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Results for “PLUTONIUM OXIDES”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Water Interactions with Actinide Oxides from First Principles: A Computational Study - 16470

The interactions between water and the actinide oxides UO{sub 2} and PuO{sub 2} are important when considering the long-term storage of spent nuclear fuel. However, experimental studies in this area are severely limited by plutonium's intense radioactivity, and hence we have recently begun to investigate these interactions computationally. In this contribution we report the results of first principles calculations of the electronic and geometric structures of AnO{sub 2} bulk, AnO{sub 2} clusters, and AnO{sub 2} surfaces (An = U, Np, Pu), as well as the interaction of water with the latter. Strongly-correlated effects are taken into account using a Hubbard corrected potential, which enables us to perform efficacious plane-wave density functional calculations of extended systems. In particular, we compare results of water adsorption on UO{sub 2} (111) with the corresponding results on CeO{sub 2}, focusing on the energetics and structural properties of molecular versus dissociative adsorption, for both partially and fully covered surfaces. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2012

Toward an Improved Understanding of Structure and Magnetism in Neptunium and Plutonium Phosphonates and Sulfonates

This grant supported the exploratory synthesis of new actinide materials with all of the actinides from thorium to californium with the exceptions of protactinium and berkelium. We developed detailed structure-property relationships that allowed for the identification of novel materials with selective ion-exchange, selective oxidation, and long-range magnetic ordering. We found novel bonding motifs and identified periodic trends across the actinide series. We identified structural building units that would lead to desired structural features and novel topologies. We also characterized many different spectroscopic trends across the actinide series. The grant support the preparation of approximately 1200 new compounds all of which were structurally characterized.

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

Graphene-based filament material for thermal ionization

The use of graphene oxide materials for thermal ionization mass spectrometry analysis of plutonium and uranium has been investigated. Filament made from graphene oxide slurries have been 3-D printed. A method for attaching these filaments to commercial thermal ionization post assemblies has been devised. Resistive heating of the graphene based filaments under high vacuum showed stable operation in excess of 4 hours. Plutonium ion production has been observed in an initial set of filaments spiked with the Pu 128 Certified Reference Material.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Measurement of PuO 2 film thickness by electron probe microanalysis (EPMA) calibration curve method

Plutonium (Pu) surfaces are highly reactive toward oxygen containing species and, therefore, invariably covered with oxides (e.g. PuO 2 ) during transport and handling. The actual thickness of the surface oxide may dictate if a plutonium part is suitable for a certain application. As a result, a cost-effective, quick, non-destructive, yet reliable means to measure the oxide layer thickness formed on Pu samples is desirable. In this study, the cross-sections of a series of room temperature grown oxides on Pu samples were trenched by focus ion beam (FIB) then observed by scanning electron microscopy (SEM) to measure the surface oxide thicknesses, which were then combined with the corresponding oxygen k-ratios provided by electron probe microanalysis (EPMA) to form calibration curves. Oxide thickness measurements for the calibration curves were made on samples within the typical SEM observable range for PuO 2 (35–400 nm). The portion of the calibration curve in the thinner oxide region (<35 nm) were approximated via Pouchou and Pichoir’s Φ(ρz) theory. Two specimens with micrometer-thick PuO 2 standards (one formed at room temperature and the other at higher temperature with a higher level of crystallinity) were made for the k-ratios in this study, allowing EPMA users to choose the standard that best suits their needs. If the surface corrosion is known to be PuO 2 (from the environment in which the Pu sample is stored) or if the stoichiometry of the surface oxide is confirmed by a preliminary/compliment technique, these calibration curves allow EPMA users to quickly and efficiently determine PuO 2 thicknesses from the measured oxygen k-ratios of their samples. The methodology presented in this study can also be used as a template for creating calibration curves for oxides grown on other actinides.

