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Title: Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

Abstract

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.

Authors:
 [1];  [1];  [2];  [1];  [3];  [1];  [4]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. Thermo-Calc Software Inc., Pittsburgh, PA (United States)
  3. Loughborough Univ., Loughborough (United Kingdom)
  4. Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1239355
Report Number(s):
LA-UR-15-22255
Journal ID: ISSN 2041-1723; ncomms9750
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 6; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; physical sciences; condensed matter; materials science

Citation Formats

Uberuaga, Blas Pedro, Tang, Ming, Jiang, Chao, Valdez, James A., Smith, Roger, Wang, Yongqiang, and Sickafus, Kurt E. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores. United States: N. p., 2015. Web. doi:10.1038/ncomms9750.
Uberuaga, Blas Pedro, Tang, Ming, Jiang, Chao, Valdez, James A., Smith, Roger, Wang, Yongqiang, & Sickafus, Kurt E. Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores. United States. https://doi.org/10.1038/ncomms9750
Uberuaga, Blas Pedro, Tang, Ming, Jiang, Chao, Valdez, James A., Smith, Roger, Wang, Yongqiang, and Sickafus, Kurt E. Thu . "Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores". United States. https://doi.org/10.1038/ncomms9750. https://www.osti.gov/servlets/purl/1239355.
@article{osti_1239355,
title = {Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores},
author = {Uberuaga, Blas Pedro and Tang, Ming and Jiang, Chao and Valdez, James A. and Smith, Roger and Wang, Yongqiang and Sickafus, Kurt E.},
abstractNote = {Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.},
doi = {10.1038/ncomms9750},
journal = {Nature Communications},
number = ,
volume = 6,
place = {United States},
year = {2015},
month = {10}
}

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Works referenced in this record:

Nuclear energy: Status and future limitations
journal, January 2012


Understanding resistance to amorphization by radiation damage
journal, November 2004


Materials challenges in nuclear energy
journal, February 2013


Recent Developments in Irradiation-Resistant Steels
journal, August 2008


Microstructure of Swift Heavyion Irradiated MgAl 2 0 4 Spinel
journal, January 1998


Ion-beam-induced spinel-to-rocksalt structural phase transformation in MgAl2O4
journal, May 2000

  • Ishimaru, Manabu; Afanasyev-Charkin, Ivan V.; Sickafus, Kurt E.
  • Applied Physics Letters, Vol. 76, Issue 18
  • DOI: 10.1063/1.126406

Röntgenographische Untersuchung der Kationenverteilung in Spinellphasen
journal, May 1961


Opportunities and Challenges for Materials Innovation in Nuclear Energy
journal, January 2013


Cation ordering and structural variations with temperature in MgAl 2 O 4 spinel: An X-ray single-crystal study
journal, September 2000

  • Andreozzi, Giovanni B.; Princivalle, Francesco; Skogby, Henrik
  • American Mineralogist, Vol. 85, Issue 9
  • DOI: 10.2138/am-2000-8-907

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


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Effects of Xe ion irradiation and subsequent annealing on the structural properties of magnesium-aluminate spinel
journal, February 2001

  • Afanasyev-Charkin, Ivan V.; Dickerson, Robert M.; Wayne Cooke, D.
  • Journal of Nuclear Materials, Vol. 289, Issue 1-2
  • DOI: 10.1016/S0022-3115(00)00689-9

Criteria for bombardment-induced structural changes in non-metallic solids
journal, January 1975


Chemical disordering in amorphization
journal, June 1988


Structural stability of Nd2Zr2O7 pyrochlore ion-irradiated in a broad energy range
journal, October 2013


Retention of Actinides in Natural Pyrochlores and Zirconolites
journal, January 1994


Prediction of Irradiation Spectrum Effects in Pyrochlores
journal, September 2014


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


Role of Antisite Disorder on Preamorphization Swelling in Titanate Pyrochlores
journal, May 2012


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


Grain boundary stoichiometry and interactions with defects in SrTiO3
journal, January 2012


Radiation-induced amorphization of rare-earth titanate pyrochlores
journal, October 2003


Radiation Tolerance of Complex Oxides
journal, August 2000


Cation disorder in high-dose, neutron-irradiated spinel
report, April 1995


The Stopping and Range of Ions in Matter
book, January 1985


Ion-beam-induced spinel-to-rocksalt structural phase transformation in MgAl2O4
journal, May 2000

  • Ishimaru, Manabu; Afanasyev-Charkin, Ivan V.; Sickafus, Kurt E.
  • Applied Physics Letters, Vol. 76, Issue 18
  • DOI: 10.1063/1.126406

Order–disorder phase transition induced by swift ions in MgAl2O4 and ZnAl2O4 spinels
journal, February 2002


First-principles prediction of disordering tendencies in pyrochlore oxides
journal, March 2009


