Taking the measure of molten uranium oxide
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nuclear (including radiation effects), materials a↗
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Uranium Measurement Control and Total Uranium Concentration Determination
Abstract Not Provided
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Translation into English of Report CEA-R-5070, issued February 1981, by Gilbert Roussotte, ‘Contribution a l'Etude d'un Alliage Industriel d'Uranium-Niobium a 6% en Poids de Niobium’ [‘Contribution to Studies of an Industrial Alloy Uranium-Niobium with 6 Weight% Niobium’]
This translation of report CEA-R-5070, from the French original, was done during September-November 2018, using Google Translate, a web-based service, translate.google.com. After the initial translation through Google Translate, the text was corrected to avoid mistranslation where the author’s intent was reasonably clear.
36 MATERIALS SCIENCE↗
Reflector-based poison-drum control on equal-size reactor cores fueled with uranium-233 and with uranium-235
Reflector based poison drum control on equal size reactor cores fueled with U-233 and U-235
Mayo, W.↗
Measurement of the total cross section of uranium-uranium collisions at root s(NN) = 192.8 GeV
N/A
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Fission Fragment Mass Distributions and Total Kinetic Energy Release of 235-Uranium and 238-Uranium in Neutron-Induced Fission at Intermediate and Fast Neutron Energies
This Ph.D. dissertation describes a measurement of the change in mass distributions and average total kinetic energy (TKE) release with increasing incident neutron energy for fission of 235 U and 238 U. Although fission was discovered over seventy-five years ago, open questions remain about the physics of the fission process. The energy of the incident neutron, En, changes the division of energy release in the resulting fission fragments, however, the details of energy partitioning remain ambiguous because the nucleus is a many-body quantum system. Creating a full theoretical model is difficult and experimental data to validate existing models are lacking. Additional fission measurements will lead to higher-quality models of the fission process, therefore improving applications such as the development of next-generation nuclear reactors and defense. This work also paves the way for precision experiments such as the Time Projection Chamber (TPC) for fission cross section measurements and the Spectrometer for Ion Determination in Fission (SPIDER) for precision mass yields.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Uranium Silicide and Uranium Silicide-Nitride Fuels: Assessing Phase Behavior for Fabrication and In-Reactor Behavior
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L. Wilson, Tashiema↗
Cost Analysis of Wind and Uranium from Seawater Acquisition symbiotic Infrastructure using Shell Enclosures
At current consumption rates, global conventional reserves of uranium, estimated to be 7.6 million tonnes, could be depleted in a little over a century. As these reserves decrease, extraction of uranium is expected to shift to lower quality sites, resulting in higher extraction costs and greater environmental impact. Fortunately, the ocean contains approximately 4.5 billion tonnes of uranium, as uranyl ions at low concentrations of about 3 ppb. Uranium from seawater is a widely studied topic due to the long term security it can assure the nuclear fuel cycle. Additionally, harvesting uranium from seawater could reduce some of the environmental impacts associated with the recovery of land-based uranium. Seawater uranium is meant to create a cost ceiling that provides economic stability and potential savings, not to act as a direct competitor to terrestrial uranium. A recent review of uranium recovery technologies by found uranium adsorption by chelating polymers to be the most promising in terms of adsorbent capacity, environmental footprint, and cost. In this technology, chelating polymers are deployed in seawater and remain submerged until the amount of captured uranium approaches the adsorption capacity. Then, an elution bath is used to strip metal ions, such as uranium, off the adsorbent polymer. A polymer may be immersed in a number of elution baths before it is regenerated by an alkali wash to free its functional groups, allowing for the reuse of the polymer. The output from the elution process undergoes purification and precipitation typical for mined uranium to produce yellowcake. Offshore systems for the extraction of uranium from seawater have been developed since the early 2000's. The system currently studied by a nationwide consortium of national laboratory and university partners utilizes continuous adsorbent polyethylene fibers that are braided around a porous polypropylene float which can be made into long lengths. However, because this deployment scheme requires the adsorbent be brought to a mother-ship for the elution process and redeployed afterward, it has significant practical and economic deployment challenges. Detailed economic analysis have identified the adsorbent production and mooring as the most expensive components of the recovery process. Based on these results, proposed an alternative deployment method that is attached to an offshore wind turbine and continuously takes the adsorbent, that is fabricated into a belt, from the ocean through an elution process and before submerging it back into the sea. However, it has been found that adsorbents with high tensile strength and durability often have very low uranium adsorption properties. Hence, the Wind and Uranium from Seawater Acquisition symbiotic Infrastructure (WUSABI) previously studied, which requires the adsorbent into a belt held in tension, could face difficulties in an ocean environment. Instead, the design, further referred to in this paper as WUSABI-Koosh, utilized a two-part system to decouple the mechanical and chemical needs of an adsorbent for seawater harvesting of uranium. In these designs, the uranium adsorbent material with high adsorbent capacity is enclosed in a hard permeable outer shell with sufficient mechanical strength and durability for use in an offshore environment and chemical resilience against elution treatments. The integration of the design of a uranium harvesting system into an offshore wind turbine tower is pursued because the development of offshore wind or uranium harvesting by themselves bears a high capital cost for the structures, but if the mooring function can be shared, the overall cost for each will be lower. Furthermore, initial design analysis and prototyping of these symbiotic systems has proven they are technically feasible. This paper presents preliminary cost analysis for comparison to uranium recovery via alternative deployment schemes.
