Actinide Materials Research Articles

The Electron‐Density Distribution of UCl4 and Its Topology from X‐ray Diffraction

AbstractThe chemistry of electrons in actinide complexes and materials is still poorly understood and represents a serious challenge and opportunity for experiment and theory. The study of the electron density distribution of the ground state of such systems through X‐ray diffraction represents a unique opportunity to quantitatively investigate different chemical bonding interactions at once, but was considered “almost impossible” on heavy‐atom systems, until very recently. Here, we present a combined experimental and theoretical investigation of the electron density distribution in UCL4 crystals and comparison with the previously reported spin density distribution from polarized neutron diffraction. All approaches provide a consistent picture in terms of electron and spin density distribution, and chemical bond characterization. More importantly, the synergy between experiments and quantum‐mechanical calculations allows to highlight the remarkable sensitivity of X‐ray diffraction to electrons in materials.

Sensitive imaging of actinide materials in shielded radioactive waste

This paper reports on the development of a method for enhanced non-destructive assay (NDA) of radioactive waste using the novel technique neutron-gamma emission tomography (NGET). The technique relies on the detection of correlated fast neutrons and gamma rays emitted in spontaneous or induced fission. It is based on fast organic scintillators and enables sensitive detection and three-dimensional (3D) localization of the fission events. The technique is passive and does not require moving components. In this work, we apply the NGET technique to the category of radioactive waste which is often referred to as historic or legacy waste. This can include mixed wastes encased in shielded containers many decades ago, before the advent of detailed waste description criteria. These low or intermediate level wastes are often associated with lacking, limited or conflicting documentation. This poses a challenge when assigning the waste to the proper disposal route as well as in deciding whether the waste needs to undergo sorting and conditioning to fulfil waste acceptance criteria both with regards to safe interim storage and to its ultimate disposal. Actinides, such as isotopes of uranium and plutonium, with their typically long half-lives and decay chains are of special interest in this regard since they may challenge the long-term safety assessment in repositories predicated on mainly shorter half-life radionuclides if undetected. Accurate identification and localisation of actinides is also important from a safeguards perspective, especially since they are generally difficult to detect and localise by established passive means due to their relatively weak radiation emissions, in particular in shielded containments and in the presence of strong radiation fields from other radioactive materials. In this paper we present findings of measurements on shielded containments of long-lived radioactive waste performed at the Studsvik site in Sweden, as well as measurements on a laboratory assembly simulating a grouted waste drum. Similarities and differences between the novel NGET technique and a commercially available gamma imaging system are also briefly discussed.

Application of Micro X-ray Fluorescence and X-ray Tomographic Analysis of Metal and Actinide Materials

Application of Micro X-ray Fluorescence and X-ray Tomographic Analysis of Metal and Actinide Materials

Review of actinide core-level photoemission

Photoelectron spectroscopy allows for the investigation of the electronic structure and chemical bonding of actinide elements and their compounds, providing insights into oxidation states, chemical environments, and electronic configurations. This knowledge can aid in comprehending reactivity, stability, and other properties of actinide materials, which is essential for ensuring safe handling, storage, and disposal in nuclear applications. We have reviewed a number of results in actinide core-level photoemission studies, with a particular focus on x-ray photoemission spectroscopy (XPS) techniques. Actinides, due to their inherent radioactivity, have not been as well studied with XPS as have other segments of the periodic table. Given the inherent safety concerns, equipment requirements, and short isotopic lifetimes associated with actinide research, we outline the strategies and precautions necessary for conducting successful and safe XPS experiments on these elements. Core-level photoemission can be a powerful proven tool for investigating the electronic structure, chemical bonding behaviors, and physical properties of actinides, providing valuable insights into an incredibly complex behavior of these systems. We highlight key findings from recent studies that demonstrate the potential of core-level photoemission in uncovering the unique properties of actinides and their compounds. Finally, we identify current knowledge gaps and future research directions that could enhance our understanding of actinide chemistry and physics.

Formation of uranium disulfide from a uranium thioamidate single-source precursor.

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US2, which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L3-edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides.

