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Molecular Models of Atomically Dispersed Uranium at MoS 2 Surfaces Reveal Cooperative Mechanism of Water Reduction

Single atoms of uranium supported on molybdenum sulfide surfaces (U@MoS 2 ) have been recently demonstrated to facilitate the hydrogen evolution reaction (HER) through electrocatalysis. Theoretical calculations have predicted uranium hydroxide moieties bound to edge-sulfur atoms of MoS 2 as a proposed transition state involved in the HER process. However, the isolation of relevant intermediates involved in this process remains a challenge, rendering mechanistic hypotheses unverified. The present work describes the isolation and characterization of a uranium-hydroxide intermediate on molybdenum sulfide surfaces using [(Cp* 3 Mo 3 S 4 )UCp*], a molecular model of a reduced uranium center supported at MoS 2 . Mechanistic investigations highlight the metalloligand cooperativity with uranium involved in the water activation pathway. The corresponding uranium-oxo analogue, [(Cp* 3 Mo 3 S 4 )Cp*U(═O)], was also accessed from the hydroxide cluster via hydrogen atom transfer and from [(Cp* 3 Mo 3 S 4 )UCp*] through an alternative direct oxygen atom transfer. These results provide an atomistic perspective on the reactivity of low-valent uranium at molybdenum sulfide surfaces toward water, modeling key intermediates associated with the HER of U@MoS 2 catalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Effects of a refractory metal protective barrier on uranium carbonitride ceramic–metallic composites exposed to a high temperature hydrogen environment

Uranium nitride has been under consideration at NASA and the Department of Energy for nuclear thermal propulsion applications intended for deep space exploration vehicles. It is critical to the success of the technology development that the behavior of the fuel system is properly characterized in operational environments. This body of work fabricated ceramic metal composites consisting of uranium ceramic fuel in a molybdenum and molybdenum–tungsten metal matrix, both with and without an exterior molybdenum barrier. Specimens were introduced to a high temperature hydrogen environment and characterized through x-ray diffraction, scanning electron microscopy, and energy dispersive spectroscopy to identify characteristic changes. A portion of the specimens was fabricated with a 1.27 mm thick molybdenum barrier in order to isolate the material from the hydrogen environment. Instability of the uranium nitride occurred as low as 2073 K, leading to aggressive instability approaching 2658 K. Carbon reactions with the metal matrix were observed as well as alloying between the uranium and metal matrix constituents. The liquid uranium resulting from the instability of the uranium nitride was observed to attack the grain boundaries of the refractory metal, resulting in the formation of a liquid uranium molybdenum eutectic melt. Specimens encased in a barrier experienced similar results. The authors conclude this is a significant challenge to applications of this cermet at these temperatures. Alternate configurations with resilient hermetic seals or lower temperature applications such as power reactors may have more success.

36 MATERIALS SCIENCE↗

Enhanced Attenuation of Uranium in the Subsurface

Over time, the focus for the Hanford Site has moved from production to decommissioning and site remediation. Several hundred metric tons of near-surface vadose zone sediment have been excavated from the 300 Area in an effort to remove the source of the uranium contamination (DOE/RL, 2011). Despite remediation efforts, uranium continues to be problematic with concentrations greater than the maximum contaminant level (MCL, which is 30 µg/L) for drinking water. Due to the close proximity of the Columbia River, the uranium continues to be a focus of investigation and remediation. After finding that the uranium concentrations were not decreasing as quickly as expected (based on the 1996 ROD) the Tri-Parties set new milestones, including an update of the conceptual model for the 300 Area uranium plume (Williams et al., 2007). In order to more accurately complete a feasibility study and identify how to remediate the uranium in the groundwater, the DOE authorized a remedial investigation/feasibility study (RI/FS). RI/FSs are designed to screen technologies to determine effectiveness, implementability, and cost (see Chapter 2b). These studies are designed to be conducted concurrently as part of the CERCLA process, so the data collected during site characterization (part of the RI) can inform the treatability studies and field tests conducted under the FS (EPA 1988). For the 300 Area, this study included laboratory, field, and modeling components as well as additional sediment and groundwater characterization to determine a suitable remediation strategy to reduce the uranium concentration in the groundwater plume within the expected time frame and cost.

