Diffusion Of Uranium Research Articles

Carboxymethyl cellulose and metal-organic frameworks immobilized into polyacrylamide hydrogel for ultrahigh efficient and selective adsorption U(VI) from seawater

Metal-organic frameworks (MOF)-polymer hybrid hydrogel solves the processable forming of MOF powder and energy consumption of uranium extraction. However, the hybrid hydrogel by conventional synthesis methods inevitably lead to MOF agglomeration, poor filler-polymer interfacial compatibility and slowly adsorption. Herein, we designed that ZIF-67 was implanted into the carboxymethyl cellulose/polyacrylamide (CMC/PAM) by network-repairing strategy. The carboxyl and amino groups on the surface of CMC/PAM drive the uniform growth of ZIF-67 inside the CMC/PAM, which form an array of oriented and penetrating microchannels through coordination bonds. Our strategy eliminate the ZIF-67 agglomeration, increase the interfacial compatibility between MOF and polymer. The method also improve the free and fast diffusion of uranium in CMC/PAM/ZIF-67 hydrogel. According to the experimental, these enhancements synergistically enabled the CMC/PAM/ZIF-67 have a maximum adsorption capacity of 952 mg g−1. The adsorption process of CMC/PAM/ZIF-67 fits well with pseudo-second-order model and Langmuir isotherm. Meanwhile, the CMC/PAM/ZIF-67 maintain a high removal rate (87.3 %) and chemical stability even during ten adsorption-desorption cycles. It is worth noting that the adsorption amount of CMC/PAM/ZIF-67 in real seawater is 9.95 mg g−1 after 20 days, which is an ideal candidate adsorbent for uranium extraction from seawater.

Preparation of solar photo-thermal driven aerogel and clarification of the mechanism for enhanced uranium adsorption

The oceans contain a significant amount of uranium, a valuable resource for nuclear power and fuel applications. However, current technologies for extracting uranium from seawater have limitations, including low efficiency and high energy consumption. Aerogels are promising materials for uranyl ion adsorption due to their high porosity and abundant active sites. This study presents a novel approach for efficient uranium extraction from seawater using a full-fiber-based PAO/PPy aerogel. This aerogel enables rapid diffusion of uranium and accelerated adsorption in the presence of heat generated by sun irradiation, achieving a high adsorption capacity of 69.66 mg g−1 under 1 kW m−2 in 50 mg L−1 solution. The dynamical and thermodynamic simulations indicate the presence of both chemisorption and physisorption throughout the adsorption process. Additionally, the composite aerogel is demonstrated antifouling performance and excellent selectivity of U(VI) in a mixed ionic solution. The present study offers a novel approach for the rational design of aerogel adsorbents that can effectively extract uranium from seawater in outdoor environments, without the need for additional energy input.

Characterizing pulse reverse-pulse uranium recovery in molten LiCl-KCl with intermittent electrochemical impedance spectroscopy

In this work, EIS was applied to characterize the temporal recovery of uranium from UCl4 onto a tungsten electrode in molten LiCl-KCl salt between sets of pulse reverse-pulse (PRP) deposition steps. Impedance measurements were fitted to an equivalent circuit (EC) model of the electrode interface using Simplex optimization to calculate the double layer capacitance, charge transfer resistance, Warburg impedance, and CPE-restricted diffusion. Diffusion of uranium towards the electrode surface dominated the surface interactions for the first 80 cycles, followed by a transition to kinetic control for the remaining 520 cycles. A decrease in the Warburg impedance showed depletion of uranium from the bulk melt, which was confirmed to be a 52.5% reduction through ICP-OES. Reduction in the phasance from CPE-restricted diffusion suggested the formation of pores in the uranium deposits, which was confirmed through SEM characterization.

