Insights into the fabrication and structure of plutonium pyrochlores

doi:10.1039/C9TA05795A

Title: Insights into the fabrication and structure of plutonium pyrochlores

Abstract

Rare earth zirconates, such as Nd₂Zr₂O₇, crystallise with the pyrochlore structure and are a group of materials which have been suggested as potential nuclear waste forms for actinide immobilisation. In this work, a new hydroxide co-precipitation route is presented to investigate the incorporation of Pu into Nd₂Zr2O₇. The plutonium content was varied between 5 and 10 mol% and the structural uptake and Pu oxidation state were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The experimental findings were complemented by DFT ab initio calculations. For all the incorporation mechanisms studied PuO₂ was used as the reference reactant state to allow for a direct comparison between the possible Pu uptake scenarios. Analysis of the experimental data suggests that Pu(IV) cations substitute for Nd(III) cations leading to structural distortion of the pyrochlore A-sites. The computed solution energies and bond-distances corroborate the experimental findings and indicate that the excess charge is balanced via the introduction of oxygen at formerly vacant sites.

Authors:

^[1];

^[2];

^[1];

^[1]; de Visser-Týnová, E. ^[3];

^[2];

^[1];

^[1]

Forschungszentrum Jülich, Institute of Energy and Climate Research – IEK-6, Nuclear Waste Management and Reactor Safety, 52425 Juelich, Germany
University of Sheffield, Department of Materials Science and Engineering, UK
Nuclear Research and Consultancy Group (NRG), Research & Innovation, The Netherlands

Publication Date:: 2020-02-04

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

Sponsoring Org.:: USDOE

OSTI Identifier:: 1592519

Alternate Identifier(s):: OSTI ID: 1669788

Grant/Contract Number:: AC02-98CH10886; AC05-00OR22725

Resource Type:: Published Article

Journal Name:: Journal of Materials Chemistry. A

Additional Journal Information:: Journal Name: Journal of Materials Chemistry. A Journal Volume: 8 Journal Issue: 5; Journal ID: ISSN 2050-7488

Publisher:: Royal Society of Chemistry

Country of Publication:: United Kingdom

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., and Brandt, F. Insights into the fabrication and structure of plutonium pyrochlores.  United Kingdom: N. p., 2020. 
        Web.  doi:10.1039/C9TA05795A.

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                    Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., & Brandt, F. Insights into the fabrication and structure of plutonium pyrochlores.  United Kingdom.  doi:10.1039/C9TA05795A.

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                    Finkeldei, S., Stennett, M. C., Kowalski, P. M., Ji, Y., de Visser-Týnová, E., Hyatt, N. C., Bosbach, D., and Brandt, F. Tue .  
        "Insights into the fabrication and structure of plutonium pyrochlores".  United Kingdom.  doi:10.1039/C9TA05795A.

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@article{osti_1592519,

  title        = {Insights into the fabrication and structure of plutonium pyrochlores},

  author       = {Finkeldei, S. and Stennett, M. C. and Kowalski, P. M. and Ji, Y. and de Visser-Týnová, E. and Hyatt, N. C. and Bosbach, D. and Brandt, F.},

  abstractNote = {Rare earth zirconates, such as Nd2Zr2O7, crystallise with the pyrochlore structure and are a group of materials which have been suggested as potential nuclear waste forms for actinide immobilisation. In this work, a new hydroxide co-precipitation route is presented to investigate the incorporation of Pu into Nd2Zr2O7. The plutonium content was varied between 5 and 10 mol% and the structural uptake and Pu oxidation state were probed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray absorption spectroscopy (XAS). The experimental findings were complemented by DFT ab initio calculations. For all the incorporation mechanisms studied PuO2 was used as the reference reactant state to allow for a direct comparison between the possible Pu uptake scenarios. Analysis of the experimental data suggests that Pu(IV) cations substitute for Nd(III) cations leading to structural distortion of the pyrochlore A-sites. The computed solution energies and bond-distances corroborate the experimental findings and indicate that the excess charge is balanced via the introduction of oxygen at formerly vacant sites.},

  doi          = {10.1039/C9TA05795A},

  journal      = {Journal of Materials Chemistry. A},

  number       = 5,

  volume       = 8,

  place        = {United Kingdom},

  year         = {2020},

  month        = {2}

}

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DOI: 10.1103/PhysRevB.94.064102

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Radiation tolerance of ceramics - Insights from atomistic simulation of damage accumulation in pyrochlores