36 MATERIALS SCIENCE↗
DOE OSTI2025

FRAM v.7.1

Fixed-energy Response-function Analysis with Multiple efficiency (FRAM) is a software code designed primarily for plutonium and uranium isotopic analysis. It is widely used in both the domestic and international safeguards community. FRAM can quickly and accurately determine the isotopic compositions of plutonium, uranium, and mixed oxides (MOX) when measuring with a high-purity germanium (HPGe), cadmium zinc telluride (CZT), or lanthanum bromide (LaBr3) detector. The capabilities of FRAM have been enhanced to analyze the data of the pixelated CZT detector (made by H3D) and to measure the mass of plutonium, uranium, and MOX. Both the isotopic composition and mass of the item can be quickly determined with one measurement using a gamma detector with FRAM v.7.1.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2025

24.1.3.4 Upgraded Fixed Energy Response Function Analysis with Multiple Efficiencies (FRAM) Software for U/Pu/MOX Mass Measurements

Fixed-energy Response-function Analysis with Multiple efficiency (FRAM) is a software code designed primarily for plutonium and uranium isotopic analysis. It is widely used in both the domestic and international safeguards community. FRAM can quickly and accurately determine the isotopic compositions of plutonium, uranium, and mixed oxides (MOX) when measuring with a high-purity germanium (HPGe), cadmium zinc telluride (CZT), or lanthanum bromide (LaBr 3 ) detector. The capabilities of FRAM have been enhanced to analyze the data of the pixelated CZT detector (made by H3D) and to measure the mass of plutonium, uranium, and MOX. Both the isotopic composition and mass of the item can be quickly determined with one measurement using a gamma detector with FRAM v.7.1.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2015

Design and testing of a combined neutron and gamma assay system for measuring fissile material in fuel and waste items - 15340

A combined neutron and gamma ray assay system for the measurement of fissile material in both fuel and waste items has been designed, modelled, developed and tested. The purpose of the system is to measure and characterize a wide range of fissile materials including uranium, plutonium, americium and mixed oxide fuel arising from a variety of processes and facilities across the United Kingdom. Dounreay Site Restoration Limited at Dounreay currently stores these items form the United Kingdom Nuclear Decommissioning Authority's un-irradiated fuel inventory. This inventory comprises historic materials from ex-United Kingdom Atomic Energy Authority nuclear fuel projects and experiments together with fast reactor fuel materials and some commercial fuel items as delivered to Dounreay for recovery. The combined assay system has been designed and constructed to support the operation of a fuel processing facility, which will be operated at Dounreay to treat these historic legacy fuel materials, making them suitable for long term storage. Appropriate characterization of the fissile material is required for safety, criticality control and nuclear materials safeguards purposes prior to final disposition. The system consists of both gamma ray and neutron measurement components. The results of a neutron measurement are combined with the gamma ray isotopic ratio measurement results to generate the assay result for the fissile material being characterized. The gamma ray component of the system employs a safeguards quality high purity Germanium detector with electro-mechanical cooling and the measurements of fissile material containers are made in a shielded chamber with a tin and copper graded lining. Containers of fissile material are rotated during the gamma ray measurement and a variable automatic steel collimator aperture mechanism is employed to adjust the measured count rate to control detector dead time. Gamma ray spectra are analysed using the plutonium and uranium isotopic ratio code PC/FRAM. The gamma ray system can also be configured to perform a direct assay of small quantities of uranium bearing material. For this assay measurement a series of cadmium filters can be positioned in front of the detector to reduce the contribution from 59 keV gamma rays from Am-241. In addition to gamma ray isotopic measurements, both active and passive neutron assay is performed by the system. The neutron-measuring component consists of a thick walled cylindrical polyethylene chamber, which provides neutron moderation for 30 one-inch diameter He-3 detector tubes located in re-entrant channels in the polyethylene moderator. Two removable polyethylene-inserts incorporating lower plug assemblies are provided, one with and one without a cadmium lining. Also two top plug units are provided, again one with cadmium and one without a cadmium liner. The Neutron Subsystem can be operated both as a passive and as an active neutron coincidence counter. In both fast and thermal active neutron mode, the neutron component employs two americium-beryllium (Am-Be) alpha-n neutron sources, one positioned in the top and the other in the bottom plug unit. The neutron sources are removed when the counter is operated in passive mode. Passive neutron detection efficiency and active neutron performance has been modelled using the MCNP Monte Carlo computer simulation code as part of the design process. In the absence of fissile samples, operation of the gamma ray component of the system has been tested initially using calibrated Eu-152 and Ba-133 gamma ray sources and the use of archived spectra from fissile material measurements. Initial testing of the neutron system has employed a calibrated Cf-252 spontaneous fission neutron source. Neutron testing has been confirmed using further MCNP simulations. The results of test measurements with the system are presented and compared with the results of MCNP measurement simulations. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

