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The Actinide Material Processing and Power (AMPP) Division supports plutonium 238 science and manufacturing for NASA exploration, Defense Programs, Advanced Recovery and Integrated Extraction System (ARIES) for nuclear non-proliferation, Materials Recovery & Recycle to enable the future of our operations, and americium production to support well logging for the United States.
This progress report (Level 4 Milestone Number M4SF-22LL010302052) summarizes research conducted at Lawrence Livermore National Laboratory (LLNL) within the Crystalline Activity Number SF-22LL01030205. The research is focused on actinide and radionuclide sequestration in steel corrosion products.
Since 2011, the LLNL-LANL-TUNL collaboration has undertaken experimental measurements of the energy evolution of the chain fission product yields (FPY) from neutron-induced fission of 235 U, 238 U, and 239 Pu using quasi-monoenergetic neutrons produced at the TUNL 10 MV Van de Graaff accelerator. Our method relies on direct, post-irradiation γ-ray spectroscopy of γ-rays emitted by fission products in actinide targets, with multiple γ-ray spectra taken continuously for a period from a half-hour to three months from the end of irradiation. The main experimental results of this study have been published for eight incident neutron energies of En = 0.58, 1.37, 2.37, 3.6, 4.6, 5.5, 8.9 and 14.8 MeV [1–4]. For each incident energy, approximately 16 cumulative FPYs were determined, nearly all being high-yield fission products, i.e., those occurring in the peaks of the mass distributions. As will be described in this report, our FPY analysis has been significantly improved in every step of the process, reducing the overall systematic uncertainties compared to previously published data.
181 Ta is a refractory metal with several nuclear applications including neutron production targets, reactors, and tools for molten actinides. An updated evaluation of 181 Ta includes new measured data, RRR extended up to 2.5 keV (ENDF/B-8.0 upper range is 330 eV), URR extended to 100 keV (ENDF/B-8.0 upper range is 5 keV), and the consistent merging of URR with fast neutron region (Herman).
Irradiation tests are a key component of nuclear fuel development and identifying typical and atypical regions in the irradiated fuel volume relies on very few characterization techniques. The goal of the effort reported here is to provide complementary measurements adding to the available parameter space for post irradiation examination as well as to inform subsequent hot cell PIE examinations by identifying typical and atypical regions with respect to microstructure, tomographic data, or isotope densities. Pulsed neutrons, enabling diffraction as well as energy-resolved neutron imaging and neutron absorption resonance spectroscopy, offer unique capabilities for this purpose. Time-of-flight neutron diffraction has the potential to offer efficient, non-destructive and non-contact microstructural characterization of irradiated fuel specimen with spatial resolution of 1 mm 3 to 1 cm 3 while for energy-resolved neutron imaging (and by extension tomography) a resolution of 100 μm 3 was demonstrated. The potential results include crystallinity vs. amorphous volumes and microstructural information such as phase compositions, lattice strains (indicative of residual stresses or chemistry variations) and textures from the diffraction data as well as distances (e.g. pellet to cladding), cracks, and isotope densities of minor actinides, fission products as well as fission gas partial pressures e.g. in the plenum from energy resolved neutron imaging.