Journal Article Devanathan, Ram ; Weber, William J ; Gale, Julian D. - Energy & Environmental Science

We have used molecular dynamics simulations to investigate the effects of radiation damage accumulation in two pyrochlore-structured ceramics, namely Gd{sub 2}Ti{sub 2}O{sub 7} and Gd{sub 2}Zr{sub 2}O{sub 7}. It is well known from experiment that the titanate is susceptible to radiation-induced amorphization, while the zirconate does not go amorphous under prolonged irradiation. Our simulations show that cation Frenkel pair accumulation eventually leads to amorphization of Gd{sub 2}Ti{sub 2}O{sub 7}, and both anion disorder and cation disorder occur during damage accumulation. Amorphization in Gd{sub 2}Ti{sub 2}O{sub 7} is accompanied by a density decrease of about 12.7% and a decrease of aboutmore »« less
DOI: 10.1039/c0ee00066c

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Citation Formats

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT journal, June 2005

Generalized Gradient Approximation Made Simple journal, October 1996

X-ray absorption studies of the local environment of Zr in high-zirconia borosilicate glasses journal, November 1999

Effect of Dopants on Zirconia Stabilization-An X-ray Absorption Study: I, Trivalent Dopants journal, January 1994

Polymerization of Pu(IV) in aqueous nitric acid solutions journal, January 1981

Dissolution of ZrO2 based pyrochlores in the acid pH range: A macroscopic and electron microscopy study journal, October 2014

Neptunium redox speciation journal, January 2001

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores journal, January 2016

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides journal, September 1976

On experimental attenuation factors of the amplitude of the EXAFS oscillations in absorption, reflectivity and luminescence measurements journal, January 1982

Radiation effects in nuclear waste forms for high-level radioactive waste journal, January 1995

X-ray-absorption studies of zirconia polymorphs. I. Characteristic local structures journal, October 1993

DFT + U as a reliable method for efficient ab initio calculations of nuclear materials journal, September 2016

Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis journal, January 2007

Np(IV)/Np(V) valence determinations from Np L3 edge XANES/EXAFS journal, February 2005

First-principles calculation of defect-formation energies in the Y 2 ( Ti , Sn , Zr ) 2 O 7 pyrochlore journal, August 2004

Systematic Studies of the Fundamental Chemistry of Pyrochlore oxides: An 2 Zr 2 O 7 [An = Pu, Am, Cm, Bk and Cf] journal, November 2002

The incorporation of plutonium in lanthanum zirconate pyrochlore journal, November 2013

Overview on advanced thermal barrier coatings journal, November 2010

The crystallographic information file (CIF): a new standard archive file for crystallography journal, November 1991

Plutonium and uranium accommodation in pyrochlore oxides journal, March 2005

Atomistic modeling of displacement cascades in La 2 Zr 2 O 7 pyrochlore journal, May 2003

The crystal structure of baddeleyite (monoclinic ZrO 2 ) and its relation to the polymorphism of ZrO 2 journal, June 1965

TRLFS of Eu3+ and Cm3+ doped La2Zr2O7: A comparison of defect fluorite to pyrochlore structures journal, February 2013

Changes in the Zr environment in zirconia–silica xerogels with composition and heat treatment as revealed by Zr K-edge XANES and EXAFS journal, January 2000

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

Radiation Tolerance of Complex Oxides journal, August 2000

Pyrochlore to Fluorite Transition: The Y 2 (Ti 1– x Zr x ) 2 O 7 (0.0 ≤ x ≤ 1.0) System journal, November 2012

High-precision sampling for Brillouin-zone integration in metals journal, August 1989

Ab initio theory and calculations of X-ray spectra journal, July 2009

Composition dependent order-disorder transition in Nd Zr1−O2−0.5 pyrochlores: A combined structural, calorimetric and ab initio modeling study journal, February 2017

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Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database journal, August 1985

Structural environment around Th4+ in silicate glasses: Implications for the geochemistry of incompatible Me4+ elements journal, November 1991

Benchmarking the DFT+ U Method for Thermochemical Calculations of Uranium Molecular Compounds and Solids journal, December 2014

Linear response approach to the calculation of the effective interaction parameters in the LDA + U method journal, January 2005

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Ceramic Waste Forms for Actinides journal, December 2006

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Actinide incorporation in a zirconia based pyrochlore (Nd1.8An0.2)Zr2O7+x (An=Th, U, Np, Pu, Am) journal, January 2009

