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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Analysis of neptunium oxides produced through modified direct denitration

Production of neptunium-237 ( 237 Np) target materials for plutonium-238 ( 238 Pu) radioisotope thermoelectric generators (RTGs) for deep space exploration requires advanced chemistry and engineering development. Currently, the domestic Pu-238 Supply Program at Oak Ridge National Laboratory produces neptunium dioxide (NpO 2 ) for target material using a modified direct denitration (MDD) flowsheet. Although the chemistry, reaction mechanisms, and product characteristics of MDD are well understood for uranium, corresponding studies of the neptunium system are still needed to continue optimization of target material properties, production equipment design, and production flowsheets. Here, the objective of this work is to characterize crystalline phases, morphology, surface texture, and particle size of NpO 2 produced via MDD reactions. Solid-phase characterization techniques, including powder X-ray diffraction (pXRD) and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), were employed to achieve this objective. Subsequent data processing using the Morphological Analysis for Material Attribution (MAMA) software was performed to analyze particle morphology and size. Broadly, the powders were found to contain a mixture of NpO 2 and Np 2 O 5 after denitration with a variety of morphologies. After high-firing, the product was found to be NpO 2 with a typical polycrystalline oxide morphology and a grain size ranging from 0.72 to 0.94 µm. These analyses provide knowledge on the reaction pathway for a non-traditional NpO 2 synthesis method and offer additional unique insight into production-scale environments for transuranic materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2012

Simplified treatment of exact resonance elastic scattering model in deterministic slowing down equation

Simplified treatment of resonance elastic scattering model considering thermal motion of heavy nuclides and the energy dependence of the resonance cross section was implemented into NJOY [1]. In order to solve deterministic slowing down equation considering the effect of up-scattering without iterative calculations, scattering kernel for heavy nuclides is pre-calculated by the formula derived by Ouisloumen and Sanchez [2], and neutron spectrum in up-scattering term is expressed by NR approximation. To check the verification of the simplified treatment, the treatment is applied to U-238 for the energy range from 4 eV to 200 eV. Calculated multi-group capture cross section of U-238 is greater than that of conventional method and the increase of the capture cross sections is remarkable as the temperature becomes high. Therefore Doppler coefficient calculated in UO{sub 2} fuel pin is calculated more negative value than that on conventional method. The impact on Doppler coefficient is equivalent to the results of exact treatment of resonance elastic scattering reported in previous studies [2-7]. The agreement supports the validation of the simplified treatment and therefore this treatment is applied for other heavy nuclide to evaluate the Doppler coefficient in MOX fuel. The result shows that the impact of considering thermal agitation in resonance scattering in Doppler coefficient comes mainly from U-238 and that of other heavy nuclides such as Pu-239, 240 etc. is not comparable in MOX fuel. (authors)

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2016

Characterization of U(VI)-Bearing Precipitates Produced by Ammonia Gas Injection Technology for Unsaturated Sediments - 16600

The processing of irradiated fuel to extract plutonium for the nuclear arsenal has resulted in a legacy of uranium contamination in the vadose zone (VZ) of the Hanford 200 Area. This contamination is a potential source for groundwater contamination, posing a risk to receptors through water uptake from contaminated wells or discharges to surface water. The injection of reactive gases is an innovative technology being evaluated for reducing the mobility of radionuclide contaminants in the Hanford vadose zone. Ammonia (NH{sub 3}) gas in particular has been used to reduce uranium mobility in laboratory scale studies and is being evaluated for field scale application. The sediment of the Hanford vadose zone is composed of a complex of mineral phases including quartz, feldspar, mica, and calcium carbonates. The silica content in the 200 Area subsurface markedly outweighs the majority of elements, with aluminum following closely. The injection of ammonia gas into the vadose zone is associated with an increase in pH conditions as the gas partitions into the pore water. The resulting alkaline conditions significantly increase the solubility of some aluminum and silicate-containing minerals within the system. As pH decreases to natural conditions, the aluminosilicate minerals will precipitate, potentially coating and sequestering the uranium contaminants. Although previous laboratory scale tests have shown decreased uranium mobility, there are many questions regarding the application of the remediation method to 200 Area vadose zone conditions. In particular, additional testing is required to understand the impact of various environmental factors on the formation of uranium mineral phases with the application of the NH{sub 3} injection method. In order to answer some of the unknowns regarding this remediation technology for the 200 Area vadose zone, an effort was made to characterize the uranium-bearing precipitates being formed with the injection of ammonia gas. Rather than a sediment-water system, a synthetic pore water solution was prepared using the ion concentrations relevant to the 200 Area vadose zone. These solutions were limited to select constituents believed to play a major role in the remediation process. The use of this carefully composed solution allows for the thorough evaluation of the contribution the variable components make to the formation of the solid analyte. The characterization of solid samples was attempted using a host of complementary analytical techniques including scanning electron microscopy with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). Though characterization of the samples is ongoing, the data produced thus far has allowed for the imaging and X-ray spectroscopy of the solid uranium phases produced as well as a tentative identification of cejkaite (Na{sub 4}(UO{sub 2})(CO{sub 3}){sub 3}) as the major uranium mineral phase. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Decommissioning of a facility in a historical reactor at SRS: achieving both historical significance preservation and effective in-situ decommissioning - 15275