The aim of this whitepaper is to highlight the current capabilities and priorities of the US Heavy Element community and to provide the framework for a coordinated advancement of nuclear science from these studies. This is an organized effort to reflect on what has been achieved in the field given the recommendations and initiatives of the 2015 NSAC Long Range Plan, and on what can be realized in the next decade given current and possibly expanded investments. Current investments have positioned the US community to be among the world leaders in studies of the nuclear and chemical properties of the heaviest elements. These include studies of reaction mechanisms, moving us ever closer to the “island of stability”, in spectroscopy, allowing us to better understand nuclear structure at these extreme proton numbers, in chemical behavior, looking to determine how these elements should be placed on the Periodic Table, in performing the first measurements where isotopes are directly identified by their mass numbers, and in laying the foundation for a potential US-led new element discovery experiment. At present, the highest priority of the US Heavy Element community is to capitalize on the current investments by supporting the operations of US facilities at optimal values. These facilities include the Argonne Tandem Linac Accelerator System at Argonne National Laboratory and other Department of Energy facilities such as the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory, which has a dedicated superheavy element program, as well as university laboratories, including Texas A&M University. The High Flux Isotope Reactor at Oak Ridge National Laboratory is crucial to providing the radioactive isotopes required for heavy element science targets. This facility should be supported to provide the actinide materials that are essential for US-based science. Production of stable, rare isotopes for beam material, including 48 Ca, 50 Ti, 54 Cr and 58 Fe, at the Stable Isotope Production and Research Center is critical to continued research in heavy element science and should be a priority. The continued development of targets for heavy element science and retaining US-based expertise is critical for the heavy element community. This is an area that is currently under pressure. For example, the target laboratory at Argonne National Laboratory serves a broad community and is currently under threat due to loss of critical personnel. The skills needed to make targets for nuclear science and develop new targetry methods need to be supported long term at Argonne, Oak Ridge and Lawrence Livermore National Laboratories as well as maintaining the programs at Oregon State University and San José State University as vital pipelines for training students. Advances in theory are the foundation to understand how nuclei behave and to predict those behaviors in new circumstances. Progress in these studies will necessitate continued and new investment and access to high-performance computing. The future health of the heavy element field is dependent on the continuous support of talented early-career professionals at all levels. It is critical that opportunities continue to be created for the next generation to become established in heavy element research so that we can ensure the field is attracting and retaining the best minds for continued success. It is also clear that to ensure diversity of ideas, perspectives and techniques, we need to recruit diverse personnel that are trained at the best facilities. The heavy element community is in support of continued investment to programs with initiatives in diversity, equity, and inclusion. Looking to the next decade of research, support needs to maintain and grow US leadership in heavy element science. Specifically, new investments in state-of-the-art instrumentation will be essential to scientific development of the field and in expanding scientific knowledge. Advances in the next generation of electron cyclotron resonance ion sources, multi-reflection time-of-flight devices, laser spectroscopy, trapping methods and next generation alpha and gamma spectroscopy systems should be prioritized.
There are many elements of interest to the weapons community that include light elements, activation products, fission products, actinides, and heavy elements. Of course, that is the whole periodic table! In this memo we summarize a down-selected list, 22 of 118+ of elements that have or could serve as radiochemical diagnostic measurements. The simulations would need cross sections for nuclides (and metastable states) of these elements to be able to calculate values for comparison with debris measurements.
The solubility of An(III), which pertains to Pu(III), Am(III), and Cm(III), in brine is an important contributor in WIPP (Waste Isolation Pilot Plant) performance assessment (PA) models to calculate the potential release of transuranic elements in the near-field environment of the WIPP repository. Americium, although present in much smaller quantities than plutonium (~ 336 kg on year 2033 is potentially WIPP-bound primarily as Am-241), has a significant impact on release due to its higher activity during the earlier times of repository history (~26% initially, decreasing to 17% and ~0% at 1000 and 10,000 years after emplacement) (SOTERM, 2019). Lanthanide analogues such as Nd 3+ possess physical and chemical characteristics that allow them to be used to examine the chemical behavior of trivalent actinides (Lucchini, et al., 2007).
During fissionable material processing, all normal and credible abnormal conditions must remain safely subcritical. Nuclear Criticality Safety (NCS) uses a number of methods to determine subcriticality, one of which is the use of neutron transport codes such as MCNP6. In order to create models for use with MCNP6, both the geometry and materials in fissionable material processes must be known, or assumptions must be made and quantified for the impact to bias. One of the systems with a significant amount of bias due to material modeling assumptions is in the area of aqueous plutonium processing. These solutions are typically plutonium nitrate solutions or plutonium chloride solutions, which are modeled as fictitious plutonium metal-water mixtures because little is known about the actual density of the solution and there is no current predictive capability approved for use at Los Alamos National Laboratory (LANL) for modeling them. This research is currently underway to fill the gap and develop an algorithm for use with MCNP6 to model the density of plutonium chloride solutions. The method is to be validated with experimental data for density, and also validated with critical experiments using MCNP6. Note that the Chlorine Worth Study (CWS) was performed in December 2021 to help bridge the gap in chlorine data for critical experiments, and is currently awaiting International Criticality Safety Benchmark Evaluation Project (ICSBEP) review. This study was performed by LANL at the National Criticality Experiments Research Center (NCERC) at the Nevada National Security Site (NNSS). Additional information regarding this experiment may currently be found in LA-UR- 22-29180. Additionally, the Chemistry-Actinide Analytical Chemistry (C-AAC) at LANL has performed a number of solution density measurements for PuCl 3 -HC 1 -H 2 O, allowing for such data be used to create a semi-empirical density via the Pitzer method. The published dataset for the measurements is documented in LA-UR-22-25454. This method has already been tested successfully for aqueous plutonium nitrate solutions in SCALE. Current solution density measurements exist of plutonium concentrations of 0-~142g/L, all at 2M HC1, at temperatures 20-40°C. Additional data was taken for HC1-corrected density values, which essentially mimics the data for a pure PuCl x -water solution. The calculations in this report aim to support the current research by demonstrating the difference in system reactivity for the current modeling method when compared to the new proposed modeling with a density law implementation, which is being written as a Python tool to be used with MCNP6.
