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Advancement of Actinide Metal–Organic Framework Chemistry via Synthesis of Pu-UiO-66

We report the synthesis and characterization of the first plutonium metal–organic framework (MOF). Pu-UiO-66 expands the established UiO-66 series, which includes transition metal, lanthanide, and early actinide elements in the hexanuclear nodes. The thermal stability and porosity of Pu-UiO-66 were experimentally determined, and multifaceted computational methods were used to corroborate experimental values, examine inherent defects in the framework, decipher spectroscopic signatures, and elucidate the electronic structure. The crystallization of a plutonium chain side product provides direct evidence of the competition that occurs between modulator and linker in MOF syntheses. Ultimately, the synthesis of Pu-UiO-66 demonstrates adept control of Pu(IV) coordination under hydrolysis-prone conditions, provides an opportunity to extend trends across isostructural UiO-66 frameworks, and serves as the foundation for future plutonium MOF chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Producing Evaluation-quality 239 Pu Average Prompt Fission Neutron Multiplicities using a Correlated Fission Model

An evaluation of the average prompt fission neutron multiplicity, $\bar{ν}_p$, of 239 Pu(n,f) is shown. This evaluation includes (a) the correlated fission model CGMF, and (b) a detailed analysis of past and recently published experimental data. Using CGMF-calculated $\bar{ν}_p$ as prior enables to link, through the use of evaluated model input parameters, $\bar{ν}_p$ to other fission observables such as the prompt fission neutron spectrum (PFNS), preneutron emission fission yields as a function of mass, and the average total kinetic energy of the fragments. These evaluated parameters produce realistic predictions of many fission observables, while the evaluated $\bar{ν}_p$ agrees well (χ 2 ≈ 1) with data. Moreover, with the new evaluated $\bar{ν}_p$, the effective neutron multiplication factor of fast Pu ICSBEP critical assemblies are predicted with a mean bias of 58 pcm compared to 18 pcm with ENDF/B-VIII.0, when paired with a new 239 Pu PFNS and fission cross section. Due to these encouraging validation results, the evaluated $\bar{ν}_p$ is currently part of a release candidate for the 239 Pu ENDF/B-VIII.1 file. Hence, a correlated fission model was used for the first time for evaluating $\bar{ν}_p$ that is of evaluation quality. This is an important step towards consistent evaluations of prompt fission observables.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Continuous-Energy ENDF/B-VIII.0 Cross Section and SCALE 6.2.4 Performance for Nuclear Criticality Safety Applications: 1 H, C, 58,60 Ni, 182,183,184,186 W, 235,238 U, 239 Pu

As part of the nuclear data evaluation and validation cycle, the ENDF/B-VIII.0 cross-section library released in 2018 requires testing to determine areas of improvement and deterioration. Previous work by the authors investigated the performance of 16 O, 56 Fe, and 63,65 Cu cross sections, with this study acting as an extension of the prior work. In addition to the isotopes and nuclear criticality safety benchmarks of interest to the prior work, benchmarks from the International Criticality Safety Benchmark Evaluation Project Handbook were selected for their k eff sensitivity to 1 H, C, 58,60 Ni, 182,183,184,186 W, 235,238U, or 239 Pu cross sections and were modeled in the SCALE code system maintained by Oak Ridge National Laboratory. In total, 253 benchmark configurations were selected for their sensitivities and modeled using SCALE 6.2.4 Criticality Safety Analysis Sequences (CSAS) continuous-energy Monte Carlo k eff calculations. This collection includes and expands upon the 99 benchmarks in the prior work. The AMPX-processed ENDF/B-VIII.0 library was decomposed into individual ENDF/B-VIII.0 datum libraries for each isotope of interest. Doing so allowed for the individual substitution of an ENDF/B-VIII.0 cross section in the place of ENDF/B-VII.1, determining isotope-specific effects of ENDF/B-VIII.0 relative to ENDF/B-VII.1. Full library calculations with entirely ENDF/B-VII.1 data or entirely ENDF/B-VIII.0 data were also executed. As a measure of performance, the average relative deviation was determined as the ratio of the deviation between calculated and experimental keff to the propagated calculational and experimental uncertainty. With calculated full library and isotope-specific ENDF/B-VIII.0 k eff ’s, an optimized combination of data libraries was estimated and confirmed with SCALE calculations. This showed that reverting 239 Pu, 58 Ni, 16 O, and 65 Cu cross sections to ENDF/B-VII.1 resulted in improved performance relative to the full ENDF/B-VIII.0 library. Across all 253 benchmarks, the average relative deviation was 1.29σ for the full ENDF/B-VII.1 library, 1.17σ for the full ENDF/B-VIII.0 library, and 0.97σ for the optimized combination. The reversion of 239 Pu, 58 Ni, 16 O, and 65 Cu cross sections to ENDF/B-VII.1 in the 99 benchmarks of the prior work resulted in further improved experimental agreement compared to the previously reported improvement from 16 O and 65 Cu alone. Therefore, it is suggested that applications with significant sensitivities to 239 Pu, 58 Ni, 16 O, and 65 Cu consider their choice of nuclear data library.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Effects of substitutional Ga on the phonons of δ -phase Pu based on density functional theory calculations

