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Uranium, thorium, and plutonium are effectively prepared by magnesium-zinc reduction, using uranium oxides, thorium dioxide, and plutonium dioxide as starting materials. This technique is also useful in performing reduction of metals such as zirconium and titanium.
Here in an oxidizing environment, the oxide formed on plutonium (Pu) metal is composed of a plutonium dioxide (PuO 2 ) top layer and a thin cubic plutonium sesquioxide (Pu 2 O 3 ) middle layer. In a reducing environment, the PuO 2 layer auto-reduces to cubic Pu 2 O 3 . The speed and extent of this conversion depend on the combination of temperature and time. While PuO 2 provides a strong diffusion barrier against unwanted Pu corrosion by gaseous species (like hydrogen), Pu 2 O 3 does not, since its crystal structure has chains of oxygen vacancies. The kinetics of the PuO 2 reduction are, therefore, of fundamental interest and enable researchers to better protect Pu from corrosion. In this report, the oxygen-diffusion-limited kinetics of the dioxide to sesquioxide conversion were obtained by dynamically heating a PuO 2 -covered Pu sample from 294 to 418 K in a high-vacuum vessel equipped with an in situ spectroscopic ellipsometer. The physical/chemical constraints in the conversion process were combined with the ellipsometry method of multi-sample analysis to track the percentage of PuO 2 and to compute the extent of Pu 2 O 3 formation. The resulting diffusion coefficients were compared against and then combined with complementary literature data to produce a comprehensive set of kinetic parameters for reliably modeling oxide conversion over a larger temperature range than spanned by prior studies. The extracted thermal activation energy barrier (43.7 kJ/mol) and pre-exponential factor (5.0 × 10 -10 cm 2 /s) for the oxygen-diffusion-limited process can be used to accurately model the PuO 2 to Pu 2 O 3 transformation in vacuum and/or inert gas applications.
Three gravimetric mixtures with 241 Am/ 243 Am isotope ratios at nominally 1:1, 20:1, and 200:1 were prepared for calibration of the thermal ionization mass spectrometer instruments used for americium isotopic and assay measurements by isotope dilution mass spectrometry. The total evaporation analytical technique was developed for high-accuracy and precision measurements of Am isotopic ratios. The technique was also applied to Am assay measurements using isotope dilution mass spectrometry. The Am isotope ratio and assay measurement techniques were utilized to characterize batches of americium oxide separated from plutonium materials in storage at Los Alamos National Laboratory in support of commercial use of 241 AmO 2 .
The thermal decomposition of plutonium oxalate to oxide is one of the most studied reactions in actinide chemistry but the intermediates have been the subject of debate for decades. Recent experimental data suggest that the decomposition of Pu(IV) oxalate in air undergoes dehydration first, then reduction to Pu(III) oxalate. The precise structural modifications that take place are unknown as experiments have not been able to fully characterize the intermediates at the microscopic level. To rectify this, we employed solid state density functional theory calculations at the PBE-D3 level with a Hubbard U correction to model the structures and energetics of potential dehydrated Pu(IV) and Pu(III) oxalate intermediate compounds. Based on the theoretical study presented here, the anhydrous analogues of the known hydrated Pu(IV) and Pu(III) oxalates are the preferred crystal structures formed through an overall exothermic reaction process. However, decomposition could proceed through the formation of a higher energy, more complicated 3D lattice structure with frustrated oxalate binding. It is expected that the intermediates presented here could be identified using spectroscopic techniques to enable further insight into the reaction mechanism.
In nuclear forensic analyses, measurements of actinide elements in a sample can assist with identifying interdicted or unknown materials. While these radiochemical signatures have been extensively investigated in uranium materials, less is known about bulk neptunium samples. This paper describes the measurement of trace actinide concentrations and isotopic profiles in a 237 Np oxide sample. Uranium, plutonium, americium, and curium concentrations and isotopic profiles in the sample were determined and deemed potentially useful for distinguishing different sources of 237 Np. Furthermore, several different potential radiochronometry systems were also investigated; discordant results indicate that the Np sample was never completely purified of other actinide elements, or that subsequent contamination of the sample occurred. Few prior studies of neptunium materials have been reported, and these data suggest that trace actinide constituents could provide unique signatures to identify material out of regulatory control.