Solvent extraction is commonly used to separate different f-metals found in spent nuclear fuel, but this process results in large volumes of highly contaminated liquid waste that must be remediated or stored at significant expense. The project funded under this award was aimed at addressing solvent-related issues encountered in conventional f-metal separations. Our strategy focused on using solvent-free mechanochemical reactions to prepare lanthanide and actinide borohydride complexes so that they could be separated based on differences in their volatility. Key deliverables described in this report include proof-of-principle results demonstrating that borohydrides called aminodiboranates can be used for volatile lanthanide/lanthanide and lanthanide/uranium separations, as we proposed. Moreover, exploration of a closely related class of borohydrides called phosphinodiboranates allowed us to identify underlying chemical factors that control the volatility of trivalent lanthanide and uranium borohydride complexes with identical structures. Details of published and pending research products are provided, and these include comprehensive synthesis and characterization efforts required to support fundamental studies related to the proposed separations. These technical efforts supported the training of nine graduate students and three undergraduate researchers, and they established air-sensitive transuranic capabilities at the University of Iowa to enhance radiochemical workforce development.
CRA (Compliance Recertification Application)-2024 will update the oxidation state specific model used to calculate actinide solubility in the WIPP (Waste Isolation Pilot Plant). The pentavalent Np(V) ion is the most stable ion in solution within the An(V) series. This valence stability of Np(V) in aqueous solution makes Np a useful representative element for studying the aqueous complex chemistry of all An(V), but in the predicted WIPP scenario, this is the only TRU component that increases in the inventory with time as it is the main daughter product of 241 Am decay (alpha, n) so its relative importance increases throughout the 10,000-year performance period of the WIPP, it is only used to represent itself. This work is focused on confirming organic, borate and carbonate effects on solubility of Np(V) in WIPP simulated brines and 5 M NaCl and reassessing the predicted model speciation to strengthen the overall WIPP An(V) model.
Noble Metal Particles (NMP) that are present in SNF play an important role in the Fuel Matrix Degradation (FMD) Model that is being considered for predicting the release rate of radionuclides from a waste package. Previous characterization of chemically separated NMP from SNF showed that these were well-crystallized nanoparticles containing Mo, Tc, Ru, Rh, and Pd with some evidence of actinides. These same chemically separated particles were re-characterized following 10 years of storage as the separated material in water. Scanning Transmission Electron Microscopy (STEM) analysis revealed that significant alteration had occurred in this material during storage, resulting in the almost complete degradation of the NMP. We hypothesized that radiolytic damaged had occurred in the material. To support these concepts, we synthesized a mixed Ru-Pd nanoparticle and subjected it to irradiation in the electron microscope in an in-situ liquid cell. We demonstrated that intense radiation can lead to the decomposition of these metallic particles.