The delta phase of Pu is stabilized by Ga doping, but the mechanism of this stabilization remains an open question. Density functional theory calculations focused on how Ga doping affects the phonons sheds some light on the phonons' contribution to the stabilization. Here, the calculated phonon modes of Ga-doped delta phase Pu fall into two distinct types: localized, high frequency Ga-dominated phonon modes, and Pu-dominated modes at lower frequencies. Increasing the Ga concentration has an effect on the Pu-dominated phonon modes opposite to that of compression: higher-frequency modes soften, and lower-frequency modes stiffen. The latter provides an indication that the stabilization mechanism is not due to a thermodynamic contribution from the phonons. Furthermore, the stiffened phonon modes include candidate modes that describe possible pathways into low-temperature phases, suggesting that doping with Ga could impede such pathways.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Erratum: Monoenergetic photon-induced fission cross-section ratio measurements for U 235 , U 238 , and Pu 239 from 9.0 to 17.0 MeV

In this erratum we report a correction to the previously published photofission cross-section ratio data. The actinide fission-chamber foils utilized in this work were extensively characterized during a new campaign using α- and γ-ray spectroscopy, and 2π alpha counting. These three techniques agreed, resulting in an improved accuracy of the fission-chamber foil masses used in the original experiment. The foil masses measured by α spectroscopy are detailed in Table I. All foils were counted on the same α spectrometer, using an identical geometry, which reduces the systematic uncertainty in the calculated mass ratios since the α spectrometer efficiency cancels out in the ratio. This results in a relative uncertainty on the mass ratio of 1.0% for 235 U/ 238 U, 0.62% for 239 Pu/ 235 U, and 1.1% for 239 Pu/ 238 U. The published cross-section ratio data are re-calculated to reflect the updated target masses and uncertainties. The new mass values cause a 2.40% decrease for the σ( 235 U(γ, f)/ 238 U(γ, f)) ratio, a 5.10% decrease for the σ( 235 U(γ, f)/ 239 Pu(γ, f)) ratio, and a 2.77% decrease for the σ( 238 U(γ, f)/ 239 Pu(γ, f)) ratio. The updated cross-section ratios are presented in Tables II, III, and IV, which are corrected versions of Tables III, IV, and V in Ref. [1]

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Description of the multinucleon transfer mechanism for Ca 48 + Pu 244 and Kr 86 + Pt 198 reactions in a quantal transport approach

