Engineering topics

Parker, Connor J.

Publications and source records attributed to Parker, Connor J..

6 records

DOE OSTI2024

Quantitative Particle Analysis of Neptunium-237 Oxides: Optimization of MAMA Analysis for Modified Direct Denitration Products

The production of plutonium-238 through irradiation of neptunium-237 ( 237 Np) target materials for the use in radioisotope thermoelectric generators is paramount for continued deep space exploration. This work employs scanning electron microscopy to analyze 237 Np materials coupled with a well-developed image analysis framework (Morphological Analysis for Material Attribution, or MAMA) to determine the degree of micron-scale homogeneity in the materials. This work demonstrated how the quantification of particle characteristics can validate production materials and affirm the qualitative similarities observed in micrographs. The 237 Np oxide particle analysis determined that the materials from five production runs were quantitatively homogenous (significant at α = 0.05) in particle area, circularity, equivalent circular diameter, and ellipse aspect ratio, with two of the sampling dates having statistically significant different means for one of the four characteristics. Furthermore, these metrics not only confirm general homogeneity of the material but also expand the application of MAMA workflows to 237 Np materials, demonstrating the utility of MAMA analysis for a wider breadth of nuclear materials than previously reported. In the open literature, this study is the first time that these microanalytical techniques were applied to 237 Np materials to this degree.

MAMA↗

DOE OSTI2024

Simultaneous Thermal Analysis of Anion and Cation Exchange Resins

The decomposition reactions of one anion exchange resin (Bio-Rad AG MP-1) and one cerium-loaded cation exchange resin (DOWEX 50W-X8), both in nitrate form, were analyzed using simultaneous thermal analysis methods. Thermogravimetric analysis, dynamic scanning calorimetry, and evolved gas analysis were deployed in combination to probe the temperature profiles, reaction enthalpies, and off-gases from these resins under process-relevant temperature ranges. Analysis indicates that both resins undergo three clear phases during heating. The first is a dehydration step with prominent off-gassing of water, the second is a decomposition step with evolution of several gaseous species, and lastly is a combustion step with a large release of CO 2 . The temperature at which combustion ends varies slightly between AG MP-1 and DOWEX 50W: combustion completed at ~690°C and ~810°C, respectively. For the DOWEX cation resin, the combustion reaction showed greater sensitivity to the availability of oxygen under the test conditions. Both resins displayed broad exotherms during the combustion step of the decomposition, but the DOWEX cation resin demonstrated a 4.5 times higher specific enthalpy than that of the AG MP-1.

36 MATERIALS SCIENCE↗

DOE OSTI2023

Analysis of neptunium oxides produced through modified direct denitration

Production of neptunium-237 ( 237 Np) target materials for plutonium-238 ( 238 Pu) radioisotope thermoelectric generators (RTGs) for deep space exploration requires advanced chemistry and engineering development. Currently, the domestic Pu-238 Supply Program at Oak Ridge National Laboratory produces neptunium dioxide (NpO 2 ) for target material using a modified direct denitration (MDD) flowsheet. Although the chemistry, reaction mechanisms, and product characteristics of MDD are well understood for uranium, corresponding studies of the neptunium system are still needed to continue optimization of target material properties, production equipment design, and production flowsheets. Here, the objective of this work is to characterize crystalline phases, morphology, surface texture, and particle size of NpO 2 produced via MDD reactions. Solid-phase characterization techniques, including powder X-ray diffraction (pXRD) and scanning electron microscopy with energy-dispersive spectroscopy (SEM-EDS), were employed to achieve this objective. Subsequent data processing using the Morphological Analysis for Material Attribution (MAMA) software was performed to analyze particle morphology and size. Broadly, the powders were found to contain a mixture of NpO 2 and Np 2 O 5 after denitration with a variety of morphologies. After high-firing, the product was found to be NpO 2 with a typical polycrystalline oxide morphology and a grain size ranging from 0.72 to 0.94 µm. These analyses provide knowledge on the reaction pathway for a non-traditional NpO 2 synthesis method and offer additional unique insight into production-scale environments for transuranic materials.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2023

Natural attenuation of uranium in a fluvial Wetland: Importance of hydrology and speciation