300 area, uranium, polyphosphate, Hanford book pro↗

Conceptual Model of Uranium in the Vadose Zone for Acidic and Alkaline Wastes Discharged at the Hanford Site Central Plateau

Historically, uranium was disposed in waste solutions of varying waste chemistry at the Hanford Site Central Plateau. The character of how uranium was distributed in the vadose zone during disposal, how it has continued to migrate through the vadose zone, and the magnitude of potential impacts on groundwater are strongly influenced by geochemical reactions in the vadose zone. These geochemical reactions can be significantly influenced by the disposed-waste chemistry near the disposal location. This report provides conceptual models and supporting information to describe uranium fate and transport in the vadose zone for both acidic and alkaline wastes discharged at a substantial number of waste sites in the Hanford Site Central Plateau. The conceptual models include consideration of how co-disposed acidic or alkaline fluids influence uranium mobility in terms of induced dissolution/precipitation reactions and changes in uranium sorption with a focus on the conditions near the disposal site. This information, when combined with the extensive information describing uranium fate and transport at near background pH conditions, enables focused characterization to support effective fate and transport estimates for uranium in the subsurface.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhancement of Extraction of Uranium from Seawater

Even at a concentration of 3 μg/L, the world’s oceans contain a thousand times more uranium than currently know terrestrial sources. In order to take advantage of this stockpile, methods and materials must be developed to extract it efficiently, a difficult task considering the very low concentration of the element and the competition for extraction by other atoms in seawater such as sodium, calcium, and vanadium. The majority of current research on methods to extract uranium from seawater are vertical explorations of the grafting of amidoxime ligand, which was originally discovered and promoted by Japanese studies in the late 1980s. Our study expands on this research horizontally by exploring the effectiveness of novel uranium extraction ligands grafted to the surface of polymer substrates using radiation. Through this expansion, a greater understanding of uranium binding chemistry and radiation grafting effects on polymers has been obtained. While amidoxime-functionalized fabrics have been shown to have the greatest extraction efficiency so far, they suffer from an extensive chemical processing step which involves treatment with powerful basic solutions. Not only does this add to the chemical waste produced in the extraction process and add to the method’s complexity, but it also significantly impacts the regenerability of the amidoxime fabric. The approach of this project has been to utilize alternative, commercially available monomers capable of extracting uranium and containing a carbon-carbon double bond to allow it to be grafted using radiation, specifically phosphate, oxalate, and azo monomers. The use of commercially available monomers and radiation grafting with electron beam or gamma irradiation will allow for an easily scalable fabrication process once the technology has been optimized. The need to develop a cheap and reliable method for extracting uranium from seawater is extremely valuable to energy independence and will extend the quantity of uranium available to the nuclear power industry far into the future. The development of this technology will also promote science in relation to the extraction of other elements from seawater which could expand the known stockpiles of other highly desirable materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Investigations into the Effect of Current Velocity on Amidoxime-Based Polymeric Uranium Adsorbent Performance

The Fuel Resources Program at the U.S. Department of Energy’s (DOE), Office of Nuclear Energy (DOE-NE) is developing adsorbent technology to extract uranium from seawater. This technology is being developed to provide a sustainable and economically viable supply of uranium fuel for nuclear reactors (DOE, 2010). Among the key environmental variables to understand for adsorbent deployment in the coastal ocean is what effect flow-rates or linear velocity has on uranium adsorption capacity. The goal is to find a flow conditions that optimize uranium adsorption capacity in the shortest exposure time. Understanding these criteria will be critical in choosing a location for deployment of a marine adsorbent farm. The objective of this study was to identify at what linear velocity the adsorption kinetics for uranium extraction starts to drop off due to limitations in mass transport of uranium to the surface of the adsorbent fibers. Two independent laboratory-based experimental approaches using flow-through columns and recirculating flumes for adsorbent exposure were used to assess the effect of flow-rate (linear velocity) on the kinetic uptake of uranium on amidoxime-based polymeric adsorbent material. Time series observations over a 56 day period were conducted with flow-through columns over a 35-fold range in linear velocity from 0.29 to 10.2 cm/s, while the flume study was conducted over a narrower 11-fold range, from 0.48 to 5.52 cm/s. These ranges were specifically chosen to focus on the lower end of oceanic currents and expand above and below the linear velocity of ~ 2.5 cm/s adopted for marine testing of adsorbent material at PNNL.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Uranium Solubility and Supernate Enrichment Testing for Accelerated Basin De-Inventory Discards to Concentration, Storage, and Transfer Facilities

