate that previously unseen highly ramified intermediate atomic clusters with a short lifetime emerge after incubation of undercooled liquid iron. The supercooled liquid iron is neither a spinodal system nor a liquid and undergoes a transition into a specific state called a quasi-liquid state within the temperature regime of 700-1250 K (0.5 T m > 0.7 T m , where the melting point is T m 1811 K). Below 700 K the supercooled system is spinodal-like and above 1300 K it behaves like an ordinary liquid with long incubation times. A two-step process is proposed to explain the anomalous drop in the incubation time in the temperature regime of 700-1250 K. The 1st step is activated aggregation of small atomic clusters followed by assembly-free nearly barrierless ultrafast growth of early ramified prenucleation clusters called germs. The display and characterization of the hidden PNCs in computer simulations could provide new perspectives on the deeper understanding of the long-standing problem of precursor development during crystal nucleation following deep quenching. Despite intensive research, little is known about the intermediate state of phase transforming materials, which may form the missing link between e.g. liquids and solids on the nanoscale.