A nuclear fuel fabrication facility released 43,500 kg of uranium into a riparian wetland located on the Savannah River Site between 1955 and 1988. Studies were undertaken to evaluate hydrological and geochemical processes influencing uranium accumulation in the wetland. Gamma-radiation-mapping surveys were conducted by systematically walking over the contaminated wetland with backpacks equipped with global positioning systems and NaI gamma detectors. Based on maps compiled from >700,000 gamma spectra and eight sediment uranium depth profiles, it was determined that 94% of the released uranium remained in the wetland. The uranium in the wetland is concentrated in five multi-hectare areas along the stream, accounting for ~11% of the land area adjacent to the stream. While land type (upland or wetland) and topography provided a reasonable first approximation of where much of the uranium was deposited, hydrological watershed modeling revealed that the stream velocity was especially slow through many of the hot spots. Here, using autoradiography combined with SEM/EDX measurements of contaminated sediments, surprisingly few hot particles were detected. Instead, uranium was evenly distributed throughout the sampled sediment, suggesting that dissolved uranium had bound to sediment particles that became suspended and later deposited in low energy (low flow velocity) portions of the stream. EXAFS suggested that U atoms were present as individual ions in disordered complexes within the sediment. Furthermore, linear combination analyses suggested that the predominant component of the U(VI) was adsorbed to sediment minerals (~70%) and a minor component (~30%) was associated with organic matter phases. Furthermore, these studies show that wetlands can be extraordinarily effective at binding and retaining uranium, thereby providing a natural barrier to the transport of uranium out of a watershed. However, significant anthropogenic or climatic changes to wetlands, such as those associated with flooding, forest fires, or land use, may disrupt the complex hydrological and biogeochemical balance necessary to maintain long-term immobilization of uranium.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2021

Uranium Attenuated by a Wetland 50 Years after Release into a Stream

: Wetlands have several important roles in the hydrological cycle, including maintaining water quality by removing surface and groundwater contaminants. Over time, the wetlands themselves can become contaminated, posing a secondary environmental threat. The objective of this study was to calculate the inventory of uranium (U) remaining in a wetland 50 years after the Fuel Fabrication Facility on the Savannah River Site located in South Carolina released 43.5 Mg of U into the nearby environment. Over 232 700 gamma spectra and their associated global positioning system (GPS) coordinates were collected and collated into a map of the contaminated land area. Five core samples were also collected that contained U concentrations as high as 14 099 mg/kg (background levels are about 2.7 mg/kg U). The contaminated area was 278 000 m2 , and it contained 36.2 Mg U, about 83% of the U released. About 80% of the U in the wetland was concentrated in a former beaver pond, a 73 000 m2 area (26% of the contaminated area). This contaminated wetland area was almost 2 km from the source, indicating that it comprised unique hydro-biogeochemical properties for immobilizing the released U. To the best of our knowledge, this is the first data-rich study to quantify the long-term effectiveness of a wetland to immobilize inorganic contaminants. Significant environmental changes to the system, such as those associated with hydrology, forest fires, or anthropogenic land use, may alter the complex hydro-biogeochemical interactions necessary for the long-term immobilization of the U.

Contaminant inventory↗

DOE OSTI2020

Dissolution of poorly soluble uranyl phosphate phases in the Metaautunite Subgroup under uranyl peroxide cage cluster forming conditions

Uranyl phosphate minerals are widespread in uranium deposits and usually exhibit very low solubility in aqueous systems. Uranyl phosphates of the autunite group and metaautunite subgroup impact the mobility of uranium in the environment and have inspired groundwater remediation strategies that emphasize their low solubility. The importance of soluble uranium-bearing macro-anions, including nanoscale uranyl peroxide cage clusters, is largely unexplored relative to solubilization of normally low-solubility uranium minerals. Eight synthetic analogs of metaautunite subgroup minerals have been prepared and placed in various alkaline aqueous solutions containing hydrogen peroxide and tetraethylammonium hydroxide. Each uranyl phosphate studied has a topologically identical anionic sheet of uranyl square bipyramids and phosphate tetrahedra combined with various cations (Li + , Na + , K + , Rb + , Cs + , Mg 2+ , Ca 2+ , Ba 2+ ) and water in the interlayer. Uranyl peroxides formed under many of the experimental conditions examined, including solid studtite [(UO 2 )(O 2 )(H 2 O) 2 ](H 2 O) 2 and soluble uranyl peroxide cage clusters containing as many as 28 uranyl ions. Uranyl phosphate solids in contact with solutions in which uranyl peroxide cage clusters formed dissolved extensively or completely. The greatest dissolution of uranyl phosphates occurred in systems that contained cations with larger hydrated radii, Li + and Na + . The details of the uranium speciation in solution depended on the pH and counter cations provided from the interlayers of the uranyl phosphate solids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