07 ISOTOPE AND RADIATION SOURCES↗
Adsorbent Alkali Conditioning for Uranium Adsorption from Seawater. Adsorbent Performance and Technology Cost Evaluation
The Fuel Resources program of the Fuel Cycle Research and Development program of the Office of Nuclear Energy (NE) is focused on identifying and implementing actions to assure that nuclear fuel resources are available in the United States. An immense source of uranium is seawater, which contains an estimated amount of 4.5 billion tonnes of dissolved uranium. This unconventional resource can provide a price cap and ensure centuries of uranium supply for future nuclear energy production. NE initiated a multidisciplinary program with participants from national laboratories, universities, and research institutes to enable technical breakthroughs related to uranium recovery from seawater. The goal is to develop advanced adsorbents to reduce the seawater uranium recovery technology cost and uncertainties. Under this program, Oak Ridge National Laboratory (ORNL) has developed a new amidoxime-based adsorbent of high surface area, which tripled the uranium capacity of leading Japanese adsorbents. Parallel efforts have been focused on the optimization of the physicochemical and operating parameters used during the preparation of the adsorbent for deployment. A set of parameters that need to be optimized are related to the conditioning of the adsorbent with alkali solution, which is necessary prior to adsorbent deployment. Previous work indicated that alkali-conditioning parameters significantly affect the adsorbent performance. Initiated in 2014, this study had as a goal to determine optimal parameters such as base type and concentration, temperature, and duration of conditioning that maximize the uranium adsorption performance of amidoxime functionalized adsorbent, while keeping the cost of uranium production low. After base-treatment at various conditions, samples of adsorbent developed at ORNL were tested in this study with batch simulated seawater solution of 8-ppm uranium concentration, batch seawater spiked with uranium nitrate at 75-100 ppb uranium, and continuous-flow natural seawater at the Pacific Northwest National Laboratory (PNNL). Fourier Transform Infrared (FTIR) spectroscopy, Nuclear Magnetic Resonance (NMR) spectroscopy, Scanning Electron Microscopy (SEM), and elemental analysis were used to characterize the adsorbent at different stages of adsorbent preparation and treatment. The study can be divided into two parts: (A) investigation of optimal parameters for KOH adsorbent conditioning and (B) investigation of other possible agents for alkali conditioning, including cost analysis on the basis of uranium production. In the first part of the study, tests with simulated seawater containing 8 ppm uranium showed that the uranium adsorption capacity increased with an increase in the KOH concentration and conditioning time and temperature at each of the KOH concentrations used. FTIR and solid state NMR studies indicated that KOH conditioning converts the amidoxime functional groups into more hydrophilic carboxylate. The longer the KOH conditioning time, up to three hours, the higher was the loading capacity from the simulated seawater solution which is composed of only uranyl, sodium, chloride, and carbonate ions. Marine testing with natural seawater, on the other hand, showed that the uranium adsorption capacity of the adsorbent increased with KOH conditioning temperature, and gradually decreased with increasing KOH conditioning time from one hour to three hours at 80 C. This behavior is due to the conversion of amidoxime to carboxylate. The carboxylate groups are needed to increase the hydrophilicity of the adsorbent; however, conversion of a significant amount of amidoxime to carboxylate leads to loss in selectivity toward uranyl ions. Thus, there is an optimum KOH conditioning time for each temperature at which an optimum ratio between amidoxime and carboxylate is reached. For the case of base conditioning with 0.44 M KOH at 80 C, the optimal conditioning time is 1 hour, with respect to the highest uranium loading capacity from natural seawater. Uptake of other metal ions such as V, Fe, and Cu follows the same trend as that of uranium. Also, the uptake of Ca, Mg, and Zn ions increased with increasing KOH conditioning time, probably due to formation of more carboxylates, which leads to conversion of uranium-selective binding sites to less selective sites. In the second part of the study, inorganic based reagents such as sodium hydroxide (NaOH), sodium carbonate (Na 2 CO 3 ), cesium hydroxide (CsOH), as well as organic based reagents such as ammonium hydroxide (AOH), tetramethylammonium hydroxide (TMAOH), tetraethylammonium hydroxide (TEAOH), triethylmethylammonium hydroxide (TEMAOH), tetrapropylammonium hydroxide (TPAOH) and tetrabutylammonium hydroxide (TBAOH), in addition to KOH, were used for alkaline conditioning. NaOH has emerged as a better reagent for alkaline conditioning of amidoxime-based adsorbent because of higher uranium uptake capacity, higher uranium uptake selectivity ...