Structure and Crystal Chemistry as a Function of Composition across the Wide Range Nonstoichiometric (1−ε)ZrO2·εSmO1.5, 0.38<ε<0.55, Oxide Pyrochlore System journal, December 1999

Energetics of defects formation and oxygen migration in pyrochlore compounds from first principles calculations journal, July 2018

Disorder in Pyrochlore Oxides journal, August 2000

Higher Order Speciation Effects on Plutonium L 3 X-ray Absorption Near Edge Spectra journal, January 2004

Reconstructing a string-inspired quintom model of dark energy journal, October 2008

Molecular Dynamic Simulation of Disorder Induced Amorphization in Pyrochlore journal, January 2005

Solid solubilities of (La Nd,)2(Zr,Ti)2O7 phases deduced by neutron diffraction journal, March 2005

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The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides journal, March 2014

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Defect formation energies in A 2 B 2 O 7 pyrochlores journal, October 2015

XANES Spectroscopic Studies of the Phase Transition in Gd 2 Zr 2 O 7 journal, June 2009

Displacement cascades in Gd2Ti2O7 and Gd2Zr2O7: a molecular dynamics study journal, August 2002

Preparation and characterisation of Pu-pyrochlore: [La1−xPux]2 Zr2O7 (x=0–1) journal, October 2000

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces journal, April 2008

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Full correction of the self-absorption in soft-fluorescence extended x-ray-absorption fine structure journal, August 1992

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

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Soft self-consistent pseudopotentials in a generalized eigenvalue formalism journal, April 1990

Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and “minor” actinides journal, June 2004

Novel Plutonium Titanate Compounds and Solid Solutions Pu2Ti2O7-Ln2Ti2O7: Relevance to Nuclear Waste Disposal journal, June 1996

Multiple-scattering calculations of the uranium L 3 -edge x-ray-absorption near-edge structure journal, November 1995

Physical Properties and Cation Arrangement of Oxides with Spinel Structures I. Cation Arrangement in Spinels journal, April 1947

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005

Generalized Gradient Approximation Made Simple
journal, October 1996

X-ray absorption studies of the local environment of Zr in high-zirconia borosilicate glasses
journal, November 1999

Effect of Dopants on Zirconia Stabilization-An X-ray Absorption Study: I, Trivalent Dopants
journal, January 1994

Polymerization of Pu(IV) in aqueous nitric acid solutions
journal, January 1981

Dissolution of ZrO2 based pyrochlores in the acid pH range: A macroscopic and electron microscopy study
journal, October 2014

Neptunium redox speciation
journal, January 2001

The role of surfaces, chemical interfaces, and disorder on plutonium incorporation in pyrochlores
journal, January 2016

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

On experimental attenuation factors of the amplitude of the EXAFS oscillations in absorption, reflectivity and luminescence measurements
journal, January 1982

Radiation effects in nuclear waste forms for high-level radioactive waste
journal, January 1995

X-ray-absorption studies of zirconia polymorphs. I. Characteristic local structures
journal, October 1993

DFT + U as a reliable method for efficient ab initio calculations of nuclear materials
journal, September 2016

Local structure and oxidation state of uranium in some ternary oxides: X-ray absorption analysis
journal, January 2007

Np(IV)/Np(V) valence determinations from Np L3 edge XANES/EXAFS
journal, February 2005

First-principles calculation of defect-formation energies in the $Y_{2} {(Ti, Sn, Zr)}_{2} O_{7}$ pyrochlore
journal, August 2004

Systematic Studies of the Fundamental Chemistry of Pyrochlore oxides: An ₂ Zr ₂ O ₇ [An = Pu, Am, Cm, Bk and Cf]
journal, November 2002

The incorporation of plutonium in lanthanum zirconate pyrochlore
journal, November 2013

Overview on advanced thermal barrier coatings
journal, November 2010

The crystallographic information file (CIF): a new standard archive file for crystallography
journal, November 1991

Plutonium and uranium accommodation in pyrochlore oxides
journal, March 2005

Atomistic modeling of displacement cascades in La 2 Zr 2 O 7 pyrochlore
journal, May 2003

The crystal structure of baddeleyite (monoclinic ZrO ₂ ) and its relation to the polymorphism of ZrO ₂
journal, June 1965

TRLFS of Eu3+ and Cm3+ doped La2Zr2O7: A comparison of defect fluorite to pyrochlore structures
journal, February 2013

Changes in the Zr environment in zirconia–silica xerogels with composition and heat treatment as revealed by Zr K-edge XANES and EXAFS
journal, January 2000

