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The authors recently reported that undercooled liquid Ag and Ag–Cu alloys both exhibit a first order phase transition from the homogeneous liquid (L-phase) to a heterogeneous solid-like G-phase under isothermal evolution. Here, we report a similar L–G transition and heterogenous G-phase in simulations of liquid Cu–Zr bulk glass. The thermodynamic description and kinetic features (viscosity) of the L-G-phase transition in Cu–Zr simulations suggest it corresponds to experimentally reported liquid–liquid phase transitions in Vitreloy 1 (Vit1) and other Cu–Zr-bearing bulk glass forming alloys. The Cu–Zr G-phase has icosahedrally ordered cores versus fcc/hcp core structures in Ag and Ag–Cu with a notably smaller heterogeneity length scale Λ . We propose the L–G transition is a phenomenon in metallic liquids associated with the emergence of elastic rigidity. The heterogeneous core–shell nano-composite structure likely results from accommodating strain mismatch of stiff core regions by more compliant intervening liquid-like medium.
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Observation of an apparent first-order glass transition in ultrafragile Pt–Cu–P bulk metallic glasses
An experimental study of the configurational thermodynamics for a series of near-eutectic Pt 80- x Cu x P 20 bulk metallic glass-forming alloys is reported where 14 < x < 27. The undercooled liquid alloys exhibit very high fragility that increases as x decreases, resulting in an increasingly sharp glass transition. With decreasing x , the extrapolated Kauzmann temperature of the liquid, T K , becomes indistinguishable from the conventionally defined glass transition temperature, T g . For x < 17, the observed liquid configurational enthalpy vs. T displays a marked discontinuous drop or latent heat at a well-defined freezing temperature, T gm . The entropy drop for this first-order liquid/glass transition is approximately two-thirds of the entropy of fusion of the crystallized eutectic alloy. Below T gm , the configurational entropy of the frozen glass continues to fall rapidly, approaching that of the crystallized eutectic solid in the low T limit. The so-called Kauzmann paradox, with negative liquid entropy (vs. the crystalline state), is averted and the liquid configurational entropy appears to comply with the third law of thermodynamics. Despite their ultrafragile character, the liquids at x = 14 and 16 are bulk glass formers, yielding fully glassy rods up to 2- and 3-mm diameter on water quenching in thin-wall silica tubes. The low Cu content alloys are definitive examples of glasses that exhibit first-order melting.
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- Award ID(s):
- 1710744
- PAR ID:
- 10139132
- Date Published:
- Journal Name:
- Proceedings of the National Academy of Sciences
- Volume:
- 117
- Issue:
- 6
- ISSN:
- 0027-8424
- Page Range / eLocation ID:
- 2779 to 2787
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript
- Journal Article:
- https://doi.org/10.1073/pnas.1916371117