An Alternative to the Continued Accumulation of Separated Plutonium in Japan: Dry Cask Storage of Spent Fuel

As of the end of 2017, Japan had a stockpile of 48 tons of separated plutonium. It will take more than a decade for Japan to convert most of that plutonium into “mixed-oxide” (MOX) fuel and load it into power reactors licensed to use such fuel. This is a very costly program. Including the cost of reprocessing, MOX fuel costs about ten times more than the low-enriched-uranium fuel that otherwise would be used by these reactors. Yet Japan has a policy to start separating more plutonium from spent reactor fuel as soon as the Rokkasho Reprocessing Plant can be put into operation – currently projected for 2021 after 24 years of delay due to a variety of technical problems and upgrades in safety requirements. Japan’s government remains committed to this costly and troubled program primarily because, pending the availability of additional spent-fuel storage space on or off site, reprocessing is seen as the only way to get spent fuel out of reactor pools that are getting full. Because of concerns about the safety of dense-packed spent-fuel pools, however, the prefectures and towns hosting Japan’s power reactors are beginning to accept on-site storage of spent fuel in dry casks. This is the option the United States and many other countries chose after they cancelled their reprocessing programs and their powerplant pools filled up. Its increasing availability in Japan, if backed by a determined policy to accelerate its introduction, should make it possible to cancel reprocessing in Japan as well.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Topographic and nanomechanical mapping of plutonium surfaces

Atomic force microscopy of gallium-stabilized δ-phase plutonium coupons has been used to map their topography and qualitative mechanical character, including Derjaguin-Muller-Toporov modulus, adhesion, deformation, and dissipation. Initial topographical results demonstrate that the plutonium surface is considerably rough and heterogeneous. Qualitative nanomechanical mapping revealed distinct striation patterns that are not observed in the topography images. Further investigation of the striations in the nanomechanical modes of imaging suggest that they are not measurement artifacts, or plutonium specific features. Similar investigations of stainless steel surfaces established a strong correlation between the mechanical working of the surface (i.e. cutting and grinding) and the appearance of the striations. Reimaging of the plutonium surface after moderate oxidation occurring within an inert Ar atmosphere (~1 ppm O 2 ) over the course of 13 months revealed a diminished striation pattern. It is suggested that surface stress/strain induced by the mechanical working of the metal surfaces results in the patterns of variable modulus, adhesion, deformation, and dissipation, and that these patterns are affected by the chemical changes and aging of the plutonium surface.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Elucidating the Radiation-Induced Redox Chemistry of Plutonium Under Used Nuclear Fuel Reprocessing Conditions