The Savannah River Site (SRS) is an 802 square-kilometer United States Department of Energy (US DOE) nuclear facility located along the Savannah River near Aiken, South Carolina, where Management and Operations are performed by Savannah River Nuclear Solutions, LLC (SRNS). In 2004, US DOE recognized SRS as a structure within the Cold War Historic District of national, state and local significance because it is composed of the first generation of facilities constructed and operated from 1950 through 1989 to produce plutonium and tritium for our nation's defense. US DOE agreed to manage the SRS 105-C Reactor Facility as a potentially historic property due to its significance in supporting the U.S. Cold War Mission and for potential for future interpretation. The Disassembly Basin (DB) in C Reactor was evaluated for action under CERCLA. Data indicated there were over 830 curies of radioactivity associated with the basin sediments and approximately 9.1 million (M) liters (L) of contaminated water, not including a large quantity of activated reactor equipment, scrap metal, and debris on the basin floor. The release of DB water could potentially migrate to the aquifer and contaminate groundwater. The need for an action was identified to reduce risks to personnel in the facility and to eliminate the possible release of contaminants into the environment. In-situ decommissioning was selected as the remedy. The remedial action proceeded in stages: -Above-grade modifications to the interior of DB building -Relocation of irradiated scrap and reactor components to the deepest segments of the DB - Construction of a metal building to house evaporators - Forced evaporation of the DB's radiologically contaminated water - Grouting with special hybrid grouts - Removal of the evaporators and temporary building. Since the building itself was not demolished and will remain unchanged in appearance with the exception of filling the DB with grout, this ISD removal action/methodology did not adversely impact the historical significance of the 105-C Reactor Building, in accordance with the National Historic Preservation Act, nor did it adversely affect the ability to determine the full extent and details of preservation at some later date. Both special hybrid grout materials met all requirements. Overall average 7-day compressive strength for the dry area mix was 1.54 MPa (223 psi) and for the underwater mix 2.94 MPa (427 psi).Overall 28-day compressive strength for the dry area mix was 2.88 MPa (417 psi) and for the underwater mix 4.99 MPa (724 psi). A limited amount of testing was also performed at 91 days, where the overall compressive strength for the dry area mix was found to be 9.40 MPa (1363 psi) and for the underwater mix 13.98 MPa (2028 psi). All compressive strength values far exceeded the 0.34 MPa (50 psi) minimum requirements. The special, flowable-fill grouts designed and used for P- and R-Reactor ISD and used again for this 105-C ISD removal action resulted in considerable labor, cost, and schedule savings versus conventional materials. As an added bonus/benefit, the CO{sub 2} footprint of the SRS C-Reactor DB ISD was minimized by using a small amount of cement and byproduct material to produce the structural fill materials. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

Behavior of fuel with zirconium alloy cladding in reactivity-initiated accident and loss-of-coolant accident - 2016-0090

