Understanding ductility or brittleness of monolithic bulk metallic glasses requires detailed knowledge of the amorphous structure. The medium-range order (MRO) of ductile Pd40Ni40P20 and brittle Zr52.5Cu17.9Ni14.6Al10Ti5 (Vit105) was characterized prior to and after notched three-point bending tests using variable-resolution fluctuation electron microscopy. Here, we show the presence of a second larger MRO correlation length in the ductile material, which is not present in the brittle material. The second larger correlation length accounts for an increased heterogeneity, which seems to enable an easier shear band formation and thus explain the difference in deformability.

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The project "Stress Corrosion Cracking of Zr-based Bulk Metallic Glasses" (SCC of Zr-BMGs) within PP1594 mainly dealt with mechanical-corrosive interactions and failure of this class of metastable materials. It focused on one of the most application-relevant zirconium (Zr)-BMG, Vit(reloy) 105, with composition Zr 52 . 5 Cu 17 . 9 Ni 14 . 6 Al 10 Ti 5 (at.%). Even though this BMG is known as an extraordinary glass former, the metallurgical processing is still a critical issue. In contrast to conventional processing, i.e., arc melting of master alloy ingots from single constituents, a different route using binary pre-alloys for the master alloys production was applied and led to superior mechanical properties upon mechanical testing under tensile and three-point-bending (3PB) conditions in air. As a reference and for a detailed understanding of failure, fracture, and cracking of Zr-based BMG in air, notched specimen 3PB experiments with in situ microscopic observation were done and the still controversial interpretation of the mechanical behavior of BMG in the framework of fracture mechanics was addressed. The specimen from the in situ 3PB tests served for transmission electron microscopy (TEM) investigations on the structural nature of shear bands in BMG on the atomistic scale. Altogether, complete crack paths could be observed and analyzed, and based on this, details of the shear band-driven crack growth are described. While in first SCC studies using a newly developed setup full cross section (3PB) bars were investigated, in recent in situ experiments, notched specimens were tested in 0.01 M NaCl, yielding strong evidence for a catastrophic failure due to hydrogen embrittlement (HE). The known susceptibility to pitting corrosion in halide-containing environments is only the initial stage for failure under SCC conditions. Once pitting is initiated, the local electrode potential is severely reduced. Further, the hydrolysis reaction of oxidized Zr 4+ to zirconyl ions ZrO 2+ during local BMG dissolution produces H + and, thus, a local acidic environment that enables proton reduction and hydrogen absorption in the stressed BMG region. The peculiar failure and fracture surface characteristics as well as the proven local reduction of the pH value in the vicinity of the notch during in situ experiments clearly account for the proposed HE-SCC failure mechanism.