Plutonium plays a critical role in the development of sustainable nuclear fuel cycles, and yet, our fundamental understanding of this element’s inherent radiation-induced redox chemistry and associated impacts on nuclear fuel cycle technologies is limited. Unanticipated changes in oxidation state distribution can influence the speciation and transport of plutonium in a given process. Control of these parameters is especially important for used nuclear fuel reprocessing technologies, wherein the separation and recovery of plutonium is typically achieved by the selective formation, maintenance, and complexation of specific oxidation states. Furthermore, plutonium’s inherent radiation-induced redox chemistry has the capacity to influence the radiolytic behavior of its complexes, the longevity of which are critical in the design of efficient and cost-effective advanced reprocessing technologies. These radiation-induced processes are unavoidable under fuel cycle conditions owing to the inherency of ionizing radiation fields to the decay of plutonium’s isotopes and to the various other radioisotopes generated by nuclear fission and neutron-capture process and the subsequent radioactive decay of their products. As such, mechanistically understanding the response of plutonium’s multiple oxidation states to multi-component ionizing radiation fields is essential for predicting the behavior of this critical element under used nuclear fuel reprocessing conditions. Here, through a combination of time-resolved (electron pulse) and steady-state (alpha and gamma) irradiation experiments complemented by quantitative, multiscale modeling calculations, we present advances in our understanding of radiation-induced plutonium redox chemistry!

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis of room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Analysis of Pu-Only Partitioning Strategies in LMFBR Fuel Cycles

Sodium cooled Fast Reactors (SFR) have been under consideration for production of electricity, fissile material production, and for destruction of transuranics for decades. The neutron economy of a SFR can be operated in one of two ways. One possibility is to operate the reactor in a transuranic burner mode which has been the focus of active R&D in the last 15 years. However, prior to that the focus was on breeding transuranics. This later mode of managing the neutron economy relies on ensuring the maximum fuel utilization possible in such a way as to maximize the amount of plutonium produced per unit of fission energy in the reactor core. The goal of maximizing plutonium production in this study is as fissile feed stock for the production of MOX fuel to be used in Light Water Reactors (LWR).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

The Application of materials attractiveness in a graded approach to nuclear materials security

The threat from terrorist groups has recently received greater attention. In this paper, material quantity and material attractiveness are addressed through the lens of a minimum security strategy needed to prevent the construction of a nuclear explosive device (NED) by an adversary. Nuclear materials are placed into specific security categories (3 or 4 categories) , which define a number of security requirements to protect the material. Materials attractiveness can be divided into four attractiveness levels, High, Medium, Low, and Very Low that correspond to the utility of the material to the adversary and to a minimum security strategy that is necessary to adequately protect the nuclear material. We propose a graded approach to materials attractiveness that recognizes for instance substantial differences in attractiveness between pure reactor-grade Pu oxide (High attractiveness) and fresh MOX fuel (Low attractiveness). In either case, an adversary's acquisition of a Category I quantity of plutonium would be a major incident, but the acquisition of Pu oxide by the adversary would be substantially worse than the acquisition of fresh MOX fuel because of the substantial differences in the time and complexity required of the adversary to process the material and fashion it into a NED.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2015

Advanced waste form and Melter development for treatment of troublesome high-level wastes

A number of waste components in US defense high level radioactive wastes (HLW) have proven challenging for current Joule heated ceramic melter (JHCM) operations and have limited the ability to increase waste loadings beyond already realized levels. Many of these “troublesome" waste species cause crystallization in the glass melt that can negatively impact product quality or have a deleterious effect on melter processing. Recent efforts at US Department of Energy laboratories have focused on understanding crystallization behavior within HLW glass melts and investigating approaches to mitigate the impacts of crystallization so that increases in waste loading can be realized. Advanced glass formulations have been developed to highlight the unique benefits of next-generation melter technologies such as the Cold Crucible Induction Melter (CCIM). Crystal-tolerant HLW glasses have been investigated to allow sparingly soluble components such as chromium to crystallize in the melter but pass out of the melter before accumulating.The Hanford site AZ-101 tank waste composition represents a waste group that is waste loading limited primarily due to high concentrations of Fe 2 O 3 (also with high Al 2 O 3 concentrations). Systematic glass formulation development utilizing slightly higher process temperatures and higher tolerance to spinel crystals demonstrated that an increase in waste loading of more than 20% could be achieved for this waste composition, and by extension higher loadings for wastes in the same group. An extended duration CCIM melter test was conducted on an AZ-101 waste simulant using the CCIM platform at the Idaho National Laboratory (INL). The melter was continually operated for approximately 80 hours demonstrating that the AZ-101 high waste loading glass composition could be readily processed using the CCIM technology. The resulting glass was close to the targeted composition and exhibited excellent durability in both the as poured state and after being slowly cooled according to the canister centerline cooling (CCC) profile. Glass formulation development was also completed on other Hanford tank wastes that were identified to further challenge waste loading due to the presence of appreciable quantities (>750 g) of plutonium in the waste tanks. In addition to containing appreciable Pu quantities, the C-102 waste tank and the 244-TX waste tank contain high concentrations of aluminum and iron, respectively that will further challenge vitrification processing. Glass formulation testing also demonstrated that high waste loadings could be achieved with these tank compositions using the attributes afforded by the CCIM technology.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Neptunium extraction by N,N-dialkylamides

