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At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Particulate plutonium released from the Fukushima Daiichi meltdowns

Traces of Pu have been detected in material released from the Fukushima Daiichi Nuclear Power Plant (FDNPP) in March of 2011; however, to date the physical and chemical form of the Pu have remained unknown. Here we report the discovery of particulate Pu associated with cesium-rich microparticles (CsMPs) that formed in and were released from the reactors during the FDNPP meltdowns. The Cs-pollucite-based CsMP contained discrete U(IV)O 2 nanoparticles, <~10 nm, one of which is enriched in Pu adjacent to fragments of Zr-cladding. The isotope ratios, 235 U/ 238 U, 240 Pu/ 239 Pu, and 242 Pu/ 239 Pu, of the CsMPs were determined to be ~0.0193, ~0.347, and ~0.065, respectively, which are consistent with the calculated isotopic ratios of irradiated-fuel fragments. Thus, considering the regional distribution of CsMPs, the long-distance dispersion of Pu from FNDPP is attributed to the transport by CsMPs that have incorporated nanoscale fuel fragments prior to their dispersion up to 230 km away from the Fukushima Daiichi reactor site.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2025

Chemometrics and visible diffuse reflectance spectroscopy to classify plutonium dioxide

Diffuse reflectance (DR) spectra in the Vis-NIR (∼380–1050 nm) region were acquired for a series of PuO 2 samples with a spot size of about 10 × 10 μm. Two batches of six PuO 2 samples, synthesized approximately 7.5 months apart, were prepared using both Pu(III) and Pu(IV) oxalate precursors at three distinct calcination temperatures (450, 650, and 950 °C). This yielded a total of 12 PuO 2 samples and 433 DR spectra. The DR spectrum of PuO 2 contained numerous peaks in the visible region, and characteristic features were identified with respect to calcination temperature and chemistry. A distinct peak multiplet near 615 nm was observed for samples prepared at low calcination temperatures, and a peak near 660 nm was observed for higher calcination temperatures. A multivariate classification strategy based on principal component analysis (PCA) was developed to distinguish PuO 2 calcination temperatures of 450, 650, and 950 °C with 100 % accuracy. Classification results also indicate the potential to distinguish chemical processing history (i.e., Pu(III) or Pu(IV)) based on the spectra with 72 % accuracy based on k-nearest neighbors applied to the PCA scores. Partial least squares discriminant analysis was used to identify variation among batches with 88 % accuracy and found that peaks near 669, 681, 811, and 970 nm were the most useful for predicting the batch identity. Here, this work demonstrates how micro-diffuse reflectance spectroscopy and chemometrics can be used to classify PuO 2 processing history based on Vis-NIR spectral features. Combining the chemometric approach with mapping sequences could provide a rapid, nondestructive approach to classify Pu oxide materials for environmental, forensics, and nonproliferation applications.

Actinide↗
DOE OSTI2020

A Single Small-Scale Plutonium Redox Reaction System Yields Three Crystallographically-Characterizable Organoplutonium Complexes