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

Radiation Tolerance of Complex Oxides
journal, August 2000

Pyrochlore to Fluorite Transition: The Y ₂ (Ti _{1– x} Zr _x ) ₂ O ₇ (0.0 ≤ x ≤ 1.0) System
journal, November 2012

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989

Ab initio theory and calculations of X-ray spectra
journal, July 2009

Composition dependent order-disorder transition in Nd Zr1−O2−0.5 pyrochlores: A combined structural, calorimetric and ab initio modeling study
journal, February 2017

Oxidation state determination of plutonium aquo ions using x-ray absorption spectroscopy
journal, January 1998

Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

Structural environment around Th4+ in silicate glasses: Implications for the geochemistry of incompatible Me4+ elements
journal, November 1991

Benchmarking the DFT+ U Method for Thermochemical Calculations of Uranium Molecular Compounds and Solids
journal, December 2014

Linear response approach to the calculation of the effective interaction parameters in the $LDA + U$ method
journal, January 2005

Behavior of 238 Pu-Doped Ceramics Based on Cubic Zirconia and Pyrochlore under Radiation Damage
journal, November 2002

Synthesis and dissolution kinetics of zirconia based ceramics
journal, April 2014

Ceramic Waste Forms for Actinides
journal, December 2006

Structure studies on lanthanide technetium pyrochlores as prospective host phases to immobilize 99technetium and fission lanthanides from effluents of reprocessed used nuclear fuels
journal, April 2011

Actinide incorporation in a zirconia based pyrochlore (Nd1.8An0.2)Zr2O7+x (An=Th, U, Np, Pu, Am)
journal, January 2009

Structure and Crystal Chemistry as a Function of Composition across the Wide Range Nonstoichiometric (1−ε)ZrO2·εSmO1.5, 0.38<ε<0.55, Oxide Pyrochlore System
journal, December 1999

Energetics of defects formation and oxygen migration in pyrochlore compounds from first principles calculations
journal, July 2018

Disorder in Pyrochlore Oxides
journal, August 2000

Higher Order Speciation Effects on Plutonium L ₃ X-ray Absorption Near Edge Spectra
journal, January 2004

Reconstructing a string-inspired quintom model of dark energy
journal, October 2008

Molecular Dynamic Simulation of Disorder Induced Amorphization in Pyrochlore
journal, January 2005

Solid solubilities of (La Nd,)2(Zr,Ti)2O7 phases deduced by neutron diffraction
journal, March 2005

Theoretical study of disorder in Ti-substituted ${La}_{2} {Zr}_{2} O_{7}$
journal, March 2002

The role of the 5f valence orbitals of early actinides in chemical bonding
journal, July 2017

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

The Thermodynamic Properties of the f -Elements and their Compounds. Part 2. The Lanthanide and Actinide Oxides
journal, March 2014

Electronic structure of actinide compounds from L III -edge x-ray absorption
journal, December 1989

Computer simulation of Pu3+ and Pu4+ substitutions in gadolinium zirconate
journal, November 2001

Defect formation energies in A 2 B 2 O 7 pyrochlores
journal, October 2015

XANES Spectroscopic Studies of the Phase Transition in Gd 2 Zr 2 O 7
journal, June 2009

Displacement cascades in Gd2Ti2O7 and Gd2Zr2O7: a molecular dynamics study
journal, August 2002

Preparation and characterisation of Pu-pyrochlore: [La1−xPux]2 Zr2O7 (x=0–1)
journal, October 2000

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008

Key Role of the Cation Interstitial Structure in the Radiation Resistance of Pyrochlores
journal, April 2009

Bond lengths in oxygen and halogen compounds of d and f elements
journal, November 1978

Full correction of the self-absorption in soft-fluorescence extended x-ray-absorption fine structure
journal, August 1992

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

Oxide pyrochlores — A review
journal, January 1983

Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990

Nuclear waste disposal—pyrochlore (A2B2O7): Nuclear waste form for the immobilization of plutonium and “minor” actinides
journal, June 2004

Novel Plutonium Titanate Compounds and Solid Solutions Pu2Ti2O7-Ln2Ti2O7: Relevance to Nuclear Waste Disposal
journal, June 1996

Multiple-scattering calculations of the uranium L 3 -edge x-ray-absorption near-edge structure
journal, November 1995

Physical Properties and Cation Arrangement of Oxides with Spinel Structures I. Cation Arrangement in Spinels
journal, April 1947