Nuclear material operations pose unique hazards that are not encountered in other chemical, energy, or manufacturing industries. One of these hazards is the potential for a nuclear criticality accident when handling fissile isotopes such as 235 U and 239 Pu. These hazards are particularly high when fissile material is dissolved in solution as the neutron behaviors of the system can change rapidly with the physical and chemical changes accessible in solution. Current estimates of solution density used for criticality safety are outdated and hinder fissile material handling. Developing new estimates for these safety calculations requires experimental characterization and the derivation of empirical density models. We have derived a density law describing PuCl 3 /HCl/H 2 O solutions from experimental data characterizing solution density. Density data was treated using a Pitzer-derived eight-parameter equation, defining density as a function of analyte concentrations, temperature, and interactions between these variables. The model is predictive across the concentration and temperature ranges from which it was derived. The potential effects of varying oxidation states of plutonium, which are easily accessible in aqueous media, on the bulk solution density of the ternary system were also investigated. The resulting Pitzer-derived density law was applied to a nuclear criticality safety model, and the impact of the experimental characterization of solution density relative to previous estimates was demonstrated to be significant and suggest that the current approach to estimating density in nuclear criticality safety calculations may lead to overly conservative controls.
Nuclear safeguards missions use gamma spectroscopy as a non-destructive measurement technique for examining nuclear materials. Despite advances in the development of detection equipment as well as software codes, one of the concerns is the lack of well-documented spectra needed to test and validate isotopic analysis codes for their applicability. To address this need, this work introduces IDB, an international database of the reference gamma spectra of uranium, plutonium and mixed oxide nuclear material samples. IDB provides access to well-characterized sets of gamma spectra described by rich metadata, including information on the sample, measurement configuration and detector specifications. These spectra are accessible in different formats, also compatible with analysis code standards, thus promoting their sustainability and maintenance.
Neutron multiplicity counting (NMC) techniques are widely used for nuclear materials accountability and international safeguards applications to quantitatively evaluate characteristic properties pertaining to fissile material. Mathematical models for NMC moments have been previously derived for systems that use capture-based detectors; however, these models are not applicable when scatter-based detectors are used because of “neutron cross talk.” Neutron cross talk occurs when a single neutron scatters and deposits energy above threshold into multiple detectors causing spurious increase in multiplicity counts; this, in turn, has caused fissile mass to be overestimated when not treated. In this paper, we propose new mathematical models derived from point kinetics to correct for neutron cross-talk effects up to any arbitrary order N, where N denotes the maximum number of counts a single neutron can cause. The new models were used to estimate the fissile mass of plutonium metal and oxide samples with effective 240 Pu mass ranging from 2.5 to 250 g. The adequacy of the models was confirmed using simulations of a conceptual scatter-based neutron multiplicity counter (e.g., organic scintillators) using MCNPX v2.7e with the PoliMi fission event generating extension. The fissile mass estimates with no correction for neutron cross-talk events yielded an average relative deviation from the true 240 Pu eff mass of 55.94% and 84.56% for metal and oxide samples, respectively. When neutron cross-talk events of order N = 2 are included in the model, the fissile mass estimates yielded an average relative deviation of 11.89% for metal and 13.21% for oxide samples. Accounting for neutron cross-talk events of order N = 3 resulted in fissile mass estimates with an average relative deviation of 9.58% and 10.51% for metal and oxide samples, respectively. These mass estimates were compared to a reference case (i.e., no neutron crosstalk effects) that yielded an average relative deviation of 6.81% and 4.77% for metal and oxide samples, respectively. In conclusion, the discrepancy between the estimates from the proposed model and the reference case is attributed to the assumed value of N, which sets a finite upper bound on the order of cross-talk events the model treats (i.e., the model for N = 3 assumes that a neutron will never cause more than three counts).
This focused review provides an overview and a framework for understanding local structure in metallic plutonium (especially the metastable fcc $δ$-phase alloyed with Ga) as it relates to self-irradiation damage. Of particular concern is the challenge of understanding self-irradiation damage in plutonium-bearing materials where theoretical challenges of the unique involvement of the 5f electrons in bonding limit the efficacy of molecular dynamics simulations and experimental challenges of working with radioactive material have limited the ability to confirm the results of such simulations and to further push the field forward. The main concentration is on extended X-ray absorption fine-structure measurements of $δ$-phase Pu, but the scope is broadened to include certain studies on plutonium intermetallics and oxides insofar as they inform the physics of damage and healing processes in elemental Pu. Here, the studies reviewed here provide insight into lattice distortions and their production, damage annealing and defect migration, and the importance of understanding and controlling sample morphology when interpreting such experiments.
