Separating the configurational and vibrational entropy contributions in metallic glasses

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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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Figure 1: Schematic representation of the excess entropy of the liquid over the crystal.
Figure 2: Differential scanning calorimetry of amorphous Cu50Zr50 and Cu46Zr46Al8.
Figure 4: Vibrational entropy of Cu50Zr50 and Cu46Zr46Al8.
Figure 3: Phonon DOS curves of Cu50Zr50.
Figure 5: Measured heat capacity of Cu50Zr50.
Figure 6: Total excess entropy of the liquid over the crystal phase of Cu50Zr50.


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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.

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Samples were prepared by H.L.S., A.H., G.R.G., D.S.K. and M.D.D. Neutron data collection was performed by H.L.S., D.L.A., M.B.S., C.W.L., A.H., G.R.G., F.C.Y., M.S.L., T.S.-W. and B.F. Heat capacity measurements were carried out by H.L.S., A.H., G.R.G. and M.D.D. Data analysis was performed by H.L.S., C.W.L., D.S.K., J.Y.Y.L., M.D.D. and B.F. The manuscript was written by H.L.S., C.W.L. M.D.D. and B.F. All authors discussed the results and provided input on the paper.

Correspondence to Hillary L. Smith or B. Fultz.

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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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