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Novel Sensor for the In Situ Measurement of Uranium Fluxes
The goal of this project was to develop a sensor that incorporates the field-tested concepts of the passive flux meter to provide direct in situ measures of flux for uranium and groundwater in porous media. Measurable contaminant fluxes [J] are essentially the product of concentration [C] and groundwater flux or specific discharge [q ]. The sensor measures [J] and [q] by changes in contaminant and tracer amounts respectively on a sorbent. By using measurement rather than inference from static parameters, the sensor can directly advance conceptual and computational models for field scale simulations. The sensor was deployed in conjunction with DOE in obtaining field-scale quantification of subsurface processes affecting uranium transport (e.g., advection) and transformation (e.g., uranium attenuation) at the Rifle IFRC Site in Rifle, Colorado. Project results have expanded our current understanding of how field-scale spatial variations in fluxes of uranium, groundwater and salient electron donor/acceptors are coupled to spatial variations in measured microbial biomass/community composition, effective field-scale uranium mass balances, attenuation, and stability. The coupling between uranium, various nutrients and micro flora can be used to estimate field-scale rates of uranium attenuation and field-scale transitions in microbial communities. This research focuses on uranium (VI), but the sensor principles and design are applicable to field-scale fate and transport of other radionuclides. Laboratory studies focused on sorbent selection and calibration, along with sensor development and validation under controlled conditions. Field studies were conducted at the Rifle IFRC Site in Rifle, Colorado. These studies were closely coordinated with existing SBR (formerly ERSP) projects to complement data collection. Small field tests were conducted during the first two years that focused on evaluating field-scale deployment procedures and validating sensor performance under controlled field conditions. In the third and fourth year a suite of larger field studies were conducted. For these studies, the uranium flux sensor was used with uranium speciation measurements and molecular-biological tools to characterize microbial community and active biomass at synonymous wells distributed in a large grid. These field efforts quantified spatial changes in uranium flux and field-scale rates of uranium attenuation (ambient and stimulated), uranium stability, and quantitatively assessed how fluxes and effective reaction rates were coupled to spatial variations in microbial community and active biomass. Analyses of data from these field experiments were used to generate estimates of Monod kinetic parameters that are ‘effective’ in nature and optimal for modeling uranium fate and transport at the field-scale. This project provided the opportunity to develop the first sensor that provides direct measures of both uranium (VI) and groundwater flux. A multidisciplinary team was assembled to include two geochemists, a microbiologist, and two quantitative contaminant hydrologists. Now that the project is complete, the sensor can be deployed at DOE sites to evaluate field-scale uranium attenuation, source behavior, the efficacy of remediation, and off-site risk. Because the sensor requires no power, it can be deployed at remote sites for periods of days to months. The fundamental science derived from this project can be used to advance the development of predictive models for various transport and attenuation processes in aquifers. Proper development of these models is critical for long-term stewardship of contaminated sites in the context of predicting uranium source behavior, remediation performance, and off-site risk.