Diffusion of tritium, technetium, cesium, and uranium from phosphate glass leachates in pore solution of clay materials

The through diffusion method at room temperature was used to study the migration of radionuclides (3H, 99Tc, 137Cs, 233U) in compacted samples of clay materials during pore diffusion from a model leachate of the RW phosphate matrix with a total salt content of about 400 mg/L. Based on the results of the experiments, the effective diffusion coeffcients and coeffcients of the sorption distribution of radionuclides for the studied barrier clay materials were determined. Regularities of the diffusion transfer of tritium, cesium and uranium depending on the structure, mineral composition of clay materials and the content of radionuclides in the pore solution are revealed. Numerical modeles are proposed for calculating the effective pore di usion coeffcients of these radionuclides. There are still insuffcient data to analyze the factors affecting the diffusion of technetium.

Post-irradiation examination of the Sirius-1 nuclear thermal propulsion fuel test

Nuclear Thermal Propulsion (NTP) systems hold promise in reducing transit times for exploration of the solar system by both crewed and uncrewed missions. NTP systems currently under investigation include a once-through high-temperature gas-cooled fission reactor to provide thermal energy to heat the coolant, which also serves as the propellant. The fuel system consists of angular UN fuel particles dispersed in a matrix of W/Re, creating a ceramic and metallic composite or cermet, which has been irradiated in Idaho National Laboratory's (INL) Transient Reactor Test Facility (TREAT). This enabled evaluation of these materials under representative nuclear heating rates (∼95 K/s) and peak surface temperatures (∼2527 K). These surface conditions were indicative of achievement of the target peak internal temperature of approximately 2850 K. These tests named Sirius-1 (UN–W/Re), have been irradiated and this paper will present post-irradiation examination results. The Sirius-1 test produced minor, stable cracks in the fuel specimen and spalling of surface material. Volatilized uranium ‘soot’ was found deposited on the inner wall of the irradiation capsule indicating loss of some fissile material from the fuel specimen. Spalling from the surfaces was also noted upon visual inspection. Uranium diffusion from the fuel particles resulted in the formation of U/Re phases and the production of a laminar microstructure on the edge of the fuel system. Overall, the specimen was stable and remained within a coolable geometry upon conclusion of multiple thermal cycles to prototypical operating temperatures.

Diffusion of Tritium, Technetium, Cesium and Uranium from Phosphate Glass Leachates in a Pore Solution of Clay Materials

Diffusion of Tritium, Technetium, Cesium and Uranium from Phosphate Glass Leachates in a Pore Solution of Clay Materials

Flexible three-dimensional covalent organic frameworks for ultra-fast and selective extraction of uranium via hydrophilic engineering.

It has been considered challenging to develop ideal adsorbents for efficient and lower adsorption time uranium extraction, especially 3D covalent organic frameworks with interpenetrating topologies and tunable porous structures. Here, a "soft" three-dimensional (3D) covalent organic framework (TAM-DHBD) with a fivefold interpenetrating structure is prepared as a novel porous platform for the efficient extraction of radioactive uranium. The resultant TAM-DHBD appears exceptional crystallinity, prominent porosity and excellent chemical stability. Based on the strong mutual coordination between phenolic-hydroxyl/imine-N on the main chain and uranium, TAM-DHBD can effectively avert the competition of other ions, showing high selectivity for uranium extraction. Impressively, the 3D ultra-hydrophilic transport channels and multi-directional uniform pore structure of TAM-DHBD lay the foundation for the ultra-high-speed diffusion of uranium (the adsorption equilibrium can be reached within 60min under a high-concentration environment). Furthermore, the utilization of lightweight structure not only increases the adsorption site density, but renders the adsorption process flexible, achieving a breakthrough adsorption capacity of 1263.8mgg-1. This work not only highlights new opportunities for designing microporous 3D COFs, but paves the way for the practical application of 3D COFs for uranium adsorption.

