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Cross, Justin Neil

Publications and source records attributed to Cross, Justin Neil.

7 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Experimental Steps toward a Density Law for Chlorine-Crediting Criticality Models of Aqueous Plutonium solutions

Criticality accident prevention is an essential safety consideration for all operations involving fissionable and fissile materials. Predictive criticality calculations using advanced neutron transport codes, such as Monte Carlo N-Particle Transport (MCNP), are invaluable tools for designing and implementing operational limits. While indispensable, these tools are limited by the quality and accuracy of the inputs that the user provides to define the modeled system. Parameters such as atomic composition, shape, and material density must be accurately defined to obtain a meaningful result. In the case of material property details for a plutonium model, accurate material characterization data is sometimes sparse. Thus limitations in calculation accuracy can be reduced by improving our knowledge of material properties in the targeted fissile systems. One of the biggest remaining challenges to accurately defining fissile systems is the description of aqueous fissile solutions. Even simple properties, such as density, are not well-known for fissile solutions relevant to nuclear energy and security. Described here are initial efforts undertaken to improve criticality calculation inputs for fissile plutonium chloride solutions in water. This effort is focused on experimentally determining accurate solution characteristics for ternary plutonium chloride/hydrochloric acid/water systems, by measurement of water activity and solution density. The effect of inputting experimental densities for these solutions into MCNP criticality calculations is compared to the traditional approach of modeling an idealized (and fictitious) plutonium-water mixture. Expansion of these efforts to a working density law for aqueous plutonium chloride solutions is also discussed.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2018

Analytical chemistry of nuclear material: case studies from Los Alamos National Laboratory

Presented here are three case studies that demonstrate the breadth of bulk actinide analytical chemistry at Los Alamos National Laboratory (LANL). This laboratory was established during the Manhattan Project and is still considered one of the premier analytical laboratories for special nuclear materials characterization around the globe. First, the analytical chemistry of 238 Pu is presented, showcasing the unique challenges of this high activity isotope. Next, the analysis of 241 AmO 2 is discussed from the perspective of supporting nascent production at LANL. Finally, the analytical chemistry support of the production of plutonium non-destructive assay standards is discussed. Furthermore these examples paint a picture of the analytical capabilities needed to meet the dynamic challenges of LANL’s nuclear programs.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Covalency in Americium(III) Hexachloride

Developing a better understanding of covalency (or orbital mixing) is of fundamental importance. Covalency occupies a central role in directing chemical and physical properties for almost any given compound or material. Hence, the concept of covalency has potential to generate broad and substantial scientific advances, ranging from biological applications to condensed matter physics. Given the importance orbital mixing combined with the difficultly in measuring covalency, estimating or inferring covalency often leads to fiery debate. Consider the 60-year controversy sparked by SEABORG and COWORKERS (1954) when it was proposed that covalency from 5f-orbitals contributed to the unique behavior of americium in chloride matrixes. Herein, we describe the use of ligand K-edge X-ray absorption spectroscopy (XAS) and electronic structure calculations to quantify the extent of covalent bonding in – arguably – one of the most difficult systems to study, the Am–Cl interaction within AmCl 6 3- . We observed both 5fand 6d-orbital mixing with the Cl-3p orbitals; however, contributions from the 6d-orbitals were more substantial. Comparisons with the isoelectronic EuCl 6 3- indicated similar bonding for the Am III 6d- and Eu III 5d-orbitals. Meanwhile, the results confirmed SEABORG’S 1954 hypothesis that Am III 5f-orbital covalency was more substantial than 4forbital mixing for Eu III .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Advances in containment methods and plutonium recovery strategies that led to the structural characterization of plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl 4 (OSPh 2 ) 3

In an attempt to further advance the understanding of plutonium coordination chemistry, we report a robust method for recycling and obtaining plutonium aqueous stock solutions that can be used as a convenient starting material in plutonium synthesis. This approach was used to prepare and characterize plutonium(IV) tetrachloride tris-diphenylsulfoxide, PuCl 4 (OSPh 2 ) 3 , by single crystal X-ray diffraction. The PuCl 4 (OSPh 2 ) 3 compound represents a rare example of a 7-coordinate plutonium(IV) complex. Structural characterization of PuCl 4 (OSPh 2 ) 3 by X-ray diffraction utilized a new containment method for radioactive crystals. The procedure makes use of epoxy, polyimide loops, and a polyester sheath to provide a robust method for safely containing and easily handling radioactive samples. Lastly, the described procedure is more user friendly than traditional containment methods that employ fragile quartz capillary tubes. Additionally, moving to polyester, instead of quartz, lowers the background scattering from the heavier silicon atoms.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Spectroscopic and computational investigation of actinium coordination chemistry

Actinium-225 is a promising isotope for targeted-α therapy. Unfortunately, progress in developing chelators for medicinal applications has been hindered by a limited understanding of actinium chemistry. This knowledge gap is primarily associated with handling actinium, as it is highly radioactive and in short supply. Hence, Ac III reactivity is often inferred from the lanthanides and minor actinides (that is, Am, Cm), with limited success. Here we overcome these challenges and characterize actinium in HCl solutions using X-ray absorption spectroscopy and molecular dynamics density functional theory. The Ac–Cl and Ac–O H 2 O distances are measured to be 2.95(3) and 2.59(3) Å, respectively. The X-ray absorption spectroscopy comparisons between Ac III and Am III in HCl solutions indicate Ac III coordinates more inner-sphere Cl 1– ligands (3.2±1.1) than Am III (0.8±0.3). Finally, these results imply diverse reactivity for the +3 actinides and highlight the unexpected and unique Ac III chemical behaviour.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2016

Extractant Design by Covalency

This project aims to provide an electronic structure-to-function understanding of extractants for actinide selective separation processes. The research entails a multi-disciplinary approach that integrates chemical syntheses, structural determination, K-edge X-ray Absorption Spectroscopy (XAS), and Density Functional Theory (DFT) calculations. In FY15, the project reached the final stage of testing the extraction performance of a new ligand design and preparing an americium-extractant complex for analysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