The calorimeter in the transfer area in Building 7920 at the US Department of Energy’s Oak Ridge National Laboratory is used to measure the amount of 238 Pu in the Plutonium Heat Source Oxide. The calorimetry measurement is taken after the oxide is packaged in an ORISC (Oak Ridge Inner Shipping Capsule)/FSO (Fuel Storage Outer) assembly before loading into the Containment Vessel and shipping container. The equipment is used in three specific configurations: zero measurement (nothing in the sample cup), FSO measurement (actual measurement of 238 Pu), and reference calibration measurement (using the reference FSO as a known heat source). System checks were performed in July 2023 in preparation for scheduled material loadout. During these checks, personnel discovered that the reference FSO had experienced an electrical short in the heater cable and was no longer functional. The calorimeter was in the reference calibration measurement configuration at this time. Facility management was notified when the damage was discovered. The data from the Yokogawa recorder were pulled and analyzed for a span of time between September 2022 and July 2023. An unusual spike was found in the sample cup temperature data that started on October 19, 2022, and ended on October 20, 2022. The sample cup reached a temperature of 191.1°C. The maximum allowable temperature for the calorimeter thermopile to reach is 220°C based on the manufacturer statement provided in Appendix B of this report [1]. The calorimeter thermopile and the sample cup thermocouple are physically close to each other; therefore, the data suggest that the calorimeter itself never saw a temperature in excess of 191.1°C. Physical damage present on the cable, tape, and insulation suggests that the temperature reached a higher value in some locations within the sample cup than the data shows. Because of this discrepancy, testing of the calorimeter was required to confirm that the calorimeter is functioning the same as it was before the electrical short. The intent of this report is to assess the functionality of the calorimeter and determine if it is acceptable to use for 238 Pu loadout material measurement. Testing showed that the calorimeter is functionally equivalent to the initial calibration that was performed in the summer of 2021, and thus, the calorimeter was cleared to be used for its intended purposes.
Estimates are presented of wastes arising from the reprocessing of 50 GWD/tonne, 5 year and 50 year cooled used nuclear fuel (UNF) from Light Water Reactors (LWRs), using the 'NUEX' solvent extraction process. NUEX is a fourth generation aqueous based reprocessing system, comprising shearing and dissolution in nitric acid of the UNF, separation of uranium and mixed uranium-plutonium using solvent extraction in a development of the PUREX process using tri-n-butyl phosphate in a kerosene diluent, purification of the plutonium and uranium-plutonium products, and conversion of them to uranium trioxide and mixed uranium-plutonium dioxides respectively. These products are suitable for use as new LWR uranium oxide and mixed oxide fuel, respectively. Each unit process is described and the wastes that it produces are identified and quantified. Quantification of the process wastes was achieved by use of a detailed process model developed using the Aspen Custom Modeler suite of software and based on both first principles equilibrium and rate data, plus practical experience and data from the industrial scale Thermal Oxide Reprocessing Plant (THORP) at the Sellafield nuclear site in the United Kingdom. By feeding this model with the known concentrations of all species in the incoming UNF, the species and their concentrations in all product and waste streams were produced as the output. By using these data, along with a defined set of assumptions, including regulatory requirements, it was possible to calculate the waste forms, their radioactivities, volumes and quantities. Quantification of secondary wastes, such as plant maintenance, housekeeping and clean-up wastes, was achieved by reviewing actual operating experience from THORP during its hot operation from 1994 to the present time. This work was carried out under a contract from the United States Department of Energy (DOE) and, so as to enable DOE to make valid comparisons with other similar work, a number of assumptions were agreed. These include an assumed reprocessing capacity of 800 tonnes per year, the requirement to remove as waste forms the volatile fission products carbon-14, iodine-129, krypton-85, tritium and ruthenium-106, the restriction of discharge of any water from the facility unless it meets US Environmental Protection Agency drinking water standards, no intentional blending of wastes to lower their classification, and the requirement for the recovered uranium to be sufficiently free from fission products and neutron-absorbing species to allow it to be re-enriched and recycled as nuclear fuel. The results from this work showed that over 99.9% of the radioactivity in the UNF can be concentrated via reprocessing into a fission-product-containing vitrified product, bottles of compressed krypton storage and a cement grout containing the tritium, that together have a volume of only about one eighth the volume of the original UNF. The other waste forms have larger volumes than the original UNF but contain only the remaining 0.1% of the radioactivity. (authors)
The panel focused on results-based project execution and ways to improve the effectiveness of program and project-specific decisions by gearing them to consistently achieving timely, cost-efficient, and sustainable results. Panelists discussed the complexities of making sound, actionable decisions in the face of budgetary, resource and technological constraints. Toward that end, the 10 panelists responded to the following questions: 1. What decision-making process has been most effective for you and your project team? 2. How effective are the incentives in your contract? 3. What would you be doing differently if your project were being executed on purely commercial terms? 4. Are your Contractor Assurance Programs effective? 5. Have we challenged industry and national laboratories to deliver revolutionary rather than evolutionary technologies to solve challenges? 6. What can we do to make stakeholder involvement more meaningful? 7. How do you apply lessons learned from events and issues like the Mixed Oxide Facility (MOX), the Plutonium Finishing Plant (PFP) event, and the Waste Isolation Pilot Plant (WIPP) incident?.