A Study on Long-Term Retardation Effect of Integrated Buffer Materials Based on Bentonite on Uranium

Buffer material has been shown to be effective over the long term for radionuclide diffusion retardation and is used as the final artificial barrier of the multi-barrier system in the high-level waste disposal repository. The method of disposal raises the possibility of radionuclides escaping and returning to the biosphere when ground water enters the natural geological barrier, risking the repository’s long-term stability and safety. Bentonite was chosen as the basic material in the integrated buffer material due to its low permeability, high swelling, and self-healing ability. Meanwhile, attapulgite served as an auxiliary, and pyrite served as a mineral additive. The buffer material B7AP was created by combining three materials, namely bentonite, attapulgite, and pyrite, with a mass ratio of 63:27:10. The diffusion of uranium in samples with a dry density of 1.70 g/cm3 was studied using a constant source diffusion experiment. The results showed that the B7AP buffer material had a good uranium retardation effect, with an apparent diffusion coefficient of 4.07 × 10−12 m2/s. In addition, using the theory of porous media contaminant migration, a simplified convection-dispersion-adsorption equation for uranium migration on integrated buffer material B7AP was established. MATLAB software was used to simulate time scales, seepage velocity, apparent diffusion coefficient, and retardation factor. The current study provides scientific evidence for improving retardation performance, screening, and optimizing the formula design of radioactive waste repository buffer materials.

Bioinspired green tea waste/graphene aerogel for solar-enhanced uranium extraction from seawater

Natural seawater is recognized to be the most promising source to satisfy the growth demands on uranium. The currently proposed seawater uranium extraction strategy faces great challenges, including the limited adsorption capacity, slow kinetics, poor selectivity and severe fouling under complex marine conditions. Inspired by water transpiration, nutrient transport and porous structure of Salvinia cuccullata, we designed and fabricated a green tea waste/graphene aerogel (GDT) with Salvinia cuccullata root-like structures and photothermal conversion characteristics for uranium capture. This biomimetic GDT exhibited efficient photothermal conversion with fast water evaporation rate (2.72 kg m−2 h−1) under 1 sun irradiation, which facilitated rapid uranium diffusion and extraction, leading to a 1.22-fold increase in adsorption capacity for GDT in natural seawater. The uranium extraction capacity on GDT achieved 11.9 mg/g from natural seawater in a month accompanied with great selectivity. Moreover, its excellent reusability of 85.1% after 10 cycles of adsorption-regeneration and good antifouling ability endowed the GDT a long service life for practical application. This work offers a novel strategy for oceanic uranium extraction, and opens a new avenue for marine resources mining.

Molecular dynamics investigation of xenon, uranium, and oxygen diffusion in UO2 nuclear fuel

In this paper, atomistic simulations based on molecular dynamics (MD) are used to calculate the diffusion coefficients of xenon, uranium and oxygen in uranium dioxide containing different percentages of xenon atoms replaced by uranium from 2%Xe to 10%Xe at ten temperatures between 300 and 2500 K (covering three temperature regimes of athermal, intermediate and intrinsic). Since we did not take the irradiation conditions into account in the simulations, the calculated diffusion coefficients are “out-of-pile”. Initially, the validity of the interatomic potential was performed by calculating the formation energies of interstitial, vacancy, Frankel and Schottky defects by using molecular statics (MS) simulations. Then, the migration energies of Xe/U/O based on considering various mechanisms were obtained by employing the Nudge Elastic Band (NEB) method. The results were generally in good agreement with those reported in the literature and the potential was validated. The simulations of UO2 containing different percentages of xenon (percentage of replacement of uranium atoms with xenon atoms) from 2 to 10 showed that with increasing the xenon percentage, the number of xenon clusters, cluster size, and radius of gyration considerably increases, and bubble nucleation was considerable in the case of 10%Xe. Then, by determining the slope of the mean square displacements, diffusion coefficients of xenon, uranium and oxygen were obtained. The results showed that they are both temperature-dependent and also dependent on the percentage of xenon (which was previously assumed to be independent of concentration). In the end, three temperature and xenon percentage dependent equations were proposed for the diffusion coefficients of xenon, uranium and oxygen. Finally, by applying a reduction factor (constant) to the diffusion coefficients, they were compared with experimental data available in the literature and significant satisfaction was obtained.

