Hidden disorder in the α'→δ transformation of Pu-1.9 at.% Ga

Jeffries, J. R.; Manley, M. E.; Wall, M. A.; Blobaum, K. J. M.; Schwartz, A. J.

doi:10.1103/PhysRevB.85.224104

Title: Hidden disorder in the α^'→δ transformation of Pu-1.9 at.% Ga

Journal Article · Wed Jun 06 00:00:00 EDT 2012 · Physical Review. B, Condensed Matter and Materials Physics

DOI:https://doi.org/10.1103/PhysRevB.85.224104· OSTI ID:1103511

Jeffries, J. R.; Manley, M. E.; Wall, M. A.; Blobaum, K. J. M.; Schwartz, A. J.

Enthalpy and entropy are thermodynamic quantities critical to determining how and at what temperature a phase transition occurs. At a phase transition, the enthalpy and temperature-weighted entropy differences between two phases are equal (ΔH=TΔS), but there are materials where this balance has not been experimentally or theoretically realized, leading to the idea of hidden order and disorder. In a Pu-1.9 at. % Ga alloy, the δ phase is retained as a metastable state at room temperature, but at low temperatures, the δ phase yields to a mixed-phase microstructure of δ- and α'-Pu. The previously measured sources of entropy associated with the α'→δ transformation fail to sum to the entropy predicted theoretically. We report an experimental measurement of the entropy of the α'→δ transformation that corroborates the theoretical prediction, and implies that only about 65% of the entropy stabilizing the δ phase is accounted for, leaving a missing entropy of about 0.5 k_B/atom. Some previously proposed mechanisms for generating entropy are discussed, but none seem capable of providing the necessary disorder to stabilize the δ phase. This hidden disorder represents multiple accessible states per atom within the δ phase of Pu that may not be included in our current understanding of the properties and phase stability of δ-Pu.

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Sponsoring Organization:: USDOE

OSTI ID:: 1103511

Journal Information:: Physical Review. B, Condensed Matter and Materials Physics, Journal Name: Physical Review. B, Condensed Matter and Materials Physics Vol. 85 Journal Issue: 22; ISSN 1098-0121

Publisher:: American Physical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 2 works

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References (38)