Separation of neptunium by solvent extraction has been based on tributylphosphate (TBP) for decades, but TBP is not fully incinerable, which adds to the burden of long-lived radioactive waste. Alternatives to TBP for uranium and plutonium extraction, such as the N , N -diakylamides, previously have been explored in the hopes of transitioning to an extractant that is incinerable. Four N , N -diakylamides, N , N -dihexylhexanamide (DHHA), N , N -dihexyloctanamide (DHOA), N , N -di(2-ethylhexyl)butanamide (DEHBA), and N , N -di(2-ethylhexyl)-iso-butanamide (DEHiBA) were considered in this work for their potential to extract millimolar concentrations of Np(IV), Np(V), and Np(VI) from nitric acid solutions into organic solutions containing 1 M extractant in Exxsol D60. Furthermore, under these conditions the branching of the alkyl substituents affects the extractability of Np(VI) and Np(IV), causing three of the dialkylamides, DHHA, DHOA and DEHBA, to extract neptunium in the expected order Np(VI) > Np(IV) > > Np(V). In contrast, branched DEHiBA is so poor an extractant for Np(IV) that the extraction order becomes Np(VI) > > Np(V) > Np(IV) between 0.1 and 5.6 M HNO 3 due to partial oxidation of the Np(V) in nitric acid.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2021

Comparing elemental measurements at packaging and after storage for signatures of chloride salt radiolysis

Radiolysis of hydrated alkaline earth chloride salts by alpha radiation from plutonium produces the chloride containing gases HCl and Cl 2 . These gases are known to diffuse out of the plutonium-containing material and contribute to corrosion outside of the convenience container. The alkaline earth elements remain with the plutonium-containing material as oxides or hydroxides. The amount of chlorine within the material after storage will be reduced compared to the amount at packaging. The fraction of the alkaline earth elements that are soluble after storage will be reduced compared to the amount at packaging. These signatures may be observable by comparing the chemical analysis measurements made at packaging and after storage. Comparison of measurements on a single Hanford container shows that the chloride does decrease and the alkaline earth elements have reduced solubility in water. Differences seen with other elements make conclusions difficult.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Mixed Metallic and Organic Transuranic Waste Incineration / Vitrification - 17539

Transuranic wastes are produced by the nuclear fuel cycle management, essentially from MOX fuel production units. These waste, contaminated with Uranium and Plutonium, have large composition variability and enclose, in current temporary conditioning, mixed metals and organics. Metals are mainly stainless steel, aluminum or copper and organics are composed of different kind of plastics, highly chlorinated for some. On purpose, a new treatment process is being studied to incinerate the organics, melt the metallic fraction and incorporate the mineral residue fraction in a glass matrix. This paper presents the outlines of the process feasibility studies: waste main characteristics, process specifications and main technical options, R and D strategy, mixed glass / metal package description, basic studies needed to develop the process and the matrix (glass/metal redox reactions, actinides partitioning...). (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