Iron and nickel oxidation state and coordination in complex sodium aluminophosphate based glasses suggested as potential matrices for immobilization of legacy high level waste currently stored in stainless steel tanks at PA «Mayak» (Ural reg., Russia) were determined by X-ray absorption fine structure spectroscopy (XAFS: XANES/EXAFS). The glasses containing (wt.%) 20-30 Na2O, 6-12 Al2O3, 40-52 P2O5, 2-5 Fe2O3, 1-3 NiO, 0-6 B2O3, 10-15 other waste oxides produced by quenching of their melts were fully amorphous or contained minor Fe and Ni free phases. Fe in the glasses was found to be predominantly trivalent with an average Fe-O distance and a coordination number (CN) in the first shell of 1.94 to 1.97 Å and 5.2 to 5.8, respectively, mostly in octahedral oxygen environment. Ni is divalent in all the glasses and has in the first shell an average Ni-O distance and CN of 1.97 to 2.03 Å and 4.9 to 5.6, respectively. The first shell of both Fe and Ni is somewhat distorted. The second and further coordination shells are weakly appeared exhibiting no clustering and homogeneous distribution of Fe and Ni ions in the glass network. The data on Fe obtained are in good agreement with those from Mössbauer study of same glasses. After annealing glasses were partly devitrified and interpretation of XAFS data is strongly complicated due to Fe and Ni partitioning among crystalline and vitreous phases.

Great research efforts to investigate the glass-forming ability (GFA) in alloys have been made, leading to an observation that a pinpoint composition produces the best glass-forming characteristics. The reason for this observation is still unknown, limiting the development of bulk metallic glasses (MGs) with a relatively large size. In this work, systematic experimental measurements coupled with calculations were performed to address this issue using the NiNb binary alloy system. It is found that the atomic-level packing efficiency and the clusters-level regularity parameters strongly contribute to their GFA. In particular, the best glass former found in a pinpoint composition possesses the local maximum of the atomic-packing efficiency and the highest degree of the cluster regularity. This work provides an understanding of GFA from atomic and cluster levels and will shed light on the development of more MGs with relatively large critical casting sizes.

Atomic structures of the Zr48Cu45Al7 as-prepared and annealed metallic glasses (MGs) were investigated by performing the reverse Monte Carlo simulation on the synchrotron radiation-based experiments. It was found that although the annealed sample remains completely amorphous, the volumes of the Al-centered clusters evidently expand, which is attributed to the relatively longer Al–Zr bonds. As a result, the role of Al atoms as the glue atoms to connect and fix the Zr- and Cu-centered large clusters is accordingly weakened, which leads to the ease of the rearrangement of atoms and clusters in the glass state. This study provides an insight into the microstructures of MGs, which extends understanding of the structural evolution in the glass alloys during annealing prior to the precipitation of nanocrystals.

The microstructures of Zr70Cu30 and Zr70Ni30 metallic glasses (MGs) were investigated via the synchrotron radiation techniques combined with the reverse Monte-Carlo simulations. Although Cu and Ni are neighbor elements in the periodic table and their atomic radii are almost the same in length, it is found that atomic- and cluster-scale structural differences occur between these two Zr-based MGs. In particular, the relatively regular clusters caused by the narrow distributions of atomic separations and bond angles are detected in Zr70Cu30. This is the structural origin of the different glass-forming abilities in ZrCu and ZrNi alloys. This work has implications for understanding of the glass-forming mechanism in this class of glassy materials.