After future Accelerated Basin De-inventory (ABD) enriched uranium discards into sludge batches (SB), portions of supernate decants during SB preparation will be blended into salt batches (StB) and the resulting feeds must meet the nuclear safety requirements for the Salt Waste Processing Facility (SWPF). During previous SB10 sampling and testing, which involved H-Canyon material containing enriched uranium being mixed with Tank 51 sludge shortly after the H-Canyon stream was neutralized, it was identified that the uranium isotopic enrichment in the supernate deviated from the uranium isotopic enrichment in the slurry. The higher uranium isotopic enrichment in the supernate introduced the risk of challenging the feed requirements of SWPF. The ABD material added to SB11 was isotopically diluted with depleted uranium, mitigating any downstream impacts. However, H-Canyon desires to eliminate or minimize future depleted uranium additions in order to meet the mission schedule.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Integration of Real-Time Geophysical Monitoring with In Situ Uranium Remedy Implementation - 19094

An in situ injection of polyphosphate amendment was conducted to address a uranium source zone for a plume near the Columbia River at the U.S. Department of Energy Hanford Site. This treatment was applied as an enhanced attenuation approach, targeting uranium in a periodically wetted zone where groundwater inundates as the water table rises in response to the seasonal high river stage. Uranium within this zone is mobilized into the groundwater at the high river stage, resulting in a persistent groundwater plume. The polyphosphate amendment creates precipitates that decrease uranium mobility so that the amount of uranium flushed into groundwater when the zone is periodically wetted is significantly decreased. With a reduced flux of uranium into the plume, the plume concentrations are expected to decrease over time. During injection, real-time geophysical monitoring was applied to provide hourly images of injected-fluid distribution. The real-time autonomous data collection, processing, and reporting enabled the electrical resistivity tomography images to provide operational feedback during injection. These data were used in conjunction with operational information (e.g., flow rate, pressures) and subsurface data from 24 monitoring wells placed within and downgradient of the treatment area (e.g., water level and specific conductance probes, uranium concentration, phosphate concentration) to assess overall performance of the treatment. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Uranium Biomineralization by Natural Microbial Phosphatase Activities in the Subsurface

In this project, inter-disciplinary research activities were conducted in collaboration among investigators at The University of Alabama (UA), Georgia Institute of Technology (GT), Lawrence Berkeley National Laboratory (LBNL), Brookhaven National Laboratory (BNL), the DOE Joint Genome Institute (JGI), and the Stanford Synchrotron Radiation Light source (SSRL) to: (i) confirm that phosphatase activities of subsurface bacteria in Area 2 and 3 from the Oak Ridge Field Research Center result in solid U-phosphate precipitation in aerobic and anaerobic conditions; (ii) investigate the eventual competition between uranium biomineralization via U-phosphate precipitation and uranium bioreduction; (iii) determine subsurface microbial community structure changes of Area 2 soils following organophosphate amendments; (iv) obtain the complete genome sequences of the Rahnella sp. Y9-602 and the type-strain Rahnella aquatilis ATCC 33071 isolated from these soils; (v) determine if polyphosphate accumulation and phytate hydrolysis can be used to promote U(VI) biomineralization in subsurface sediments; (vi) characterize the effect of uranium on phytate hydrolysis by a new microorganism isolated from uranium-contaminated sediments; (vii) utilize positron-emission tomography to label and track metabolically-active bacteria in soil columns, and (viii) study the stability of the uranium phosphate mineral product. Microarray analyses and mineral precipitation characterizations were conducted in collaboration with DOE SBR-funded investigators at LBNL. Thus, microbial phosphorus metabolism has been shown to have a contributing role to uranium immobilization in the subsurface.

59 BASIC BIOLOGICAL SCIENCES↗

Depleted Uranium Discrimination Using Spectral Ratios from Data-Starved Spectra - 18619

