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Title: Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation

Abstract

The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO2)(O2)(H2O)2·2H2O, into metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO2)(O2)(H2O)2·2H2O → (UO2)(O2)(H2O)2 + 2H2O reaction is ΔS0 = +80 J·mol–1·K–1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similar to bulk H2O(l), the bulk modulus of (UO2)(O2)(H2O)2·2H2O increases with temperature, contrasting with (UO2)(O2)(H2O)2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.

Authors:
 [1];  [2]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Univ. of Nevada, Las Vegas, NV (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1324610
Report Number(s):
SAND2016-5343J
Journal ID: ISSN 1932-7447; 641393
Grant/Contract Number:  
AC04-94AL85000
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 30; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Weck, Philippe F., and Kim, Eunja. Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.6b05967.
Weck, Philippe F., & Kim, Eunja. Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation. United States. https://doi.org/10.1021/acs.jpcc.6b05967
Weck, Philippe F., and Kim, Eunja. Mon . "Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation". United States. https://doi.org/10.1021/acs.jpcc.6b05967. https://www.osti.gov/servlets/purl/1324610.
@article{osti_1324610,
title = {Uncloaking the thermodynamics of the studtite to metastudtite shear-induced transformation},
author = {Weck, Philippe F. and Kim, Eunja},
abstractNote = {The interplay between thermodynamics and mechanical properties in the transformation of studtite, (UO2)(O2)(H2O)2·2H2O, into metastudtite, (UO2)(O2)(H2O)2, two important corrosion phases observed on the surface of uranium dioxide exposed to water, is revealed using density functional perturbation theory. Phonon calculations within the quasi-harmonic approximation predict that the standard entropy change for the (UO2)(O2)(H2O)2·2H2O → (UO2)(O2)(H2O)2 + 2H2O reaction is ΔS0 = +80 J·mol–1·K–1 for the production of water in the liquid state and +389 J·mol–1·K–1 for water vapor. Similar to bulk H2O(l), the bulk modulus of (UO2)(O2)(H2O)2·2H2O increases with temperature, contrasting with (UO2)(O2)(H2O)2 which features the typical Anderson–Gruneisen temperature dependence of oxide solids. Upon removal of interstitial H2O in studtite, the most important changes in the shear modulus, the parameter limiting the mechanical stability, arise in the planes normal to chain propagation directions. Lastly, the present findings have important implications for the dehydration of other hygroscopic materials.},
doi = {10.1021/acs.jpcc.6b05967},
journal = {Journal of Physical Chemistry. C},
number = 30,
volume = 120,
place = {United States},
year = {2016},
month = {7}
}

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Works referenced in this record:

Observation of Studtite and Metastudtite on Spent Fuel
journal, January 2002


Corrosion of commercial spent nuclear fuel. 1. Formation of studtite and metastudtite
journal, January 2005


Corrosion of commercial spent nuclear fuel. 2. Radiochemical analyses of metastudtite and leachates
journal, January 2005


Alpha-radiolysis effects on UO2 alteration in water
journal, January 2001


Stability of Peroxide-Containing Uranyl Minerals
journal, November 2003


Uranyl peroxide enhanced nuclear fuel corrosion in seawater
journal, January 2012

  • Armstrong, C. R.; Nyman, M.; Shvareva, T.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 6
  • DOI: 10.1073/pnas.1119758109

Nuclear Fuel in a Reactor Accident
journal, March 2012

  • Burns, Peter C.; Ewing, Rodney C.; Navrotsky, Alexandra
  • Science, Vol. 335, Issue 6073
  • DOI: 10.1126/science.1211285

On the Reactivity of Uranouranic Oxide, (I) [八三酸化ウランの反応活性に関する研究, (I)]
journal, January 1959

  • Ukazi, R.
  • Journal of the Atomic Energy Society of Japan / Atomic Energy Society of Japan, Vol. 1, Issue 7
  • DOI: 10.3327/jaesj.1.405