Along with our colleagues at the Japan Atomic Energy Research Institute (JAERI) and Japan Atomic Energy Agency (JAEA), we have performed extensive research programs for more than 2 decades and have developed a better understanding of fuel behavior under accident conditions. Data and findings from these research programs have provided the technical basis directly and indirectly for regulatory criteria in Japan and other countries. This paper reviews and summarizes the major outcomes from the research programs performed at JAERI and JAEA facilities and identifies further research needs. The programs aim to generate data and models to (1) evaluate the adequacy of present safety criteria and safety margins; (2) create a database for the future regulation of higher-burnup UO{sub 2} and mixed-oxide (MOX) fuels, new cladding, and pellets; (3) provide adequately mechanistic computer codes for regulatory application; (4) promote a better understanding of phenomena that appear in high-burnup regions and MOX fuels, such as rim effect and an effect of plutonium agglomerates in MOX fuels, and to evaluate those effects on fuel behavior in accident conditions; and (5) to assess fuel behaviors with higher fuel duty, such as plant power uprates, longer operating cycles, and water chemistry changes. The programs comprise reactivity-initiated accident studies, including pulse-irradiation experiments in the Nuclear Safety Research Reactor, cladding mechanical tests, and the development and verification of RANNS; loss-of-coolant accident tests, including integral thermal shock tests, oxidation rate measurements, and cladding mechanical tests; development and verification of a computer code FEMAXI-6 that simulates high-burnup fuel behavior under normal operating and abnormal transient conditions; and studies on phenomena specific to high-burnup regions, including thermal property measurements, experimental and analytical simulation of rim structure formation, cladding mechanical tests on effects of hydrides, etc. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2016

Thermal Safety Analyses for the Production of Plutonium-238 at the High Flux Isotope Reactor

There has been a considerable effort over the previous few years to demonstrate and optimize the production of plutonium-238 ( 238 Pu) at the High Flux Isotope Reactor (HFIR). This effort has involved resources from multiple divisions and facilities at the Oak Ridge National Laboratory (ORNL) to demonstrate the fabrication, irradiation, and chemical processing of targets containing neptunium-237 ( 237 Np) dioxide (NpO 2 )/aluminum (Al) cermet pellets. A critical preliminary step to irradiation at the HFIR is to demonstrate the safety of the target under irradiation via documented experiment safety analyses. The steady-state thermal safety analyses of the target are simulated in a finite element model with the COMSOL Multiphysics code that determines, among other crucial parameters, the limiting maximum temperature in the target. Safety analysis efforts for this model discussed in the present report include: (1) initial modeling of single and reduced-length pellet capsules in order to generate an experimental knowledge base that incorporate initial non-linear contact heat transfer and fission gas equations, (2) modeling efforts for prototypical designs of partially loaded and fully loaded targets using limited available knowledge of fabrication and irradiation characteristics, and (3) the most recent and comprehensive modeling effort of a fully coupled thermo-mechanical approach over the entire fully loaded target domain incorporating burn-up dependent irradiation behavior and measured target and pellet properties, hereafter referred to as the production model. These models are used to conservatively determine several important steady-state parameters including target stresses and temperatures, the limiting condition of which is the maximum temperature with respect to the melting point. The single pellet model results provide a basis for the safety of the irradiations, followed by parametric analyses in the initial prototypical designs that were necessary due to the limiting fabrication and irradiation data available. The calculated parameters in the final production target model are the most accurate and comprehensive, while still conservative. Over 210 permutations in irradiation time and position were evaluated, and are supported by the most recent inputs and highest fidelity methodology. The results of these analyses show that the models presented in this report provide a robust and reliable basis for previous, current and future experiment safety analyses. In addition, they reveal an evolving knowledge of the steady-state behavior of the NpO 2 /Al pellets under irradiation for a variety of target encapsulations and potential conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2015

The thermal conductivity of mixed fuel U x Pu 1-x O 2 : molecular dynamics simulations

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.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2019

MIS High-Purity Uranium/Plutonium Oxide Metal Oxidation Product SCP711-56 (SSR135): Final Report