The Institute for Clean Energy Technology (ICET) has developed mobile surveying platforms for the retrieval of fired depleted uranium (DU) munitions. ICET surveying platforms are fitted with differential global positioning system (GPS), scintillation detectors, and central processing units (CPUs). The surveying technology has historically been used to assist facilities where DU contamination is a concern to locate, retrieve, and remediate DU-contaminated areas. Residence times over DU sources for mobile systems normally do not produce enough data to use gamma ray spectroscopy to verify the source type. Discussed is a potential method used to discriminate DU signatures in data-starved gamma ray spectral data collected during field surveys. Laboratory tests have shown that data-starved gamma ray spectra for zero-valence, oxide, and uranium ores can be distinguished from each other and from background by spectral ratioing. Zero-valence DU and DU oxide gamma ray signatures differ due to the attenuation of low-energy gammas emitted from U-238 daughters. DU signatures can be differentiated from naturally occurring uranium spectra due to the presence of daughters below U-234, primarily bismuth (Bi)-214, in the uranium decay series. Three primary regions of interest (ROI) within the analyzed test spectra are used to roughly characterize the shape of each test spectrum and compare them to background. The three ROIs are focused around the gamma-emitting daughters of U-238: thorium (Th)-234, protactinium (Pa)-234 metastable (m), and Bi-214. One of the three regions is considered the base region. This region is used to estimate what the counts in the other two regions should be by multiplying the counts in the ROIs by a ratio of background counts from an area previously found to be impacted. Using this spectral ratioing technique, a non-zero difference in spectral ratio values indicates a shift in the test spectra away from background. Calculating ratios between the base region and the other two regions allows for a graphical representation of the data in a two-dimensional spectral ratioing space, which is used to differentiate between the types of uranium sources previously mentioned. Surveying processes that are based on gross counts from scintillation counters can result in a large number of false positives as a result of shifting background signals or the presence of naturally occurring uranium. Application of the spectral ratioing technique can further assist in site characterization by analyzing all of the data-starved survey spectra to identify false positives or the need for additional data collection. Accurate surveys of DU testing and training ranges reduces the costs associated with range clean-up by discriminating clean areas from those requiring remediation. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Water Solubility of Plutonium and Uranium Compounds and Residues at TA-55

Understanding the water solubility of plutonium and uranium compounds and residues at TA-55 is necessary to provide a technical basis for appropriate criticality safety, safety basis and accountability controls. Individual compound solubility was determined using published solubility data and solution thermodynamic modeling. Residue solubility was estimated using a combination of published technical reports and process knowledge of constituent compounds. The scope of materials considered includes all compounds and residues at TA-55 as of March 2016 that contain Pu-239 or U-235 where any single item in the facility has more than 500 g of nuclear material. This analysis indicates that the following materials are not appreciably soluble in water: plutonium dioxide (IDC=C21), plutonium phosphate (IDC=C66), plutonium tetrafluoride (IDC=C80), plutonium filter residue (IDC=R26), plutonium hydroxide precipitate (IDC=R41), plutonium DOR salt (IDC=R42), plutonium incinerator ash (IDC=R47), uranium carbide (IDC=C13), uranium dioxide (IDC=C21), U 3 O 8 (IDC=C88), and uranium filter residue (IDC=R26). This analysis also indicates that the following materials are soluble in water: plutonium chloride (IDC=C19) and uranium nitrate (IDC=C52). Equilibrium calculations suggest that PuOCl is water soluble under certain conditions, but some plutonium processing reports indicate that it is insoluble when present in electrorefining residues (R65). Plutonium molten salt extraction residues (IDC=R83) contain significant quantities of PuCl 3 , and are expected to be soluble in water. The solubility of the following plutonium residues is indeterminate due to conflicting reports, insufficient process knowledge or process-dependent composition: calcium salt (IDC=R09), electrorefining salt (IDC=R65), salt (IDC=R71), silica (IDC=R73) and sweepings/screenings (IDC=R78). Solution thermodynamic modeling also indicates that fire suppression water buffered with a commercially-available phosphate buffer would significantly reduce the solubility of PuCl 3 by the precipitation of PuPO 4 .

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A case study on the use of carbon sticky tabs for microbeam uranium isotope measurement with an emphasis on understanding the influence of subtle variations in substrate composition

