As part of strengthening pyro safety measures, the Korea Atomic Energy Research Institute is developing LIBS (Laser-Induced Breakdown Spectroscopy) application technology to analyze molten salt components in electrolytic recovery device in real time. LIBS performs qualitative and quantitative analysis by analyzing the spectrum of energy emitted by atomizing and ionizing elements on the surface of a salt sample with a high-focused laser. Since salt easily corrodes metal, it must be managed in an environment with a dew point of -40°C or lower. In this study, we designed and manufactured a device that places a rod-type sampling stick on a mounting base, automatically moves it to the optimal measurement position for LIBS, and retrieves the sample. Its characteristics are as follows. First, LIBS is stationary and does not move. Second, the sample stick is placed on a mounting base and can rotate 360 degrees. Third, according to the command, the sample stick automatically moves to the optimal measurement position of LIBS with three degrees of freedom (X, Y, Z). Fourth, the salt attached to the sampling stick is recovered for chemical analysis by driving the gripper mounted at the bottom of the Z axis, Z axis, and rotation axis (R). The X, Y, and Z movement distances of this device are each 100 mm, rotation is 360 degrees, grip stroke is 50 mm, and position accuracy is ±20 m. Once the performance test of the automated salt sample analysis device is completed, it will be installed in a dry room with a dew point of - 40°C or lower. Samples will be collected remotely in connection with the electrolytic recovery device and gantry robot built in the dry room. We plan to conduct experiments to seat the sample stick. Ultimately, we plan to conduct comprehensive experiments in conjunction with LIBS.

The homogeneity of radioactive spent ion exchange resins (IERs) distribution inside waste form is one of the important characteristics for acceptance of waste forms in long-term storage because heterogenous immobilization can lead to the poor structural stability of waste form. In this study, the homogeneity of metakaolin-based geopolymer waste form containing simulant IERs was evaluated using a laser-induced breakdown spectroscopy (LIBS) and statistical approach. The cation-anion mixed IERs (IRN150) were used to prepare the simulant spent IERs contaminated by non-radioactive Cs, Fe, Cr, Mn, Ni, Co, and Sr (0.44, 8.03, 6.22, 4.21, 4.66, 0.48, and 0.90 mg/g-dried IER, respectively). The K2SiO3 solution to metakaolin ratio was kept constant at 1.2 and spent IERs loading was 5wt%. For the synthesis of homogeneous geopolymer waste form, spent IERs were mixed with K2SiO3 solution and metakaolin first, and then the fresh mixture slurry was poured into plastic molds (diameter: 2.9 cm and height: 6.0 cm). The heterogeneous geopolymer waste form was also fabricated by stacking two kinds of mixtures (8wt% IERs loading in bottom and 2wt% in top) in one mold. Geopolymers were cured for 7d (1d at room temperature and 6d at 60°C). The hardened geopolymers were cut into top, middle, and bottom parts. The LIBS spectra and intensities for Cs were obtained from the top and bottom of each part. Cs was selected for target nuclide because of its good sensitivity for measurement. Shapiro-Wilk test was performed to determine the normality of LIBS data, and it revealed that data from the homogeneous sample is normal distribution (p-value = 0.9246, if p-value is higher than 0.05, it is considered as normal distribution). However, data from the heterogeneous sample showed abnormal distribution (p-value = 7.765×10-8). The coefficient of variation (CoV) was also calculated to examine the dispersion of data. It was 31.3% and 51.8% from homogeneous and heterogeneous samples, respectively. These results suggest that LIBS analysis and statistical approaches can be used to evaluate the homogeneity of waste forms for the acceptance criterion in repositories.

During electrorefining, fission products, such as Sr and Cs, accumulate in a eutectic LiCl-KCl molten salt and degrade the efficiency of the separation process by generating high heat and decreasing uranium capture. Thus, the removal of the fission products from the molten salt bath is essential for reusing the bath, thereby reducing the additional nuclear waste. While many studies focus on techniques for selective separation of fission products, there are few studies on processing monitoring of those techniques. In-situ monitoring can be used to evaluate separation techniques and determine the integrity of the bath. In this study, laser-induced breakdown spectroscopy (LIBS) was selected as the monitoring technique to measure concentrations of Sr and Cs in 550°C LiCl-KCl molten salt. A laser spectroscopic setup for analyzing high-temperature molten salts in an inert atmosphere was established by coupling an optical path with a glove box. An air blower was installed between the sample and lenses to avoid liquid splashes on surrounding optical products caused by laser-liquid interaction. Before LIBS measurements, experimental parameters such as laser pulse energy, delay time, and gate width were optimized for each element to get the highest signal-to-noise ratio of characteristic elemental peaks. LIBS spectra were recorded with the optimized conditions from LiCl-KCl samples, including individual elements in a wide concentration range. Then, the limit of detections (LODs) for Sr and Cs were calculated using calibration curves, which have high linearity with low errors. In addition to the univariate analysis, partial least-squares regression (PLSR) was employed on the data plots to obtain calibration models for better quantitative analysis. The developed models show high performances with the regression coefficient R2 close to one and root-mean-square error close to zero. After the individual element analysis, the same process was performed on samples where Sr and Cs were dissolved in molten salt simultaneously. The results also show low-ppm LODs and an excellent fitted regression model. This study illustrates the feasibility of applying LIBS to process monitoring in pyroprocessing to minimize nuclear waste. Furthermore, this high-sensitive spectroscopic system is expected to be used for coolant monitoring in advanced reactors such as molten salt reactors.

For the fabrication of the Si negative electrode in Li-ion batteries (LIBs) containing the cross-linking polymer binder, in this work, the urethane acrylate (UA) oligomer was synthesized via a simple synthetic process. The cross-linked poly(urethane acrylate) (CPUA)/carbone black (CB)/Si composite (CPUA/CB/Si composite) was fabricated through reactions between their reactive vinyl segments in the UA oligomer. Interestingly, the CPUA/CB/Si composite showed better cycle performance than the poly(vinylidene fluoride) (PVdF)/CB/Si composite (PVdF/CB/Si composite) and the polyurethane (PU)/CB/Si composite (PU/CB/Si composite). The CPUA/CB/Si composite had the best lithiation of about 2586 mAh g-1. The UA oligomer showed a good compatibility with the electrode materials and current collector after and before a curing process.