A high-purity uranium/plutonium mixed oxide material from the Material Identification and Surveillance (MIS) Program inventory has been studied with regard to gas generation and corrosion in a storage environment. Sample SCP711-56 represents process plutonium oxides from mixed oxides at the Hanford Site, byproduct plutonium/uranium mixed oxides at the Rocky Flats Plant, Hanford Site mixed oxides at Savannah River, mixed oxides from alloy oxidation at Savannah River, scrap mixed oxides at Savannah River and plutonium/uranium oxide at Los Alamos National Laboratory that are currently stored in 3013 containers. After calcination to 950°C the material contains 17% fuel grade plutonium and 68% uranium with approximately 1.5% impurities and the remainder principally oxygen. This study followed over time the gas pressure of a sample with nominally 0.1 wt% water in a sealed container with an internal volume scaled to 1/500th of the volume of a 3013 container. Gas compositions were measured periodically over approximately 4 years. The maximum observed gas pressure was 115 kPa. The increase over the initial pressure of 83 kPa was primarily due to generation of carbon dioxide and nitrogen gases. A small amount of hydrogen was generated and oxygen was consumed. At the completion of the study, the internal components of the sealed container showed signs of corrosion, including pitting.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Thermal decomposition of neptunyl ammonium nitrate: mechanistic insights and structural characterization of the Np 2 O 5 intermediate phase

Neptunium (Np) possesses a rich and unique chemistry that often diverges from other actinide elements yet remains relatively underexplored compared with the other light actinides. A resurgence of interest in Np has been spurred by the application of 237 Np for plutonium-238 ( 238 Pu) production for use in radioisotope thermoelectric generators (RTGs), necessitating evaluation of Np chemical reactions and materials. The work presented here studied the thermal decomposition of neptunyl ammonium nitrate (NH 4 Np VI O 2 (NO 3 ) 3 ) for synthesis of neptunium dioxide (NpO 2 ), which is the target material used for production of 238 Pu. Additionally, structural characterization of the intermediate solid Np pentoxide (Np 2 O 5 ) was performed. Advanced solid-state characterization techniques, including simultaneous thermal analysis (STA), powder X-ray diffraction (pXRD), Raman spectroscopy, and density functional theory (DFT) modeling have been combined to study the reaction pathways. Analysis revealed that NH 4 Np VI O 2 (NO 3 ) 3 thermally decomposes to a proposed neptunyl nitrate intermediate, followed by Np 2 O 5 and finally NpO 2 , all within the temperature range of 150 °C–600 °C. Further characterization of the pentoxide intermediate provided the first Raman spectra of pure-phase Np 2 O 5 and associated DFT modeling confirmed Raman peak assignments for this phase. These findings provide mechanistic information to advance production of the critical radioisotope 238 Pu and advance the state of knowledge on Np materials chemistry using modern characterization techniques.

Lawson, Kathryn M. [Oak Ridge National Laboratory ↗
DOE OSTI2023

Characterization of Aluminum Metal Powders for Plutonium-238 Program

As part of radioisotope thermoelectric generator (RTG) production for power sources in deep space exploration, Oak Ridge National Laboratory (ORNL) produces plutonium-238 ( 238 Pu). To produce 238 Pu, neptunium-237 ( 237 Np) targets are fabricated at ORNL and subsequently irradiated at the High Flux Isotope Reactor (HFIR) at ORNL and the Advanced Test Reactor (ATR) at Idaho National Laboratory (INL). Specifically, current flowsheets utilize neptunium dioxide ( 237 NpO 2 ) targets. Aluminum (Al) powder is blended with 237 NpO 2 target material to improve thermal conductivity during irradiation. The current composition of 237 NpO 2 /Al pellets (i.e., cermets, or ceramic–metallics) is 20% 237 NpO 2 , 70% Al, and 10% void space. Al powders utilized by the 238 Pu program are high-fired under vacuum before blending into targets. The primary objective of this work is to measure the physical, chemical, and thermal properties of Al before and after the high-firing process. Properties of interest include the morphology, surface texture, particle size, crystal phase(s), and thermal conductivity of the material. These properties are measured with existing materials characterization equipment at ORNL, including powder x-ray diffraction (pXRD), scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS), laser flash analysis (LFA), and thermogravimetric analysis (TGA). A secondary objective of this work is to compare the Al powders before and after the high-firing procedure to determine the effects of high-firing on chemical, physical, and thermal properties and to determine the efficacy of the high-firing process.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Milestone report: The simulation of radiation driven gas diffusion in UO 2 at low temperature