54 ENVIRONMENTAL SCIENCES↗
XAFS Investigation of Uranium Binding by Seawater-Contacted Amidoxime Adsorbents
Extraction of uranium from seawater constitutes an important avenue for ensuring nuclear fuel availability beyond the coming century. With a predicted 100 years of uranium remaining in terrestrial ores, efficient extraction of the 4.5 billion tons of uranium dissolved in ocean water would enable access to an effectively limitless supply. More near-term benefits include establishment of a backstop technology, preventing runaway price inflation for this critical resource. The current state-of-the-art material for seawater extraction of uranium is a polymeric adsorbent composed of a robust trunk material subsequently surface functionalized by copolymerization of polyacrylonitrile and a hydrophilic comonomer. Treatment of this material with hydroxylamine results in the formation of poly-amidoxime functionalities which have been known to bind strongly with uranium since the early 1980's. Despite more than three decades of investigation, many questions remain unanswered regarding how these adsorbents bind uranium in seawater. The physical characteristics of the polymer prohibit many classical characterization techniques, while most spectroscopic approaches are impeded by the relatively low concentration of uranium compared to the polymer itself and other metals extracted by the adsorbent. The traditional approach has been to investigate small molecule analogues of uranyl - dioxouranium (VI), the form of uranium present in seawater - as bound by amidoxime or amidoxime derivatives, and assert the findings to be representative of the larger polymer system. Computational efforts have also been recently leveraged to a similar end. This approach is not without difficulty, as it has been routinely proposed that the treatment with hydroxylamine and subsequent alkaline conditioning results in formation of a cyclic imide dioxime site, which is truly responsible for uranium binding, as opposed to the 'open chain' amidoxime. Further complications ensue from considering the possibility of cooperative binding interactions from the different hydrophilic comonomers which are known to be necessary for optimizing uranium capacity. Finally, application of different surface polymerization techniques has the potential to directly affect the morphology of the surface polymer by influencing the degree of grafting, extent of polymer crosslinking, and polymer density. The impact of these morphological considerations on the uranyl binding environment cannot be easily replicated with small molecule studies or by computation. Ultimately, the precise binding environment of uranium is unknown, but constitutes critical knowledge for the design and engineering of advanced adsorbent materials capable of selective extraction of uranium from seawater. Analysis of the EXAFS fits reveals three of the four polymer morphologies appear to bind uranium in different chemical environments, none of which were predicted by crystallographic study or computational investigation, challenging numerous long-held assumptions. Both AI-8 and AN/HEA spectra possess features which could be attributable to cooperative binding of uranium by comonomers, but this cannot be definitively determined by EXAFS without further investigation. Unlike AF-1, neither AI-8 or AN/HEA require an adjacent μ{sup 2}-oxo-bridged transition metal to obtain a reasonable fit. The fit for Cyclic AF-1 is refined to almost identical parameters to the fit of the original AF-1 adsorbent, with the only difference is the contracting of the light elements in the second coordination sphere. It is thus proposed that the DMSO and heat treatment of the AF-1 fiber does very little to change the uranium binding site, and any differences in uptake are more readily explained by changes in the morphology of the graft polymer. There is no evidence for cyclic amidoxime functionality contributing significantly to the extraction of uranium from seawater, and efforts to maximize the number of these binding sites should be discontinued. While molecular interactions necessarily occur in adsorption processes, these results clearly reveal physical phenomena at the mesoscale play a critical role in adsorbent behavior, even to the extent that the binding environment differs from those predicted by small molecule studies. In contrast to the current paradigm where chemical functionality is varied, improvements in the performance of polymer-based amidoxime-functionalized adsorbents for extraction of uranium from seawater need also be pursued through interrogation and modulation of bulk morphology and improvements in polymer hydrophilicity. (authors)
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
A Higher Fidelity Cost Analysis of Wind and Uranium from Seawater Acquisition symbiotic Infrastructure
