Liquid-to-liquid phase transition underlying the structural crossover in a supercooled metallic liquid

The existence of a 'crossover region' in glass-forming liquids has long been considered as a general phenomenon that is as important as the glass transition. One potential origin for the crossover behavior is a liquid-to-liquid phase transition (LLPT). Although a LLPT is thought to exist in all forms of liquids, structural evidence for this, particularly in supercooled liquids, is scarce, elusive, and in many cases controversial. A key challenge to the search for a LLPT in a supercooled liquid is the interference of crystallization during cooling. Crystallization induces major structural changes, which can overwhelm and therefore mask the more subtle changes associated with a LLPT. Here, we report the results of an in-situ containerless synchrotron study of a metallic-glass-forming liquid (Zr57Nb5Al10Cu15.4Ni12.6) that show distinct changes in the liquid structure at ~1000 K, a temperature well below the melting temperature of the liquid and 150 K above the crystallization temperature. The structural transition is characterized by growing short- and extended-range order below the transition temperature, and is accompanied by a concurrent change in density. These data provide strong evidence for a LLPT in the supercooled metallic liquid, particularly in the light of a recent computer simulation study. That a LLPT is found in a metallic liquid supports the increasingly widely held view that a LLPT may be a common feature of a variety of liquids.