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The compositional dependence and influence of relaxation state on the deformation behavior of a Pt–Pd-based bulk metallic glasses model system was investigated, where platinum is systematically replaced by topologically equivalent palladium atoms. The hardness and modulus increased with rising Pd content as well as by annealing below the glass transition temperature. Decreasing strain-rate sensitivity and increasing serration length are observed in nano indentation with increase in Pd content as well as thermal relaxation. Micro-pillar compression for alloys with different Pt/Pd ratios validated the greater tendency for shear localization and brittle behavior of the Pd-rich alloys. Based on total scattering experiments with synchrotron X-ray radiation, a correlation between the increase in stiffer 3-atom cluster connections and reduction in strain-rate sensitivity, as a measure of ductility, with Pd content and thermal history is suggested.

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 65.5 Ni 22.5 Cu 12 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. Ti 58 Zr 7.5 Ni 18.5 Cu 12 S 4 ) 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.