• Nuclear Engineering and Technology
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• 제56권4호
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• pp.1339-1346
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• 2024

Electrorefining in molten salts is used for purifying actinides. Optimizing electrorefining is key to minimizing processing time and radiological waste. One possible way of improving electrorefining efficiency is using an AC superimposed DC waveform. This waveform has demonstrated potential benefits in aqueous solutions but has never been utilized in a molten metal, molten salt application. This work investigates the effects of using an AC superimposed DC waveform on molten bismuth electrorefining in a molten LiCl-KCl-CaCl2 eutectic. Bismuth has been identified as a potential surrogate for plutonium electrorefining and a potential cathode in electrorefining used nuclear fuel (UNF). All electrorefining runs resulted in a high purity cathode ring and high yield with exception of the run using a low-frequency, high-amplitude superimposed AC waveform, which experienced some contamination and a lower yield. The other three AC superimposed DC runs experienced an average yield 6.7 % higher than the average yield of the DC runs. The electrorefining run using the high-frequency, high-amplitude superimposed AC signal had the highest yield. It is recommended in future studies to investigate the statistical variability of electrorefining yield and current efficiency and the impact of AC superimposed DC waveforms on solidified bismuth anodes.

• 한국재료학회지
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• 제27권12호
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• pp.672-678
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• 2017

In the production of zirconium cladding tube, a pickling acid solution is used to remove surface contaminants, which generates tons of pickling acid waste. The waste pickling solution is a valuable resource of Hf-free Zr. Many studies have investigated separating the Hf-free Zr source from the waste pickling acid. The results showed that $Ba_2ZrF_8$ precipitates prepared from the waste pickling acid were useful as an electrolyte for the electrorefining of Zr in molten salt. In the present work, electrorefining was performed in a $Ba_2ZrF_8-LiF$ binary electrolyte to recover Zr from a Hf-free CuZr ingot anode prepared by electroreduction. Before electrorefining, two pretreatments are performed. First, electrolyte melting was carried out to determine the eutectic temperature, and second, the electrolyte was treated to eliminate impurities, mainly hydride. After electrorefining, the cathode deposits were analyzed by $O_2$ gas analyzer and SEM-EDX to explore the possibility of recovering nuclear-grade Zr metal. Moreover, the anode was analyzed by SEM-EDX to determine the Zr dissolution depth.

• 한국방사성폐기물학회:학술대회논문집
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• 한국방사성폐기물학회 2004년도 학술논문집
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• pp.319-329
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• 2004

The electrorefining experiments with an anode composed of U, Y, Gd, Nd and Ce (or U, Gd, Dy and Ce) were carried out in the KC1-LiCl eutectic melt at $500^{\circ}C$, Uranium was the major component in the cathode deposits at the high initial uranium concentration, and the separation factors of the uranium with respect to the rare earths (REs) were calculated according to the applied voltage and the uranium concentration in the molten salt. The current efficiency was inversely in proportion to the applied voltage in the range of 1.0 V to 1, 9 V (vs. STS304L). The dependency of the applied voltage on the current efficiency as well as the deposition rate was discussed in terms of the microstructural feature and crystal structure of the deposit.

• 한국물환경학회지
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• 제22권4호
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• pp.658-665
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• 2006

The removal characteristics of silver ion from waste photographic solution have been investigated by recovering silver electrochemically. Cyclic voltammetry for synthetic and actual wastewater which containing silver ion was investigated to understand its electrochemical behavior. For both synthetic and actual wastewater, the recovery of silver according to the electrowinning time was observed to be increased as the applied potential was raised. In addition, the applicable potential for the electrowinning of silver was found to be lower for synthetic wastewater compared with actual wastewater. As the temperature was increased, more silver was recovered for both wastewater, which indicated the electrowinning reaction was endothermic. The electrowinned silver was refined electrochemically to increase its purity and the variation of the purity of silver was examined according to the electrorefining potential.