Mixed oxides (MOX), in the context of nuclear fuels, are a mixture of the oxides of heavy actinide elements such as uranium, plutonium and thorium. The interest in the UO 2 -PuO 2 system arises from the fact that these oxides are used both in fast breeder reactors (FBRs) as well as in pressurized water reactors (PWRs). The thermal conductivity of UO 2 fuel is an important material property that affects fuel performance since it is the key parameter determining the temperature distribution in the fuel, thus governing, e.g., dimensional changes due to thermal expansion, fission gas release rates, etc. For this reason it is important to understand the thermal conductivity of MOX fuel and how it differs from UO 2 . Here, molecular dynamics (MD) simulations are carried out to determine quantitatively, the effect of mixing on the thermal conductivity of U x Pu 1-x O 2 , as a function of PuO 2 concentrations, for a range of temperatures, 300 – 1500 K. The results will be used to develop enhanced continuum thermal conductivity models for MARMOT and BISON by INL. These models express the thermal conductivity as a function of microstructure state-variables, thus enabling thermal conductivity models with closer connection to the physical state of the fuel.
We present and discuss the operational principle of a new fast-neutron detector concept suitable for either energy-selective imaging or for imaging spectroscopy. The detector is comprised of a series of energy-selective stacks of converter foils immersed in a noble-gas based mixture, coupled to a position-sensitive charge readout. Each foil in the various stacks is made of two layers of different thicknesses, fastened together: a hydrogen-rich (plastic) layer for neutron-to-proton conversion, and a hydrogen-free coating to selectively stop/absorb the recoil protons below a certain energy cut-off. The neutron-induced recoil protons, that escape the converter foils, release ionization electrons in the gas gaps between consecutive foils. The electrons are then drifted towards and localized by a position-sensitive charge amplification and readout stage. Comparison of the images detected by stacks with different energy cut-offs allows energy-selective imaging. Neutron energy spectrometry is realized by analyzing the responses of a sufficient large number of stacks of different energy response and unfolding techniques. In this paper, we present the results of computer simulation studies and discuss the expected performance of the new detector concept. Potential applications in various fields are also briefly discussed, in particularly, the application of energy-selective fast-neutron imaging for nuclear safeguards application, with the aim of determining the plutonium content in Mixed Oxide (MOX) fuels.
The U.S. Department of Energy (DOE) is preparing a Surplus Plutonium Disposition (SPD) Supplemental Environmental Impact Statement (SEIS). Included in the evaluation are up to 6 metric tons (MT) of plutonium in the form of impure oxides and metals for which a disposition plan has not been decided, among options that include preparation as feed for the Mixed Oxide Fuel Fabrication Facility; disposing to high-level waste through the Savannah River Site (SRS) HB Line and H Canyon; can-in-canister disposal using the SRS Defense Waste Processing Facility; and preparation for disposal at the Waste Isolation Pilot Plant (WIPP). DOE and SRS have identified at least 0.5 MT of plutonium that, because of high levels of chemical and isotopic impurities, is impractical for disposition by methods other than the WIPP pathway. Characteristics of these items and the disposition strategy are discussed.