The vastness of the worlds oceans makes the low concentration of naturally existing uranium, 3.3 ppb, appealing as a recoverable natural resource. Although ample uranium is available currently through conventional means, uranium from seawater is a widely studied topic due to the long term security it can assure the nuclear fuel cycle. It is important to mention that seawater uranium is not meant to act as a direct competitor to terrestrial uranium, but instead create a cost ceiling that provides economic stability and potential savings. Additionally, seawater uranium could circumvent some of the environmental impacts associated with recovery of any land based resource. The system currently studied by a nation-wide consortium of national lab and university partners involves the passive recovery of uranium using polymer based adsorbents. High Density Polyethylene fibers undergo a radiation induced graft co-polymerization process involving amidoxime, to attract uranium, and a polar co-monomer to increase hydrophilicity. After further chemical conditioning adsorbent fibers are braided into 60 meter strands for marine deployment. Braids are moored to the ocean floor for the duration of their soaking campaign. After sufficient seawater exposure they are winched up so the adsorbed uranium may be eluted off the braids. This deployment and elution process is repeated multiple times before the adsorbent's ultimate disposal, where its lifetime is dictated by the degradation it suffers with each re-cycle. Previous economic analyses have identified the adsorbent production and mooring as the most expensive components of the recovery process. Therefore, a later publication by Picard et al. proposed an alternative deployment method in an effort to reduce seawater uranium production cost. The Wind and Uranium from Seawater Acquisition symbiotic Infrastructure (WUSABI) couples uranium recovery with off shore wind to reduce mooring capital cost. The uranium harvesting structure attached to the underwater base of the wind turbine supports elution tanks and an adsorbent pulley system. This allows for a nearly autonomous mooring and elution procedure as adsorbent is in constant motion, reaching the elution tanks at the end of its soaking campaign. Although the original publication did include a short economic section, further analysis was carried out to provide a higher fidelity production cost estimate for uranium recovered by this system. Sufficient detail was provided regarding the capital and operating costs of the novel uranium harvesting units. The adsorbent production and uranium elution and purification steps however were estimated by simpler methods, for example applying a previously reported cost for producing a unit mass of adsorbent. This methodology, although satisfactory for the zeroth-order approximation desired in the original publication, overlooks many of the complexities and feedbacks embedded in the full cost model, which are necessary to provide a more accurate estimate. Perhaps more importantly, given the constant updates regarding adsorbent synthesis and performance this value quickly become outdated. Syncing an improved estimate for the WUSABI harvesting units with the existing economic analysis for adsorbent production and elution, which evolves in tandem with the technology, provides a more robust production cost estimate that will remain current over time. In addition to the updates and higher level of detail provided in this independent analysis, consistency in methodology allows for accurate comparison of uranium production costs across recovery methods. (authors)
07 ISOTOPE AND RADIATION SOURCES↗
Design of a Symbiotic Device to Harvest Uranium from Seawater through the use of Shell Enclosures
At the current consumption rate, the global conventional reserves of uranium, 7.6 million tonnes, could be depleted in a little over a century. As reserves decrease, future uranium is expected to come from lower quality sites, resulting in higher extraction costs and even greater environmental impact. Fortunately, uranium is present in the ocean as uranyl ions at low concentrations of 3 ppb, which, over the total volume of the oceans, amounts to approximately 4.5 billion tonnes of uranium, nearly a thousand times that of conventional reserves. Methods to extract uranium from seawater have been studied since the early 1960's, when, at a time when uranium production was uncertain, post-World War II Britain desired a secure uranium supply. A recent review of uranium recovery technologies by found that uranium adsorbent by chelating polymers was the most promising in terms of adsorbent capacity, environmental footprint, and cost. In this technology, chelating polymers are deployed in seawater and remain submerged until the amount of captured uranium approaches the adsorption capacity. Then, an elution bath is used to strip metal ions, such as uranium, off the adsorbent polymer. A polymer may be immersed in a number of elution baths before it is regenerated by an alkali wash to free its functional groups, allowing for the reuse of the polymer. The output from the elution process undergoes purification and precipitation typical for mined uranium to produce yellowcake. Offshore systems for the extraction of uranium from seawater have been developed since the early 2000's. In these systems, the adsorbent is deployed and moored for extended periods of time, brought back to shore for the elution process, and redeployed afterward. The first system, developed by, used non-woven adsorbents that were immersed for 30 days in seawater. Due to the low mechanical strength of these fibers, they had to be incorporated into stacks composed of spacer nets and holders placed on large, heavy, floating frames, which resulted in a design that was too costly for implementation. More recently, buoyant braided adsorbents have been studied as a way to decrease the weight and cost of the system. In these systems, continuous polyethylene fibers are braided around a porous polypropylene float that can be made into long lengths. However, because this deployment scheme requires the adsorbent be brought back to shore for the elution process and redeployed afterward, this stand-alone, intermittent operation system has significant practical and economic deployment challenges and to date none of these systems have become economically viable. Detailed