Engineering topics
Publications and source records attributed to Burns, Peter C..
He 2+ -beam irradiation of the uranyl peroxide cage cluster Li–U 28 to high doses leads to breakdown of the cage cluster and ultimately to the formation of uranyl carbonate species.
First reported (Np VI O 2 ) 2 (PO 4 ) 2 2− sheets based upon the uranophane anion topology, that are bonded via π–π interactions between the Np VI O 2 (Terpy) 2+ ligands that are perpendicular to the sheets.
This project was initially funded in 2007 and the current technical report is for 2019-2022. The specific objectives of this project (2019-2022) were: (1) Synthesis of actinide peroxide compounds in molten salt eutectics, (2) Studies of new uranyl minerals with fascinating structures and compositions, (3) Drop-solution calorimetric studies of actinide compounds extending into the transuranium elements, with an emphasis on the uranyl-sulfate system, (4) Continuation of studies of uranyl vanadate clusters synthesized using ionic liquids, (5) The training of Ph.D. graduate students in actinide chemistry, and to introduce undergraduate students to actinide research through providing research assistantships and supervision. The report lists 67 archival journal papers describing the work, of which 23 were since 2019. Highlights of the work are summarized for the period 2019-2022.
We report the first crystal structure of a Pu(VI)-oxalate compound. This compound, [PuO 2 (C 2 O 4 )(H 2 O)]·2(H 2 O) (1), crystallizes in space group P21/c with a = 5.5993(3) Å, b = 16.8797(12) Å, c = 9.3886(6) Å, and β = 98.713(6)°. It is isostructural with the previously reported U(VI) compound, [UO 2 (C 2 O 4 )(H 2 O)]·2(H 2 O). Each plutonyl ion (PuO 2 2+ ) is coordinated in the equatorial plane by two side-on bidentate oxalates, creating an infinite chain along [001]. A coordinated water molecule and twisting of the oxalates lead to a distorted pentagonal bipyramidal geometry of the Pu. A photochemical degradation was observed for 1, which resulted in the formation of a secondary crystalline phase. The absorption spectrum of this secondary phase confirmed the presence of Pu(IV), but it did not match the spectrum of Pu(C 2 O 4 ) 2 ·6H 2 O, which is considered to be the primary product of Pu-oxalate precipitation. While compound 1 has previously been proposed to exist in solution, this is the first time it has been isolated via crystallization. Although redox interactions between Pu and oxalate have been documented in the literature, the present study is the first observation of a photochemical reduction of Pu(VI)-oxalate. Finally, this study has expanded on the limited understanding of the Pu(VI)-oxalate system, which is important for nuclear fuel cycle applications.
ABSTRACT Shinkolobweite, Pb1.333[U5+O(OH)(UO2)5O4.67(OH)5.33](H2O)5, is a new lead uranyl oxide-hydroxide hydrate mineral containing hexavalent and pentavalent uranium from the Shinkolobwe mine, Democratic Republic of Congo. Crystals of shinkolobweite are dark reddish-brown prisms up to 0.5 mm in length, occurring on a matrix of massive uraninite associated with fourmarierite, rutherfordine, soddyite, and sklodowskite. Crystals are translucent with subadamantine luster and light bronze-yellow streak, are flattened on {010}, are elongated on [001], and exhibit the forms {100}, {010}, {101}, and . The mineral is non-fluorescent under both longwave and shortwave ultraviolet illumination. It has a Mohs hardness of ∼2 and exhibits brittle tenacity with perfect cleavage on {010}, imperfect cleavage on {100}, and even fracture. The calculated density is 5.853 g/cm3 based on the empirical formula. Electron probe microanalysis provided the empirical formula Pb1.290U6+4.876U5+1.166O27H16.633 based on 27 O apfu and U5+:U6+ determined by X-ray photoelectron spectroscopy. Shinkolobweite is orthorhombic, superspace group Pnnm(0b0)000, a = 14.4808(4), b = 7.0681(8), c = 11.9423(3) Å, V = 1222.32(15) Å3, modulation wave vector [0 1/3 0], and Z = 2. The structure was refined from 8959 reflections to a final R1 = 0.0736 for all reflections. Uranyl oxide-hydroxide sheets in shinkolobweite adopt the β-U3O8 topology and possess (3 + 1) commensurately modulated ordering that results from the long-range ordering of U5+ and U6+ in the sheet, as well as the position and occupancy of interlayer Pb2+ cations. Observations of a topological transition between α-U3O8 and β-U3O8 type sheets in shinkolobweite supplements our understanding of U5+ mineral oxidation and stability.