Limits for ordered magnetism in Pu from muon spin rotation spectroscopy Heffner, R. H.; Morris, G. D.; Fluss, M. J. Physical Review B, Vol. 73, Issue 9 https://doi.org/10.1103/PhysRevB.73.094453	journal	March 2006
Atomic structure and phase transformations in Pu alloys Schwartz, A. J.; Cynn, H.; Blobaum, K. J. M. Progress in Materials Science, Vol. 54, Issue 6 https://doi.org/10.1016/j.pmatsci.2009.03.003	journal	August 2009
Reproducible phase transformation in a single Pu–1.9 at.% Ga specimen Jeffries, J. R.; Blobaum, K. J. M.; Wall, M. A. Journal of Nuclear Materials, Vol. 384, Issue 3 https://doi.org/10.1016/j.jnucmat.2008.11.021	journal	February 2009
Absence of magnetic moments in plutonium Lashley, J. C.; Lawson, A.; McQueeney, R. J. Physical Review B, Vol. 72, Issue 5 https://doi.org/10.1103/PhysRevB.72.054416	journal	August 2005
Nucleation and growth of the α′ martensitic phase in Pu–Ga alloys Blobaum, K.; Krenn, C.; Wall, M. Acta Materialia, Vol. 54, Issue 15 https://doi.org/10.1016/j.actamat.2006.04.033	journal	September 2006
Large Harmonic Softening of the Phonon Density of States of Uranium Manley, M. E.; Fultz, B.; McQueeney, R. J. Physical Review Letters, Vol. 86, Issue 14 https://doi.org/10.1103/PhysRevLett.86.3076	journal	April 2001
EXPGUI , a graphical user interface for GSAS Toby, Brian H. Journal of Applied Crystallography, Vol. 34, Issue 2 https://doi.org/10.1107/S0021889801002242	journal	April 2001
Partially gapped Fermi surface in the heavy-electron superconductor ${URu}_{2}$ ${Si}_{2}$ Maple, M. B.; Chen, J. W.; Dalichaouch, Y. Physical Review Letters, Vol. 56, Issue 2 https://doi.org/10.1103/PhysRevLett.56.185	journal	January 1986
In situ X-ray diffraction study of the δ to α′ isothermal martensitic transformation kinetics in a Pu–Ga alloy Blobaum, K. J. M.; Jeffries, J. R.; Schwartz, A. J. Journal of Nuclear Materials, Vol. 412, Issue 3 https://doi.org/10.1016/j.jnucmat.2011.03.029	journal	May 2011
Microstructural evidence for conditioning-dependent δ→α′ transformations in retained δ-phase Pu–Ga Jeffries, J. R.; Blobaum, K. J. M.; Wall, M. A. Acta Materialia, Vol. 57, Issue 6 https://doi.org/10.1016/j.actamat.2008.11.045	journal	April 2009
Evidence of transformation bursts during thermal cycling of a Pu-Ga alloy Blobaum, K. J. M.; Krenn, C. R.; Haslam, J. J. Metallurgical and Materials Transactions A, Vol. 37, Issue 3 https://doi.org/10.1007/s11661-006-0029-7	journal	March 2006
Melting of the light actinides Lawson, A. C.; Artinez, B. M.; Roberts, J. A. Philosophical Magazine B, Vol. 80, Issue 1 https://doi.org/10.1080/13642810008218339	journal	January 2000
Supporting evidence for double-C curve kinetics in the isothermal δ→α′ phase transformation in a Pu–Ga alloy Oudot, B.; Blobaum, K. J. M.; Wall, M. A. Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.159	journal	October 2007
Experimental Electronic Heat Capacities of $α$ - and $δ$ -Plutonium: Heavy-Fermion Physics in an Element Lashley, J. C.; Singleton, J.; Migliori, A. Physical Review Letters, Vol. 91, Issue 20 https://doi.org/10.1103/PhysRevLett.91.205901	journal	November 2003
Vibrational and electronic entropy of β-cerium and γ-cerium measured by inelastic neutron scattering Manley, Michael E.; McQueeney, Robert J.; Fultz, Brent Physical Review B, Vol. 65, Issue 14 https://doi.org/10.1103/PhysRevB.65.144111	journal	April 2002
Invar effect in Pu-Ga alloys Lawson, A. C.; Roberts, J. A.; Martinez, B. Philosophical Magazine B, Vol. 82, Issue 18 https://doi.org/10.1080/1364281021000040396	journal	December 2002
Suppression of the γ–α structural phase transition in Ce _0.8 La _0.1 Th _0.1 by large magnetic fields Drymiotis, F.; Singleton, J.; Harrison, N. Journal of Physics: Condensed Matter, Vol. 17, Issue 7 https://doi.org/10.1088/0953-8984/17/7/L01	journal	February 2005
A High-Pressure Structure in Curium Linked to Magnetism Heathman, S. Science, Vol. 309, Issue 5731 https://doi.org/10.1126/science.1112453	journal	July 2005
Unusual Phonon Softening in $δ$ -Phase Plutonium McQueeney, R. J.; Lawson, A. C.; Migliori, A. Physical Review Letters, Vol. 92, Issue 14 https://doi.org/10.1103/PhysRevLett.92.146401	journal	April 2004