economic analysis by found that a major cost driver of seawater uranium extraction is the mooring and recovery of the adsorbent. Based on these results, first developed the development of a system that is attached to an offshore wind turbine and continuously takes the adsorbent from the ocean through an elution process and then returns it to the ocean. More recent designs by further build upon this idea. The integration of the design of a uranium harvesting system into an offshore wind turbine tower is pursued because the development of offshore wind or uranium harvesting by themselves bears a high capital cost for the structures, but if the mooring function can be shared, the overall cost for each will be lower. Furthermore, initial design analysis and prototyping of these symbiotic systems has proven they are technical feasible. (authors)
07 ISOTOPE AND RADIATION SOURCES↗
Investigations Into the Reusability of Amidoxime-Based Polymeric Uranium Adsorbents
Significant advancements in amidoxime-based polymeric adsorbents to extract uranium from seawater are achieved in recent years. The success of uranium adsorbent development can help provide a sustainable supply of fuel for nuclear reactors. To bring down the production cost of this new technology, in addition to the development of novel adsorbents with high uranium capacity and manufacture cost, the development of adsorbent re-using technique is critical because it can further reduce the cost of the adsorbent manufacture. In our last report, the use of high concentrations of bicarbonate solution (3M KHCO3) was identified as a cost-effective, environmental friendly method to strip uranium from amidoxime-based polymeric adsorbents. This study aims to further improve the method for high recovery of uranium capacity in re-uses and to evaluate the performance of adsorbents after multiple re-use cycles. Adsorption of dissolved organic matter (DOM) on the uranium adsorbents during seawater exposure can hinder the uranium adsorption and slow down the adsorption rate. An additional NaOH rinse (0.5 M NaOH, room temperature) was applied after the 3 M KHCO3 elution to remove natural organic matter from adsorbents. The combination of 3 M KHCO3 elution and 0.5 M NaOH rinse significantly improves the recovery of uranium adsorption capacity in the re-used adsorbents. In the first re-use, most ORNL adsorbents tested achieve ~100% recovery by using 3 M KHCO3 elution + 0.5 M NaOH rinse approach, in comparison to 54% recovery when only 3 M KHCO3 elution was applied. A significant drop in capacity was observed when the adsorbents went through more than one re-use. FTIR spectra revealed that degradation of amidoxime ligands occurs during seawater exposure, and is more significant the longer the exposure time. Significantly elevated ratios of Ca/U and Mg/U in re-used adsorbents support the decrease in abundance of amidoxime ligands and increase carboxylate group from FT-IR analysis. The impact of the length of seawater exposure cycle in adsorbent re-use was evaluated by comparing the adsorption capacity for a common adsorbent formulation (ORNL AI8 formulation) under different exposure cycle (28 days and 42 days). Adsorbents with a 28 days seawater exposure cycle had higher recovery of uranium capacity than adsorbent with 42 days of seawater exposure. Under different cumulative seawater exposure time, the adsorbent with 28 days seawater exposure cycle also had less amidoxime ligands degradation than the adsorbent with 42 days seawater exposure cycle. These observations support the negative impact of prolonged seawater exposure on amidoxime ligands stability. Recovery of uranium capacity in re-uses also varies across different adsorbent formulations. Among three different ORNL adsorbents tested (AI8, AF8, AF1-DMSO), AI8 had the best recovery in each re-use, followed by AF8 and then AF1-DMSO. This demonstrates that continuing efforts on developing new adsorbents with high capacity and stability is critical. The overall performance of adsorbents in multiple re-use cycles can be evaluated by calculation total harvestable uranium, the summation of adsorbed uranium from each seawater exposure cycle. In this assessment, the ORNL AI8 braid with 28 days seawater exposure cycle can reach total harvestable uranium 10g Uranium/kg adsorbent in ~140 days; while the same type of braid but with 42 days seawater exposure cycle reach the same level in ~170 days. Notably, the performance of total harvestable uranium also varies among different adsorbent formulations (AI8 > AF1-DMSO > AF8). Short seawater exposure cycle is associated with high re-use frequency. The development of low-cost offshore adsorbent deployment/extraction is essential for high frequency reuse operation. This study also highlights the importance to examine the re-use performance of newly developed uranium adsorbents for selection of optimal adsorbents for ocean deployment.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Enhancement of the Extraction of Uranium from Seawater