Combustion reactions in europium nitrate – acetylacetone – 2-methoxyethanol solutions and gels were investigated to produce europium (III) oxide (Eu 2 O 3 ) nanocrystalline materials and thin films. Thermal analyses of solutions indicated that the 2-methoxyethanol solvent also acts as a fuel in the absence of acetylacetone. Adding acetylacetone increases the overall heat of the reaction. Thermal analysis results revealed that the slow oxidation of unburned hydrocarbon residues follows the primary combustion reaction. Time-temperature profile measurements of the bulk combustion synthesis process in air and nitrogen atmospheres enabled the extraction of the maximum reaction temperature and the heating and cooling rates in the combustion zone. Several direct correlations exist between measured combustion parameters and the phase composition of the products. Combustion in air results in mixed-phase cubic and monoclinic nanocrystalline Eu 2 O 3 . Increasing the acetylacetone concentration in solutions increases the synthesis temperature and decreases the quantity of cubic Eu 2 O 3 . Here, the reaction of solutions in a nitrogen atmosphere or diluted with Eu 2 O 3 provides control of the product phase composition and reduces the quantity of the monoclinic phase. Transmission electron microscopy imaging shows that the Eu 2 O 3 end products are highly porous aggregates of nanocrystalline particles. Electrospraying of reactive solutions onto different substrates followed by short annealing makes the preparation of Eu 2 O 3 materials with diverse morphologies possible.
A simple and efficient target preparation method is developed combining spin coating and solution combustion synthesis. Multiple smooth and uniform UO 2 targets have been prepared using this method on a variety of backings (aluminium, carbon, silicon) used in nuclear physics experiments. The thicknesses of the targets can be precisely tuned by changing the number of coatings within the range of ~50-1000 µm/cm 2 . These targets are highly uniform (<5% deviation), robust, and remain strongly adherent to their backings even after being irradiated by high doses (10 17 ions/ cm 2 ) of 1.7 MeV Ar 2+ ions.
Plutonium(IV) oxalate hexahydrate (Pu(C 2 O 4 ) 2 ∙ 6H 2 O; PuOx) is an important intermediate in the recovery of plutonium from used nuclear fuel. Its formation via precipitation is well studied, yet its crystal structure remains unknown. Instead, the crystal structure of PuOx is assumed to be isostructural with neptunium(IV) oxalate hexahydrate (Np(C 2 O 4 ) 2 ∙ 6H 2 O; NpOx) and uranium(IV) oxalate hexahydrate (U(C 2 O 4 ) 2 ∙ 6H 2 O; UOx) despite the high degree of unresolved disorder that exists when determining water positions in the crystal structures of the latter two compounds. Such assumptions regarding the isostructural behavior of the actinide elements have been used to predict the structure of PuOx for use in a wide range of studies. Herein, we report the first crystal structures for PuOx and Th(C 2 O 4 ) 2 · 6H 2 O (ThOx). This data, along with new characterization of UOx and NpOx, has resulted in the full determination of the structures and resolution of the disorder around the water molecules. Specifically, we identify the coordination of two water molecules with each metal center, which necessitates a change in oxalate coordination mode from axial to equatorial that has not been reported in the literature. Here this work exemplifies the need to revisit previous assumptions regarding fundamental actinide chemistry, which are heavily relied upon within the current nuclear field.
