Bulk metallic glass formation in the (Ti,Zr)-(Ni,Cu)-S system

New bulk glass-forming alloy compositions, exceeding a critical casting thickness of 1 mm, are developed in the (quasi-ternary) (Ti,Zr)-(Ni,Cu)-S system. The ternary eutectic composition Ti_65.5Ni_22.5Cu₁₂ is stepwise modified through additions of S (0-8 at%) and Zr (0-22.5 at%) at the expense of Ni and Ti, respectively. By increasing the plate thickness of the casted samples from 500 µm to 1.25 mm, the primary precipitating phases are identified which is for the best glass-formers (e.g. Ti₅₈Zr_7.5Ni_18.5Cu₁₂S₄) an icosahedral phase. In calorimetric experiments, several exothermic crystallization events are observed upon heating glassy samples. The first exothermic event, obscuring the glass transition, is attributed to the formation of the icosahedral phase. As the icosahedral phase forms upon heating and cooling for the best glass-formers, the origin of the increased glass-forming ability might be attributed to a pronounced icosahedral short-range order in the liquid state, impeding the formation of the stable crystalline phases.