Actinide targets for the synthesis of superheavy nuclei

The use of heavy actinide targets, including 243Am, 240,242,244Pu, 245,248Cm, 249Bk, and 249Cf, irradiated by intense heavy ion beams of 48Ca has resulted in a significant expansion of the periodic table since 2000, including the discovery of five new heaviest elements and more than 50 new isotopes. These actinide materials can only be produced by intense neutron irradiation in very high flux reactors followed by chemical processing and purification in specialized hot cell facilities available in only a few locations worldwide. This paper reviews the reactor production of heavy actinides, the recovery and chemical separation of actinide materials, and the preparation of actinide targets for superheavy element experiments. The focus is on 248Cm, 249Bk, mixed 249−251Cf, and 254Es, including current availabilities and new production processes. The impacts of new facilities, including the Superheavy Element Factory at Dubna, accelerator and separator upgrades at RIKEN, and proposed upgrades to the High Flux Isotope Reactor at Oak Ridge are also described. Examples of recent superheavy element research are discussed as well as future opportunities for superheavy research using actinide targets.

Sorting of Cluster-Confined Metallic Single-Walled Carbon Nanotubes for Fabricating Atomically Vacant Uranium Oxide.

Single-walled carbon nanotube (SWCNT) heterostructures have shown great potential in catalysis, magnetism, and nanofluidics, in which host SWCNTs with certain conductivity (metallic or semiconducting) are highly required. Herein, inspired by the large molecular weight and redox properties of polyoxometalate (POM) clusters, we reported the selective separation of POM encapsulated metallic SWCNTs (POM@m-SWCNTs) with a uniform diameter through density gradient ultracentrifugation (DGU). The confined POMs increased the SWCNT density and amplified the nanotubes' density difference, thus greatly lowering the centrifugal force (70,000g) of DGU. With this strategy, a series of POM@m-SWCNTs of ∼1.2 nm with high purity were sorted. The mechanism supported by theoretical and experimental evidence showed that the separation of m-SWCNTs depended on not only nanotube/cluster size but also the conductivity of SWCNTs. The smallest 1.2 nm m-SWCNT that can exactly accommodate a 0.9 nm-{Mo6} cluster exhibited the maximum electron transfer to inner clusters; thus, intertube π-π stacking of such m-SWCNTs was greatly loosened, leading to the preferential dispersion into individual ones and partitioning in the uppermost layer after DGU. As a proof-of-concept application, this sorting strategy was extended to separate heavy-element 238U-encapsulated m-SWCNTs. The phase-pure, tiny (1-2.5 nm) U4O9 crystals with atomic vacancy clusters were fabricated on m-SWCNTs through growth kinetic control. This work may provide a general way to construct desired actinide materials on specific SWCNTs.

CO Oxidation to CO2 on Uranium Dioxide Molecules through Intermediate O2U(η1-CO).

Investigations on the reactions of uranium oxide molecules with CO offer new inspiration for the design of promising high-efficiency catalysts for CO activation using actinide materials. Herein, we contribute a combined matrix-isolation infrared spectroscopic and theoretical study of CO oxidation to CO2 on uranium dioxide (UO2) molecules in solid argon. The reaction intermediate O2U(η1-CO) is generated spontaneously at the bands of 1893.0, 870.6, and 801.3 cm-1 during codeposition and annealing. Upon the following irradiation, CO2 is substantially produced by the consumption of O2U(η1-CO), indicating the catalytic conversion of CO to CO2 through the intermediate O2U(η1-CO). In C18O isotopic substitution experiments, the yields of 16OC18O convincingly confirm that one of the oxygen atoms in CO2 derives from UO2. The reaction pathways are discussed based on the theoretical and experimental results.

A data analysis method to rapidly characterize gallium concentration in plutonium matrices using LIBS

The processing of actinide samples is a complex and costly endeavor that requires compositional analysis at various stages. Laser-induced breakdown spectroscopy (LIBS) has been used to analyze actinide-containing samples in many nuclear applications including waste management, fuel processing and forensics. The LIBS spectrum obtained from actinide materials are generally extremely complex, exhibiting many thousands of strong emission lines. This makes it difficult to identify other elements within the sample of interest, given the rich and dominant actinide spectrum. In this article we describe a recent effort to identify and quantify impurities and alloying constituents in plutonium matrices using a hand-held LIBS instrument that is used to rapidly and efficiently measure an emission spectrum from a material sample. We tabulate the emission line positions and intensities of plutonium. We report the development of machine-learning software that can identify gallium and quantify its concentration in plutonium matrices. This work has the potential to provide a rapid and nearly non-destructive technique that allows more confidence in characterizing the composition of materials that are present within complex actinide associated targets. We describe how our LIBS measurements and data analysis methods have successfully quantified the gallium concentration in a variety of samples.