Combustion synthesis is used to prepare thin UO 2 films on aluminum alloy substrates. This simple preparation method involves electrospraying uranyl nitrate + acetylacetone + 2-methoxyethanol solution on the substrate, followed by a short annealing at 350 or 550 °C. The irradiation of films with a 40 Ar 2+ ion beam (energy of 1.7 MeV and fluences of 7.7 × 10 16 and 1.3 × 10 17 ions/cm 2 ) is conducted to investigate irradiation-induced restructuring processes. High-resolution transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) investigations show that the annealing temperature significantly influences the crystallinity and stability of materials during irradiation. A small amount of Mg in the alloy substrate diffuses into the amorphous Al 2 O 3 interfacial layer between the film and the substrate. Local thermal spikes from the incoming ions facilitate the irradiation-induced mixing of immiscible Al 2 O 3 and UO 2 for the materials prepared at 350 °C. This mass diffusion produces relatively large cavities at the interface. Selective diffusion of a more significant amount of Mg for the materials prepared at 550 °C suppresses the mixing of the Al 2 O 3 interlayer with the film but forms Mg y U 1–y O 2±x solid solutions during irradiation. Local thermal heating triggers the precipitation of a discontinuous crystalline MgO layer close to the film surface. As a result, the enhanced and selective diffusion of Mg into the film makes the materials prepared at 550 °C more robust and mechanically stable than those prepared at 350 °C.
Finchite (IMA2017-052), Sr(UO 2 ) 2 (V 2 O 8 )·5H 2 O, is the first uranium mineral known to contain essential Sr. The new mineral occurs as yellow-green blades up to ~10 µm in length in surface outcrops of the calcrete-type uranium deposit at Sulfur Springs Draw, Martin County, Texas, U.S.A. Crystals of finchite were subsequently discovered underground in the Pandora mine, La Sal, San Juan County, Utah, U.S.A., as diamond-shaped golden-yellow crystals reaching up to 1 mm. In this work, the crystal structure of finchite from both localities was determined using single-crystal X-ray diffraction and is orthorhombic, Pcan, with a = 10.363(6) Å, b = 8.498(5) Å, c = 16.250(9) Å, V = 1431.0(13) Å 3 , Z = 4 (R 1 = 0.0555) from Sulfur Springs Draw; and a = 10.3898(16), b = 8.5326(14), c = 16.3765(3) Å, V = 1451.8(4) Å 3 , Z = 4 (R 1 = 0.0600) from the Pandora mine. Electron-probe microanalysis provided the empirical formula (Sr 0.88 K 0.17 Ca 0.10 Mg 0.07 Al 0.03 Fe 0.02 ) Σ1.20 (UO 2 ) 2 (V 2.08 O 8 )·5H 2 O for crystals from Sulfur Springs Draw, and (Sr 0.50 Ca 0.28 Ba 0.22 K 0.05 ) Σ0.94 (U 0.99 O 2 ) 2 (V 2.01 O 8 )·5H 2 O for crystals from the Pandora mine, based on 17 O atoms per formula unit. The structure of finchite contains uranyl vanadate sheets based upon the francevillite topology. Finchite is a possible immobilization species for both uranium and the dangerous radionuclide 90 Sr because of the relative insolubility of uranyl vanadate minerals in water.
Two uranium dioxide (UO 2 ) targets of (414 ± 23) nm and (1092 ± 93) nm thicknesses were prepared on 6061 aluminum alloy and puratronic grade aluminum backing materials. The targets were deposited with a novel method combining spin coating and solution combustion synthesis (SCS). The target layers consisted of small (3–7 nm) UO 2 grains and uniformly distributed ultra-small (1–3 nm) pores. The prepared targets were tested at the Los Alamos National Laboratory’s LANSCE facility for neutron irradiation damage and suitability for neutron capture experiments. The samples showed no signs of target material loss after the irradiation. However, irradiation caused a significant increase in the grain size (4–10 nm), as well as upward mass diffusion and coalescence of the pores due to the thermal spikes. The magnesium in the aluminum 6061 alloy backing also diffused into the UO 2 layer during neutron irradiation. The structural changes in the target after the irradiation do not affect the data from neutron capture. As a result, the new method can be used more broadly to prepare other actinide targets for nuclear physics experiments.