Multinucleon transfer (MNT) reactions involving heavy projectile and target combinations stand as a promising method for synthesizing new neutron-rich exotic nuclei, which may not be possible using hot or cold fusion reactions or fragmentation. Exploring the mechanisms behind MNT reactions is essential and it requires a comprehensive theoretical framework that can explain the physical observables in these reactions. This work aims to show that the quantal diffusion approach based on the stochastic mean-field (SMF) theory is capable of explaining the reaction dynamics observed in MNT reactions. Primary product mass distributions in 48 Ca + 244 Pu reaction at E c.m. = 203.2 MeV and 86 Kr + 198 Pt reaction at E c.m. = 324.2 MeV are calculated and compared with the available experimental data. In this work, we utilize the time-dependent Hartree-Fock (TDHF) calculations to analyze the mean-field reaction dynamics computationally in the reactions 48 Ca + 244 Pu and 86 Kr + 198 Pt for a broad range of initial angular momenta. Quantal transport description based on the SMF approach is used to calculate quantal diffusion coefficients and mass variances in 48 Ca + 244 Pu and 86 Kr + 198 Pt systems. The primary products arising from quasifission reactions are described by joint probability distribution in the SMF approach and those arising from fusion-fission are estimated by using the statistical deexcitation code gemini + +. Mean values of charge and mass numbers, scattering angles of the primary reaction products, and the total kinetic energies after the collision are calculated within the TDHF framework for a broad range of initial angular momenta. Throughout all the collisions, drift toward the mass symmetry and large mass dispersion associated with this drift are observed. Here, the calculated primary fragment and mass distributions using the SMF approach successfully explain experimental observations for the 48 Ca + 244 Pu and 86 Kr + 198 Pt systems. The primary mass distributions, mean values of binary products, and mass dispersions are determined and results are compared with the available experimental data. The observed agreement between the experimental data and SMF results highlights the effectiveness of the quantal diffusion mechanism based on the SMF approach, which does not include any adjustable parameters other than standard parameters of Skyrme energy density functional.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Distribution of U, Pu and Np in a Mo-99 Recovery Process using Sachtopore NP (titania based) Absorbent Material

A laboratory scale mockup of a prototypical Mo-99 recovery process has been operated in a radioactive materials hood at Savannah River National Laboratory. This equipment has been operated with realistic concentrations of uranium (U-238), plutonium (94% Pu-239), neptunium (Np-237), and non-radioisotopes of common fission products (including Mo). The goal of this work was to determine the amounts of U, Pu, and Np in the liquid waste streams created by the wash streams for the production process. The key question was how the initial acid wash volume will be handled, as this solution contains residual raffinate which amounted to ~ 3% ofthe mass ofthe feed solution in this experiment. If the initial 1.9 bed volumes (BV) of acid wash were recycled as in this experiment then the combined wash solutions can be expected to contain 0.4 g U/L, 2.7 pg Pu/L and < 14 pg Np/L. If, on the other extreme, the entire acid wash solution was discarded as waste, then the combined wash solutions can be expected to contain 11 g U/L, 3.8 pg Pu/L and ~ 80 pg Np/L. The Sachtopore NP absorbent (for Mo-99 recovery) retains a minuscule fraction ofthe U (2.3 mg U per g titania or 0.03% ofthe U in the feed). The uncertainties are too large to determine how close the absorbent is to saturation with U. Less mass but a higher fraction ofthe total Np was retained by the absorbent (0.7 pg Np per g titania or ~2% of the Np in the feed). As has been reported elsewhere, a large fraction ofthe Pu fed to the titania bed was retained by the absorbent (92% of Pu in the feed or 20 pg per g titania).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Final Design for Thermal/Epithermal eXperiments using High 240 Pu Content Plutonium/Aluminum Zero Power Research Reactor Plates with Polyethylene Moderator (IER 520 Final Design CED-2 Report)

The US Department of Energy Nuclear Criticality Safety Program (NCSP) convened a multinational Thermal Epithermal eXperiments (TEX) meeting in July of 2011 to discuss the data and experimental needs of criticality safety practitioners. The number one and two priority integral experiment data needs were for 239 Pu and 240 Pu, with special emphasis on cross section performance in the intermediate energy range (from 0.625 eV to 100 keV). LLNL measured five critical configurations with LANL for the plutonium test bed (IER-184) and published the experiments as International Criticality Safety Benchmark Evaluation Project evaluation PUMET-MIXED-002. Modeling of the benchmark configurations using ENDF/B-VIII.0 nuclear data showed significant overprediction of reactivity for configurations that had a large percentage of fissions in the intermediate energy regime. This report documents a variation on the TEX plutonium test bed to provide a test of 240 Pu cross sections, with sensitivity of the configuration to 240 Pu radiative capture and fission cross sections a priority for the design.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Parallel-Plate Avalanche Counter (PPAC) Fabrication for 240 Pu PFNS Measurement [Slides]

