When a spatially uniform temperature change is imposed on a solid with more than one phase, or on a polycrystal of a single, non-cubic phase (showing anisotropic expansion-contraction), the resulting thermal strain is inhomogeneous (non-affine). Thermal cycling induces internal stresses, leading to structural and property changes that are usually deleterious. Glasses are the solids that form on cooling a liquid if crystallization is avoided--they might be considered the ultimate, uniform solids, without the microstructural features and defects associated with polycrystals. Here we explore the effects of cryogenic thermal cycling on glasses, specifically metallic glasses. We show that, contrary to the null effect expected from uniformity, thermal cycling induces rejuvenation, reaching less relaxed states of higher energy. We interpret these findings in the context that the dynamics in liquids become heterogeneous on cooling towards the glass transition, and that there may be consequent heterogeneities in the resulting glasses. For example, the vibrational dynamics of glassy silica at long wavelengths are those of an elastic continuum, but at wavelengths less than approximately three nanometres the vibrational dynamics are similar to those of a polycrystal with anisotropic grains. Thermal cycling of metallic glasses is easily applied, and gives improvements in compressive plasticity. The fact that such effects can be achieved is attributed to intrinsic non-uniformity of the glass structure, giving a non-uniform coefficient of thermal expansion. While metallic glasses may be particularly suitable for thermal cycling, the non-affine nature of strains in glasses in general deserves further study, whether they are induced by applied stresses or by temperature change.
The outstanding efficiency of Fe‐based metallic glass powders in degrading organic water contaminants is reported. While the glassy alloy contains 24% chemically inactive metalloid elements, the powders are capable to completely decompose the C32H20N6Na4O14S4 azo dye in aqueous solution in short time, about 200 times faster than the conventional Fe powders. The metastable thermodynamic nature and the particle surface topography are the major factors controlling the chemical performance of the metallic glass. Our findings may open a new opportunity for functional applications of metallic glasses.
This manuscript explores the influence of atomic structure on glass forming ability and thermal stability in binary metallic glasses. A critical assessment gives literature data for 628 alloys from 175 binary glass systems. The atomic structure is quantified for each alloy using the efficient cluster packing model. Comparison of atomic structure with amorphous thickness and thermal stability gives the following major results. Binary glasses show a strong preference for discrete solute to solvent atomic radius ratios R*, which give efficient local atomic packing. Of 15 possible R* values, only five are common and only four represent the most stable glasses. The most stable binary glasses are also typically solute rich, with enough solute atoms to fill all the solute sites and roughly one-third of the solvent sites. This suggests that antisite defects, where solutes occupy solvent atom sites, are important in the glass forming ability of the most stable glasses. This stabilising effect results from an increase in the number of more stable solute-solvent bonds in solute rich glasses. Solute rich glasses also enable efficient global atomic packing. Together, these structural constraints represent only a narrow range of topologies and thus give a useful predictive tool for the exploration and discovery of new binary bulk metallic glasses (BMGs).
The lack of new functional applications for metallic glasses hampers further development of these fascinating materials. In this letter, we report for the first time that the MgZn-based metallic glass powders have excellent functional ability in degrading azo dyes which are typical organic water pollutants. Their azo dye degradation efficiency is about 1000 times higher than that of commercial crystalline Fe powders, and 20 times higher than the Mg-Zn alloy crystalline counterparts. The high Zn content in the amorphous Mg-based alloy enables a greater corrosion resistance in water and higher reaction efficiency with azo dye compared to crystalline Mg. Even under complex environmental conditions, the MgZn-based metallic glass powders retain high reaction efficiency. Our work opens up a new opportunity for functional applications of metallic glasses.
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