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Title: Separating the configurational and vibrational entropy contributions in metallic glasses

Abstract

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? 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.

Authors:
 [1];  [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [6];  [1];  [1]
+ Show Author Affiliations
  1. California Inst. of Technology (CalTech), Pasadena, CA (United States. Dept. of Applied Physics and Materials Science
  2. Univ. of California, Riverside, CA (United States). Dept. of Mechanical Engineering
  3. Air Force Research Lab. (AFRL), Wright-Patterson AFB, OH (United States)
  4. California State Univ. Channel Islands (CI), Camarillo, CA (United States). Dept. of Applied Physics
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Data Analysis and Visualization Division
  6. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Quantum Condensed Matter Division
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
OSTI Identifier:
1471839
Grant/Contract Number:  
AC05-00OR22725; FG02-03ER46055; DMR-0520547
Resource Type:
Accepted Manuscript
Journal Name:
Nature Physics
Additional Journal Information:
Journal Volume: 13; Journal Issue: 9; Journal ID: ISSN 1745-2473
Publisher:
Nature Publishing Group (NPG)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Smith, Hillary L., Li, Chen W., Hoff, Andrew, Garrett, Glenn R., Kim, Dennis S., Yang, Fred C., Lucas, Matthew S., Swan-Wood, Tabitha, Lin, Jiao Y. Y., Stone, Matthew B., Abernathy, Douglas L., Demetriou, Marios D., and Fultz, B. Separating the configurational and vibrational entropy contributions in metallic glasses. United States: N. p., 2017. Web. doi:10.1038/nphys4142.
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Smith, Hillary L., Li, Chen W., Hoff, Andrew, Garrett, Glenn R., Kim, Dennis S., Yang, Fred C., Lucas, Matthew S., Swan-Wood, Tabitha, Lin, Jiao Y. Y., Stone, Matthew B., Abernathy, Douglas L., Demetriou, Marios D., & Fultz, B. Separating the configurational and vibrational entropy contributions in metallic glasses. United States. https://doi.org/10.1038/nphys4142
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Smith, Hillary L., Li, Chen W., Hoff, Andrew, Garrett, Glenn R., Kim, Dennis S., Yang, Fred C., Lucas, Matthew S., Swan-Wood, Tabitha, Lin, Jiao Y. Y., Stone, Matthew B., Abernathy, Douglas L., Demetriou, Marios D., and Fultz, B. Mon . "Separating the configurational and vibrational entropy contributions in metallic glasses". United States. https://doi.org/10.1038/nphys4142. https://www.osti.gov/servlets/purl/1471839.
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@article{osti_1471839,
title = {Separating the configurational and vibrational entropy contributions in metallic glasses},
author = {Smith, Hillary L. and Li, Chen W. and Hoff, Andrew and Garrett, Glenn R. and Kim, Dennis S. and Yang, Fred C. and Lucas, Matthew S. and Swan-Wood, Tabitha and Lin, Jiao Y. Y. and Stone, Matthew B. and Abernathy, Douglas L. and Demetriou, Marios D. and Fultz, B.},
abstractNote = {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? 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.},
doi = {10.1038/nphys4142},
journal = {Nature Physics},
number = 9,
volume = 13,
place = {United States},
year = {Mon May 29 00:00:00 EDT 2017},
month = {Mon May 29 00:00:00 EDT 2017}
}
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https://doi.org/10.1038/nphys4142
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