This study explores the impact of metal doping on the surface structure of spent nuclear fuels (SNFs), particularly uranium dioxide (UO2). SNFs undergo significant microstructural changes during irradiation, affecting their physical and chemical properties. Certain elements, including actinides and lanthanides, can integrate into the UO2 lattice, leading to non-stoichiometry based on their oxidation state and environmental conditions. These modifications are closely linked to phenomena like corrosion and oxidation of UO2, making it essential to thoroughly characterize SNFs influenced by specific element doping for disposal or interim storage decisions. The research employs X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy to investigate the surface structure of UO2 samples doped with elements such as Nd3+, Gd3+, Zr4+, Th4+, and ε-particles (Mo, Ru, Pd). To manufacture these samples, UO2 powders are mixed and pelletized with the respective dopant oxide powders. The resulting pellet samples are sintered under specific conditions. The XRD analysis reveals that the lattice parameters of (U,Nd)O2, (U,Gd)O2, (U,Zr)O2, and (U,Th)O2 linearly vary with increasing doping levels, suggesting the formation of solid solutions. SEM images show that the grain size decreases with higher doping levels in (U,Gd)O2, (U,Nd)O2, and (U,Zr)O2, while the change is less pronounced in (U,Th)O2. Raman spectroscopy uncovers that U0.9Gd0.1O2-x and U0.9Nd0.1O2-x exhibit defect structures related to oxygen vacancies, induced by trivalent elements replacing U4+, distorting the UO2 lattice. In contrast, U0.9Zr0.1O2 shows no oxygen vacancy-related defects but features a distinct peak, likely indicating the formation of a ZrO8-type complex within the UO2 lattice. ε-Particle doped uranium dioxide shows minimal deviations in surface properties compared to pure UO2. This structural characterization of metal-doped and ε-particle-doped UO2 enhances our understanding of spent nuclear fuel behavior, with implications for the characterization of radioactive materials. This research provides valuable insights into how specific element doping affects the properties of SNFs, which is crucial for managing and disposing of these materials safely.

Heavy water (deuterium oxide, D2O) is water in which hydrogen atoms (1H, H), one of the constituent elements of water molecules, have been replaced with deuterium (2H, D), a heavier isotope. Heavy water is used in a variety of industries, including semiconductors, nuclear magnetic resonance, infrared spectroscopy, neutron deceleration, neutrino detection, metabolic rate studies, neutron capture therapy, and the production of radioactive materials such as plutonium and tritium. In particular, heavy water is used as a neutron moderator or coolant in nuclear reactors and as a fuel for nuclear fusion energy, methods for measuring heavy water are becoming increasingly important. There are methods with density, mass spectrometry, and infrared (IR) spectroscopy. In this study, Fourier transform infrared spectroscopy (FT-IR) was used, which is commonly used in IR spectroscopy because of its relatively high analytical sensitivity, low operating costs, and easy online analysis. Heavy water was identified in the range of 2,300-2,600 cm-1 wavenumber (O-D) and the range of 1,200-1,300 cm-1 wavenumber (D-O-D), which are known to be the range with strong infrared absorption. As a result, the linearity of infrared absorbance for each heavy water concentration was confirmed within the relative expansion uncertainty (k=2).

Noble metal phase, present in used fuel, are fission products that can be found as metallic precipitates in used nuclear fuel. They exist as small particles (nm~um) in grain boundaries of the used fuels. Since they are particles deposited between the grain structures, they can be considered as defects in the pellet structure. Thermal expansion of fuels with noble metal is slightly higher than that of bare fuels. The fuels at high temperature, such as immediately after being discharged from nuclear reactors, may be subject to fuel failure if sufficient cooling is not provided. Recent research has shown that the noble metals can migrate into the rim space between the pellet and the cladding, and be deposited in the inner layer of the claddings. therefore, the mechanical integrity of the cladding can be degraded by noble metals, as well as the pellets. The concentration of the noble metal phase should be considered to evaluate the effect of the noble metals on the fuel integrity, after discharge from the reactors. SCALE/ORIGEN code was used to evaluate the noble metals in fuel assembly-scale, and the radial distribution in the fuel assembly. The radial distribution of the reactor power was derived from the SCALE/TRITON, considering Westinghouse 17×17. Square cell model was chosen for the geometry and 1/4 model was applied to reduce the computation time.