Superconductivity and magnetic order in a strongly interacting fermi-system: URu2Si2 Schlabitz, W.; Baumann, J.; Pollit, B. Zeitschrift f�r Physik B Condensed Matter, Vol. 62, Issue 2 https://doi.org/10.1007/BF01323427	journal	June 1986
Ambient pressure phase diagram of plutonium: A unified theory for α-Pu and δ-Pu Söderlind, P. Europhysics Letters (EPL), Vol. 55, Issue 4 https://doi.org/10.1209/epl/i2001-00447-3	journal	August 2001
Superconducting and Magnetic Transitions in the Heavy-Fermion System U ${Ru}_{2}$ ${Si}_{2}$ Palstra, T. T. M.; Menovsky, A. A.; Berg, J. van den Physical Review Letters, Vol. 55, Issue 24 https://doi.org/10.1103/PhysRevLett.55.2727	journal	December 1985
Vibrational thermodynamics of materials Fultz, Brent Progress in Materials Science, Vol. 55, Issue 4 https://doi.org/10.1016/j.pmatsci.2009.05.002	journal	May 2010
Colloquium : Hidden order, superconductivity, and magnetism: The unsolved case of ${URu}_{2} {Si}_{2}$ Mydosh, J. A.; Oppeneer, P. M. Reviews of Modern Physics, Vol. 83, Issue 4 https://doi.org/10.1103/RevModPhys.83.1301	journal	November 2011
Cancellation of spin and orbital magnetic moments in δ-Pu: Theory Söderlind, Per Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.084	journal	October 2007
Phase stability and phase transformations in Pu–Ga alloys Hecker, S. S.; Harbur, D. R.; Zocco, T. G. Progress in Materials Science, Vol. 49, Issue 3-4 https://doi.org/10.1016/S0079-6425(03)00032-X	journal	January 2004
Local moment physics in heavy electron systems Coleman, P. LECTURES ON THE PHYSICS OF HIGHLY CORRELATED ELECTRON SYSTEMS VI: Sixth Training Course in the Physics of Correlated Electron Systems and High-Tc Superconductors, AIP Conference Proceedings https://doi.org/10.1063/1.1509142	conference	January 2002
Gallium stabilization of $δ − Pu$ : Density-functional calculations Sadigh, Babak; Wolfer, Wilhelm G. Physical Review B, Vol. 72, Issue 20 https://doi.org/10.1103/PhysRevB.72.205122	journal	November 2005
Unexpected elastic softening in $δ$ -plutonium Migliori, A.; Ledbetter, H.; Lawson, A. C. Physical Review B, Vol. 73, Issue 5 https://doi.org/10.1103/PhysRevB.73.052101	journal	February 2006
No role for phonon entropy in the $fcc \to fcc$ volume collapse transition in ${Ce}_{0.9} {Th}_{0.1}$ at ambient pressure Manley, M. E.; McQueeney, R. J.; Fultz, B. Physical Review B, Vol. 67, Issue 1 https://doi.org/10.1103/PhysRevB.67.014103	journal	January 2003
Thermostatics and kinetics of transformations in Pu-based alloys Turchi, P. E. A.; Kaufman, L.; Zhou, Shihuai Journal of Alloys and Compounds, Vol. 444-445 https://doi.org/10.1016/j.jallcom.2006.10.046	journal	October 2007
Evidence for nascent equilibrium nuclei as progenitors of anomalous transformation kinetics in a Pu-Ga alloy Jeffries, J. R.; Blobaum, K. J. M.; Wall, M. A. Physical Review B, Vol. 80, Issue 9 https://doi.org/10.1103/PhysRevB.80.094107	journal	September 2009
Phonon density of states of $α$ - and $δ$ -plutonium by inelastic x-ray scattering Manley, M. E.; Said, A. H.; Fluss, M. J. Physical Review B, Vol. 79, Issue 5 https://doi.org/10.1103/PhysRevB.79.052301	journal	February 2009
Density-Functional Calculations of $α$ , $β$ , $γ$ , $δ$ , $δ^{'}$ , and $ϵ$ Plutonium Söderlind, Per; Sadigh, Babak Physical Review Letters, Vol. 92, Issue 18 https://doi.org/10.1103/PhysRevLett.92.185702	journal	May 2004
Two-dimensional detector software: From real detector to idealised image or two-theta scan Hammersley, A. P.; Svensson, S. O.; Hanfland, M. High Pressure Research, Vol. 14, Issue 4-6, p. 235-248 https://doi.org/10.1080/08957959608201408	journal	January 1996
When magnetism can stabilize the crystal structure of metals Soderlind, P.; Moore, K. Scripta Materialia, Vol. 59, Issue 12 https://doi.org/10.1016/j.scriptamat.2008.08.031	journal	December 2008
Electronic structure theory of the hidden-order material ${URu}_{2} {Si}_{2}$ Oppeneer, P. M.; Rusz, J.; Elgazzar, S. Physical Review B, Vol. 82, Issue 20 https://doi.org/10.1103/PhysRevB.82.205103	journal	November 2010
Invar model for δ-phase Pu: thermal expansion, elastic and magnetic properties Lawson, A. C.; Roberts, J. A.; Martinez, B. Philosophical Magazine, Vol. 86, Issue 17-18 https://doi.org/10.1080/14786430500155262	journal	June 2006

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