skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Free energy of grain boundary phases: Atomistic calculations for Σ 5 ( 310 ) [ 001 ] grain boundary in Cu

Abstract

Atomistic simulations are employed to demonstrate the existence of a well-defined thermodynamic phase transformation between grain boundary (GB) phases with different atomic structures. The free energy of different interface structures for an embedded-atom-method model of the Σ5 (310) [001] symmetric tilt boundary in elemental Cu is computed using the nonequilibrium Frenkel-Ladd thermodynamic integration method through molecular dynamics simulations. It is shown that the free-energy curves predict a temperature-induced first-order interfacial phase transition in the GB structure in agreement with computational studies of the same model system. Moreover, the role of vibrational entropy in the stabilization of the high-temperature GB phase is clarified. The calculated results are able to determine the GB phase stability at homologous temperatures less than 0.5, a temperature range particularly important given the limitation of the methods available hitherto in modeling GB phase transitions at low temperatures. Lastly, the calculation of GB free energies complements currently available 0 K GB structure search methods, making feasible the characterization of GB phase diagrams.

Authors:
 [1];  [2];  [3];  [2]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  3. Univ. of California, Berkeley, CA (United States). Dept. of Materials Science and Engineering; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF)
OSTI Identifier:
1477156
Alternate Identifier(s):
OSTI ID: 1469261
Report Number(s):
LLNL-JRNL-754459
Journal ID: ISSN 2475-9953; PRMHAR; 941097
Grant/Contract Number:  
AC52-07NA27344; DMR-1507033
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 9; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 36 MATERIALS SCIENCE

Citation Formats

Freitas, Rodrigo, Rudd, Robert E., Asta, Mark, and Frolov, Timofey. Free energy of grain boundary phases: Atomistic calculations for Σ5(310)[001] grain boundary in Cu. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.093603.
Freitas, Rodrigo, Rudd, Robert E., Asta, Mark, & Frolov, Timofey. Free energy of grain boundary phases: Atomistic calculations for Σ5(310)[001] grain boundary in Cu. United States. doi:10.1103/PhysRevMaterials.2.093603.
Freitas, Rodrigo, Rudd, Robert E., Asta, Mark, and Frolov, Timofey. Sat . "Free energy of grain boundary phases: Atomistic calculations for Σ5(310)[001] grain boundary in Cu". United States. doi:10.1103/PhysRevMaterials.2.093603. https://www.osti.gov/servlets/purl/1477156.
@article{osti_1477156,
title = {Free energy of grain boundary phases: Atomistic calculations for Σ5(310)[001] grain boundary in Cu},
author = {Freitas, Rodrigo and Rudd, Robert E. and Asta, Mark and Frolov, Timofey},
abstractNote = {Atomistic simulations are employed to demonstrate the existence of a well-defined thermodynamic phase transformation between grain boundary (GB) phases with different atomic structures. The free energy of different interface structures for an embedded-atom-method model of the Σ5 (310) [001] symmetric tilt boundary in elemental Cu is computed using the nonequilibrium Frenkel-Ladd thermodynamic integration method through molecular dynamics simulations. It is shown that the free-energy curves predict a temperature-induced first-order interfacial phase transition in the GB structure in agreement with computational studies of the same model system. Moreover, the role of vibrational entropy in the stabilization of the high-temperature GB phase is clarified. The calculated results are able to determine the GB phase stability at homologous temperatures less than 0.5, a temperature range particularly important given the limitation of the methods available hitherto in modeling GB phase transitions at low temperatures. Lastly, the calculation of GB free energies complements currently available 0 K GB structure search methods, making feasible the characterization of GB phase diagrams.},
doi = {10.1103/PhysRevMaterials.2.093603},
journal = {Physical Review Materials},
number = 9,
volume = 2,
place = {United States},
year = {2018},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Segregation-induced phase transformations in grain boundaries
journal, July 2015


Atomic Structure of Symmetric Tilt Grain Boundaries in NiO
journal, December 1987


A General Structure for Coincidence Twist Grain Boundaries in Rock-Salt-Structured Oxides
journal, September 1984


Size effect on melting temperatures of alumina nanocrystals: Molecular dynamics simulations and thermodynamic modeling
journal, April 2018


Diffusion and segregation of silver in copper Σ 5(310) grain boundary
journal, April 2012


Nonequilibrium free-energy calculation of solids using LAMMPS
journal, February 2016


Dynamic simulation of structural phase transitions in magnetic iron
journal, September 2017


Diffuse interface model for structural transitions of grain boundaries
journal, January 2006


Grain Boundary Transitions in Binary Alloys
journal, August 2006


Fast Parallel Algorithms for Short-Range Molecular Dynamics
journal, March 1995


Layering transitions at grain boundaries
journal, October 2016


Grain boundary phases in bcc metals
journal, January 2018

  • Frolov, T.; Setyawan, W.; Kurtz, R. J.
  • Nanoscale, Vol. 10, Issue 17
  • DOI: 10.1039/C8NR00271A

Free energies of interfaces from quasi-harmonic theory: A critical appraisal
journal, January 1994

