• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.17 no.2
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• pp.127-137
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• 2019

Zr electrorefining is demonstrated herein using Zirlo tubes in a chloride-fluoride mixed molten salt in the presence of $AlF_3$. Cyclic voltammetry reveals a monotonic shift in the onset of metal reduction kinetics towards positive potential and an increase in intensity of the additional peaks associated with Zr-Al alloy formation with increasing $AlF_3$ concentration. Unlike the galvanostatic deposition mode, a radial plate-type Zr growth is evident at the top surface of the salt during Zr electrorefining at a constant potential of -1.2 V. The diameter of the plate-type Zr deposit gradually increases with increasing $AlF_3$ concentration. Scanning electron microscopy-energy-dispersive X-ray spectroscopy (SEM-EDX) and X-ray photoelectron spectroscopy (XPS) analyses for the plate-type Zr deposit show that trace amount of Al is incorporated as Zr-Al alloys with different chemical compositions between the top and bottom surface of the deposit. Addition of $AlF_3$ is effective in lowering the residual salt content in the deposit and in improving the current efficiency for Zr recovery.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.15 no.2
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• pp.125-133
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• 2017

KAERI is conducting research on spent cladding hulls and additive metals to generate a solidification host matrix for the noble metal fission product waste in anode sludge from the electro-refining process to minimize the volume of waste that needs to be disposed of. In this study, alloy compositions Zr-17Cr, Zr-22Cr, and Zr-27Cr were prepared with or without eight noble metals representing fuel waste using induction melting. The microstructures of the resulting alloys were characterized and electrochemical corrosion tests were conducted to evaluate their corrosion characteristics. All the compositions had better corrosion characteristics than other Zr-based alloys that were evaluated for comparison. Analysis of the leach solution after the corrosion test of the Zr-22Cr-8NM specimen indicated that the noble metals were not leached during corrosion under 500 mV imposed voltage, which simulates a highly oxidizing disposal environment. The results of this study confirm that Zr-Cr based compositions will likely serve as chemically stable waste forms.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.69-75
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls was demonstrated to investigate the effect of the oxidation process on the reaction rate of the chlorination reaction. In chlorination reaction experiments performed for 6 h, where reaction products were collected every 2 h, it was observed that a significant decrease in the reaction rate was caused by the oxidation process ($500^{\circ}C$, 10 h under an air atmosphere) within the reaction period of 0 - 2 h. The amount of reaction residue increased from 0.95 to 1.65wt% of initial weights in the fresh and Zry-500-10 (Zry-4 hulls oxidized at $500^{\circ}C$ for 10 h under an air atmosphere) hulls, respectively. The purity of the recovered Zr was identical at 99.61wt% for the fresh Zry-4 and Zry-500-10 hulls. Quantitative analysis of the chlorination reaction rate was performed by varying the reaction time from 0.5 to 1.0, 2.0, and 4.0 h. The fitting results showed that the relationship between weight loss and reaction time can be interpreted by a linear line with a slope of 23.35wt%/h for the fresh Zry-4 case, while two linear lines were necessary to fit the results of Zry-500-10. In addition, the slope values were 17.12 and 27.16wt%/h for (0 - 20) and (20 - 100)wt% loss regions, respectively.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.12 no.3
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• pp.235-243
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• 2014

Surface oxidation behavior of ZIRLO (ZIRconium Low Oxidation) hulls was investigated using an X-ray photoelectron spectroscopy (XPS) technique. The effects of oxidation time (10-336 h at $500^{\circ}C$) and temperature ($400-700^{\circ}C$ for 10 h) were studied. Deconvolution results of the hulls oxidized at $500^{\circ}C$ revealed that a $ZrO_2$ phase appeared after 24 h (11.86%), and an increase in the $ZrO_2$ ratio was observed when the hulls were oxidized for 336 h (17.93%). On the other hand, the ZrO phase which employed 5.68% in the 10 h oxidized sample disappeared when the oxidation time increased to 24 h. The XPS results also showed that an increase in the oxidation temperature resulted in an increase in the ratio of ZrO, which increased from 0 to 5.68, 8.31, and 9.16% when the oxidation temperature increased from 400 to 500, 600, and $700^{\circ}C$, respectively. $ZrO_2$ phase was observed only in the sample that was oxidized at $700^{\circ}C$. The mechanism of ZrO formation was not conclusive, but it was suggested that a formation of hydroxide might have been accelerated at elevated temperatures leading to a formation of a $Zr(OH)_4$ phase. The relationship between the surface oxidation status of the hulls oxidized at $500^{\circ}C$ and their chlorination reaction feasibility was discussed, and it was suggested that the thickness of the oxide layer is an important parameter that determines the chlorination reaction feasibility.