• 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.13 no.1
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• pp.11-19
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• 2015

The production of nuclear fuel cladding tube is expected to increase with the nuclear power plant expansion. Zirconium(Zr) scrap that is generated during manufacturing is also expected to increase. Zr electrorefining experiment was carried out in the fluoride salt of LiF-KF-ZrF₄ using multiple electrode for scale up and improving throughput Zr electrorefiner develop-ment. The Zr reduction peak observed at-0.8 V(vs.Ni). Polarization behavior showed that the amount of applied current increases because of decreasing cell resistance as the number of cathode increases. Experimental results showed the highest recovery rate about 98% at lowest current density of 25.64 mA/cm² using 6 electrodes. XRD and TG analysis result show that pure Zr was recovered 99.92% and ICP analysis shows that lower impurity content than conventional impurity content of the Anode(97.8%). Electrorefining consumes energy about 7.15 kWh/kg less than 39.7% compared to the Kroll process using 6 electrode width of 20 mm and height of 65 mm. Because of increasing cell efficiency and recovery rate, using multiple cathode is determined as an efficient technique for scale up electrorefining Zr scrap.

• Analytical Science and Technology
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• v.16 no.4
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• pp.261-268
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• 2003

To investigate the matrix effect of sample for hydrogen analysis by inert gas fusion-thermal conductivity detection, calibration factor for the hydrogen analyser of the inert gas fusion-thermal conductivity detection method was measured with hydrogen standard materials in Ti, Zr-2.5Nb and by hydrogen gas dosing method. Also the hydrogen extraction efficiency for the different sample matrix, Ti and Zr-2.5Nb, was evaluated without adding tin flux. The calibration factor of the hydrogen analyser which was calibrated by hydrogen standard material in Zr-2.5Nb and Ti was 2~3% and 14% higher than that by hydrogen gas dosing method, respectively. Based on the results of calibration factor measurement, it could be concluded that the hydrogen extraction efficiency of the Ti matrix sample will be 12% lower than that of the Zr-2.5Nb. And according to the experimental results of hydrogen recovery test by no tin flux, the hydrogen recovery percentage of the Ti and Zr-2.5Nb matrix sample was about 70% but the recovery rate of Ti matrix sample was slightly lower than that of Zr-2.5Nb.

• Resources Recycling
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• v.26 no.6
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• pp.29-37
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• 2017

Nuclear fuel cladding tube is fabricated by pilgering and annealing process. In order to remove impurity and oxygen layer on the surface, pickling process is carried out. When Zirconium(Zr) is dissolved and saturated in acid solution during the pickling process, all the waste acid including Zr is disposed. Therefore, $BaF_2$ is added into the waste acid to extract Zr and $Ba_2ZrF_8$ is subsequently formed. To recycle Zr by electrowinning process, $Ba_2ZrF_8$ is used as electrolyte, but it has high melting point ($1053^{\circ}C$). $ZrF_4$ should be added into $Ba_2ZrF_8$ to decrease the melting point. In this paper, it was investigated that $Ba_2ZrF_8$ was separated to $BaF_2$ and $ZrF_4$ by vacuum distillation. Firstly, $BaF_2$ with different particle size ($1{\mu}m$, $35{\mu}m$, $110{\mu}m$) was added into the waste acid and the respective precipitation property was estimated. $BaF_2$ obtained by vacuum distillation was shattered by ball-milling with different time. The precipitation efficiency was compared with $1{\mu}m$ of ${BaF_2}^{\prime}s$ one, which was not used as precipitation agent.

• Proceedings of the Korean Institute of Resources Recycling Conference
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• 2005.10a
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• pp.266-270
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• 2005

본 연구는 Ta, Nb, Zr, 및 희토류 등을 복합적으로 함유한 복합광을 대상으로 사염화탄소에 의한 염화반응을 알아보기 위한 기초연구로서 각 산화물의 염화반응 특성을 알아보고 이를 토대로 복합광의 염화반응을 비교하여 보았다. 실험결과 산화물 상태의 Nb, Ta 및 Zr은 비교적 낮은 온도에서 염화반응이 일어나고 염화물이 휘발됨을 알 수 있었다. 복합광을 반응 온도 $400^{\circ}C,\;CCl_4$ 분압 0.28 일때 반응시간이 10분에서 60분으로 변함에 따라 니오븀 및 탄탈륨은 $91%{\sim}99%$의 높은 회수율을 나타내었으나 지르코늄은 각각 16.5%에서 27.5%로 약간 증가하는 경향을 나타내었다. 희토류의 경우 세륨은 반응율이 71.7에서 73% 정도였고 란타늄은 51%에서 54% 정도의 반응율을 나타내었다.

• Resources Recycling
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• v.26 no.5
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• pp.97-104
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• 2017

Nuclear fuel cladding tubes are manufactured through pilgering and the annealing process. In order to remove the oxidized layer and impurities on the surface of the tube, a pickling process is required. Zirconium (Zr) is dissolved in a HF and $HNO_3$ acid mixture during the process and the pickling waste acid, including the dissolved Zr, is completely discarded after neutralization. This study observes the effects of the residual impurities (Ba) in the pickling solution regenerated from the $BaF_2$ precipitation process on the waste pickling solution. In addition, the concentration of Ba and Zr for the actual nuclear fuel cladding tube process was optimized. The regenerated pickling solution was tested through a pilot plant pickling process device that simulates the commercial pickling process of nuclear fuel cladding tubes, and the pickling efficiency was analyzed through AFM analysis of the roughness of the cladding tube surface.

• 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.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.3
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• pp.229-243
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• 2013

An in situ solute migration system was designed and installed in KAERI Underground Research Tunnel (KURT) constructed in the site of Korea Atomic Energy Research Institute (KAERI) in order to investigate the migration and retardation of non-sorbing and sorbing tracers through a rock fracture. The system is composed of three main parts including injection, extraction, and data treatment. For the selection of a water-conducting fracture, boreholes were drilled. The fractures in the drilled boreholes were investigated using borehole image analysis using borehole image processing system (BIPS). The results of BIPS analysis showed that borehole YH 3-1 and YH 3-2 were connected each other. Moreover, hydraulic tests were carried out to determine the test section with connectivity for the in situ experiments. The in situ solute migration experiments were accomplished to understand the migration of solutes through fractures in KURT using non-sorbing tracers which were fluorescein sodium, eosin-B, bromide and sorbing tracers which were rubidium, nickel, zirconium, and samarium.