Due to the limited uranium resources available for recovery through mining and ore processing and to the environmental problems associated with these operations, the future of nuclear power depends, to a large extent, on the feasibility of recovery of uranium from the ocean. While the amounts of uranium in the ocean are sufficient to fulfill the nuclear industry for many thousands of years, recovery of uranium from the ocean is hampered by its low concentration (3.3 parts per billion) and the presence of many other solutes in seawater at comparable or much higher concentrations. Thus, the only hope for economically viable recovery of uranium from the ocean lies in the development of adsorbents with high capacity and high selectivity for uranium as present in the seawater environment (pH 8.1, U(VI) oxidation state, anionic carbonate complexes). Moreover, it is quite unlikely that economically viable recovery of uranium could be achieved if the adsorbent could be used only once. Thus it is essential to develop adsorbents that can be used through multiple cycles of uranium adsorption followed by elution of the uranium to regenerate the adsorbent without significant degradation of their capacity and selectivity for uranium. Adsorbents used in the large majority of studies aimed at recovery of uranium from seawater are based on the use of radiation grafting to produce polymeric supports, in particular polyethylene, with attached amidoxime groups. This configuration has been concluded to offer the best candidate for use in recovery based on studies which were performed in the early 1980’s. Substantial progress has been made in improving the amidoxime-based adsorbents. The basic approach undertaken by the authors of the proposal, on the other hand, has been to test ligands which have not been included in the scoping studies of the 1980’s or have been developed since then. So far, 18 such ligands have been tested, of which three, including B2MP (an organic phosphate), DAOx (an organic oxalate), and Br-PADAP (an azo compound) have been selected for further investigation. In addition, Winged Nylon 6 has been identified as a promising polymeric support in view of its large surface area and high chemical stability. Furthermore, improved grafting techniques intended to achieve high grafting density under “green chemistry” conditions, i.e., in aqueous media, have been developed. These techniques include the use of surfactants to enhance the solubility of ligands in water and the use of a homopolymerization inhibitor to promote grafting rather than homopolymerization. Furthermore, unlike amidoxime-based adsorbents, which require a chemical treatment step following the radiation grafting to convert a nitrile group to amidoxime, the adsorbents developed by the authors do not require an additional step after grafting. Highly effective regeneration has been demonstrated for the phosphate-grafted polymeric adsorbent over at least 21 adsorption/elution cycles without significant loss of capacity. The currently proposed study is intended to build upon the progress made so far in developing alternative systems for removal of uranium from seawater. It will focus on the following objectives: Continued searches will be conducted for high-capacity, high-selectivity ligands based on systematic characterization of structural features favorable to uranium adsorption. (For instance, phosphates have been found to be much more effective than the corresponding phosphonates). At the same time, development and testing of the three ligands selected so far will continue, focusing on issues such as high grafting densities and effective regeneration. Testing will be conducted in non-spiked sweater (3.3 µg/L U) and lightly spiked seawater (up to 10 µg/L U). The authors have recently been able to refurbish an ICP-MS spectrometer for this purpose. Improved grafting techniques will be developed and refined for specific ligands. These techniques will include the use of surfactants to allow grafting of ligands with low solubility in water, the use of homopolymerization inhibitors, modifying the chemical structure of ligands to introduce C=C bonds, investigating possible modification of the surface of the polymeric support, and mechanistic analysis of the effects of grafting conditions, in particular accumulated dose and dose rate. Improvements in the characterization of adsorbents before and after contact with seawater will be implemented using techniques such as XPS, SEM-EDS, and zeta potential measurements to investigate the mechanism of uranium adsorption. Effective techniques of multi-cycle regeneration of promising adsorbents without degradation of their performance will be developed and refined through testing of mild, preferably near-neutral eluant solutions. The kinetics of adsorption and desorption of uranium will be investigated. This study is of great operational value and it will also greatly contribute to improved understanding of adsorption/desorption mechanism on promising adsorbents.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Experience of Graphite Crucibles during the Pyrometallurgical Processing of Uranium
Throughout the history of processing molten uranium, various materials have been investigated and utilized for the containment of uranium at temperatures greater than 1135oC. Of these, graphite is the most prevalent material due to its ease of fabrication, expense, compatibility with induction systems, and robust characteristics. Graphite in contact with molten uranium will react to form uranium carbide species, thus a coating or mold is needed to prevent reaction of the uranium and the subsequent adherence of the solidified metal. During the pyrometallurgical treatment of used nuclear fuel for uranium recovery at the Idaho National Laboratory, two operational steps utilize graphite crucibles for containment of molten uranium. The cathode processor step separates molten salt from the uranium while the casting step blends uranium for de-enrichment and allows molten sampling of the uranium. Zirconia and yttria based materials on graphite are employed for the cathode processor and casting steps, respectively. For the cathode processor, zirconia coatings were