NASA and the Department of Energy (DOE) are currently working together to reestablish a 238Pu supply capability using DOE's existing facilities and reactors. The effort is being led by Oak Ridge National Laboratory (ORNL). Target rods, containing neptunium oxide (NpO2), are fabricated at ORNL and irradiated in the ORNL High Flux Isotope Reactor (HFIR) currently and soon will be irradiated in the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). Irradiated targets are processed in hot cells at the ORNL Radiochemical Engineering Center to recover the plutonium (Pu) product and unconverted neptunium (Np) for recycle. The 238PuO2 product is shipped to Los Alamos National Laboratory (LANL) for fabrication of heat source pellets. Key activities, such as the transport of the neptunium to ORNL, irradiation of neptunium, and chemical processing to recover the newly generated 238Pu, have been demonstrated with the initial amounts of ~100 g heat-source plutonium oxide (HS PuO2) produced. Product samples have been shipped to LANL for evaluation, including chemical impurity analysis. This paper will examine the status of producing new 238Pu from irradiated targets.
Oak Ridge National Laboratory (ORNL) is investigating flowsheets to enhance processing efficiencies and to address waste streams associated with recovery of americium (Am) and curium (Cm) from Mark-42 (Mk-42) target materials stored at ORNL. The objective of this work was to identify the most effective flowsheet with which to process the 104 Mk-42 oxide capsules holding a total of 80 g of plutonium (Pu), 190 g of Cm, 480 g of Am, and 5 kg of lanthanide (Ln) oxides for the recovery and purification of the Am/Cm for future use as feedstock for heavy actinide production. Studies were also conducted to solidify the process flowsheet waste streams for disposal. ORNL is investigating flowsheets to enhance processing efficiencies and address waste streams associated with recovery of Am and Cm from Mk-42 target materials stored at ORNL. A series of small-scale runs are being performed to demonstrate an improved process to recover Am/Cm and to optimize the separations of Ln fission products from the Am/Cm constituents. The first of these runs has been completed using one of the Am/Cm/Ln oxide capsules stored at ORNL. The demonstration run showed promising results with a Ln DF of 40 for the Am/Cm product and an Am/Cm DF of 75 for the Ln product. In addition, the total losses of Am, Cm, and Ln to the waste solvents and raffinates were very low at <0.2%, 0.02%, and 0.04%, respectively. However, the Ln-actinide separation was less than desired. For future Reverse TALSPEAK demonstration runs, several parameters will be adjusted (flow rates, the ratio of scrub to strip stages, etc.) to improve the removal of Ln from the actinides. The next step will also include scale-up of the processing flowsheet to use more concentrated solutions (15 g/L Ln versus 5 g/L) and larger volumes and to recycle the HDEHP solvent. This should improve the overall processing efficiency and further reduce losses to waste streams. Studies have been performed with simulated wastes to develop solidification processes for disposal of the secondary waste streams generated by this flowsheet. Formulations were successfully developed for all the waste simulants. Additional tests with actual waste will be the next step in this effort. Future plans are to process all of the remaining 103 capsules in storage at ORNL. A nine-capsule test is now under way to provide additional information to scale-up the process to a target 20-capsule batch size for future processing runs. (authors)
In the system UO{sub 2}(NO{sub 3}){sub 2}–PuO{sub 2}(NO{sub 3}){sub 2}–HNO{sub 3}–H{sub 2}O with the ratio Pu/(U + Pu) = 0.3–0.5 and stabilization of the pair U(VI)–Pu(VI), the crystallization of (U, Pu)O{sub 2}(NO{sub 3}){sub 2}·6H{sub 2}O occurs in accordance with the metric of the phase diagram of the system UO{sub 2}(NO{sub 3}){sub 2}–HNO{sub 3}–H{sub 2}O with coefficient of cocrystallization of plutonium 0.804 ± 0.028. This condition holds in the sector of the working lines of the crystallization process that correspond to the minimum content of uranium in the mother solution. The degree of enrichment of the mother solution is determined by the crystallization temperature, i.e., the mass fraction of the mother solution in the total mass of the system. The constancy of the coefficient of cocrystallization with the technologically important parameters of the process makes it possible to use the metric of the solubility diagram of the system UO{sub 2}(NO{sub 3}){sub 2}–HNO{sub 3}–H{sub 2}O to calculate the crystallization of (U, Pu)O{sub 2}(NO{sub 3}){sub 2}·6H{sub 2}O with the crystalline phase with the required composition being obtained.