Zirconium(Zr) alloys are commonly used in the nuclear industry for applications such as fuel cladding and pressure tubes. To minimize the levels and volumes of radioactive waste, molten salts have been employed for decontaminating Zr alloys. Recently, a two-step Zr metal recovery process, combining electrolysis and thermal decomposition, has been proposed. In the electrolysis process, potentiostatic electrorefining is utilized to control the chemical form of electrodeposits(ZrCl). Although Zr metals are expected to dissolve into molten salts, reductive alloy elements can also be co-dissolved and deposited on the cathode. Therefore, a better understanding of the anodic side’s response during potentiostatic electrorefining is necessary to ensure the purity of recovered Zr and long-term process operation. As the first step, potentiodynamic polarization curves were obtained using Zr, Nb, and Zr-Nb alloy to investigate the anodic dissolution behavior in the molten salts. Nb, which has a redox potential close to Zr, and Zr exhibit active or passivation dissolution mechanisms depending on the potential range. It was confirmed that Zr-Nb alloy also has a passivation region between -0.223 to -0.092 V influenced by the major elements Zr and Nb. Secondly, active dissolution of Zr-Nb was performed in the range of -0.9 to -0.6 V. The dissolution mechanism can be explained by percolation theory, which is consistent with the observed microstructure of the alloy. Thirdly, passivation dissolution of Zr, Nb, and Zr-Nb alloy was investigated to identify the pure passivation products and additional products in the Zr-Nb alloy case. K2ZrCl6 and K3NbCl6 were identified as the pure passivation products of the major elements. In the Zr-Nb alloy case, additional products, such as Nb and NbZr, produced by the redox reaction of nanoparticles in the high viscous salt layer near the anode, were also confirmed. The anodic dissolution mechanism of Zr-Nb alloy can be summarized as follows. During active dissolution, only Zr metal dissolves into molten salts by percolation. Above the solubility near the anode, passivation products begin to form. The anode potential increases due to the disturbance of passivation products on ion flow, leading to co-dissolution of Nb. When the concentration of Nb ion exceeds the solubility, a passivation product of Nb also forms. In this scenario, a high viscous salt layer is formed, which traps nanoparticles of Zr metal, resulting in redox behavior between Zr metal and Nb ion. Some nanoparticles of Zr and Nb metal are also present in the form of NbZr.
RUCAS (Recycling-Underlying Computational Dose Assessment System), a dose assessment program based on the RESRAD-RECYCLE framework, is designed to evaluate dose for recycling scenarios of radioactive waste in metals and concrete. To confirm the validity of the recycling scenarios provided by RUCAS, comparative evaluations will be conducted with RESRAD-RECYCLE for metal radioactive waste recycling scenarios and with MicroShield® for concrete radioactive waste recycling scenarios. In the evaluation of metal recycling scenarios without shielding, RUCAS showed similar results when compared to both MicroShield® and RESRAD-RECYCLE. This validates the function of dose assessments using RUCAS for metal recycling scenarios. However, when shielding was present, RUCAS produced results that were comparable to MicroShield®, but differed from those of RESRAD-RECYCLE. The underestimation of dose values up to 1.66E+08 times difference by RESRAD-RECYCLE could potentially decrease reliability and safety in evaluated doses, further emphasizing the importance of RUCAS. Because validation is also necessary for the expanded calculation capabilities resulting from methodological changes of RUCAS (i.e., various radiation source geometries), based on prior validations, it was determined that additional validations are required for different radiation source materials and shielding conditions. In case where the radiation source and shielding materials were identical, RUCAS and MicroShield® produced similar results according to both the Kalos et al. (1974) and Lin and Jiang (1996) methodologies. This demonstrates that the that differences in methodology are inconsequential when considering the same source and shielding materials. However, when the atomic number of the radiation source materials was larger than that of shielding material (HZ-LZ condition), RUCAS obtained results similar to MicroShield® only for the Kalos et al. (1974) methodology. While Lin and Jiang (1996) methodology yield higher results than MicroShield®. Lastly, in case where the atomic number of the radiation source material was smaller than that of the shielding material (LZ-HZ condition,) both methodologies yielded results comparable to MicroShield®. In conclusion, the validity of RUCAS’s shielding calculations has been verified, confirming improvements in dose assessment compared to RESRAD-RECYCLE. Additionally, we observed that shielding effectiveness calculations differ depending on the methodology of build-up effect. If the validity of these methodologies is confirmed, it is expected that selecting the most advantageous methodology for each condition will enable more rational dose assessments. Consequently, in future research, we plan to evaluate the validity of Lin and Jiang (1996) methodology using particle transport codes based on the Monte Carlo method, such as MCNP and Geant 4, rather than MicroShield®.
Electroanalytical study for the rotating cylinder electrode in molten LiCl-KCl eutectic salt (58– 42mol%) containing MgCl2 (0.1wt%) at 600°C is conducted. The researches of rotating cylinder electrode have been widely conducted for the century. The advantage of the electrode is that it can mitigate the unintended natural convection by providing a controlled diffusion boundary layer thickness. However, the experimental data for the high temperature molten salts is barely existed. The study adopts the electrochemical techniques such as cyclic voltammetry for the static cell and linear sweep voltammetry for the dynamic cell to calculate the diffusion coefficient. The peak current density and limiting current density are measured according to the scan rate. In order to evaluate the mass transfer under hydrodynamic flow condition, the revolution speeds of cylindrical electrode are varied from 10 rpm to 500 rpm which are corresponded to the Reynolds number of 4 and 185 respectively. The flow regime covers from the laminar to semi-turbulent regime (transient) as the critical Reynolds number Recrit is 200. The limiting current density shows a linear trend with the revolution speed and agrees well with the existing mass transfer correlations. For the extended flow regime, a new mass transfer correlation is suggested as the relation of non-dimensional numbers (Sh = aRebScc) based on the dimensionless analysis.