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Title: The effects of cation–anion clustering on defect migration in MgAl2O4

Abstract

Magnesium aluminate spinel (MgAl2O4), like many other ceramic materials, offers a range of technological applications, from nuclear reactor materials to military body armor. For many of these applications, it is critical to understand both the formation and evolution of lattice defects throughout the lifetime of the material. We use the Speculatively Parallel Temperature Accelerated Dynamics (SpecTAD) method to investigate the effects of di-vacancy and di-interstitial formation on the mobility of the component defects. From long-time trajectories of the state-to-state dynamics, we characterize the migration pathways of defect clusters, and calculate their self-diffusion constants across a range of temperatures. We find that the clustering of Al and O vacancies drastically reduces the mobility of both defects, while the clustering of Mg and O vacancies completely immobilizes them. For interstitials, we find that the clustering of Mg and O defects greatly reduces O interstitial mobility, but has only a weak effect on Mg. Lastly, these findings illuminate important new details regarding defect kinetics relevant to the application of MgAl2O4 in extreme environments.

Authors:
 [1];  [1];  [1];  [1];  [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1329597
Report Number(s):
LA-UR-16-23859
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 29; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; material science

Citation Formats

Zamora, Richard J., Voter, Arthur F., Perez, Danny, Perriot, Romain, and Uberuaga, Blas P. The effects of cation–anion clustering on defect migration in MgAl2O4. United States: N. p., 2016. Web. https://doi.org/10.1039/C6CP03931F.
Zamora, Richard J., Voter, Arthur F., Perez, Danny, Perriot, Romain, & Uberuaga, Blas P. The effects of cation–anion clustering on defect migration in MgAl2O4. United States. https://doi.org/10.1039/C6CP03931F
Zamora, Richard J., Voter, Arthur F., Perez, Danny, Perriot, Romain, and Uberuaga, Blas P. Tue . "The effects of cation–anion clustering on defect migration in MgAl2O4". United States. https://doi.org/10.1039/C6CP03931F. https://www.osti.gov/servlets/purl/1329597.
@article{osti_1329597,
title = {The effects of cation–anion clustering on defect migration in MgAl2O4},
author = {Zamora, Richard J. and Voter, Arthur F. and Perez, Danny and Perriot, Romain and Uberuaga, Blas P.},
abstractNote = {Magnesium aluminate spinel (MgAl2O4), like many other ceramic materials, offers a range of technological applications, from nuclear reactor materials to military body armor. For many of these applications, it is critical to understand both the formation and evolution of lattice defects throughout the lifetime of the material. We use the Speculatively Parallel Temperature Accelerated Dynamics (SpecTAD) method to investigate the effects of di-vacancy and di-interstitial formation on the mobility of the component defects. From long-time trajectories of the state-to-state dynamics, we characterize the migration pathways of defect clusters, and calculate their self-diffusion constants across a range of temperatures. We find that the clustering of Al and O vacancies drastically reduces the mobility of both defects, while the clustering of Mg and O vacancies completely immobilizes them. For interstitials, we find that the clustering of Mg and O defects greatly reduces O interstitial mobility, but has only a weak effect on Mg. Lastly, these findings illuminate important new details regarding defect kinetics relevant to the application of MgAl2O4 in extreme environments.},
doi = {10.1039/C6CP03931F},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 29,
volume = 18,
place = {United States},
year = {2016},
month = {6}
}

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Works referenced in this record:

Insights into dynamic processes of cations in pyrochlores and other complex oxides
journal, January 2015

  • Uberuaga, Blas Pedro; Perriot, Romain
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/c5cp03372a

Temperature-accelerated dynamics for simulation of infrequent events
journal, June 2000

  • So/rensen, Mads R.; Voter, Arthur F.
  • The Journal of Chemical Physics, Vol. 112, Issue 21
  • DOI: 10.1063/1.481576

Interpreting oxygen vacancy migration mechanisms in oxides using the layered structure motif
journal, June 2015


Structure of Spinel
journal, December 1999


Exploiting past visits or minimum-barrier knowledge to gain further boost in the temperature-accelerated dynamics method
journal, January 2002

  • Montalenti, F.; Voter, A. F.
  • The Journal of Chemical Physics, Vol. 116, Issue 12
  • DOI: 10.1063/1.1449865

The Modern Temperature-Accelerated Dynamics Approach
journal, June 2016


Low- and high-temperature spinel (MgAl 2 O 4 ): studies on natural single crystals by neutron diffraction
journal, August 1981

  • Baumgartner, O.; Preisinger, A.; Heger, G.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 37, Issue a1
  • DOI: 10.1107/s0108767381093963

Defect processes in MgAl2O4 spinel
journal, June 2008


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Interstitial and vacancy mediated transport mechanisms in perovskites: A comparison of chemistry and potentials
journal, December 2013


Defect kinetics in spinels: Long-time simulations of Mg Al 2 O 4 , Mg Ga 2 O 4 , and Mg In 2 O 4
journal, March 2007


Frequency factors and isotope effects in solid state rate processes
journal, January 1957


Cation diffusion in magnesium aluminate spinel
journal, February 2009


Atomistic simulations of radiation-induced defect formation in spinels: Mg Al 2 O 4 , Mg Ga 2 O 4 , and Mg In 2 O 4
journal, December 2006


An extended hardness limit in bulk nanoceramics
journal, May 2014


Cation disorder in Mg X 2 O 4 ( X = Al, Ga, In) spinels from first principles
journal, July 2012


Heavy ion induced damage in MgAl2O4, an inert matrix candidate for the transmutation of minor actinides
journal, June 1999


Defect Reactions and the Controlling Mechanism in the Sintering of Magnesium Aluminate Spinel
journal, April 1999


Materials research on inert matrices: a screening study
journal, August 1999


Materials research on inert matrices: a screening study
journal, August 1999


Heavy ion induced damage in MgAl2O4, an inert matrix candidate for the transmutation of minor actinides
journal, June 1999


Defect kinetics in spinels: Long-time simulations of Mg Al 2 O 4 , Mg Ga 2 O 4 , and Mg In 2 O 4
journal, March 2007


Insights into dynamic processes of cations in pyrochlores and other complex oxides
journal, January 2015

  • Uberuaga, Blas Pedro; Perriot, Romain
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 37
  • DOI: 10.1039/C5CP03372A

Atomistic simulations of radiation-induced defect formation in spinels: Mg Al 2 O 4 , Mg Ga 2 O 4 , and Mg In 2 O 4
journal, December 2006


Low- and high-temperature spinel (MgAl 2 O 4 ): studies on natural single crystals by neutron diffraction
journal, August 1981

  • Baumgartner, O.; Preisinger, A.; Heger, G.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 37, Issue a1
  • DOI: 10.1107/S0108767381093963

Cation disorder in Mg X 2 O 4 ( X = Al, Ga, In) spinels from first principles
journal, July 2012


    Works referencing / citing this record:

    Speculation and replication in temperature accelerated dynamics
    journal, February 2018

    • Zamora, Richard J.; Perez, Danny; Voter, Arthur F.
    • Journal of Materials Research, Vol. 33, Issue 7
    • DOI: 10.1557/jmr.2018.17