Synchrotron radiation techniques and their application to actinide materials

The actinides comprise a 15-member group of metallic radioactive elements occupying the bottom row of the periodic table. Electron localization accompanied by the formation of large magnetic moments due to the strong Coulomb repulsion is balanced by hybridization with neighboring-atom electronic states. This hybridization promotes an opposite tendency toward itinerancy and the emergence of complex behavior. This review shows how x-ray synchrotron radiation techniques provide a variety of powerful tools to unravel the complexity of actinide materials. Experimental techniques, theoretical background, and applications to actinide materials are covered in detail.

Neutronics analysis of UN-PuN fuel for 300MW pressurized water reactor using SRAC-COREBN code

Nuclear Power Plants (NPP) is one of alternative energy that can be used to replace fossil energy. NPP is a clean energy that doesn't emit CO2 as a residue from the power plant. Pressurized Water Reactor (PWR) is the most widely used commercial reactor to date. This reactor usually uses UO2 as fuel with enrich U-235 and produce plutonium as a waste nuclear. In this study, the fuel uses natural uranium and the addition of plutonium from the spent fuel of PWR, calling it Uranium-Plutonium Nitride (UN-PuN) fuel. Plutonium from spent fuel PWR (U-fueled) consists of Pu-238, Pu-239, Pu-240, Pu-241 and Pu-242, which Pu-239 and Pu-241 are fissile material. The aim of using plutonium is to reduce the amount of nuclear waste and prevent the use of plutonium as a nuclear weapon. The addition of neptunium and protactinium is also carried out in the fuel. Neptunium is one of the minor actinide materials which have high toxicity, so add Np-237 it is very useful to reduce the amount of neptunium in the world. And also, the addition of Np-237 and Pa-231 aims to decrease the keff value both in the Beginning of Life (BOL) and End of Life (EOL) in the reactor. This research calculates the neutronic calculations for PWR use SRAC2006 with COREBN Code and Japanese Evaluated Nuclear Data Library 4.0 (JENDL-4.0) for the nuclear data library. The COREBN code is a calculation method based on interpolation of macroscopic cross-section and finite-difference diffusion theory. The optimum design reached the maximum k-eff value 1.017077 and the maximum power density was 58.47 W/cc. The results obtained are the excess reactivity value of 1.68 % smaller than previous study which produces an excess reactivity value of 11.94 %. So this design has the potential to be applied in the PWR design

UCoO4/Co3O4 Heterojunction as a Low-Cost and Efficient Electrocatalyst for Oxygen Evolution.

The development of actinide materials has provided new strategies for the utilization of nuclear waste, such as depleted uranium, a mildly radioactive waste in the nuclear power industry, which could be a precious resource for many fields, especially water splitting. The catalytic performance of water splitting is limited by the slow kinetics of the oxygen evolution reaction (OER), and it is extremely challenging to design efficient OER catalysts that are highly stable and inexpensive. Here, we design and describe a series of U5-35%-Co3O4 electrocatalysts, which were synthesized using uranyl nitrate as a precursor via a simple and scalable method. Interestingly, when the U/Co molar ratio was 20%, a UCoO4/Co3O4 heterojunction formed with high catalytic efficiency and excellent long-term electrolytic stability. The UCoO4/Co3O4 heterojunction catalyst shows a lower overpotential (280 mV) at a current density of 10 mA cm-2, and the slope of Tafel is 43.8 mV decade-1 in a 0.1 M KOH alkaline solution. Soft X-ray absorption spectroscopy shows that the cooperative effect of UCoO4 and Co3O4 can improve the electrochemical activity of the material. This study produced an active U/Co-based catalyst for OER, which provides a simple, scalable, low-cost, and highly efficient catalyst for overall water splitting.