Most of the C-14 produced is in the organic form, generated as methane (14CH4), methanol (14CH3OH), formaldehyde (14CH2O), and formic acid (14CO2H2). When analyzing C-14, it is transformed into the form of 14CO2, and its concentration is determined using LSC. Typical examples include the wet oxidation method, the combustion or Pyrolysis. The wet oxidation method uses strong acids and involves repeated operations, which generates large amounts of acid waste and secondary radioactive waste. The combustion method uses high temperatures, which requires an oxygen device. Pyrolysis also requires high temperature in a vacuum and catalysts. Catalysts are expensive because they are platinum-based. To compensate for these shortcomings, a C-14 analysis method using UV irradiation was developed. In this study, 100 mL of distilled water mixed with formic acid (CO2H2), potassium persulfate (K2S2O8), and silver nitrate (AgNO3) was irradiated with a 320-390 nm UV lamp to conduct a CO2 production reaction experiment. The UV range was measured using a photometer (UV Power puck II). The beaker was made of quartz in 150 mL size with three inlets : a temperature measurement, a sample inlet, and a collection tube connector. We changed the UV lamp used from a 450 W halogen lamp to a 100 W LED, which has a lower temperature and is safer. As a result of the experiment, CO2 bubbles were generated in the collection tube, due to the UV irradiation react, which uses oxidizer and catalysts. The maximum temperature of the solution irradiated with the LED UV lamp was less than 56°C. It confirmed the rate of bubble generation changed depending on the lamp distance, the amount of sample, oxidizer, and catalyst. In an experiment to confirm the reaction caused by heat, it was found that although a reaction occurred due to heat, the reaction was significantly lower than when using a UV lamp. The reproducibility experiment was conducted three times in total under the same conditions. It showed the same pattern. In the future, we plan to select mock samples, collect 14CO2 in Carbo- Sorb, and analyze them using LSC. The results of this research will be used as a technology to recover C-14 more safely and efficiently and will also be used to expand its application to the treatment of other wastes such as waste liquid and waste resin through simulated samples.

Bis (2-ethylhexyl)phosphoric acid (HDEHP) is a renowned extractant, favored for its affinity to selectively remove uranium via its P=O groups. We previously synthesized HDEHP-functionalized mesoporous silica microspheres for solid-phase uranium adsorption. Herein, we investigated the kinetic and isothermal behavior of uranyl ion adsorption in mesoporous silica microspheres functionalized with phosphate groups. Adsorption experiments were conducted by equilibrating 20 mg of silica samples with 50 mL of uranium solutions, with concentrations ranging from 10 to 100 mgU L−1 for isotherms and 100 mgU L−1 for kinetics. Three distinct samples were prepared with varying HDEHP to TEOS molar ratios (x = 0.16 and 0.24) and underwent hydrothermal treatment at different temperatures, resulting in distinct textural properties. Contact times spanned from 1 to 120 hours. For x = 0.16 samples, it took around 50 and 11 hours to reach equilibrium for the hydrothermally treated samples at 343 K and 373 K, respectively. Adsorbed quantities were similar (99 and 101 mg g-1, respectively), indicating consistent functional group content. This suggests that the key factor influencing uranium adsorption kinetics is pore size of the silica. The sample treated at 373 K, with a larger pore size (22.7 nm) compared to 343 K (11.5 nm), experienced less steric hindrance, allowing uranium species to diffuse more easily through the mesopores. The data confirmed the excellent fit of pseudo-second-order kinetic model (R2 > 0.999) and closely matched the experimental value, suggesting that chemisorption governs the rate-controlling step. To gain further insights into uranium adsorption behavior, we conducted an adsorption isotherm analysis at various initial concentrations under a constant pH of 4. Both the Langmuir and Freundlich isotherm models were applied, with the Langmuir model providing a superior fit. The relatively high R2 value indicated its effectiveness in describing the adsorption process, suggesting homogenous sorbate adsorption on an energetically uniform adsorbent surface via a monolayer adsorption and constant adsorption site density, without any interaction between adsorbates on adjacent sites. Remarkably, differences in surface area did not significantly impact uranium removal efficiency. This observation strongly suggests that the adsorption capacity is primarily governed by the loading amount of HDEHP and the inner-sphere complexation with the phosphoryl group (O=P). Our silica composite exhibited an impressive adsorption capacity of 133 mg g-1, surpassing the results reported in the majority of other silica literature.

