The scientifically fascinating question of the spatial extent and bonding of the 5f orbitals of Pu and its six different phases extends to its δ-retained alloys and the mechanism by which Ga and a number of other unrelated elements stabilize its low density face-centered-cubic (fcc) structure. This issue of phase stability is also important technologically because of its significance to Science-Based Stockpile Stewardship. Answering these questions requires information on the local order and structure around the Ga and its effects on the Pu. We have addressed this by characterizing the structures of a large number of Pu-Ga and two Pu-In and one Pu-Ce δ alloys, including a set of high purity δ Pu 1−x Ga x materials with 1.7 ࣘ x ࣘ 6.4 at. % Ga that span the low [Ga] portion of the δ region of the phase diagram across the ß3.3 at. % Ga metastability boundary, with extended x-ray absorption fine structure (EXAFS) spectroscopy that probes the element specific local structure, supplemented by x-ray pair distribution function analysis that gives the total local structure to longer distances, and x-ray diffraction that gives the long-range average structure of the periodic component of the materials. Detailed analyses indicate that the alloys at and below a nominal composition of ß3.3 at. % Ga are heterogeneous and in addition to the δ phase also contain up to ß20% of a novel, coexisting "σ " structure for Pu that forms in nanometer scale domains that are locally depleted in Ga. The invariance of the Ga EXAFS with composition indicates that this σ structure forms in Ga-depleted domains that result from the Ga atoms in the δ phase self-organizing into a quasi-intermetallic with a stoichiometry of Pu 25−35 Ga so that δ Pu-Ga is neither a random solid solution nor the more stable Pu 3 Ga + α. Above this 3.3 at. % Ga nominal composition, the δ Pu-Ga alloy is homogeneous, and no σ phase is present. These results that demonstrate that collective and cooperative behavior in the interactions between the alloy elements as well as local elastic forces are crucial in determining the properties of complex materials and contradict the conventional mechanism for martensitic transformations, in this case indicating that nucleation is not the rate limiting step.

δ Pu−Ga alloys and their response to self-irradiation are important scientifically because of the unique complexity of Pu and technologically because of their importance in Science Based Stockpile Stewardship. The local order and structure and the role of the Ga are crucial to understanding the phase stability and the aging effects. X-ray diffraction that gives the long-range average structure of the periodic component of the materials and pair distribution functions analysis and X-ray absorption fine structure that give the overall and the element specific local structure have been used to examine a variety of new and aged materials, including a set of high purity δ Pu 1−x Ga x alloys with 1.7 ≤ x ≤ 6.4 atom % Ga that span the low [Ga] portion of the δ region of the phase diagram across the ∼3.3 atom % Ga metastability boundary, a ∼1.7 atom % Ga alloy that was enriched with Pu 238 to accelerate the aging process, and others. We find that metastable alloys contain tens of percents of a novel, "σ", Pu structure that we attribute to rearrangement of the Ga-depleted regions after the self-organization of the Ga to form quasi-intermetallic Pu 25−35 Ga. This collective and cooperative behavior involving the Ga and other defects in terms of a tendency to aggregate into domains with structures that differ from the δ host and the resulting nanoscale heterogeneity also appears to play an important role in the observation of analogous locally ordered structures in aged materials. This description of these materials and their aging is radically different from current conceptual basis derived from other experiments that are insensitive to ordering on the angstrom−nanometer length scale.

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Lead is a hazardous material, and the U.S. Congress has mandated the rapid reduction of all hazardous waste generation as a matter of national policy. With the large amount of plutonium handling in numerous projects including the development of mixed oxide (MOX) fuel, 238Pu power sources, etc., hand glove protection for the emitted alpha, beta, and low energy photons is an important issue. Leaded gloves are the prime shields used for radiological hand protection. U.S. Department of Energy laboratories require a substitute material for the lead oxide in the gloves as a way to reduce mixed waste. To solve this problem, a new blend of non-hazardous materials that have the same radiological properties and approximately the same cost of production have been investigated. The investigations have produced alternative materials using calculations and experiments. The selection of the constituent compounds for the new composite materials was based on the k-absorption edge energy of the main constituent element(s) in the compounds. The formulations of these composites were fashioned on the principle of blending Neoprene rubber formulation with several constituent compounds. Calculations based on the Lambert-Beer attenuation law together with the mass attenuation coefficient values from the XCOM cross section database program were used to determine the transmission fractions of these proposed composite materials. Selected composite materials that compared favorably with the leaded-Neoprene were fabricated. These fabricated composite materials were tested with attenuation experiments and the results were in excellent agreement with the calculations using the Lambert-Beer attenuation law.