A LANL-LLNL joint program has been developed successfully to measure PFNS and established the most precisely determined $\chi$ matrices for 235,238 U and 239 Pu. It has been extended to 240 Pu now and possibly to 233 U in the future. An alternative method was developed to fabricate 240 Pu and a total of 12 targets were made with a total mass of 17.9 mg. The PFNS measurement for 240 Pu will begin in June, 2022 when the new beam cycle starts and the data analysis follows immediately afterward.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

New NBL Pu Isotopic Standards C137A and C136A as Working Reference Materials for Radiochronometry in Nuclear Forensics

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.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

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↗

The Melt Enthalpy of Pu 6 Fe

Schwartz, et al., previously reported calorimetry measurements conducted on a Pu-Pu 6 Fe mixture, from which they derived a melt enthalpy of 31.2 J/g (46.6 kJ/mol) for Pu 6 Fe. This was the first—and remains the only—such value to appear in the literature. We reanalyze those results in light of two contributions to the measured heat flow not considered in the original report: the melt enthalpy of the excess Pu and the subsequent heating of the liquid mixture. These corrections yield a revised value of 24.4 J/g (36.3 kJ/mol), which we show to be consistent with the melt enthalpy of U 6 Fe.

36 MATERIALS SCIENCE↗

Proposed Lunar Measurements of r-Process Radioisotopes to Distinguish the Origin of Deep-sea 244 Pu

Abstract 244 Pu has recently been discovered in deep-sea deposits spanning the past 10 Myr, a period that includes two 60 Fe pulses from nearby supernovae. 244 Pu is among the heaviest r -process products, and we consider whether it was created in supernovae, which is disfavored by nucleosynthesis simulations, or in an earlier kilonova event that seeded the nearby interstellar medium with 244 Pu that was subsequently swept up by the supernova debris. We discuss how these possibilities can be probed by measuring 244 Pu and other r -process radioisotopes such as 129 I and 182 Hf, both in lunar regolith samples returned to Earth by missions such as Chang’e and Artemis, and in deep-sea deposits.

79 ASTRONOMY AND ASTROPHYSICS↗

Experimental geochemistry of Pu and Sm and the thermodynamics of trace element partitioning

An experimental study of the partitioning of Pu and Sm between diopside/liquid and whitlockite/liquid supports the hypothesis that Pu behaves as a light rare earth element during igneous processes in reducing environments. D-Pu/D-Sm is found to be about 2 for both diopsidic pyroxene and whitlockite, and the amount of fractionation would be decreased further if Pu were compared to Ce or Nd. Data indicate that temperature, rather than melt composition, is the most important control on elemental partitioning, and that P2O5 in aluminosilicate melts serves as a complexing agent for the actinides and lanthanides.

Jones, John H.↗

Nuclear Fuel and Pu Redox Studies from The Glenn T. Seaborg Institute at Idaho National Laboratory