During the initial cooling period of spent nuclear fuel, Cs-137 and Sr-90 constitute a large portion of the total decay heat. Therefore, separating cesium and strontium from spent nuclear fuel can significantly decrease decay heat and facilitate disposition. This study presents analytical technique based on the gas pressurized extraction chromatography (GPEC) system with cation exchange resin for the separation of Sr, Cs, and Ba. GPEC is a micro-scaled column chromatography system that allows for faster separation and reduction volume of elution solvent compared to conventional column chromatography by utilizing pressurized nitrogen gas. Here, we demonstrate the comparative study of the conventional column chromatography and the GPEC method. Cation exchange resin AG 50W-X12 (200~400 mesh size) was used. The sample was prepared at a 0.8 M hydrochloric acid solution and gradient elution was applied. In this case, we used the natural isotopes 88Sr, 133Cs, and 138Ba instead of radioactive isotopes for the preliminary test. Usually, cesium is difficult to measure with ICP-OES, because its wavelengths (455.531 nm and 459.320 nm) are less sensitive. So, we used ICP-MS to determine the identification and the recovery of eluate. In this study, optimized experimental conditions and analytical result including reproducibility of the recovery, total analysis time and volume of eluents will be discussed by comparing GPEC and conventional column chromatography.

Bisphenol-A, also known as BPA, is commonly used as a building block for epoxy and polycarbonate plastics. However, it has been recently identified as a major source of water pollution due to its release into the water from plastic products. BPA-based resins can also contaminate the water with high concentrations of BPA, which can enter the water bodies through production units and wastewater discharge. Photocatalysis, particularly the photo-Fenton process, is an effective method for wastewater treatment and degrading pollutants. Titanium dioxide (TiO2) is usually chosen based on its high photocatalytic properties and high performance. However, its wide band gap energy is a major issue for the photocatalytic process. This means that the catalyst can only exhibit high photocatalytic performance under UV-light irradiation and usually requires an acidic pH, which limits its use. In order to address the aforementioned issues, a visible-light photoactive photo-Fenton reaction has been successfully developed to degrade bisphenol A at natural pH using H2O2. The process was highly efficient, achieving complete degradation of phenol in just three hours of visible light irradiation with Cu-MOF. This environmentally friendly Fenton process has the advantage of occurring at natural pH levels with the presence of H2O2, providing a new perspective for efficient degradation. The photocatalyst was characterized using single X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), Fourier Transform Infrared Spectroscopy (FTIR), and UV–vis diffuse reflectance spectroscopy (DRS).

Some consumer goods containing radioactive substances are in circulation and used in everyday life. In accordance with the Nuclear Safety Act, consumer goods with radioactivity are regulated. However, since most consumer goods distributed in Korea have no information that can confirm the amount of radiation, it is necessary to analyze the radiation for safety regulation. Among these consumer goods, GTLS (Gaseous Tritium Light Source) contains gaseous tritium (tritium, written as 3H or T), which is a radioactive material. The gaseous composition ratio in GTLS was analyzed using a precision gas mass spectrometer (Thermo Fisher, model MAT 271). As a result of GTLS analysis, the H2, HD or H3 +(T) or 3He, HT or D2 or He, DT, and T2, which correspond to the mass-to-charge ratio (m/z) 2 to 6 and the air components were detected. In addition, substances corresponding to m/z=24 and m/z=21 were also detected. These were compared with pure CH4 and those fragmentation patterns. The ratios of CT4 (m/z = 24) to CT3 (m/z = 21) and CH4 (m/z = 16) to CH3 (m/z = 15) were compared and they agree within the measurement uncertainty. We also performed additional experiments to separate the water component in the GTLS samples, considering the possibility that the m/z = 21 to m/z = 24 region is tritium compounds based on H2O. Despite the removal of the water components, peaks were detected at m/z=21 and m/z=24. Therefore, we confirmed that the component of m/z = 24 in the GTLS sample was CT4.