Below 1000 K it is thought that fission gas diffusion in nuclear fuel during irradiation occurs through atomic mixing due to radiation damage. This is an important process for nuclear reactor performance as it affects fission gas release, particularly from the periphery of the pellet where such temperatures are normal. Here we present a molecular dynamics study of Xe and Kr diffusion due to irradiation. Thermal spikes and cascades have been used to study the electronic stopping and ballistic phases of damage, respectively. Our results predict that O and Kr exhibit the greatest diffusivity and U the least, while Xe lies in between. It is concluded that the ballistic phase does not sufficiently account for the experimentally observed diffusion. Preliminary thermal spike calculations indicate that the electronic stopping phase generates greater fission gas displacement than the ballistic phase, although further calculation must be carried out to confirm this. A good description of the system by the empirical potentials is important over the very wide temperatures induced during thermal spike and damage cascade simulations. This has motivated the development of a parameter set for gas-actinide and gas-oxygen interactions that is complementary for use with a recent many-body potential set. A comprehensive set of density functional theory (DFT) calculations were used to study Xe and Kr incorporation at a number of sites in CeO 2 , ThO 2 , UO 2 and PuO 2 . These structures were used to fit a potential, which was used to generate molecular dynamics (MD) configurations incorporating Xe and Kr at 300 K, 1500 K, 3000 K and 5000 K. Subsequent matching to the forces predicted by DFT for these MD configurations was used to refine the potential set. This fitting approach ensured weighted fitting to configurations that are thermodynamically significant over a broad temperature range, while avoiding computationally expensive DFT-MD calculations. The resultant gas potentials were validated against DFT binding energies and are suitable for simulating combinations of Xe and Kr in solid solutions of CeO 2 , ThO 2 , UO 2 and PuO 2 , providing a powerful tool for the atomistic simulation of conventional nuclear reactor fuel UO 2 as well as advanced MOX fuels.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Neptunium mononitride as a target material for Pu-238 production

Deep space exploration requires specialized sources for both thermal and power applications. Radioactive decay heat of plutonium-238 (238Pu) provides these sources in the form of radioisotope thermoelectric generators (RTGs). The 238 Pu is produced via neutron capture reaction involving neptunium-237 ( 237 Np) target material. Continual optimization of 237 Np target materials and evaluation of potential alternative targets for production of 238 Pu RTGs are advantageous for meeting ongoing space power system resource requirements. Current production of 238 Pu for RTGs for the United States space program utilizes neptunium dioxide ( 237 NpO 2 ) targets; however, the use of neptunium mononitride ( 237 NpN) presents an opportunity to increase the mass of 237 Np per target compared to the dioxide form, as well as increase the thermal conductivity of the target. To assess the viability of a 237 NpN target material, the material chemistry must be thoroughly evaluated, including synthesis methods and dissolution and reprocessing schemes. This review presents a summary of synthesis pathways for 237 NpN based on published literature on actinide mononitrides. Specific literature on 237 NpN is limited, necessitating evaluation of other actinide systems to gather parallels. This suggests a need for additional experimental studies on 237 NpN. A particular limitation in the existing literature is a lack of information on the differences in material characteristics, such as morphology, particle size, and trace chemical impurities, as a function of synthesis method. These parameters may affect subsequent reactor performance or dissolution of irradiated targets. The evaluation of existing literature is presented with a focus on the efficacy of 237 NpN targets for 238 Pu production.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

MIS High-Purity Plutonium/Uranium Oxide Hydride Product 5501407 (SSR129): Final Report