In this paper we integrate laser induced breakdown spectroscopy (LIBS), large geometry secondary ion mass spectrometry (LG-SIMS), laser ablation—multi collector—inductively coupled plasma—mass spectrometry (LA-MC-ICP-MS), and trace elemental compositions obtained by bulk digestion from a suite of commercially available carbon sticky tabs to determine if subtle variations in the tab’s composition can be tied to shifts in the observed uranium isotopic composition of the IRMM-2020 standard relative to its ‘true’ value. The results suggest that, although clear differences exist in the relative abundances of carbon and hydrogen across the various carbon sticky tabs examined, as well as differences in their trace elemental and total uranium concentrations, these differences do not appear to influence the LG-SIMS or LA-MC-ICP-MS uranium isotope ratio measurements, or the appearance of the uranium mass spectrum scans. Instead, the quality (i.e., precision and accuracy) of the LG-SIMS and LA-MC-ICP-MS results are directly proportional to the observed signal intensity at the time of analysis. For the LG-SIMS measurements, there does appear to be a direct correlation between 235U1H hydride formation rates and vacuum conditions within the instrument’s analytical chamber. Furthermore, none of the carbon sticky tabs examined by LG-SIMS displayed evidence of elevated background uranium content. While a preliminary correlation was observed between the uranium isotope background signal during LA-MC-ICP-MS and the total uranium concentrations determined by isotope dilution, none of the tabs displayed a high enough analytical background to affect the isotope ratio measurements.

Zirakparvar, Alex [ORNL] (ORCID:0000000337797730)↗

Atomistic simulations of temperature and direction dependent threshold displacement energies in α - and γ -uranium

We performed a systematic study of the threshold displacement energy (E d ) in metallic uranium as a function of both the recoil direction and temperature using Molecular Dynamics simulations. We developed a novel orientation sampling scheme that utilizes crystallographic symmetrical geodesic grids to select directions from the orientation fundamental zone to study the directional dependency. Additionally, we studied the temperature dependency by considering both the α-uranium phase, corresponding to the ground state for temperatures ranging from 0 K to 600 K, and the γ-uranium phase, corresponding to high-temperature state for temperatures above 900 K. In this study, we compared several definitions of the threshold energy: a direction-specific threshold displacement energy (E d (θ,Φ)), an angle-averaged threshold energy ($E_d^{ave}$), a production probability threshold displacement energy ($E_d^{pp}$), and a defect count threshold displacement energy ($E_d^{dc}$). The direction-specific threshold displacement energies showed large angular anisotropy and variations in E d results in accordance with crystallographic considerations. Specifically, preferred defect channeling directions were observed in the [120], [1$\bar{2}$0], [1$\bar{1}$1] directions for the α-uranium, and [001], [111] directions for the γ-uranium. The production probability threshold displacement energy ($E_d^{pp}$) is calculated as approximately 99.2659 eV at 10 K (α-U), 103.4980 eV at 300 K (α-U), 76.0915 eV at 600 K (α-U), and 42.9929 eV at 900 K (γ-U). With exception of those calculated at 10 K, threshold displacement energies decrease with increasing temperature. Analyses of the stable defect structures showed that the most commonly observed interstitial configuration in α-uranium consists of a ( 0 1 0 ) dumbbell-like interstitial; while in γ-uranium no preferential defect configuration could be identified due to thermally-induced lattice instabilities at the elevated temperatures.

36 MATERIALS SCIENCE↗

Rapid isotopic analysis of uranium microparticles via SP-ICP-TOF-MS

Inductively coupled plasma – time-of-flight – mass spectrometry (ICP-TOF-MS) was employed for the isotopic analysis of uranium particles of varying 235 U enrichment levels. Here, a single particle (SP)-based introduction scheme was employed such that individual particles, in a suspension, were analyzed. The uranium oxide microparticles were comprised of depleted uranium (DU, 235 U/ 238 U of 0.0017316(14)), natural uranium (NU, 235 U/ 238 U of 0.0072614(39)), and low enriched uranium (LEU, 235 U/ 238 U of 0.051025(15)). The percent relative difference of the SP-ICP-TOF-MS measured isotopic ratios compared to the expected values for the DU, NU, and LEU particle populations were 8.75, 0.12, and 1.23 %, respectively. After characterization, the DU and NU particles were doped within a complex sample matrix (Arizona Test Dust) containing Fe, Ti, Al, and Si particles, among others. Then, the suspension was analyzed via SP-ICP-TOF-MS and the detected particles were classified as DU or NU based on their measured 235 U/ 238 U ratio. In the same analysis, the matrix particles (i.e., Al, Fe, and Ti) were detected, demonstrating the simultaneous nuclide detection provided by the measurement platform. The presented SP-ICP-TOF-MS methodology for uranium particle characterization proved to be a high throughput method for detecting and isotopically discerning uranium particles with varying enrichment levels, in a complex matrix.