X-ray diffraction data on hydrated uranium peroxide
journal, June 1963


Studtite, [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 : The first structure of a peroxide mineral
journal, July 2003

  • Burns, Peter C.; Hughes, Karrie-Ann
  • American Mineralogist, Vol. 88, Issue 7
  • DOI: 10.2138/am-2003-0725

Ab initio study of uranyl peroxides: Electronic factors behind the phase stability
journal, February 2007


Structures of uranyl peroxide hydrates: a first-principles study of studtite and metastudtite
journal, January 2012

  • Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
  • Dalton Transactions, Vol. 41, Issue 32
  • DOI: 10.1039/c2dt31242e

Energetics of metastudtite and implications for nuclear waste alteration
journal, November 2014

  • Guo, Xiaofeng; Ushakov, Sergey V.; Labs, Sabrina
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 50
  • DOI: 10.1073/pnas.1421144111

Powder X-ray diffraction of Metastudtite, (UO 2 )O 2 (H 2 O) 2
journal, February 2016

  • Rodriguez, Mark A.; Weck, Philippe E.; Sugar, Joshua D.
  • Powder Diffraction, Vol. 31, Issue 1
  • DOI: 10.1017/S0885715615000895

Thermal decomposition of uranium peroxide hydrate
journal, January 1961


Pseudomorphic decomposition of uranium peroxide into UO3
journal, May 1963

  • Cordfunke, E. H. P.; Van Der Giessen, A. A.
  • Journal of Inorganic and Nuclear Chemistry, Vol. 25, Issue 5
  • DOI: 10.1016/0022-1902(63)80240-7

Thermal decomposition of hydrated uranium peroxides
journal, January 1963

  • Cordfunke, E. H. P.; Aling, P.
  • Recueil des Travaux Chimiques des Pays-Bas, Vol. 82, Issue 3
  • DOI: 10.1002/recl.19630820309

Effect of temperature on studtite stability: Thermogravimetry and differential scanning calorimetry investigations
journal, March 2009


Determination of the equilibrium formation constants of two U(vi)–peroxide complexes at alkaline pH
journal, January 2011

  • Meca, S.; Martínez-Torrents, A.; Martí, V.
  • Dalton Transactions, Vol. 40, Issue 31
  • DOI: 10.1039/c0dt01672a

Physical Characterization and Reactivity of the Uranyl Peroxide [UO 22 -O 2 )(H 2 O) 2 ]·2H 2 O: Implications for Storage of Spent Nuclear Fuels
journal, July 2012

  • Mallon, Colm; Walshe, Aurora; Forster, Robert J.
  • Inorganic Chemistry, Vol. 51, Issue 15
  • DOI: 10.1021/ic3010823

Solubility study and point of zero charge of studtite (UO2O2·4H2O)
journal, October 2014


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


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Density Functional Analysis of the Trigonal Uranyl Equatorial Coordination in Hexahomotrioxacalix[3]arene-based Macrocyclic Complexes
journal, February 2010

  • Weck, Philippe F.; Kim, Eunja; Masci, Bernardo
  • Inorganic Chemistry, Vol. 49, Issue 4
  • DOI: 10.1021/ic901694g

One-dimensional uranium–organic coordination polymers: crystal and electronic structures of uranyl-diacetohydroxamate
journal, January 2011

  • Weck, Philippe F.; Gong, Cynthia-May S.; Kim, Eunja
  • Dalton Transactions, Vol. 40, Issue 22
  • DOI: 10.1039/c1dt10267b

On the role of strong electron correlations in the surface properties and chemistry of uranium dioxide
journal, January 2013

  • Weck, Philippe F.; Kim, Eunja; Jové-Colón, Carlos F.
  • Dalton Transactions, Vol. 42, Issue 13
  • DOI: 10.1039/c3dt32536a