applied initially to graphite crucibles but more recently a zirconia castable material has been molded into the graphite. Although not perfect, zirconia has been found to be compatible with both molten salt and uranium whereas yttria will react with molten salts if carried over to the casting operation. With development, the uranium losses associated with the reaction of uranium and zirconia have been reduced to approximately 1 wt. % of the total uranium throughput. Losses from yttria coating reaction during casting are typically an order of magnitude less than zirconia. The real benefit of these materials is their cost effectiveness given the multiple number of times the graphite crucibles can be reused and/or recoated. Nearly thirty uses have been recorded for graphite crucibles at both the cathode processor and casting operations. The amount of impurity pickup to the uranium products from the graphite crucibles has been minimal (<300 ppm) in terms of carbon, oxygen, zirconium, and yttrium content. Based on the promising results with the zirconia castable at the cathode processor, zirconia material has been cast into a graphite casting crucible and will be tested for comparison in the absence of salt.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Potential uranium supply from phosphoric acid: A U.S. analysis comparing solvent extraction and Ion exchange recovery
Phosphate rock contains significant amounts of uranium, although in low concentrations. Recovery of uranium as a by-product from phosphoric acid, an intermediate product produced during the recovery of phosphorus from phosphate rock, is not unprecedented. Phosphoric acid plants ceased to produce uranium as a by-product in the early 1990s with the fall of uranium prices. In the last decade, this topic has regained attention due to higher uranium prices and expected increase in demand for uranium. Our study revisits the topic and estimates how much uranium might be recoverable from current phosphoric acid production in the United States and what the associated costs might be considering two different recovery processes: solvent extraction and ion exchange. Based on U.S. phosphoric acid production in 2014, 5.5 million pounds of U 3 O 8 could have been recovered, more than domestic U.S. mine production of uranium in the same year. Annualized costs for a hypothetical uranium recovery plant are US$48-66 per pound U 3 O 8 for solvent extraction, the process used historically in the United States to recover uranium from phosphoric acid. For ion exchange, not yet proven at a commercial scale for uranium recovery, the estimated costs are US$33-54 per pound U 3 O 8 . Our results suggest that it is technically possible for the United States to recover significant quantities of uranium from current phosphoric acid production. And for this type of uranium production to be economically attractive on a large scale, either recovery costs must fall or uranium prices rise.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Extraction of Uranium from Seawater: Design and Testing of a Symbiotic System
The U.S. Department of Energy in October 2014 awarded the Massachusetts Institute of Technology (MIT) a Nuclear Energy University Program grant (DE-NE0008268) to investigate the design and testing of a symbiotic system to harvest uranium from seawater. As defined in the proposal, the goals for the project are: 1. Address the design of machines for seawater uranium mining. 2. Develop design rules for a uranium harvesting system that would be integrated into an offshore wind power tower. 3. Fabricate a 1/50th size scale prototype for bench and pool-testing to verify initial analysis and theory. 4. Design, build, and test a second 1/10th size scale prototype in the ocean for more comprehensive testing and validation. This report describes work done as part of DE-NE0008268 from 10/01/2014 to 11/30/2017 entitled, “Extraction of Uranium from Seawater: Design and Testing of a Symbiotic System.” This effort is part of the Seawater Uranium Recovery Program. This report details the publications and presentations to date on the project, an introduction to the project’s goals and background research into previous work done to achieve these goals thus far. From there, the report describes an algorithm developed during the project used to optimize the adsorption of uranium by changing mechanical parameters such as immersion time and adsorbent reuses is described. Next, a design tool developed as part of the project to determine the global feasibility of symbiotic uranium harvesting systems. Additionally, the report details work done on shell enclosures for uranium adsorption. Moving on, the results from the design, building, and testing of a 1/50th physical scale prototype of a highly feasible symbiotic uranium harvester is described. Then, the report describes the results from flume experiment used to determine the affect of enclosure shells on the uptake of uranium by the adsorbent they enclose. From there the report details the design of a Symbiotic Machine for Ocean uRanium Extraction (SMORE). Next, the results of the 1/10th scale physical scale prototype of a highly feasible symbiotic uranium harvester are presented. The report then details the design and results of an experiment to examine the hydrodynamic effects of a uranium harvester on the offshore wind turbine it is attached to using a 1/150th Froude scale tow tank test. Finally, the report details the results of an initial cost-analysis for the production of uranium from seawater from such a symbiotic device.
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