Here, an approach to obtaining substantial amounts of data from a hazardous starting material that can only be obtained and handled in small quantities is demonstrated by the investigation of a single small-scale reaction of cyclooctatetraene, C 8 H 8 , with a solution obtained from the reduction of Cp' 3 Pu (Cp' = C 5 H 4 SiMe 3 ) with potassium graphite. This one reaction coupled with oxidation of a product has provided single-crystal X-ray structural data on three organoplutonium compounds as well as information on redox chemistry thereby demonstrating an efficient route to new reactivity and structural information on this highly radioactive element. The crystal structures were obtained from the reduction of C 8 H 8 by a putative Pu(II) complex, (Cp' 3 Pu II ) 1– , generated in situ, to form the Pu(III) cyclooctatetraenide complex, [K(crypt)][(C 8 H 8 ) 2 Pu III ], 1-Pu , and the tetra(cyclopentadienyl) Pu(III) complex, [K(crypt)][Cp' 4 Pu III ], 2-Pu . Oxidation of the sample of 1-Pu with Ag(I) afforded a third organoplutonium complex that has been structurally characterized for the first time, (C 8 H 8 ) 2 Pu IV , 3-Pu . Complexes 1-Pu and 3-Pu contain Pu sandwiched between parallel (C 8 H 8 ) 2– rings. The (Cp' 4 Pu III ) – anion in 2-Pu features three η 5 -Cp' rings and one η 1 -Cp' ring, which is a rare example of a formal Pu–C η 1 -bond. In addition, this study addresses the challenge of small-scale synthesis imparted by radiological and material availability of transuranium isotopes, in particular that of pure metal samples. A route to an anhydrous Pu(III) starting material from the more readily available Pu IV O 2 was developed to facilitate reproducible syntheses and allow complete spectroscopic analysis of 1-Pu and 2-Pu . Pu IV O 2 was converted to Pu III Br 3 (DME) 2 (DME = CH 3 OCH 2 CH 2 OCH 3 ) and subsequently Pu III Br 3 (THF) x , which was used to independently synthesize 1-Pu , 2-Pu , and 3-Pu .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2022

Plutonium Hybrid Materials: A Platform to Explore Assembly and Metal–Ligand Bonding

In this work, we report the synthesis of five new hybrid materials containing the [PuCl 6 ] 2- anion and charge balancing, non-covalent interaction donating 4-X-pyridinium (X = H, Cl, Br, I) cations. Single crystals of the title compounds were grown and harvested from acidic, chloride-rich, aqueous media and their structures were determined via X-ray diffraction. Compounds 1-4, (4XPyH) 2 [PuCl 6 ] and 5, (4IPyH) 4 [PuCl 6 ] · 2Cl, exhibit two distinct sheet-like structure types. Structurally relevant non-covalent interactions were tabulated from crystallographic data and verified computationally using electrostatic surface potential maps and the quantum theory of atoms in molecules (QTAIM) approach. The strength of the hydrogen and halogen bonds was quantified using Kohn-Sham density functional theory and a hierarchy of acceptor-donor pairings established. In turn, the PuIV-Cl bonds were studied using the QTAIM and natural localized molecular orbital (NLMO) approaches to delineate the underlying bond mechanism and hybrid atomic orbital contributions therein. Energy decomposition (ED) and natural ED analyses were also explored to probe the bond mechanism and, more broadly, explore the efficacy of these techniques in studying these anionic systems. The results of the PuIV-Cl bond analyses were compared across composition via analogous treatments of previously reported [PuO 2 Cl 4 ] 2- and [PuCl 3 (H 2 O) 5 ] molecular units. In summary, our study indicates that the Pu-Cl bonds are predominately ionic, yet exhibit small varying degrees of covalent character that increase from [PuCl 3 (H 2 O) 5 ], [PuO 2 Cl 4 ] 2- , to [PuCl 6 ] 2- , while the participation of the Pu based s/d and f orbitals concurrently decrease and increase, respectively.

transuranic↗
DOE OSTI2023

The crystal chemistry of plutonium( iv ) borophosphate

Pu IV borophosphate crystallized from a complex solution in a borosilicate glass vial after one year. The suspected leaching of B from the glass vial could have important implications for the corrosion of vitrified nuclear waste.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Caustic Neutralization and Precipitation of Acidic Dissolved Simulated Stainless Steel–Clad Plutonium and Plutonium/Uranium Nuclear Fuel