The Glenn T. Seaborg Institute at Idaho National Laboratory (INL-GTSI) focuses on advancing fundamental research in the actinide sciences by providing unique opportunities to early career scientists and engineers to gain experience studying the actinide elements and their associated systems. The INL-GTSI is built from three focus areas that are based on the expertise and supporting infrastructure at INL and include solid state chemistry and physics, solution phase chemistry and physics, and forensic and isotope science. INL is the lead Laboratory for nuclear energy research and development in the U. S. and the research on nuclear fuels performed under the INL-GTSI gives good examples of solid state studies. Uranium-Molybdenum (U-Mo) alloys are leading fuel candidates for conversion of high performance research and test reactors to low-enriched fuels. During irradiation, generated fission gas accumulates into bubbles and self-organizes into a gas bubble superlattice (GBS) that effectively stores fission gases and inhibits fuel swelling. A study on the early self- organizing behavior of the GBS shows that not only grain boundaries but the interfaces between the U-Mo matrix and uranium carbide (UC) impurities are important to GBS formation.[1] In solution, understanding the complex redox behavior of plutonium in aqueous environments is critical for establishing optimized nuclear waste reprocessing solvent systems and storage tank environments. INL-GTSI researchers have produced an experimentally validated multi-scale model of the gamma radiation induced behavior of plutonium ions in concentrated aqueous HNO3 solutions.[2] Here, gamma radiation effected only minimal steady state changes in the redox distribution of the plutonium oxidation states. The redox cycling between Pu(IV) and Pu(III) is demonstrated to be mediated by the •OH/NO3• radical oxidation of Pu(III) and the H2O2/HNO3 driven reduction of Pu(IV). The INL-GTSI offers young researchers the unique chance to work directly with actinide bearing materials in a U. S. National Laboratory environment. Further topical areas of interest to the INL-GTSI include, but are not limited to, fundamental actinide properties, structure/property (electronic, magnetic, thermal) relations, actinide quantum criticality, f- electron interactions, electron correlations, computational studies, new phases, defect effects, interface interactions, isotope production and separation, forensic analytical chemistry, structure and dynamic properties of actinides in non-aqueous media, separations chemistry and kinetics for advanced nuclear fuel cycles, radiation effects, and innovative and advanced ligand design for complexation of the actinides.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Materials Data on Pu(IO3)4 by Materials Project

Pu(O3I)4 crystallizes in the tetragonal P4_2/n space group. The structure is one-dimensional and consists of two Pu(O3I)4 ribbons oriented in the (0, 0, 1) direction. Pu4+ is bonded in a body-centered cubic geometry to eight O2- atoms. There are four shorter (2.34 Å) and four longer (2.37 Å) Pu–O bond lengths. There are three inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Pu4+ and one I5+ atom. The O–I bond length is 1.85 Å. In the second O2- site, O2- is bonded in a single-bond geometry to one I5+ atom. The O–I bond length is 1.81 Å. In the third O2- site, O2- is bonded in a 2-coordinate geometry to one Pu4+ and one I5+ atom. The O–I bond length is 1.87 Å. I5+ is bonded in a 3-coordinate geometry to three O2- atoms.

36 MATERIALS SCIENCE↗

Materials Data on Pu(SO6)2 by Materials Project

PuO4(SO4)2 is Silicon tetrafluoride-derived structured and crystallizes in the orthorhombic Fddd space group. The structure is zero-dimensional and consists of sixteen sulfuric acid molecules and eight PuO4 clusters. In each PuO4 cluster, Pu is bonded in a distorted rectangular see-saw-like geometry to four equivalent O atoms. All Pu–O bond lengths are 1.80 Å. O is bonded in a single-bond geometry to one Pu atom.

36 MATERIALS SCIENCE↗

Proposed Updates to Pu Evaluation for ENDF/B-VIII.0β 2 [Slides]

This presentation shows current status of in ENDF/B-VIII.0 and ENDF/B-VIII.0β 1 Pu evaluations. With a focus on the Pu thermal solutions (PST) and sanity check on fast metal assemblies (PMF). Pu ENDFβ 1 file in the low-energy region included updates in RRR (up to 2.5 keV), TNC and PFNS. Discussed are improvements over ENDF/B-VIII.0 in the C/E benchmarks (PST 81 cases) with preliminary ν p and cross section covariance generation for the resolved resonance energy range up to 2.25 keV. Highlighted are proposed updates for ENDFβ 2 with an extension of the RRR evaluation up to 5 keV, inclusion of Mosby’s data including proper resolution function (thanks to Marian J.), and a particular focus on η energy dependence from thermal up to 10 eV with the impact of the capture-to-fission ratio at 0.29 eV. This presentation concludes with an updated ν p and cross section covariance generation for the resolved resonance energy range up to 5 keV. And additional validation to test performance at about 2 eV and in the keV region.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