Generality of abnormal viscosity drop on cooling of CuZr alloy melts and its structural origin

Abstract It has been widely accepted that the viscosity of alloy melts increases monotonically with temperature decreasing after exceeding the liquidus temperature. However, a distinct viscosity-drop has been observed in several alloy melts in our previous works. To further understand this dynamic anomaly, we investigated the viscosity of CuZrAl and CuZrTiNi melts by gradually changing the compositions of alloy systems. The results suggest that when the amounts of doping elements (Al, Ti, Ni) become large enough, this abnormal viscosity-drop disappears. For CuZr binary alloys, the anomaly exists when the composition of Zr ranges between 27.3–66.7%, which nearly corresponds to the available content of Zr in CuZr bulk metallic glasses. By conducting molecular dynamics simulation, the mechanism that four icosahedron-like clusters with high fragility evolves with temperature in Cu62Zr38 melts has been recognized. In contrast to general aggregation or growth of clusters during cooling process, an unexpected tendency that more segregations are formed among these clusters and the clusters become further dispersed in liquids has been discovered around 1400 K; meanwhile, the viscosity-drop in our experiments begins simultaneously at this temperature. Below 1300 K, these icosahedron-like clusters aggregate abruptly again. Experimental results from differential scanning calorimeter (DSC) and high-resolution transmission electron microscope (HRTEM) further approve the influence of these fragile icosahedron-like clusters on crystallization processes. This finding uncovers the same structural origin that underlies both the formation of bulk metallic glasses and the dynamic anomaly in melts, and demonstrates the dominant role of fragile icosahedron-like clusters in the feature of liquid dynamics.