Intrinsic Nanoscience of δ Pu-Ga Alloys: Local Structure and Speciation, Collective Behavior, Nanoscale Heterogeneity, and Aging Mechanisms

Journal Article · Thu Apr 24 00:00:00 EDT 2014 · Journal of Physical Chemistry C, 118(16):8541-8563

DOI:https://doi.org/10.1021/jp5004038· OSTI ID:1136583

Conradson, Steven D.; Bock, Nicolas; Castro, Julio M.; Conradson, Dylan R.; Cox, Lawrence E.; Dmowski, Wojtek; Dooley, David E.; Egami, Takeshi; Espinosa-Faller, Francisco J.; Freibert, Franz J.; Garcia-Adeva, Angel J.; Hess, Nancy J.; Holmstrom, Erik; Howell, Rafael C.; Katz, Barbara A.; Lashley, Jason C.; Martinez, Raymond J.; Moore, David P.; Morales, Luis A.; Olivas, J David ; Pereyra, Ramiro A.; Ramos, Michael; Terry, Jeff H.; Villella, Phillip M.

Because diffraction measurements are sensitive only to the long range average arrangement of the atoms in the coherent portion of a crystal, complementary local structure measurements are required for a complete understanding of the structure of a complex material. This is particularly an issue in solid solutions where even random distributions of a solute will result in nanometer-scale fluctuations in the local composition. The structure will be further complicated if collective and cooperative phenomena organize the solute distribution via longer range interactions between non-bonded solute sites. If the solute affects the phase stability then the question is raised of whether the atoms in domains with local compositions outside the limits of the bulk phase will rearrange into the structure stable for that composition and temperature or if the resulting stress would prevent such a local phase transition. If the former, then phase separated, heterogeneous structures at or below the diffraction limit will form. This nanometerscale competition between the phase transition and the epitaxial mismatch – exacerbated by the added strain if the transition involves a volume change – raises the potential for the formation of novel structures that do not occur in bulk material, e.g., fcc Fe. This coupling over multiple scales between inhomogeneity ordering, elastic forces, phase competition, and texture in the form of coexisting structures is a hallmark of martensites, a class of complex materials that includes δ-stabilized PuGa and that often exhibit correlated atomic and electronic properties. The enigmatic and extreme nature of Pu is consistent with its exhibiting unusual structural behavior of this type, including nanoscale heterogeneity in δ-stabilized PuGa and its enhanced homogeneity on aging that has been suggested based on earlier X-ray Absorption Fine Structure (XAFS) spectroscopy and x-ray pair distribution function (pdf) measurements. Measurements on a defined set of laboratory-prepared materials now corroborate and better describe this heterogeneity while additional aged samples demonstrate the role of heterogeneity in aging processes in Pu.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 1136583
• Report Number(s): PNNL-SA-50832; KP1302000
• Journal Information: Journal of Physical Chemistry C, 118(16):8541-8563, Journal Name: Journal of Physical Chemistry C, 118(16):8541-8563
• Country of Publication: United States
• Language: English