Robust and versatile metal–organic frameworks (MOFs) have emerged as sophisticated scaffolds to meet the critical needs of the nuclear community, but their performance depends on their underexplored structural integrities in high- radiation fields. The contributions of selected metal nodes in the radiation stability of MOFs within the isostructural M-UiO-66 series (where M = Zr, Ce, Hf, Th, and Pu; Zr-UiO-66 experiments were executed in a previous work) have been determined. Ce-, Hf-, and Th-UiO-66 MOF samples were irradiated via gamma and He-ion methodologies to obtain doses up to 3 MGy and 85 MGy, respectively, the latter strikingly higher than that obtained in most other studies. Appreciable self-irradiation constituted the total absorbed doses, up to 31 MGy of the gamma-irradiated Pu-UiO-66 samples. Structural degradation was ascertained by powder X-ray diffraction, X-ray total scattering, vibrational spectroscopy, and, where possible, N 2 physisorption isotherms. Diffuse reflectance infrared Fourier transform spectroscopy provided atomic-level mechanistic insights to reveal that the node-linker connection was most susceptible to radiation damage. Density functional theory calculations were performed on cluster models to evaluate the binding energy of the linkers to each metal node. Here, while the isostructures disclosed the same breakdown signatures, distinct radiation sensitivity as a function of metal selection was evident and followed the trend Hf-UiO-66 ~ Zr-UiO-66 > Th-UiO-66 > Pu-UiO-66 > Ce-UiO-66. We anticipate that these endeavors will contribute to the rational design of radiation-resistant materials for targeted applications.
Spraying-assisted combustion synthesis with uranyl nitrate – acetylacetone – 2-methoxyethanol solutions was used to prepare UO 2 films on an aluminum alloy substrate. The tuning of the spraying parameters and annealing temperatures allowed the preparation of UO 2 films with thicknesses varying from 10–300 nm and 5–10 nm UO 2 grain size. High-resolution electron microscopy and X-ray photoelectron spectroscopy showed that increasing the annealing temperature promotes Mg diffusion from the substrate into the films. The incorporation of Mg reduced the overall crystallinity of the films. The irradiation with Ar 2+ ions (1.7 MeV energy and a fluence of 2 × 10 16 ions/cm 2 ) did not degrade the quality of the films. However, the Mg content significantly influenced the irradiation-induced restructuring of the UO 2 films. Irradiated films with low or no Mg content exhibit high crystallinity, and the UO 2 /Al interfacial layer becomes highly porous. Films with higher Mg content are mostly amorphized after irradiation. The origin of irradiation-induced amorphization was related to the formation of Mg y U 1-y O 2±x solid solutions. Chemically complex, pore-free, and amorphous Mg-Al-O film/substrate interfacial layers enable continuous Mg diffusion during irradiation. As a result, the gradual increase in Mg amounts triggers irradiation-induced precipitation of a crystalline MgO-rich phase within the amorphous films.
Aqueous solutions of lithium uranyl triperoxide, Li 4 [UO 2 (O 2 ) 3 ] (LiUT), were irradiated with gamma rays at room temperature and found to form the uranyl peroxide cage cluster, Li 24 [(UO 2 )(O 2 )(OH)] 24 (Li–U 24 ). Raman spectroscopy and 18 O labeling were used to identify the Raman-active vibrations of LiUT. With these assignments, the concentration of LiUT was tracked as a function of radiation dose. A discrepancy between monomer removal and cluster formation suggests that the reaction proceeds by the assembly of an intermediate. Non-negative matrix factorization was used to separate Raman spectra into components and resulted in the identification of a unique intermediate species. Much of the conversion appears to be driven by water radiolysis products, particularly the hydroxyl radical. Furthermore, this differs from the 18 O-labeled copper-catalyzed formation of U 24 , which progresses at a steady rate with no observation of intermediates. Li–U 24 in solution decomposes at high radiation doses resulting in a solid insoluble product similar to Na-compreignacite, Na 2 (UO 2 ) 6 O 4 (OH) 6 ·7H 2 O, which contains uranyl oxyhydroxy sheets.
Mechanochemistry enables transformations of highly insoluble materials such as uranium dioxide or the mineral studtite [(UO 2 )(O 2 )(H 2 O) 2 ]·(H 2 O) 2 into uranyl triperoxide compounds that can subsequently assemble into hydroxide-bridged uranyl peroxide dimers in the presence of lithium hydroxide. Dissolution of these solids in water yields uranyl peroxide nanoclusters including U 24 , Li 24 [(UO 2 )(O 2 )(OH)] 24 . Insoluble uranium solids can transform into highly soluble uranyl peroxide phases in the solid state with miniscule quantities of water. Furthermore, such reactions are potentially applicable to uranium processing in the front and back end of the nuclear fuel cycle.