Investigation of diffusion and binding properties of uranium in the diffusive gradients in thin-films technique

Environmental context Monitoring uranium concentrations and speciation in aquatic systems is important for pollution control and for environmental studies. Although an in situ speciation technique based on diffusion and uptake of uranium has been developed, known as DGT, there were uncertainties over some parameters affecting the accuracy of the measurements. This study resolved those uncertainties by investigating diffusion and binding properties of uranium in DGT and provided confidence in monitoring uranium in the environment. Rationale Diffusive gradients in thin-films (DGT) ha been used for uranium speciation measurements since 2006, but interpretational difficulties have arisen due to uncertainties in the pH dependence of U diffusion coefficients (D) within the diffusive gel. This work tested the hypothesis that differences in measured D values between laboratories are due to methodological artifacts. Methodology The properties of uranium binding and diffusion of U within DGT were systematically investigated at different conditions between pH 3–8 and ionic strength from 1 to 500 mmol L−1. Previous uncertainties were attributed to loss of U by adsorption within the diffusion cell, identified by mass balance calculations, and a binding efficiency dependent on the type of binding gel. Results The diffusion coefficient in an agarose cross-linked polyacrylamide gel measured using Metsorb DGT of 5.26 ± 0.17 × 10−6 cm2 s−1 agreed well with both values obtained using a pre-conditioned diffusion cell (< 7% difference) and by modelling. The binding efficiencies for Chelex DGT (BChelex = 0.86–0.89) and Fe-oxide DGT (BFe-oxide = 0.64 were smaller than for Metsorb DGT (BMetsorb = 1). No significant differences were found for BChelex at different pH. Discussion This work demonstrated that the diffusion coefficient of uranium is independent of pH and the binding gel used, provided the binding efficiency (B) is taken into account. These findings indicate that DGT equipped with either Metsorb or Chelex binding gels should be capable of measuring U for a wide range of environmental conditions provided the appropriate diffusion coefficients and binding efficiencies are used.

Laser Heating Study of the High-Temperature Interactions in Nanograined Uranium Carbides.

Nanograined nuclear materials are expected to have a better performance as spallation targets and nuclear fuels than conventional materials, but many basic properties of these materials are still unknown. The present work aims to contribute to their better understanding by studying the effect of grain size on the melting and solid–solid transitions of nanograined UC2−y. We laser-heated 4 nm–10 nm grain size samples with UC2−y as the main phase (but containing graphite and UO2 as impurities) under inert gas to temperatures above 3000 K, and their behavior was studied by thermal radiance spectroscopy. The UC2−y solidification point (2713(30) K) and α-UC2 to β-UC2 solid–solid transition temperature (2038(10) K) were observed to remain unchanged when compared to bulk crystalline materials with micrometer grain sizes. After melting, the composite grain size persisted at the nanoscale, from around 10 nm to 20 nm, pointing to an effective role of carbon in preventing the rapid diffusion of uranium and grain growth.

RGO-based covalent organic framework hydrogel for synergistically enhance uranium capture capacity through photothermal desalination

Capturing of uranium from the natural seawater is considered to be one of the most promising methods to meet the current demand for nuclear energy. Herein, we prepared a reduced graphene oxide-based (rGO-based) covalent organic framework hydrogel (KTG) with three-dimensional porous structure as a platform for enhancing uranium capture capacity through photothermal desalination. Under light irradiation, the KTG produces a local heat that can be used to generate steam while promoting the rapid diffusion of uranium inside the hydrogel 3D network, thereby increasing the adsorption efficiency and capacity of uranium. KTG can achieve exceptional uranium capture capacity (521.6 mg g−1) under one sun irradiation, which is 42.4% higher than that under dark conditions. In addition, excellent photocatalytic activity and mechanical properties make KTG possess high anti-biofouling activity, good reusability, and achieving continuous uranium capture and solar distillation.

Reaction: Goal-Oriented PAF Design for Uranium Extraction from Seawater

Guangshan Zhu received his BSc (1993) and PhD (1998) degrees in chemistry from Jilin University. He is now a full professor at Northeast Normal University. Driven by the demands in sustainable energy and environments, his current research interest focuses on the design and synthesis of porous aromatic frameworks for gas adsorption, separation, and uranium capture.