Simulated dissolved stainless steel (SS) clad Pu and Pu/U nuclear fuel in HNO 3 was neutralized to a free hydroxide (OH - ) concentration of 0.6 M. A thermal neutron poison, Gd, was added to the simulants at concentrations of either ~3 - 6 g/L or ~37 - 38 g/L. The supernate Pu concentration the day of neutralization ranged from 0.48 to 8.75 mg/L. The supernate Pu concentration of a simplified simulant neutralized to 0.6 M OH - above precipitated solids containing Pu was demonstrated to decrease over 18 days. A significant portion of precipitated Pu was found to be insoluble in 8 M HNO 3 at ambient temperature, but essentially quantitative Pu dissolution was achieved in 11.5 M HNO 3 /0.1 M KF at 100 °C. The difficulty in dissolving the Pu precipitate is believed to be due to the formation of refractory PuO 2 •xH 2 O during the neutralization process. Initial Gd concentrations of ~37 – 38 g/L were found to result in a greater Al precipitation when neutralized to 0.6 M OH - than initial Gd concentrations of ~3 – 6 g/L. Physical properties of the resultant slurries were measured and used to calculate limiting flowrates and slurry velocities by gravity only in transfer piping between the Savannah River Site’s H-Canyon Facility and the Concentration, Storage, and Transfer Facility (CSTF). These results were compared to calculated deposition velocities to predict if solids would settle during the transfer. The Newtonian model was found to be reasonable for each diluted slurry evaluated. Deposition velocities of Pu containing slurries are lower than nuclear fuel slurries primarily composed of U due to the high density of Pu solids. In conclusion, dilution of slurries reduces the margin between the slurry and deposition velocities due to the reduction in viscosity because higher viscous forces on the particles promote maintained suspension.

Actinide Neutralization↗
DOE OSTI2021

Plutonium in the WIPP

Explore the source record for details and available documents.

Inorganic and Physical Chemistry↗
DOE OSTI2023

Criticality Experiments to Reduce Compensating Errors in Plutonium Nuclear Data

Compensating errors between nuclear data observables in a library can adversely impact application simulations. The primary goal of the EUCLID project (Experiments Underpinned by Computational Learning for Improvements in Nuclear Data) is to reduce compensating errors in nuclear data. A new criticality experiment, described in this work, was designed with the specific target nuclear data of 239 Pu fission, inelastic scattering, elastic scattering, capture, nu-bar, and prompt fission neutron spectrum (PFNS). This work will focus on the design and execution of the EUCLID experiment, performed on the Planet vertical lift critical assembly machine at the National Criticality Experiments Research Center (NCERC). The criticality experiment includes two different configurations with very different geometries: one is cube-like to minimize neutron leakage while the other is slab-like to maximize leakage. Having these two widely varying configurations allows the scattering sensitivities of 239 Pu to the neutron multiplication factor to be greatly changed while minimally impacting the other cross section sensitivities. Both configurations utilize the Pu ZPPR (Zero Power Physics Reactor) plates as fuel. The experiments were designed using a D-Optimality criteria, which is an optimization method minimizing the log-determinant of the adjusted nuclear data covariance for the target reactions. These experiments include not only inference of k eff , as done in all critical benchmark experiments, but several other responses as well, such as neutron multiplication measurements and reaction rate ratios. After analysis of the measured data is complete, adjustment of nuclear data will be performed to assess whether the new experimental data successfully reduced compensating errors.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2020

Experimental and Modeling Review of the Plutonium-Zirconium (Pu-Zr) System: Lost in Translation and Over Time?

This article presents a review of the phase equilibria of the Pu-Zr system and discusses the contradictory reports on the experimental phase diagram and misinterpretations that have led to confusion over time. In addition, a review of the few Pu-Zr CALPHAD (CALculation of PHAse Diagrams) assessments is presented with emphasis on the heat of formation of the bcc phase, highlighting a disagreement between CALPHAD and ab initio calculations. Based on the information gathered in this study, a critical re-assessment of the Pu-Zr system involving the ζ (Pu 28 Zr), θ (Pu 4 Zr), kinetically hindered κ (PuZr 2 ), and once observed ι phases is called for.

36 MATERIALS SCIENCE↗