A high-purity uranium/plutonium mixed oxide material from the Material Identification and Surveillance (MIS) Program inventory has been studied with regard to gas generation and corrosion in a storage environment. Sample 5501579 represents process plutonium oxides from high purity mixed oxides and mixed oxides from alloy oxidation at Hanford, hydride oxide from Rocky Flats, and mixed oxides from alloy oxidation and scrap mixed oxides at Savannah River that are currently stored in 3013 containers. This study followed over time the gas pressure of two samples of this material with nominally 0.5 wt% water in a sealed container with an internal volume scaled to 1/500th of the volume of a 3013 container. The first experiment studied a mixture of 60% as-received material (AR) and 40% material that had been calcined at 950 °C. The mixture contained 66% weapons grade plutonium and 11% uranium, with approximately 7.3% impurities and the remainder principally oxygen. A second experiment studied material calcined at 950 °C which contained approximately 4.3% impurities and similar uranium and plutonium content. Gas compositions were measured periodically over approximately 3.5 years in the first container and 20 months for the second container, which was terminated early due to an inadvertent container pumpdown. The maximum observed gas pressures were 152 kPa and 161 kPa, respectively. The increase over the initial pressures of 82 kPa and 88 kPa, respectively, was primarily due to generation of carbon dioxide and nitrogen gases. In the container with the AR/calcined mixture, a small amount of hydrogen and oxygen was generated and was consumed. In the container with calcined material only, hydrogen partial pressure of 18.9 kPa was measured. A small amount of oxygen was generated and was consumed. At the completion of the study, the internal components of both sealed containers showed signs of corrosion

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Destruction of Oxalate in HB-Line using Sodium Permanganate

During HB-Line Pu-239 operations, plutonium (Pu) is precipitated as Pu(IV) oxalate [Pu(C2O 4 )2] using oxalic acid (H 2 C 2 O 4 ). Following the removal of precipitate by filtration, the H 2 C 2 O 4 must be removed from solution before the filtrate can be discharged to H-Canyon under one criticality-control strategy. HB-Line uses sodium permanganate (NaMnO 4 ) solution to oxidize H 2 C 2 O 4 to carbon dioxide (CO 2 ) and water. Excess NaMnO 4 , which reacts to form manganese dioxide (MnO 2 ) solids, is converted to soluble manganese via a reaction with sodium nitrite (NaNO 2 ). HB-Line Engineering requested the Savannah River National Laboratory (SRNL) to verify the quantities and addition rates of NaMnO4 and NaNO 2 required to react excess oxalic acid and MnO 2 solids without over-pressurization of the reaction vessel.

Pierce, R. A.↗
DOE OSTI2022

MIS Shelf-Life Final Report for Plutonium Oxide Item CAN92 (SSR147) from Rocky Flats Analytical Laboratory Operations

A plutonium/uranium oxide material from the Material Identification and Surveillance (MIS) Program inventory has been studied to determine the gas generation and corrosion behavior in a storage environment. Sample CAN92 represents plutonium/uranium oxides stored in 3013 containers. The material originated in the analytical laboratory at Rocky Flats. This study followed over time the gas pressure and composition of a sample with nominally 0.5 wt% water in a sealed container with an internal volume scaled to 1/400th of the volume of a 3013 container. Gas compositions had been measured periodically over 5 ½ years. The maximum observed gas pressure from gas generation was 117 kPa. The increase over the initial pressure of 77.5 kPa was largely due to the generation of nitrogen and carbon dioxide with minor amounts of hydrogen and nitrous oxide. The internal components of SSR147 were inspected 6.5 years after it was removed from the array. The inside surfaces of the inner bucket exposed to the original sample for 1,937 days had an etched appearance and general corrosion. No pitting was observed on the inner bucket that held the sample.