This study was performed to evaluate the separation of Sr, Cs, Ba, La, Ce, and Nd using gas pressurized extraction chromatography (GPEC) with anion exchange resin for the quantitation of Neodymium. GPEC is a micro-scaled column chromatography system that provides a constant flow rate by utilizing nitrogen gas. It is overcome the disadvantages of conventional column chromatography by reducing the volume of elution solvent and shortening the analysis time. Here, we compared the conventional column chromatography and the GPEC method. The whole analysis time was decreased by nine times and radioactive wastes were reduced by five times using the GPEC system. Anion exchange resin 1-X4 (200~400 mesh size) was used. The sample was prepared at a 0.8 M nitric acid in methanol solution. The elution solvent was used at a 0.01 M nitric acid in methanol solution. Finally the eluate was analyzed by ICP-MS to determine the identification and recovery. In this case, we applied the natural isotopes of LREEs (139La, 140Ce, and 144Nd) and high activity nuclides (88Sr, 133Cs, and 138Ba) instead of radioactive isotopes for the preliminary test; as a result, unnecessary radioactive waste was not produced. The recoveries were 93.9%, 105.9%, 91.9%, 47.6%, 35.9%, and 79.9% of Sr, Cs, Ba, La, Ce, and Nd, respectively. The reproducibility of recoveries by GPEC were in the range 2.8%–10.9%.

Confirmation of the thermal behavior of spent fuel is one of the important points in the management of high-level radioactive waste. This is because various fission products exist in spent nuclear fuel, and a management plan according to their behavior is required. Among the fission products, epsilon particles exist in the form of metal deposits and have a great influence on their physical and chemical properties. However, observing the thermal behavior of epsilon particles is important for understanding spent fuel behavior in thermally environment, but it is difficult to maintain a consistent thermal environment. In this work, we report the thermal behaviors study of uranium oxide with epsilon particle using in situ high temperature X-ray diffraction. We measured the variation of temperature on the size of crystalline, which is a cell parameter in the reaction process. And then, the change of lattice parameters is calculated by Rietveld refinement.

Noble metal precipitates are fission products that can be found as metallic alloys in used nuclear fuel. They do not exist homogenously inside the fuel pellets, but exists in grain boundaries in the form of immiscible particles. The first drawback that comes because they exist in grain boundaries is the degradation of mechanical integrity. The particles in the grain boundaries can be considered as defect n solid solution of uranium oxide pellets, and they can change the lattice volume. Therefore, it is known that it can cause stress corrosion cracking of fuel pellets. Furthermore, there is a negative effect from the perspective of used fuel management. However, they also have a positive effect on used fuel management. Since the noble metal has galvanic reduction effect, the particles serve as an oxidation inhibitor for uranium. There are many other effects regarding to the noble metal precipitates. However, in any case, quantifying the particles is important in order to quantitatively analyze these effects from the perspective of used fuel management. SCALE/TRITON code was applied to calculate the noble metal isotopes including Mo, Tc, Ru, Rh and Pd. In order to calculate the distribution inside the pin, the multiregion cell model was selected. In particular, a cylindrical geometry was used, and the pellet was divided into several layers. In addition, coolant and cladding surrounded the pellet. Finally, the radial distribution was evaluated using the computational code, along with neutron flux map.