Induced Ferromagnetism in Epitaxial Uranium Dioxide Thin Films.

Actinide materials have various applications that range from nuclear energy to quantum computing. Most current efforts have focused on bulk actinide materials. Tuning functional properties by using strain engineering in epitaxial thin films is largely lacking. Using uranium dioxide (UO2 ) as a model system, in this work,the authors explore strain engineering in actinide epitaxial thin films and investigate the origin of induced ferromagnetism in an antiferromagnet UO2 . It is found that UO2+ x thin films are hypostoichiometric (x<0) with in-plane tensile strain, while they are hyperstoichiometric (x>0) with in-plane compressive strain. Different from strain engineering in non-actinide oxide thin films, the epitaxial strain in UO2 is accommodated by point defects such as vacancies and interstitials due to the low formation energy. Both epitaxial strain and strain relaxation induced point defects such as oxygen/uranium vacancies and oxygen/uranium interstitials can distort magnetic structure and result in magnetic moments. This work reveals the correlation among strain, point defectsand ferromagnetism in strain engineered UO2+ x thin films and the results offer new opportunities to understand the influence of coupled order parameters on the emergent properties of many other actinide thin films.

A New Concept of Radiation Detection Based on a Fluorochromic and Piezochromic Nanocluster.

Developing materials that possess colorimetric responses to external stimuli is a promising strategy for addressing the current challenges in radiation dosimetry. Currently, colorimetric ionizing-radiation-responsive materials remain underexplored, and those with multistimuli response are rare. Herein, the integration of thorium cation and photoresponsive terpyridine carboxylate ligand gives rise to a thorium nanocluster, Th-101, which displays the second case of fluorochromic response and unprecedented piezochromic behavior among all actinide materials. The emission color of Th-101 exhibits a gradual transition from blue to cyan to green upon irradiation with accumulated dose, which renders colorimetric dosimetry of ionizing radiation based on a red-green-blue (RGB) concept. Further fabricating Th-101 into a custom-built optoelectronic device allows for on-site quantification of radiation dose with merits of ease of operation, rapid readout, and cost-effectiveness.

X-ray synchrotron radiation studies of actinide materials.

By reviewing a selection of X-ray diffraction (XRD), resonant X-ray scattering (RXS), X-ray magnetic circular dichroism (XMCD), resonant and non-resonant inelastic scattering (RIXS, NIXS), and dispersive inelastic scattering (IXS) experiments, the potential of synchrotron radiation techniques in studying lattice and electronic structure, hybridization effects, multipolar order and lattice dynamics in actinide materials is demonstrated.

A spectroscopic hike in the U-O phase diagram.

The U-O phase diagram is of paramount interest for nuclear-related applications and has therefore been extensively studied. Experimental data have been gathered to feed the thermodynamic calculations and achieve an optimization of the U-O system modelling. Although considered as well established, a critical assessment of this large body of experimental data is necessary, especially in light of the recent development of new techniques applicable to actinide materials. Here we show how in situ X-ray absorption near-edge structure (XANES) is suitable and relevant for phase diagram determination. New experimental data points have been collected using this method and discussed in regard to the available data. Comparing our experimental data with thermodynamic calculations, we observe that the current version of the U-O phase diagram misses some experimental data in specific domains. This lack of experimental data generates inaccuracy in the model, which can be overcome using in situ XANES. Indeed, as shown in the paper, this method is suitable for collecting experimental data in non-ambient conditions and for multiphasic systems.

UCN@Cs(6)-C82: An Encapsulated Triangular UCN Cluster with Ambiguous U Oxidation State [U(III) versus U(I)

Understanding the chemical behavior of actinide elements is essential for the effective management and use of actinide materials. In this study, we report an unprecedented η2 (side-on) coordination of U by a cyanide in a UCN cluster, which was stabilized inside a C82 fullerene cage. UCN@Cs(6)-C82 was successfully synthesized and fully characterized by mass spectrometry, single crystal X-ray crystallography, cyclic voltammetry, spectroscopy, and theoretical calculations. The bonding analysis demonstrates significant donation bonding between CN- and uranium, and covalent interactions between uranium and the carbon cage. These effects correlate with an observed elongated cyanide C-N bond, resulting in a rare case where the oxidation state of uranium shows ambiguity between U(III) and U(I). The discovery of this unprecedented triangular configuration of the uranium cyanide cluster provides a new insight in coordination chemistry and highlights the large variety of bonding situations that uranium can have.

