Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses

Smith, Hillary L.; Saunders, Claire N.; Bernal-Choban, Camille; Lohaus, Stefan H.; Stoddard, Colby J.; Decker, Lucy K.; Lin, Jiao Y. Y.; Niedziela, Jennifer L.; Abernathy, Douglas L.; Na, Jong-Hyun; Demetriou, Marios D.; Fultz, B.

doi:10.1016/j.mtla.2023.101710

Title: Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses

Abstract

Here, the lattice vibrational dynamics in ultra-fragile Pt₅₇Cu₂₃P₂₀ and Pt₆₀Cu₂₀P₂₀ glasses were investigated using in situ inelastic neutron scattering to measure the evolution of the phonon density of states (DOS) through the glass transition, into the undercooled liquid phase, and through crystallization. The phonon DOS curves are remarkably similar for the undercooled liquids and the amorphous solids. The vibrational entropy was obtained with these phonon DOS curves, and changes in vibrational entropy caused by the glass transition are less than 0.05 k_B/atom. For these highly fragile metal/metalloid glasses, the excess vibrational entropy of the undercooled liquid is about 0.5–1.5 Jmol^-1 K^-1, compared to 0.1 Jmol^-1 K^-1 reported earlier for stronger Cu–Zr glasses. Our work suggests that, consistent with our previous report for less fragile metallic glasses, the fraction of the total excess entropy that is vibrational is small, and the discontinuity in excess entropy at the glass transition is mainly due to configurational entropy.

Authors:

^[1];

^[2];

^[2]; Lohaus, Stefan H. ^[2]; Stoddard, Colby J. ^[1];

^[3];

^[4];

^[4]; Na, Jong-Hyun ^[5]; Demetriou, Marios D. ^[5];

^[2]

Swarthmore College, Swarthmore, PA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Glassimetal Technology Inc., Pasadena, CA (United States)

Publication Date:: Wed Feb 08 00:00:00 EST 2023

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); American Chemical Society Petroleum Research Fund (ACS-PRF)

OSTI Identifier:: 1965216

Grant/Contract Number:: AC05-00OR22725; FG02-03ER46055; 62045-UNI10

Resource Type:: Accepted Manuscript

Journal Name:: Materialia

Additional Journal Information:: Journal Volume: 27; Journal ID: ISSN 2589-1529

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 36 MATERIALS SCIENCE; metallic glasses; glass transition; liquids; glass; neutron scattering

Citation Formats


                    Smith, Hillary L., Saunders, Claire N., Bernal-Choban, Camille, Lohaus, Stefan H., Stoddard, Colby J., Decker, Lucy K., Lin, Jiao Y. Y., Niedziela, Jennifer L., Abernathy, Douglas L., Na, Jong-Hyun, Demetriou, Marios D., and Fultz, B. Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses.  United States: N. p., 2023. 
Web.  doi:10.1016/j.mtla.2023.101710.

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                    Smith, Hillary L., Saunders, Claire N., Bernal-Choban, Camille, Lohaus, Stefan H., Stoddard, Colby J., Decker, Lucy K., Lin, Jiao Y. Y., Niedziela, Jennifer L., Abernathy, Douglas L., Na, Jong-Hyun, Demetriou, Marios D., & Fultz, B. Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses.  United States.  https://doi.org/10.1016/j.mtla.2023.101710

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                    Smith, Hillary L., Saunders, Claire N., Bernal-Choban, Camille, Lohaus, Stefan H., Stoddard, Colby J., Decker, Lucy K., Lin, Jiao Y. Y., Niedziela, Jennifer L., Abernathy, Douglas L., Na, Jong-Hyun, Demetriou, Marios D., and Fultz, B. Wed .  
"Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses".  United States.  https://doi.org/10.1016/j.mtla.2023.101710.  https://www.osti.gov/servlets/purl/1965216.

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@article{osti_1965216,

  title        = {Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses},

  author       = {Smith, Hillary L. and Saunders, Claire N. and Bernal-Choban, Camille and Lohaus, Stefan H. and Stoddard, Colby J. and Decker, Lucy K. and Lin, Jiao Y. Y. and Niedziela, Jennifer L. and Abernathy, Douglas L. and Na, Jong-Hyun and Demetriou, Marios D. and Fultz, B.},

  abstractNote = {Here, the lattice vibrational dynamics in ultra-fragile Pt57Cu23P20 and Pt60Cu20P20 glasses were investigated using in situ inelastic neutron scattering to measure the evolution of the phonon density of states (DOS) through the glass transition, into the undercooled liquid phase, and through crystallization. The phonon DOS curves are remarkably similar for the undercooled liquids and the amorphous solids. The vibrational entropy was obtained with these phonon DOS curves, and changes in vibrational entropy caused by the glass transition are less than 0.05 kB/atom. For these highly fragile metal/metalloid glasses, the excess vibrational entropy of the undercooled liquid is about 0.5–1.5 Jmol-1 K-1, compared to 0.1 Jmol-1 K-1 reported earlier for stronger Cu–Zr glasses. Our work suggests that, consistent with our previous report for less fragile metallic glasses, the fraction of the total excess entropy that is vibrational is small, and the discontinuity in excess entropy at the glass transition is mainly due to configurational entropy.},

  doi          = {10.1016/j.mtla.2023.101710},

  journal      = {Materialia},

  number       = ,

  volume       = 27,

  place        = {United States},

  year         = {Wed Feb 08 00:00:00 EST 2023},

  month        = {Wed Feb 08 00:00:00 EST 2023}

}

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Title: Vibrational dynamics in the undercooled liquid of ultra-fragile metallic glasses