Thermodynamics and kinetics of cation ordering in MgAl 2 O 4 spinel up to 1600 degrees C from in situ neutron diffraction
journal, March 1999

  • Redfern, Simon A. T.; Harrison, Richard J.; O'Neill, Hugh St. C.
  • American Mineralogist, Vol. 84, Issue 3
  • DOI: 10.2138/am-1999-0313

Order–Disorder Transformations in Ln 2 Ti 2 O 7 (Ln = Lu, Yb, Tm, Gd)
journal, January 2004


Neutron irradiation damage in MgO, Al2O3 and MgAl2O4 ceramics
journal, July 1982


Anisotropic dislocation loop nucleation in ion-irradiated MgAl2O4
journal, September 1992


Cation distribution and oxygen parameter in magnesium gallate, MgGa 2 O 4
journal, November 1966


Irradiation-Induced Amorphization and Order-Disorder Transformation in the Tungsten δ-phase Oxides Yb[sub 6]W[sub 1]O[sub 12] and Y[sub 6]W[sub 1]O[sub 12]
conference, January 2009

  • Tang, M.; Valdez, J. A.; Uberuaga, B. P.
  • APPLICATION OF ACCELERATORS IN RESEARCH AND INDUSTRY: Twentieth International Conference, AIP Conference Proceedings
  • DOI: 10.1063/1.3120205

Atomistic structures of metastable and amorphous phases in ion-irradiated magnesium aluminate spinel
journal, January 2002

  • Ishimaru, Manabu; Hirotsu, Yoshihiko; Afanasyev-Charkin, Ivan V.
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 6
  • DOI: 10.1088/0953-8984/14/6/311

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

Atomistic structures of metastable and amorphous phases in ion-irradiated magnesium aluminate spinel
journal, January 2002

  • Ishimaru, Manabu; Hirotsu, Yoshihiko; Afanasyev-Charkin, Ivan V.
  • Journal of Physics: Condensed Matter, Vol. 14, Issue 6
  • DOI: 10.1088/0953-8984/14/6/311

Radiation resistance of the oxide spinel: the role of stoichiometry on damage response
journal, August 1996

  • Sickafus, Kurt E.; Yu, Ning; Nastasi, Michael
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 116, Issue 1-4
  • DOI: 10.1016/0168-583X(96)00015-8

Energetics and concentration of defects in Gd2Ti2O7 and Gd2Zr2O7 pyrochlore at high pressure
journal, February 2011


The order–disorder transition in ion-irradiated pyrochlore
journal, March 2003


Structure and Mobility of Defects Formed from Collision Cascades in MgO
journal, March 2004


Disorder in Pyrochlore Oxides
journal, August 2000


Enhanced radiation tolerance in nanocrystalline MgGa2O4
journal, June 2007

  • Shen, Tong D.; Feng, Shihai; Tang, Ming
  • Applied Physics Letters, Vol. 90, Issue 26
  • DOI: 10.1063/1.2753098

Why ion irradiation does not lead to the same structural changes in normal spinels ZnAl2O4, MgAl2O4 and MgCr2O4?
journal, June 2008

  • Baldinozzi, G.; Simeone, D.; Gosset, D.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 266, Issue 12-13
  • DOI: 10.1016/j.nimb.2008.03.218

Effect of Structure and Thermodynamic Stability on the Response of Lanthanide Stannate Pyrochlores to Ion Beam Irradiation
journal, February 2006

  • Lian, J.; Helean, K. B.; Kennedy, B. J.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 5
  • DOI: 10.1021/jp055266c

Disorder-induced amorphization
journal, November 1997


Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds
journal, April 2007

  • Lumpkin, Gregory R.; Pruneda, Miguel; Rios, Susana
  • Journal of Solid State Chemistry, Vol. 180, Issue 4
  • DOI: 10.1016/j.jssc.2007.01.028

Role of the interface on radiation damage in the SrTiO 3 /LaAlO 3 heterostructure under Ne 2+ ion irradiation
journal, March 2014

  • Bi, Zhenxing; Uberuaga, Blas P.; Vernon, L. J.
  • Journal of Applied Physics, Vol. 115, Issue 12
  • DOI: 10.1063/1.4870052

Effect of Structure and Thermodynamic Stability on the Response of Lanthanide Stannate Pyrochlores to Ion Beam Irradiation
journal, February 2006

  • Lian, J.; Helean, K. B.; Kennedy, B. J.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 5
  • DOI: 10.1021/jp055266c

Epitaxial cobalt oxide films on Ir(100)—the importance of crystallographic analyses
journal, March 2013


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Der Magnesium-Gallium-Spinell
journal, November 1932


Comparison of Ion-Beam Irradiation Effects in X2YO4 Compounds
journal, December 1999


Systematics of the spinel structure type
journal, January 1979

  • Hill, Roderick J.; Craig, James R.; Gibbs, G. V.
  • Physics and Chemistry of Minerals, Vol. 4, Issue 4
  • DOI: 10.1007/BF00307535