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

Chemical Differences Between Sludge Solids at the F and H Area Tank Farms

The primary source of waste solids received into the F Area Tank Farm (FTF) was from PUREX processing performed to recover uranium and plutonium from irradiated depleted uranium targets. In contrast, two primary sources of waste solids were received into the H Area Tank Farm (HTF): a) waste from PUREX processing; and b) waste from H-modified (HM) processing performed to recover uranium and neptunium from burned enriched uranium fuel. Due to the differences between the irradiated depleted uranium targets and the burned enriched uranium fuel, the average compositions of the F and H Area wastes are markedly different from one another. Both F and H Area wastes contain significant amounts of iron and aluminum compounds. However, because the iron content of PUREX waste is higher than that of HM waste, and the aluminum content of PUREX waste is lower than that of HM waste, the iron to aluminum ratios of typical FTF waste solids are appreciably higher than those of typical HTF waste solids. Other constituents present at significantly higher concentrations in the typical FTF waste solids include uranium, nickel, ruthenium, zinc, silver, cobalt and copper. In contrast, constituents present at significantly higher concentrations in the typical HTF waste solids include mercury, thorium, oxalate, and radionuclides U-233, U-234, U-235, U-236, Pu-238, Pu-242, Cm-244, and Cm-245. Because of the higher concentrations of Pu-238 in HTF, the long-term concentrations of Th-230 and Ra-226 (from Pu-238 decay) will also be higher in HTF. The uranium and plutonium distributions of the average FTF waste were found to be consistent with depleted uranium and weapons grade plutonium, respectively (U-235 comprised 0.3 wt% of the FTF uranium, and Pu-240 comprised 6 wt% of the FTF plutonium). In contrast, at HTF, U-235 comprised 5 wt% of the uranium, and Pu-240 comprised 17 wt% of the plutonium, consistent with enriched uranium and high burn-up plutonium. X-ray diffraction analyses of various FTF and HTF samples indicated that the primary crystalline compounds of iron in sludge solids are Fe 2 O 3 , Fe 3 O 4 , and FeO(OH), and the primary crystalline compounds of aluminum are Al(OH) 3 and AlO(OH). Also identified were carbonate compounds of calcium, magnesium, and sodium; a nitrated sodium aluminosilicate; and various uranium compounds. Consistent with expectations, oxalate compounds were identified in solids associated with oxalic acid cleaning operations. The most likely oxidation states and chemical forms of technetium are assessed in the context of solubility, since technetium-99 is a key risk driver from an environmental fate and transport perspective. The primary oxidation state of technetium in SRS sludge solids is expected to be Tc(IV). In salt waste, the primary oxidation state is expected to be Tc(VII). The primary form of technetium in sludge is expected to be a hydrated technetium dioxide, TcO 2 ⋅ xH 2 O, which is relatively insoluble and likely co-precipitated with iron. In salt waste solutions, the primary form of technetium is expected to be the very soluble pertechnetate anion, TcO 4 - . The relative differences between the F and H Tank Farm waste provide a basis for anticipating differences that will occur as constituents of FTF and HTF waste residue enter the environment over the long-term future. If a constituent is significantly more dominant in one of the Tank Farms, its long-term environmental contribution will likely be commensurately higher, assuming the environmental transport conditions of the two Tank Farms share some commonality. It is in this vein that the information cited in this document is provided - for use during the generation, assessment, and validation of Performance Assessment modeling results.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2014

Supercritical Fluid Extraction and Separation of Uranium from Other Actinides

This paper investigates the feasibility of separating uranium from other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of an extraction and counter current stripping technique, which would be a more efficient and environmentally benign technology for used nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U(VI), Np(VI), Pu(IV), and Am(III)) were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, the separation of uranium from plutonium in sc-CO2 modified with TBP was successful at nitric acid concentrations of less than 3 M in the presence of acetohydroxamic acid or oxalic acid, and the separation of uranium from neptunium was successful at nitric acid concentrations of less than 1 M in the presence of acetohydroxamic acid, oxalic acid, or sodium nitrite.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2013

Fabrication of Cerium Oxide and Uranium Oxide Microspheres for Space Nuclear Power Applications

Cerium oxide and uranium oxide microspheres are being produced via an internal gelation sol-gel method to investigate alternative fabrication routes for space nuclear fuels. Depleted uranium and non-radioactive cerium are being utilized as surrogates for plutonium-238 (Pu-238) used in radioisotope thermoelectric generators and for enriched uranium required by nuclear thermal rockets. While current methods used to produce Pu-238 fuels at Los Alamos National Laboratory (LANL) involve the generation of fine powders that pose a respiratory hazard and have a propensity to contaminate glove boxes, the sol-gel route allows for the generation of oxide microsphere fuels through an aqueous route. The sol-gel method does not generate fine powders and may require fewer processing steps than the LANL method with less operator handling. High-quality cerium dioxide microspheres have been fabricated in the desired size range and equipment is being prepared to establish a uranium dioxide microsphere production capability.

07 ISOTOPE AND RADIATION SOURCES↗