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Title: A novel cage for actinides: A 6 W 4 Al 43 ( A   =  U and Pu)

Abstract

We report on synthesis and characterization of the compounds A 6W4Al43 (A  =  U and Pu), that form in the hexagonal Ho6Mo4Al43 caged-structure family. The A ions reside within W/Al cages where the A–A nearest neighbors form dimers between adjacent W/Al cages, with U–U and Pu–Pu distances of 3.3892 and 3.4080 , respectively. While the W/Al networks provide environments similar to those of other cage-like materials (e.g. filled skutterudites), the atomic displacement parameters from single crystal x-ray diffraction measurements show that the A-ions do not exhibit rattling behavior. We find that there is site interchange disorder on one of the W/Al sites. Magnetic susceptibility measurements show that U6W4Al43 displays anisotropic Curie–Weiss behavior where it fits to the data yield an effective magnetic moment near 2.0 /U. At low temperatures the magnetic susceptibility deviates from the Curie–Weiss temperature dependence and eventually saturates to a constant value. In contrast, Pu6W4Al43 displays nearly temperature independent Pauli paramagnetism for all temperatures, as would be expected if the 5f -electrons are delocalized. The electrical resistivity for U6W4Al43 increases slightly with the decreasing temperature, suggesting that it is dominated by f -electronic hybridization effects and disorder scattering that originates from the W/Al site interchange. Specific heat measurements for U6W4Al43 furthermore » reveal an enhanced electronic Sommerfeld coefficient that is consistent with a moderately enhanced charge carrier effective mass. Together these measurements expose these materials as hosts for unstable f -electron magnetism, where the novel cage-like structures control the phenomena through the spacing between the A ions. Through this combination of mild magnetism, the low cost elements of the Al–W cages, and chemical tunability that has been shown for related materials in the same structure, the A 6W4Al43 compounds emerge as promising nuclear waste-forms for transuranics, while the wider family of materials makes an appealing environment for studying f -electron physics in a novel structure.« less

Authors:
; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Actinide Science & Technology (CAST); Florida State Univ., Tallahassee, FL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1566673
DOE Contract Number:  
SC0016568
Resource Type:
Journal Article
Journal Name:
Journal of Physics. Condensed Matter
Additional Journal Information:
Journal Volume: 31; Journal Issue: 16; Journal ID: ISSN 0953-8984
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
nuclear, defects, mechanical behavior, corrosion, charge transport, superconductivity, magnetism and spin physics, separations, geophysics/geochemistry, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (predictive), synthesis (scalable processing)

Citation Formats

Huang, K., Nelson, W. L., Chemey, A. T., Albrecht-Schmitt, T. E., and Baumbach, R. E. A novel cage for actinides: A 6 W 4 Al 43 ( A   =  U and Pu). United States: N. p., 2019. Web. doi:10.1088/1361-648x/aafe9e.
Huang, K., Nelson, W. L., Chemey, A. T., Albrecht-Schmitt, T. E., & Baumbach, R. E. A novel cage for actinides: A 6 W 4 Al 43 ( A   =  U and Pu). United States. doi:10.1088/1361-648x/aafe9e.
Huang, K., Nelson, W. L., Chemey, A. T., Albrecht-Schmitt, T. E., and Baumbach, R. E. Mon . "A novel cage for actinides: A 6 W 4 Al 43 ( A   =  U and Pu)". United States. doi:10.1088/1361-648x/aafe9e.
@article{osti_1566673,
title = {A novel cage for actinides: A 6 W 4 Al 43 ( A   =  U and Pu)},
author = {Huang, K. and Nelson, W. L. and Chemey, A. T. and Albrecht-Schmitt, T. E. and Baumbach, R. E.},
abstractNote = {We report on synthesis and characterization of the compounds A 6W4Al43 (A  =  U and Pu), that form in the hexagonal Ho6Mo4Al43 caged-structure family. The A ions reside within W/Al cages where the A–A nearest neighbors form dimers between adjacent W/Al cages, with U–U and Pu–Pu distances of 3.3892 and 3.4080 , respectively. While the W/Al networks provide environments similar to those of other cage-like materials (e.g. filled skutterudites), the atomic displacement parameters from single crystal x-ray diffraction measurements show that the A-ions do not exhibit rattling behavior. We find that there is site interchange disorder on one of the W/Al sites. Magnetic susceptibility measurements show that U6W4Al43 displays anisotropic Curie–Weiss behavior where it fits to the data yield an effective magnetic moment near 2.0 /U. At low temperatures the magnetic susceptibility deviates from the Curie–Weiss temperature dependence and eventually saturates to a constant value. In contrast, Pu6W4Al43 displays nearly temperature independent Pauli paramagnetism for all temperatures, as would be expected if the 5f -electrons are delocalized. The electrical resistivity for U6W4Al43 increases slightly with the decreasing temperature, suggesting that it is dominated by f -electronic hybridization effects and disorder scattering that originates from the W/Al site interchange. Specific heat measurements for U6W4Al43 further reveal an enhanced electronic Sommerfeld coefficient that is consistent with a moderately enhanced charge carrier effective mass. Together these measurements expose these materials as hosts for unstable f -electron magnetism, where the novel cage-like structures control the phenomena through the spacing between the A ions. Through this combination of mild magnetism, the low cost elements of the Al–W cages, and chemical tunability that has been shown for related materials in the same structure, the A 6W4Al43 compounds emerge as promising nuclear waste-forms for transuranics, while the wider family of materials makes an appealing environment for studying f -electron physics in a novel structure.},
doi = {10.1088/1361-648x/aafe9e},
journal = {Journal of Physics. Condensed Matter},
issn = {0953-8984},
number = 16,
volume = 31,
place = {United States},
year = {2019},
month = {2}
}

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