Surrogate Model for Multi-Component Diffusion of Uranium through Opalinus Clay on the Host Rock Scale

Multi-component (MC) diffusion simulations enable a process based and more precise approach to calculate transport and sorption compared to the commonly used single-component (SC) models following Fick’s law. The MC approach takes into account the interaction of chemical species in the porewater with the diffuse double layer (DDL) adhering clay mineral surfaces. We studied the shaly, sandy and carbonate-rich facies of the Opalinus Clay. High clay contents dominate diffusion and sorption of uranium. The MC simulations show shorter diffusion lengths than the SC models due to anion exclusion from the DDL. This hampers diffusion of the predominant species CaUO2(CO3)32−. On the one side, species concentrations and ionic strengths of the porewater and on the other side surface charge of the clay minerals control the composition and behaviour of the DDL. For some instances, it amplifies the diffusion of uranium. We developed a workflow to transfer computationally intensive MC simulations to SC models via calibrated effective diffusion and distribution coefficients. Simulations for one million years depict maximum uranium diffusion lengths between 10 m and 35 m. With respect to the minimum requirement of a thickness of 100 m, the Opalinus Clay seems to be a suitable host rock for nuclear waste repositories.

Fuel-cladding chemical interaction of a prototype annular U-10Zr fuel with Fe-12Cr ferritic/martensitic HT-9 cladding

As an alternative fuel form, the annular metallic fuel design eliminates the liquid sodium bond between the fuel and the cladding, providing back-end fuel cycle and other benefits. The fuel-cladding chemical interaction (FCCI) of annular fuel also presents new features. Here, state-of-the-art electron microscopy and spectroscopy techniques were used to study the FCCI of a prototype annular U-10wt%Zr (U-10Zr) fuel with ferritic/martensitic HT-9 cladding irradiated to 3.3% fission per initial heavy atom. Compared with sodium-bonded solid fuels, negligible amounts of lanthanides were found in the FCCI layer in the investigated helium-bonded annular fuel. Instead, most lanthanides were retained in the newly formed UZr2 phase in the fuel center region. The interdiffusion of iron and uranium resulted in tetragonal (U,Zr)6Fe phase (space group I4/mcm) and cubic (U,Zr)(Fe,Cr)2 phase (space group Fd3¯m). The (U,Zr)(Fe,Cr)2phase contains a high density of voids and intergranular uranium monocarbides of NaCl-type crystal structure (space group Fm3¯m). At the interdiffusion zone and inner cladding interface, a porous lamellar structure composed of alternating Cr-rich layers and U-rich layers was observed. Next to the lamellar region, the unexpected phase transformation from body-centered cubic ferrite (α-Fe) to tetragonal binary Fe-Cr σ phase (space group P42/mnm) occurred, and tetragonal Fe-Cr-U-Si phase (space group I4/mmm) was identified. Due to the diffusion of carbon into the interdiffusion zone, carbon depletion inside the HT-9 led to the disappearance of the martensite lath structure, and intergranular U-rich carbides formed as a result of the diffusion of uranium into the cladding. These detailed new findings reveal the unique features of the FCCI behavior of annular U-Zr fuels, which could be a promising alternative fuel form for high burnup fast reactor applications.

First-principles study of intrinsic point defects and Xe impurities in uranium monocarbide

Based on density functional theory (DFT) calculations, we perform an extensive investigation of intrinsic point defects and Xe impurities in uranium monocarbide (UC). The DFT calculations involve both the conventional generalized gradient approximation (GGA) and the GGA+U approach with the Hubbard parametric term (U), using up to 5×5×5 supercells. GGA calculations for the formation energy of intrinsic defects demonstrate the significant effect of using larger supercells than in previous studies. Results confirm that the ⟨111⟩ and ⟨100⟩ dumbbell interstitials are the most stable interstitial configurations for U and C, respectively. The interstitial mechanisms are favored for self-diffusion of both uranium and carbon and diffusion of Xe under equilibrium conditions. Calculations also reveal that the Xe substitutional defect at the C lattice site tends to adopt an off-site configuration, which can be interpreted as a Xe interstitial–C vacancy complex. We also utilize GGA+U to assess the impact of effective U parameter (Ueff) on the results. Moreover, we introduce a method to estimate the carbon chemical potential by fitting the phase diagram composition data and propose a selection Ueff=1.25 eV based on the experimental Xe diffusion activation energy. With this approach, GGA+U calculations reproduce the available experimental data for the formation energy of the carbon Frenkel pair and can explain the stepwise recovery of intrinsic properties and burst Xe release behavior in UC observed in annealing experiments.

