• Korean Journal of Materials Research
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• v.26 no.12
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• pp.681-687
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• 2016

Zirconium(Zr) nuclear fuel cladding tubes are made using a three-time pilgering and annealing process. In order to remove the oxidized layer and impurities on the surface of the tube, a pickling process is required. Zr is dissolved in HF and $HNO_3$ mixed acid during the process and pickling waste acid, including dissolved Zr, is totally discarded after being neutralized. In this study, the waste acid was recycled by adding $BaF_2$, which reacted with the Zr ion involved in the waste acid; $Ba_2ZrF_8$ was subsequently precipitated due to its low solubility in water. It is very difficult to extract zirconium from the as-recovered $Ba_2ZrF_8$ because its melting temperature is $1031^{\circ}C$. Hence, we tried to recover Zr using an electrowinning process with a low temperature molten salt compound that was fabricated by adding $ZrF_4$ to $Ba_2ZrF_8$ to decrease the melting point. Change of the Zr redox potential was observed using cyclic voltammetry; the voltage change of the cell was observed by polarization and chronopotentiometry. The structure of the electrodeposited Zr was analyzed and the electrodeposition characteristics were also evaluated.

• Korean Journal of Metals and Materials
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• v.46 no.8
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• pp.482-488
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• 2008

For a better understanding of the correlation between a corrosion and a microstructure, it is necessary to study a phase transformation with an annealing condition for Zr-Nb alloy. Zr-5wt.%Nb alloy with different phase characteristics was prepared with various annealing conditions. A microstructural study and corrosion test were performed to investigate the effect of a phase such as the phase type, fraction, and size on corrosion. The corrosion behavior of the Zr-5Nb alloy was very sensitive to the annealing condition, which affected the formation of the ${\beta}$-phases (${\beta}$-Nb or ${\beta}$. The corrosion rate of the Zr-5Nb alloy annealed at $500^{\circ}C$ with the formation of the ${\beta}$-Nb phase was lower than that of the Zr-5Nb alloy annealed from 600 to $800^{\circ}C$ with the formation of the ${\beta}$-Zr phase. The highest corrosion rate was observed for the ${\beta}$-quenched Zr-5Nb alloy. After a consideration of the corrosion rate and micro structure of the Zr-5Nb alloy, the corrosion resistance of that alloy was improved due to the formation of a small sized ${\beta}$-Nb phase which could be controlled by the annealing condition.

• 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.

• Korean Journal of Materials Research
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• v.8 no.12
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• pp.1099-1109
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• 1998

To investigate the effect of V and Sb on the corrosion behavior of Zr- based alloys, corrosion tests were performed on 6 kinds of Zr alloys in an autoclave at $360^{\circ}C$ for 100 days. The transition of the corrosion rate occurred in the sample containing 0.1wt.%V after 10 days but did not occur in the samples containing 0.2wt.%V and 0.4wt.%V. The corrosion resistance of V containing alloys increased with increasing V contents from 0.1 to 0.4wt.% and the alloys containing 0.4wt.%V showed the best corrosion resistance. In the ternary alloys containing 0.1wt.%Sb and 0.4wt.%Sb, the corrosion rate increased significantly from the short exposure time. It was observed that the optimal Sb content for corrosion resistance was 0.2wt.%. The size and volume fraction of precipitates increased with increasing V and Sb contents. The superior corrosion resistance was observed in the Zr alloy having precipitate size of 0.11-0.13$\mu\textrm{m}$. From the result of corrosion behavior and the obserbation of precipitates, the optimal size of the precipitate appear to control the electron conduction in the cathodic reaction and play an important role in maintaining a stable oxide microstructure.

• Korean Journal of Materials Research
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• v.8 no.4
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• pp.368-374
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• 1998

The corrosion characteristics of zirconium alloys have been investigated in various aqueous solutions of LiOH. NaOH, KOH, RbOH. and CsOH at 3S$0^{\circ}C$. The concentrations of solutions were set to 4.3 mmol and 32.Smmol with equimolar $M^+$ and OH . The oxide characterization was performed using TEM on the samples corroded in 32. Smmol LiOH, NaOH, and KOH solution. The samples were prepared to have the same oxide thickness for the pretransition and post- transition regimes. Considering the trend of experimental data, the cation would playa major role in the corrosion process of Zr alloys in alkali hydroxide solutions. The microstructures of the oxides formed in various solutions were quite different. In LiOH solution the oxides grown in pre-transition as well as post-transition had the equiaxed structures with many pores and open grain boundaries. The oxides grown in NaOH solution had the protective columnar structures in pre-transition and the equiaxed structures with many open grain boundaries in post- transition. On the other hand. in KOH solution the columnar structure was maintained from pre- transition to post- transition. It was considered that the cation incorporation into zirconium oxide controlled the oxide characteristics and the corrosion acceleration in alkali hydroxide solutions.

• 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.