Abstract

Citation Formats

Perspective: Supercooled liquids and glasses journal, August 2012

A thermodynamic connection to the fragility of glass-forming liquids journal, April 2001

Structural instability and relaxation in liquid and glassy phases near the fragile liquid limit journal, June 1988

Kinetic and thermodynamic studies of the fragility of bulk metallic glass forming liquids journal, September 2010

Source of JG-Relaxation in the Entropy of Glass journal, February 2019

Nature of the Glass Transition and the Glassy State journal, March 1958

On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids journal, July 1965

Viscous liquids and the glass transition. V. Sources of the excess specific heat of the liquid journal, June 1976

Separating the configurational and vibrational entropy contributions in metallic glasses journal, May 2017

Thermal behavior and melt fragility number of Cu 100-x Zr x glassy alloys in terms of crystallization and viscous flow journal, January 2009

Superior glass-forming ability of CuZr alloys from minor additions journal, July 2006

Spectroscopy simulation and scattering, and the medium range order problem in glass journal, August 1985

Zr–(Cu,Ag)–Al bulk metallic glasses journal, May 2008

Observation of an apparent first-order glass transition in ultrafragile Pt–Cu–P bulk metallic glasses journal, January 2020

Fragility of iron-based glasses journal, October 2011

Mantid—Data analysis and visualization package for neutron scattering and μ SR experiments journal, November 2014

Event-based processing of neutron scattering data at the Spallation Neutron Source journal, May 2018

Anharmonic phonon quasiparticle theory of zero-point and thermal shifts in insulators: Heat capacity, bulk modulus, and thermal expansion journal, August 2015

Thermodynamics, kinetics, and crystallization of Pt57.3Cu14.6Ni5.3P22.8 bulk metallic glass journal, February 2007

Formation of Glasses from Liquids and Biopolymers journal, March 1995

Origin of liquid fragility journal, October 2020

Supercooled liquids and the glass transition journal, March 2001

The impact of fragility on the calorimetric glass transition in bulk metallic glasses journal, December 2014

Direct determination of kinetic fragility indices of glassforming liquids by differential scanning calorimetry: Kinetic versus thermodynamic fragilities journal, December 2002

Fragility and thermodynamics in nonpolymeric glass-forming liquids journal, August 2006

Perspective: Supercooled liquids and glasses
journal, August 2012

A thermodynamic connection to the fragility of glass-forming liquids
journal, April 2001

Structural instability and relaxation in liquid and glassy phases near the fragile liquid limit
journal, June 1988

Kinetic and thermodynamic studies of the fragility of bulk metallic glass forming liquids
journal, September 2010

Source of JG-Relaxation in the Entropy of Glass
journal, February 2019

Nature of the Glass Transition and the Glassy State
journal, March 1958

On the Temperature Dependence of Cooperative Relaxation Properties in Glass‐Forming Liquids
journal, July 1965

Viscous liquids and the glass transition. V. Sources of the excess specific heat of the liquid
journal, June 1976

Separating the configurational and vibrational entropy contributions in metallic glasses
journal, May 2017

Thermal behavior and melt fragility number of Cu _100-x Zr _x glassy alloys in terms of crystallization and viscous flow
journal, January 2009

Superior glass-forming ability of CuZr alloys from minor additions
journal, July 2006

Spectroscopy simulation and scattering, and the medium range order problem in glass
journal, August 1985

Zr–(Cu,Ag)–Al bulk metallic glasses
journal, May 2008

Observation of an apparent first-order glass transition in ultrafragile Pt–Cu–P bulk metallic glasses
journal, January 2020

Fragility of iron-based glasses
journal, October 2011

Mantid—Data analysis and visualization package for neutron scattering and $μ$ SR experiments
journal, November 2014

Event-based processing of neutron scattering data at the Spallation Neutron Source
journal, May 2018

Anharmonic phonon quasiparticle theory of zero-point and thermal shifts in insulators: Heat capacity, bulk modulus, and thermal expansion
journal, August 2015

Thermodynamics, kinetics, and crystallization of Pt57.3Cu14.6Ni5.3P22.8 bulk metallic glass
journal, February 2007

Formation of Glasses from Liquids and Biopolymers
journal, March 1995

Origin of liquid fragility
journal, October 2020

Supercooled liquids and the glass transition
journal, March 2001

The impact of fragility on the calorimetric glass transition in bulk metallic glasses
journal, December 2014

Direct determination of kinetic fragility indices of glassforming liquids by differential scanning calorimetry: Kinetic versus thermodynamic fragilities
journal, December 2002

Fragility and thermodynamics in nonpolymeric glass-forming liquids
journal, August 2006