A novel amidoxime functionalized porous resins for rapidly selective uranium uptake from solution

Traditional adsorption resin prepared by a low efficiency method has a low porosity and surface area, which limits the adsorption performance of the resin. Therefore, a novel porous resin was developed by structural design of the resins through post- modification with HPA and a post-crosslinked method. The novel porous post-modification resin was successfully prepared by the multistep method. Meanwhile, the high surface area and abundant micropores in HCR-AO can improve the adsorption rate by accelerating the diffusion of uranium in the external diffusion stage. The removal capacity of HCR-AO increased 366% for HCR and 120% for PSD-AO at the same initial concentration. HCR-AO takes less time to reach equilibrium than PSD-AO and HCR. Excitingly, the adsorption amount of the material dropped only slightly even after 8 cycles. The short equilibrium time and outstanding removal efficiency makes it a novel candidate for further extraction of U (VI) from seawater.

Simulation of diffusive uranium transport and sorption processes in the Opalinus Clay

Diffusive transport and sorption processes of uranium in the Swiss Opalinus Clay were investigated as a function of partial pressure of carbon dioxide pCO2, varying mineralogy in the facies and associated changes in porewater composition. Simulations were conducted in one-dimensional diffusion models on the 100 m-scale for a time of one million years using a bottom-up approach based on mechanistic surface complexation models as well as cation exchange to quantify sorption. Speciation calculations have shown, uranium is mainly present as U(VI) and must therefore be considered as mobile for in-situ conditions. Uranium migrated up to 26 m in both, the sandy and the carbonate-rich facies, whereas in the shaly facies 16 m was the maximum. The main species was the anionic complex CaUO2(CO3)32−. Hence, anion exclusion was taken into account and further reduced the migration distances by 30 %. The concentrations of calcium and carbonates reflected by the set pCO2 determine speciation and activity of uranium and consequently the sorption behaviour. Our simulation results allow for the first time to prioritize on the far-field scale the governing parameters for diffusion and sorption of uranium and hence outline the sensitivity of the system. Sorption processes are controlled in descending priority by the carbonate and calcium concentrations, pH, pe and the clay mineral content. Therefore, the variation in porewater composition resulting from the heterogeneity of the facies in the Opalinus Clay formation needs to be considered in the assessment of uranium migration in the far field of a potential repository.

Redistribution of radionuclides in irradiated AGR-1 UCO TRISO fuel after 1800 °C safety testing

Release of radionuclides from intact tristructural-isotropic (TRISO) coated particle fuel at normal and accident conditions is a primary metric of fuel performance. The distribution of fission products and actinides in the TRISO layers of individual particles provides insight on radionuclide transport and release behavior and was determined using scanning electron microscopy analysis. Particles were isolated from an irradiated fuel compact (AGR-1 Compact 4-4-2) and analyzed as-irradiated or after individual particle safety-testing at 1800 °C for 650 h. Particles were selected for comparison based on their remaining 110mAg fission product inventory. These comparisons corroborated the observation that the 110mAg inventory is a marker for relative irradiation temperature based on observed radionuclide distribution in the SiC layer. The comparison also indicated that the in-pile behavior influences the fission product and actinide species interactions with the TRISO layers during high temperature exposure after irradiation. The analysis confirms both palladium and uranium diffusion, as well as other species, are active in the UCO TRISO fuel system at 1800 °C and that palladium transport is active at lower temperatures relative to uranium. While diffusion across the SiC layer was observed, the intact nature of the SiC layer after the 1800 °C, 650-h exposure indicates the SiC layer maintained its functionality as a fission product barrier by mitigating release of radionuclides at beyond accident margin temperatures.