Molten salts have gained significant attention as a potential medium for heat transfer or energy storage and as liquid nuclear fuel, owing to their superior thermal properties. Various fluoride- and chloride-based salts are being explored as potential liquid fuels for several types of molten salt reactors (MSRs). Among these, chloride-based salts have recently received attention in MSR development due to their high solubility in actinides, which has the potential to increase fuel burnup and reduce nuclear water production. Accurate knowledge of the thermal physical properties of molten salts, such as density, viscosity, thermal conductivity, and heat capacity, is critical for the design, licensing, and operation of MSRs. Various experimental techniques have been used to determine the thermal properties of molten salts, and more recently, computational methods such as molecular dynamics simulations have also been utilized to predict these properties. However, information on the thermal physical properties of salts containing actinides is still limited and unreliable. In this study, we analyzed the available thermal physical property database of chloride salts to develop accurate models and simulations that can predict the behavior of molten salts under various operating conditions. Furthermore, we conducted experiments to improve our understanding of the behavior of molten salts. The results of this study are expected to contribute to the development of safer and more efficient MSRs.

In this study, we evaluated the performance of phosphate-functionalized silica in adsorbing uranium and provided insights into optimizing the initial conditions of the uranium solution (concentration and pH), which are often overlooked in uranium adsorption studies. While most studies take into account the effect of pH on both the surface charge of the adsorbents and the dissolved speciation of uranium in solution, they often overlook the formation of solid phases such as β-UO2(OH)2 (cr) and UO3· 2H2O(cr), leading to an overestimation of the adsorption capacity. To address this issue, we considered the speciation of U(VI) calculated using thermodynamic data. Our findings suggest that it is reasonable to evaluate the adsorption performance at pH 4 and concentration below 1.35 mM. The formation of β-UO2(OH)2 (cr) starts at 23 μM (pH 5) and 1 μM (pH 6) and increases sharply with increasing concentration. To avoid interference from the formation of solid phases, experiments should be conducted at lower concentrations, which in turn require very small msorbent/Vsolution ratios. However, controlling small amounts of sorbent can be challenging, and increasing the volume of the solution can generate significant amounts of radioactive waste. We also used UV-vis spectra analysis to investigate the formation of solid phases. We found that a 100 mg L-1 uranium solution resulted in the formation of colloidal particles in the solid phase after 2.5 hours at pH 6, while at pH 4, no significant changes in absorbance were observed over 120 hours, indicating a stable ion phase. Based on these conditions, we obtained an excellent adsorption capacity of 110 mg g-1.

The removal of aqueous pollutants, including dye molecules from wastewater remains one of the pressing problems in the world. Because of chemical stability and conjugated structure, dye molecules cannot be easy decomposed by heat with oxidizing reagents such as H2O2 and light. The most common representative of widespread organic pollutant is methylene blue (MB) with molecular formula C16H18ClN3S, which is important colorant and used in various chemical and biological production industries and causes serious environment problems. Porous materials, including MOFs (metal-organic frameworks) have been applied for efficient MB photocatalytic degradation. However, one of the main barriers to using most MOFs to break down aromatic organics is wide band gap energy, which means that the catalyst can exhibit high photocatalytic performance only under UVlight irradiation. Moreover, most MOFs usually show the poor water stability of frameworks, which tend to dissolve in water with total destruction. In this work we report about two new copper based MOFs with high photocatalytic properties for efficient MB degradation from wastewater under UV-light and natural sunlight. Time, required for 100% MB degradation, equals 7 minutes under UV (source 4 W 254 nm VL-4.LC UV-lamp) and 60 minutes under natural sunlight irradiation in the presence of H2O2. Crystal structure information is provided using single crystal X-ray diffraction data. The composition and comparative characteristics of MOFs are given using powder X-ray diffraction, UV–visible diffuse reflectance spectroscopy, UVvisible spectroscopy and Fourier-transform infrared spectroscopy.

