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Formation of an icosahedral phase in the bulk glass forming Ti40Zr29Be14Cu9Ni8 alloy during crystallization from amorphous phase and solidiἀcation from melt is investigated. The icosahedral phase with a size of 10 to 15 nm forms as a thermodynamically stable phase at intermediate temperature during the transformation from amorphous to crystalline phases such as Laves and β-(Ti-Zr) phases, indicating that the existence of the icosahedral cluster in the undercooled liquid. On the other hand, the icosahedral phase forms as a primary solidification phase even though the Laves phase is stable at high temperature, which is can be explained based on the high nucleation rate of icosahedral phase relative to that of competing crystalline Laves phase due to lower interfacial energy between icosahedral and liquid phases.
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