Fluid flow and chemical transport in porous media are the macroscopic consequences of pore structure, which integrates geometry (e.g., pore size and surface area, pore-size distribution) and topology (e.g., pore connectivity). Low-permeability geological media whose pores are poorly interconnected will exhibit the characteristics of anomalous diffusion and sample size-dependent effective porosity, which will strongly impact long-term net diffusion and retention of radionuclides in geological repository settings involving different host rocks and barrier materials. A suite of innovative and complementary experimental approaches is utilized to study the microscopic pore structure and macroscopic fluid flow & chemical transport for a range of host rocks and barrier materials, in addition to standard clay minerals and reference rocks. With a particular focus on quantifying the presence and magnitude of “isolated” pores for a reduced effective porosity in low-permeability geomedia, the integrated methodologies for basic properties and pore structure characterization of these geomedia include X-ray diffraction, thin section petrography, grain size distribution, water immersion porosimetry after vacuum-pulling for full saturation, mercury intrusion porosimetry, nitrogen physisorption, scanning electron microscopy, X-ray computed tomography, and (ultra-)small angle neutron (X-ray) scattering. In addition, custom-designed gas diffusion, tracer recipe involving a range of anionic and cationic chemicals with subsequent analyses by laser ablation and inductively coupled plasma-mass spectrometry, along with batch sorption, column transport, and imbibition tests were conducted for coupled effects of pore structure and chemical retention/transport. From the perspectives of pore structure in conjunction with multiple and complementary approaches to examining a range of sample sizes under different observational scales, we find that the poor pore connectivity is prevalent in low-permeability media (mudstone and crystalline rock) that is related to geological processes (e.g., compaction, diagenesis and thermal maturation). For example, the deep and organic matter-rich mudstones have a much smaller effective porosity than the total porosity (as a result of poor pore connectivity) and associated diffusion coefficient, and the effective porosity & diffusion coefficients are also dependent upon the sample sizes used in the measurement. Similarly, most of the pore space in the shallow mudstone is also controlled by pore-throat diameters in the 5-50 nm range of intergranular pore types from its fine-grained nature, but with an overall good pore connectivity. However, the nm-sized pore space (physically pore-network architecture) and strong sorption capacities (chemical retention from clay minerals) of both shallow and deep mudstones lead to the synergistic retention of cationic radionuclides and their utilities as effective host rocks and barrier materials. Our unique approaches of studying how the micro-scale pore structure affect macro-scale fluid flow, diffusion & retention, and chemical transport produce improved mechanistic understanding, and realistic quantification, of diffusion and retention of typical radionuclides in a range of generic host rocks and barrier materials (clay/shale, salt, crystalline rock, and tuff), with the overall results leading to scientifically-based understanding of enhanced isolation (from both diffusion and retention) of radionuclides and improved confidence on the long-term performance of geological repository to store high-level radioactive wastes. In addition to the training of 25 undergraduates, graduates, and postdocs of UTA, the scientists (organizations) involved in performing this work (e.g., discussion, sample sharing, and operation of SANS and SAXS instruments) include Ed Matteo, Yifeng Wang, and Kristopher Kuhlman (Sandia National Laboratories), Jens Birkholzer, Liange Zheng, Tim Kneafsey, and Sharon Borglin (Lawrence Berkeley National Laboratory), Mavrik Zavarin (Lawrence Livermore National Laboratory), Yukio Tachi and Yuta Fukatsu (Japan Atomic Energy Agency), Mieke de Craen (Euridice, Belgium), Markus Bleuel (NIST), Wei-Ren Chen, Gergely Nagy, Changwoo Do, William Heller, Larry Anovitz, and Kenneth Littrell (ORNL), as well as Jan Illvsky, Ivan Kuzmenko, Ju-Sang Park and Jon Almers (ANL). Key deliverables include a total of 13 peer-reviewed journal articles (nine published and three under review), 23 presentations at scientific conferences (AAPG, AAPG Southwest Section, AGU, Asian Clay Conference, GSA, GSA South-Central Section, IHLRWM, InterPore, International Conference on Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, International Conference on Coupled Processes in Fractured Geological Media: Observation, Modeling and Application), and academic institutions (UTA, New Mexico State University; University of Poitiers, France; University of Helsinki, Finland; Uppsala University, Sweden; Istanbul Technical University, Turkey) and other organizations (Andra, France; Posiva Oy, Finland).