Stanberry, Jordan S. [Oak Ridge National Laborator↗

New Resonance Ionization Mass Spectrometry Scheme for Improved Uranium Analysis

Resonance ionization mass spectrometry (RIMS) combines tunable laser spectroscopy with mass spectrometry to provide here a high-efficiency means of analyzing solid materials. We previously showed a very high useful yield of 24% for analysis of uranium using three lasers to excite and ionize atoms sputtered from metallic uranium and uranium dioxide. A new resonance ionization scheme using only two lasers achieves a higher useful yield of 38% by accessing both the ground electronic state and a low-lying electronic state of atomic uranium that is significantly populated by sputtering. The major loss channel in analyzing uranium dioxide is the formation of UOx molecules during sputtering. Prebombardment of the surface with 3 keV noble gas ions prior to analysis reduces the surface and results in a sputtered flux with a greatly enhanced proportion of atomic U. This method of surface reduction results in uranium useful yields as high as 6.6% for uranium dioxide analysis, compared to 2% from previous work.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The synthesis and versatile reducing power of low-valent uranium complexes

This Perspective provides a detailed overview of the chemistry of low-valent (di- and trivalent) uranium. The reactivity of uranium(II) and uranium(III) complexes is discussed both to illustrate the general types of reactions that might be expected and to highlight the many unusual modes of reactivity observed with this element. A particular emphasis is given to redox reactions with uranium(III) species, including reduction of small molecules, multi-electron reductions involving redox-active ligands, and formation of uranium–ligand multiple bonds. Redox-neutral adduct formation with uranium(III) complexes as well as the current state of the young field of uranium(II) redox chemistry are also covered. In addition, synthetic protocols to prepare a wide range of low-valent compounds are presented.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Density of Uranium Hydride Formed Under Mechanical Load

The conversion of uranium metal (ρ = 19 g/cc) to uranium hydride (theoretical ρ = 11 g/cc) results in a large volumetric expansion due to both the density decrease and the substantial porosity of the hydride if not volumetrically constrained. This transformation from a monolithic solid to a particulate material can generate substantial forces when the growing hydride impacts a nearby target. The resulting displacement of the target is dependent upon both its resistance to motion and the strength of the growing hydride. We have observed columns of growing uranium hydride apply forces of hundreds to thousands of pounds to flex high-strength cantilever beams, and have measured applied forces of over 5000 pounds when growing hydride columns impacted rigid targets. The force/displacement behavior of growing uranium hydride was originally modeled by finite element methods to develop an elastic, perfectly plastic constitutive model of UH 3 . The UH 3 constitutive model was then applied to simulate the response of components impacted by growing uranium hydride. More recently we have used an experimental apparatus that simultaneously and independently provides measurement of applied force and target displacement during uranium hydride formation. These efforts confirm previous work and allow for increased confidence in modeling results. The design, testing, and experimental results using such an apparatus over a variety of system stiffnesses and with a variety of sample sizes has been completed. This work extended our understanding of UH 3 growth dynamics and mechanics and enabled the development of a higher fidelity constitutive Drucker-Prager model for UH 3 , and greater confidence in predictions of component behavior in systems impacted by uranium hydride formation.

36 MATERIALS SCIENCE↗

Innovative Elution Processes for Recovering Uranium and Transition Metals from Amidoxime-based Adsorbents

Amidoxime-based polymer fibers are considered one of the most promising materials for sequestering uranium from seawater. The high-surface-area polymer fibers containing amidoxime and carboxylate groups synthesized by Oak Ridge National Lab (ORNL-AF1) show very high uranium adsorption capacities known in the literature. Effective elution of uranium and repeated use of the adsorbent are important factors affecting the cost of producing uranium from seawater using this material. Traditional acid leaching of uranium followed by KOH conditioning of the fiber causes chemical changes and physical damage to the ORNL-AF1 adsorbent. Two alkaline solution leaching methods were developed by this project, one uses a highly concentrated (3 M) potassium bicarbonate solution at pH 8.3 and 40 °C; the other uses a mixture of sodium carbonate and hydrogen peroxide at pH 10.4. Both elution methods do not require KOH conditioning prior to reusing the fiber adsorbent. The conditions of eluting uranium from the amidoxime-based adsorbent using these alkaline solutions are confirmed by thermodynamic calculations. The bicarbonate elution method is selective for uranium recovery compared to other elution methods and causes no chemical change to the fiber material based on FTIR spectroscopy

36 MATERIALS SCIENCE↗