Layered uranium( vi ) hydroxides: structural and thermodynamic properties of dehydrated schoepite α-UO 2 (OH) 2
journal, January 2014


On the mechanical stability of uranyl peroxide hydrates: implications for nuclear fuel degradation
journal, January 2015

  • Weck, Philippe F.; Kim, Eunja; Buck, Edgar C.
  • RSC Advances, Vol. 5, Issue 96
  • DOI: 10.1039/C5RA16111H

Projector augmented-wave method
journal, December 1994


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


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


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

First-principles calculations of the ferroelastic transition between rutile-type and CaCl 2 -type SiO 2 at high pressures
journal, October 2008


Necessary and sufficient elastic stability conditions in various crystal systems
journal, December 2014


FactSage thermochemical software and databases
journal, June 2002


Finite Elastic Strain of Cubic Crystals
journal, June 1947


The Compressibility of Media under Extreme Pressures
journal, September 1944

  • Murnaghan, F. D.
  • Proceedings of the National Academy of Sciences, Vol. 30, Issue 9
  • DOI: 10.1073/pnas.30.9.244

Universal features of the equation of state of solids
journal, March 1989


Derivation of Wachtman's Equation for the Temperature Dependence of Elastic Moduli of Oxide Compounds
journal, April 1966


ELATE: an open-source online application for analysis and visualization of elastic tensors
journal, May 2016

  • Gaillac, Romain; Pullumbi, Pluton; Coudert, François-Xavier
  • Journal of Physics: Condensed Matter, Vol. 28, Issue 27
  • DOI: 10.1088/0953-8984/28/27/275201

ElAM: A computer program for the analysis and representation of anisotropic elastic properties
journal, December 2010

  • Marmier, Arnaud; Lethbridge, Zoe A. D.; Walton, Richard I.
  • Computer Physics Communications, Vol. 181, Issue 12
  • DOI: 10.1016/j.cpc.2010.08.033

    Works referencing / citing this record:

    Infrared and Raman spectroscopy of α-ZrW 2 O 8 : A comprehensive density functional perturbation theory and experimental study
    journal, May 2018

    • Weck, Philippe F.; Gordon, Margaret E.; Greathouse, Jeffery A.
    • Journal of Raman Spectroscopy, Vol. 49, Issue 8
    • DOI: 10.1002/jrs.5396

    Mechanical properties of anhydrous oxalic acid and oxalic acid dihydrate
    journal, January 2019

    • Colmenero, Francisco
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 5
    • DOI: 10.1039/c8cp07188h

    Anomalous mechanical behavior of the deltic, squaric and croconic cyclic oxocarbon acids
    journal, January 2019


    Periodic density functional theory study of the Raman spectrum of the hydrated uranyl oxyhydroxide mineral becquerelite
    journal, March 2019

    • Colmenero, Francisco; Cobos, Joaquín; Timón, Vicente
    • Theoretical Chemistry Accounts, Vol. 138, Issue 3
    • DOI: 10.1007/s00214-019-2437-y

    Becquerelite mineral phase: crystal structure and thermodynamic and mechanical stability by using periodic DFT
    journal, January 2018

    • Colmenero, Francisco; Fernández, Ana María; Timón, Vicente
    • RSC Advances, Vol. 8, Issue 43
    • DOI: 10.1039/c8ra04678f

    Structure–thermodynamics relationship of schoepite from first-principles
    journal, January 2019

    • Weck, Philippe F.; Jové-Colón, Carlos F.; Kim, Eunja
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 46
    • DOI: 10.1039/c9cp04117f

    Structural, mechanical, spectroscopic and thermodynamic characterization of the copper-uranyl tetrahydroxide mineral vandenbrandeite
    journal, January 2019

    • Colmenero, Francisco; Plášil, Jakub; Cobos, Joaquín
    • RSC Advances, Vol. 9, Issue 69
    • DOI: 10.1039/c9ra09047a