Chlorination of Zr alloy cladding with sulfur-chloride reagents is being considered as a means of separating the main metal from alloying elements, imbedded U, actinides, and fission and activation products to purify the Zr. This would allow the Zr to be disposed of as low-level nuclear waste or possibly be recycled. A multistage process was developed that involves several steps and waste streams. Recycling of sulfur-chloride reagents S 2 Cl 2 and SOCl 2 is planned to minimize the waste stream. The generation of off-gas and entrainment of volatiles is anticipated to be minimized. However, given the complex nature of spent nuclear fuel (SNF), some volatile components will be generated, including the solvents themselves; Cl 2 used for the regeneration of S 2 Cl 2 ; volatile fission product chlorides, such as Sb and 3 H; and chlorinated alloying components, such as Sn, Nb, Fe, and Mo. This report discusses the chemical phenomena that might give rise to volatile species and their planned capture. The volatility of the transition metals will depend on their oxidation state and the compounds that are formed, such as Zr tritide. Loading radionuclides in the process off-gas will depend on the inputs to the process. For instance, processing separated Zr to reduce waste will have a much lower loading of radionuclides than if alternative chlorination were used for decladding SNF. Much of the volatile process streams will be part of the solvent recycling, which may involve online scrubbing. Generally, a caustic scrubber should be included in the off-gas to remove acidic vapors (e.g., Cl 2 , SOCl 2 ). The decontamination procedures for removing these species could involve pretreatment (i.e., heating) options or reduction by contact with H 2 . This report discusses these options along with a framework for testing these alternatives in future experiments. Technologies for off-gas capture will leverage those developed in the Materials Recovery and Waste Forms program.
The Actinide Analytical Chemistry (CAAC) group at Los Alamos National Laboratory (LANL) uses the LabWare LIMS (LabWare 7) system to manage our samples and material at risk. The LIMS system also provides other functionality which the Plasma Spectroscopy (PS) team has developed along with our LIMS team to provide streamlining and automation of all sample related actions required by PS.
The overarching goal of this research project is quantitative microscopic modeling of phase diagrams and solubility of actinides and lanthanide-fission products in molten salts for molten salt reactors. Application of molten salts as coolants and liquid fuels for next-generation reactors requires quantitative understanding of phase diagrams, equations of state and transport properties of binary and ternary molten salt mixtures, as well as solubility of fuel, fission products and reactor-wall corrosion products, but these remain beyond the reach of current first-principles computational techniques. We will address this fundamental capability gap using a novel hybrid framework for thermodynamic integration to directly predict absolute free energies of solid and molten salts at any specified conditions of composition, temperature and pressure. This framework will combine a hierarchy of first-principles, molecular dynamics and continuum techniques to deliver first-principles-level accuracy at a fraction of the computational cost of conventional ab initio molecular dynamics approaches. In particular, this technique is expected to provide first-principles accuracy, while off-loading most of the computational work on much less expensive classical molecular dynamics and continuum techniques.
Lawrence Livermore National Laboratory (LLNL) and the NBL Program Office (NBL PO) are collaborating on production of purified sub-units of the former NBS 936, 937 and 938 plutonium isotopic reference materials, which will be certified for plutonium isotopic composition and sold as certified reference materials (CRMs) C136A, C137A, and C138A, respectively. These reference materials are used throughout the United States and international community as standards for isotopic measurement method calibration and quality control and were first produced over 50 years ago. To reduce quantities of in-grown daughter products and potentially enable their use as Pu radiochronometry reference materials, the materials undergo a two-stage anion exchange purification to significantly reduce the quantities of U, Am, and Np in the source material. The purified Pu is aliquoted into ~1 mg units in the nitrate form, which will facilitate easier shipping and use compared to the 0.25 g parent units. The production process has been completed for the high- and medium- burnup isotopic standards C137A and C136A and will soon be performed for the weapons-grade Pu standard C138A. This report describes the measurement of trace actinide progeny of the Pu isotopes ( 234 U, 235 U, 236U, 241 Am and 237 Np) in purified C137A and 136A isotopic standards to provide informational values and assess the possibility of their use as working reference materials for radiochronometry.
It has been demonstrated that rare-earth and actinide metals can be purified via conversion to chlorides and heating to volatilize impurities. To this end, BYU has been working towards designing, building, and testing a system that incorporates the chlorine gas generation method into the chloride volatility process. The efforts made towards the project tasks listed in the Statement of Work are addressed in the following sections. Finally, a report on information related to this project that has been published or presented is addressed. By the end of the contract period, small-scale tests using LaCl 3 -CaCl 2 to generate Cl 2 had been conducted, the produced Cl 2 was successfully reacted with Ce foil to create CeCl 3 , initial designs for the large-scale apparatus were completed, and manufacturing for the large-scale apparatus had begun.