In situ studies of ion irradiated inverse spinel compound magnesium stannate (Mg2SnO4)
journal, June 2009


Thermodynamics and kinetics of phase transformations induced by ion irradiation
journal, February 1991


First observation of' amorphization in single-crystal MgA1 2 O 4 spinel
journal, October 1994

  • Yu, Ning; Sickafus, Kurt E.; Nastasi, Michael
  • Philosophical Magazine Letters, Vol. 70, Issue 4
  • DOI: 10.1080/09500839408240980

Derivative Crystal Structures
journal, January 1947

  • Buerger, M. J.
  • The Journal of Chemical Physics, Vol. 15, Issue 1
  • DOI: 10.1063/1.1746278

Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides
journal, February 2007

  • Sickafus, Kurt E.; Grimes, Robin W.; Valdez, James A.
  • Nature Materials, Vol. 6, Issue 3
  • DOI: 10.1038/nmat1842

Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides
journal, February 2007

  • Sickafus, Kurt E.; Grimes, Robin W.; Valdez, James A.
  • Nature Materials, Vol. 6, Issue 3
  • DOI: 10.1038/nmat1842

Radiation Tolerance of Complex Oxides
journal, August 2000


Formation enthalpies of rare earth titanate pyrochlores
journal, June 2004


Why is magnesia spinel a radiation-resistant material?
journal, March 1995


Special quasirandom structures
journal, July 1990


Non-stoichiometry in MgAl 2 O 4 spinel
journal, March 2010


Order-to-disorder phase transformation in ion irradiated uranium-bearing delta-phase oxides RE6U1O12 (RE=Y, Gd, Ho, Yb, and Lu)
journal, April 2010


Atomic structure and disordering induced by 350MeV Au ions in MgAl2O4
journal, September 2006

  • Yasuda, K.; Yamamoto, T.; Shimada, M.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 250, Issue 1-2
  • DOI: 10.1016/j.nimb.2006.04.164

Cation disorder in high dose, neutron-irradiated spinel
journal, March 1995


Amorphization of intermetallic compounds under irradiation — A review
journal, April 1997


Heavy-ion irradiation effects in Gd2(Ti2−xZrx)O7 pyrochlores
journal, February 2001


Cation ordering and structural variations with temperature in MgAl 2 O 4 spinel: An X-ray single-crystal study
journal, September 2000

  • Andreozzi, Giovanni B.; Princivalle, Francesco; Skogby, Henrik
  • American Mineralogist, Vol. 85, Issue 9
  • DOI: 10.2138/am-2000-8-907

Cation disordering in magnesium aluminate spinel crystals induced by electron or ion irradiation
journal, December 2000


Why ion irradiation does not lead to the same structural changes in normal spinels ZnAl2O4, MgAl2O4 and MgCr2O4?
journal, June 2008

  • Baldinozzi, G.; Simeone, D.; Gosset, D.
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 266, Issue 12-13
  • DOI: 10.1016/j.nimb.2008.03.218

Retention of Actinides in Natural Pyrochlores and Zirconolites
journal, January 1994


Microstructure of Al2O3 and MgAl2O4 irradiated at low temperatures
journal, March 1998


Nanoscale Manipulation of Pyrochlore: New Nanocomposite Ionic Conductors
journal, September 2001


Der Magnesium-Gallium-Spinell
journal, November 1932


Works referencing / citing this record:

Novel defect-fluorite pyrochlore sodium niobate nanoparticles: solution-phase synthesis and radiation tolerance analysis
journal, January 2019

  • Ali, Rana Faryad; Ovens, Jeffrey S.; Starosta, Krzysztof
  • Nanoscale, Vol. 11, Issue 12
  • DOI: 10.1039/c8nr10385b

Evidence for percolation diffusion of cations and reordering in disordered pyrochlore from accelerated molecular dynamics
journal, September 2017


Effect of Chemical Bonding Characteristics on Ordering Structure in Li Spinel Oxides
journal, November 2018

  • Ryoo, Hyewon; Lee, Sang-Gil; Kim, Jin-Gyu
  • Advanced Functional Materials, Vol. 29, Issue 2
  • DOI: 10.1002/adfm.201805972

First Principles Simulations on Migration Paths of Oxygen Interstitials in MgAl 2 O 4
journal, October 2018

  • Platonenko, Alexander; Gryaznov, Denis; Zhukovskii, Yuri F.
  • physica status solidi (b), Vol. 256, Issue 5
  • DOI: 10.1002/pssb.201800282

Mg‐Ion Inversion in MgO@MgO−Al 2 O 3 Oxides: The Origin of Basic Sites
journal, May 2019

  • Hiremath, Vishwanath; Kwon, Hyuk Jae; Jung, In‐Sun
  • ChemSusChem, Vol. 12, Issue 12
  • DOI: 10.1002/cssc.201900072