Glassy materials exist in nature and play a critical role in technology, but key differences between the glass, liquid and crystalline phases are not well understood. Over several decades there has been controversy about the specific heat absorbed as a glass transforms to a liquid—does this originate from vibrational entropy or configurational entropy? Here we report direct in situ measurements of the vibrational spectra of strong and fragile metallic glasses in the glass, liquid and crystalline phases. For both types of material, the measured vibrational entropies of the glass and liquid show a tiny excess over the crystal, representing less than 5% of the total excess entropy measured with step calorimetry. These results reveal that the excess entropy of metallic glasses is almost entirely configurational in origin, consistent with the early theories of Gibbs and co-workers describing the glass transition as a purely configurational transition.
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The authors would like to acknowledge S. Randolph for her help with data collection. A portion of this research at Oak Ridge National Laboratory’s Spallation Neutron Source was sponsored by the Scientific User Facilities Division, Office of Basic Energy Sciences, US Department of Energy. This work benefited from DANSE software developed under NSF Grant No. DMR-0520547. This work was supported by DOE BES under contract DE-FG02-03ER46055.
The authors declare no competing financial interests.
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Smith, H., Li, C., Hoff, A. et al. Separating the configurational and vibrational entropy contributions in metallic glasses. Nature Phys 13, 900–905 (2017) doi:10.1038/nphys4142
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