Hydrogen-bonded organic frameworks (HOFs) are a new type of porous crystalline material that are constructed by intermolecular hydrogen bonding of organic building blocks to form twodimensional (2D) and three-dimensional (3D) crystalline networks. High-quality HOF single crystals are easily grown for direct superstructure analysis using single crystal X-ray diffraction, which is essential for revealing the relationship between structure and properties. The unique advantages of HOF, such as high crystallinity, porosity and fast regeneration, have allowed it to be used in a variety of applications including catalysis and gas separation. Squaric acid (SQA) is a non-carboxylic, organic acid with proton donor and acceptor ability which is known to take on a variety of coordination modes with metal ions. Pyrazine is a six-membered aromatic heterocycle bearing two nitrogen atoms, which has sp2 hybridized C atoms with C-H hydrogen bonds. This work describes the synthesis and structural characteristics of HOF based on squaric acid and pyrazine. Based on single crystal X-ray diffraction data, this MOF crystallizes in the triclinic P-1 space group. Each asymmetric unit is composed of H2SQ and pyrazine. All squaric acid molecules share one H atom with the N atom of pyrazine molecules. The layer distance between nearby O atoms from squaric acid in different layers equals 5.29 Å. Also, our HOF showed high adsorption capacity the during experiments. The composition and comparative characteristics of HOF are given using SCXRD, PXRD, SEM and UV-vis.

Viscosity is a fundamental physical property that is important in any system in which fluid movement occurs. In addition, most of the elements exist as ions in molten state in high-temperature molten salt, and electrical conductivity in such molten state is closely related to viscosity as a transport property. Molten salt reactor (MSR) and pyroprocess are representative processes dealing with high-temperature molten salts, actinide elements, and other radioactive materials. In MSR and pyroprocesses, the viscosity data must be provided as one of the fundamental physical property data required for safe process operations and countermeasures to severe accidents. In order to measure the viscosity of highly corrosive molten salt at high temperatures, we have built a in-house developed molten salt viscosity measurement system based on the Brookfield rotationary viscometer. We also developed a special correction technique to improve the accuracy of the viscosity measurement. In this study, the viscosity was measured at 500°C for NaCl-MgCl2 molten salt, which is selected as the base salt material of MSR system under development in Korea Atomic Energy Research Institute (KAERI), using our viscosity measurement system installed in a oxygen- and moisture-free Ar-atmosphere glovebox. Our viscosity measurement system was calibrated using a LiCl-KCl eutectic mixture with well-known viscosity value, and viscosity values obtained using our own correction methodology were compared with those of other conventional correction methods. In our further study, we plan to measure the NaCl-MgCl2-UCl3 system at various compositions and temperatures.

In Korea, 483,102 assemblies of spent fuel have been discharged and stored in sites, as of 2019. However, total capacity for site storage is 529,748 assemblies, and more than 90% is already saturated. Wolsong site, the most saturated site, started to construct more dry storage to extend the capacity in 2020. Spent fuel and high-level waste (HLW) is a big concern in Korean nuclear industry. Then, master plan for management of spent fuel is once announced by Ministry of Trade, Industry and Energy (MOTIE) in 2016 and reviewed by civil committee in 2019. The core contents of the plan are establishing schedule for construction of HLW management facility in one area, and construction of temporary dry storage in each site, if unavoidable. For HLW management facility, there are three following schedules: siting of Underground Research Laboratory (URL) and Interim Storage by 2020, operation of facilities initiated by 2030, and operation of final disposal facility initiated by 2050. Final repository will be designed as deep geological repository. The concept of deep geological disposal is that spent nuclear fuel is placed in disposal containers that can withstand corrosion and pressure in long-term, permanently isolated from the human sphere of life, and dumped in deep geological media, such as crystalline rocks and clay layer, at a depth of 300 to 1,000 meters underground. The safety assessment of waste disposal sites focuses on determining whether the disposal sites meet the safety requirements of national regulatory authority. This safety assessment evaluates the potential radiation dose of radionuclides from the disposal site to humans or the environment. In this case, the calculation is performed assuming that all engineering barriers of the disposal site have collapsed in a long-term period. Then radionuclides are released from the waste, and migrated in groundwater. The dose resulting from the release and migration of radionuclides on the concentration of nuclides in groundwater. In general, metallic nuclides may exist in water in various ionic states, but some form colloids. This colloid allows more nuclides to exist in water than in solubility. Therefore, more doses may occur than we know generally predict. To determine the impact of colloids, we performed the safety assessment of the Yucca Mountain repository as an example.