Bayesian Approach for Multigamma Radionuclide Quantification Applied on Weakly Attenuating Nuclear Waste Drums

Gamma spectrometry is a passive nondestructive assay method used to quantify radionuclides present in nuclear objects. Basic methods using empirical calibration with a standard to quantify the activity of nuclear materials by determining the calibration coefficient are ineffective on nonreproducible nuclear objects such as waste packages. Package specifications such as composition or geometry change from one package to another and exhibit large variability of objects. The current standard quantification process uses numerical modeling of the measured scene with few available data such as geometry or composition, in particular density, material, screen, geometric shape, matrix composition, matrix, and source distribution. Some of them are strongly dependent on package data knowledge and operator backgrounds. The French Atomic Energy Commission (CEA) is developing a methodology to quantify nuclear materials in waste packages and waste drums without operator adjustment and internal package configuration knowledge. This method suggests combining a stochastic approach which uses, among others, surrogate models available to simulate the gamma attenuation behavior, a Bayesian approach considering conditional probability densities and prior information of problem inputs, and Markov Chain Monte Carlo (MCMC) algorithms which solve inverse problems, with gamma ray emission radionuclide spectra, and the outside dimensions of the objects of interest. The methodology has been tested to quantify actinide activity with a low bulk density matrix, weakly attenuating compositions, without information on the distribution of the source in terms of actinide masses and materials composing the drums. Activity uncertainties are taken into account.

Double-Layer Nitrogen-Rich Two-Dimensional Anionic Uranyl-Organic Framework for Cation Dye Capture and Catalytic Fixation of Carbon Dioxide.

A novel two-dimensional double-layer anionic uranyl-organic framework, U-TBPCA {[NH2(CH3)2][(UO2)(TBPCA)], where H3TBPCA = 4,4',4″-s-triazine-1,3,5-triyltripamino-methylene-cyclohexane-carboxylate}, with abundant active sites and stability was obtained by assembling UO2(NO3)2·6H2O and a triazine tricarboxylate linker, TBPCA3-. Due to the flexibility of the ligand and diverse coordination modes between carboxyl groups and uranyl ions, U-TBPCA exhibits an intriguing topological structure and steric configuration. This double-layer anionic uranyl-organic framework is highly porous and can be used for selective adsorption of cationic dyes. Due to the presence of high-density metal ions and basic -NH- groups, U-TBPCA acts as an effective heterogeneous catalyst for the cycloaddition reaction of carbon dioxide with epoxy compounds. Moreover, the various modes of coordination between the tricarboxylic ligand and uranyl ion were studied by density functional theory calculations, and several simplified models were established to probe the influence of hydrogen bonding between carbon dioxide and U-TBPCA on the ability of U-TBPCA to bind carbon dioxide. This work should aid in improving our understanding of the coordination behavior of uranyl ion as well as the development and utilization of new actinide materials.

Topology of the Electron Density and of Its Laplacian from Periodic LCAO Calculations on f-Electron Materials: The Case of Cesium Uranyl Chloride.

The chemistry of f-electrons in lanthanide and actinide materials is yet to be fully rationalized. Quantum-mechanical simulations can provide useful complementary insight to that obtained from experiments. The quantum theory of atoms in molecules and crystals (QTAIMAC), through thorough topological analysis of the electron density (often complemented by that of its Laplacian) constitutes a general and robust theoretical framework to analyze chemical bonding features from a computed wave function. Here, we present the extension of the Topond module (previously limited to work in terms of s-, p- and d-type basis functions only) of the Crystal program to f- and g-type basis functions within the linear combination of atomic orbitals (LCAO) approach. This allows for an effective QTAIMAC analysis of chemical bonding of lanthanide and actinide materials. The new implemented algorithms are applied to the analysis of the spatial distribution of the electron density and its Laplacian of the cesium uranyl chloride, CsUOCl, crystal. Discrepancies between the present theoretical description of chemical bonding and that obtained from a previously reconstructed electron density by experimental X-ray diffraction are illustrated and discussed.