  • Hairie, A.; Hairie, F.; Lebouvier, B.
  • Interface Science, Vol. 2, Issue 1
  • DOI: 10.1007/BF00188816

Tracer diffusion of Au and Cu in a series of near Σ=5 (310)[001] symmetrical Cu tilt grain boundaries
journal, January 1999


A genetic algorithm for predicting the structures of interfaces in multicomponent systems
journal, February 2010

  • Chua, Alvin L. -S.; Benedek, Nicole A.; Chen, Lin
  • Nature Materials, Vol. 9, Issue 5
  • DOI: 10.1038/nmat2712

Hydrogen segregation to inclined twin grain boundaries in nickel
journal, August 2016


Structural stability and lattice defects in copper: Ab initio , tight-binding, and embedded-atom calculations
journal, May 2001


New Monte Carlo method to compute the free energy of arbitrary solids. Application to the fcc and hcp phases of hard spheres
journal, October 1984

  • Frenkel, Daan; Ladd, Anthony J. C.
  • The Journal of Chemical Physics, Vol. 81, Issue 7
  • DOI: 10.1063/1.448024

Simulated quenching to the zero‐temperature limit of the grand‐canonical ensemble
journal, August 1992

  • Phillpot, S. R.; Rickman, J. M.
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463053

Temperature dependence of grain boundary free energy and elastic constants
journal, March 2010


Thermodynamic and structural properties of [001] twist boundaries in gold
journal, May 1991

  • Najafabadi, R.; Srolovitz, D. J.; LeSar, R.
  • Journal of Materials Research, Vol. 6, Issue 5
  • DOI: 10.1557/JMR.1991.0999

On the structure of twist grain boundaries in ionic oxides
journal, June 1983


Structures and transitions in bcc tungsten grain boundaries and their role in the absorption of point defects
journal, October 2018


Direct dynamical calculation of entropy and free energy by adiabatic switching
journal, December 1990


Grain boundary complexions
journal, January 2014


Phases, phase equilibria, and phase rules in low-dimensional systems
journal, July 2015

  • Frolov, T.; Mishin, Y.
  • The Journal of Chemical Physics, Vol. 143, Issue 4
  • DOI: 10.1063/1.4927414

Thermodynamics of coherent interfaces under mechanical stresses. I. Theory
journal, June 2012


Grain-boundary layering transitions in a model bicrystal
journal, December 2013


Phonons in nanocrystalline Ni 3 Fe
journal, January 1998


Atomistic modeling of interfaces and their impact on microstructure and properties
journal, February 2010


Multiple grain boundary transitions in ceramics: A case study of alumina
journal, September 2007


Molecular dynamics investigation of the crystal–fluid interface. VI. Excess surface free energies of crystal–liquid systems
journal, May 1986

  • Broughton, J. Q.; Gilmer, G. H.
  • The Journal of Chemical Physics, Vol. 84, Issue 10
  • DOI: 10.1063/1.449884

A molecular dynamics study of grain boundary free energies, migration mechanisms and mobilities in a bcc Fe–20Cr alloy
journal, February 2012


Evaluation of harmonic methods for calculating the free energy of defects in solids
journal, June 1994


Temperature dependence of the surface free energy and surface stress: An atomistic calculation for Cu(110)
journal, January 2009


Grain-boundary layering transitions and phonon engineering
journal, September 2016


Predicting phase behavior of grain boundaries with evolutionary search and machine learning
journal, February 2018


Embedded-atom method: Derivation and application to impurities, surfaces, and other defects in metals
journal, June 1984


Molecular dynamics simulations of temperature-induced structural transitions at twist boundaries in silicon
journal, December 2007


On the multiplicity of structures and grain boundaries
journal, February 1983


Effect of Interface Phase Transformations on Diffusion and Segregation in High-Angle Grain Boundaries
journal, June 2013


Thermodynamic Criteria for Grain-Boundary Melting: A Molecular-Dynamics Study
journal, June 1986


Einstein crystal as a reference system in free energy estimation using adiabatic switching
journal, January 1996


A dislocation model for the structure of [001] twist boundaries in ionic oxides
journal, January 1986


Structural phase transformations in metallic grain boundaries
journal, May 2013

  • Frolov, Timofey; Olmsted, David L.; Asta, Mark
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2919

Phase transformations at interfaces: Observations from atomistic modeling
journal, October 2016


Size-dependent evolution of the atomic vibrational density of states and thermodynamic properties of isolated Fe nanoparticles
journal, October 2012


Simulation of solids at nonzero temperatures in the grand-canonical ensemble
journal, March 1994


The importance of grain boundary complexions in affecting physical properties of polycrystals
journal, October 2016

  • Dillon, Shen J.; Tai, Kaiping; Chen, Song
  • Current Opinion in Solid State and Materials Science, Vol. 20, Issue 5
  • DOI: 10.1016/j.cossms.2016.06.003

Step free energies at faceted solid surfaces: Theory and atomistic calculations for steps on the Cu(111) surface
journal, April 2017


Dislocation-Pairing Transitions in Hot Grain Boundaries
journal, January 2011


Grain boundaries in ionic crystals
journal, August 1986