• 한국표면공학회지
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• 제42권3호
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• pp.103-108
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• 2009

The effect of Arsenic in copper-sulfate solutions during electrorefining of copper was investigated using scanning electron microscopy, X-ray diffraction and cyclic voltammetry analysis. Electrodeposition was carried out using Arsenic, Antimony and bismuth addition to sulfate electrolytes: 45 g/l $Cu^{2+}$ and 170 g/l $H_2SO_4$. Arsenic in sulfate electrolytes changed the morphology and structure of the copper deposits as compared with those obtained from impurity free solutions. When arsenic was present in the sulfate electrolytes, $Cu-3$As intermetallic phase was formed locally on the deposits.

• 방사성폐기물학회지
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• 제17권3호
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• pp.347-353
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• 2019

파이로프로세싱의 전해환원공정에서 생산된 금속전환체의 조성은 전해정련공정 운전의 중요한 운전변수인 용융염 중 $UCl_3$의 농도변화에 영향을 미친다. 따라서, 본 연구에서는 금속전환체에 함유된 TRU와 RE 원소의 함량 및 금속전환체에 동반되어 전해정련 전해조에 유입될 수 있는 $Li_2O$ 농도가 전해정련 전해조의 $UCl_3$ 농도 변화에 미치는 영향을 검토하였다. 금속전환체의 TRU 원소와 RE 원소의 농도만을 고려하였을 때 전해정련 운전 batch 수 증가에 따라 $UCl_3$ 농도가 감소하였다. 전해정련 1 campaign(20 batch)를 운전하기 위해서는 $UCl_3$를 3회 이상 추가 보충해야 함을 알 수 있었다. 한편, 금속전환체에 동반되어 전해정련 전해조에 유입되는 $Li_2O$의 유입량 증가에 따라 $UCl_3$ 농도 감소의 영향이 크게 나타났으며, 이에 따라 운전 가능 batch 수가 급격히 감소하게 되어 전해정련 운전에 중요한 운전 변수임을 보여주었다. 이러한 결과는 전해정련 운전 중 $UCl_3$ 농도 유지를 위해 금속전환체에 포함된 TRU 및 RE 원소뿐만 아니라 금속전환체에 동반되어 유입될 가능성이 있는 $Li_2O$의 영향도 고려하여 전해정련 운전모드를 설정하여야 함을 보여주었다.

• 방사성폐기물학회지
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• 제5권1호
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• pp.1-7
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• 2007

흑연음극을 이용하여 LiCl-KCl공융염내에서 금속우라늄의 전해정련을 수행하였다. Uraniurn-Graphite Intercalation Compound(U-GIC)의 형성에 의하여 우라늄 전착물의 sell-scraping이 일어나며 전해정련에서 stripping과정을 생략함으로서 전해효율을 높일 수 있다. 우라늄 전착물내의 희토류 원소 오염은 무시할 만 하였으나 약 300ppm정도의 탄소가 오염되어 있는 것으로 관찰되었다. 탄소 오염은 이트륨을 이용한 정제공정 등을 거칠 경우 제거 가능하리라 사료된다. 회수된 우라늄 전착물의 조직 특성을 분석하였으며, 스틸 음극에 의해 회수된 전착물과 비교하였다. 이 결과는 초기 실험결과 이며 보다 심층적 연구를 통하여 사용 후 금속핵연료의 전해정련 개념을 개선시킬 수 있을 것으로 판단된다.

• Nuclear Engineering and Technology
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• 제42권2호
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• pp.131-144
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• 2010

The Korea Atomic Energy Research Institute (KAERI) has been developing pyroprocessing technology for recycling useful resources from spent fuel since 1997. The process includes pretreatment, electroreduction, electrorefining, electrowinning, and a waste salt treatment system. This paper briefly addresses unit processes and related innovative technologies. As for the electroreduction step, a stainless steel mesh basket was applied for adaption of granules of uranium oxide. This basket was designed for ready handling and transfer of feed material. A graphite cathode was used for the continuous collection of uranium dendrite in the electrorefining system. This enhances the throughput of the electrorefiner. A particular mesh type stirrer was designed to inhibit uranium spill-over at the liquid Cd crucible. A residual actinide recovery system was also tested to recover TRU tracer. In order to reduce the waste volume, a crystallization method is employed for Cs and Sr removal. Experiments on the unit processes were tested successfully, and based on the results, engineering-scale equipment has been designed for the PRIDE (PyRoprocess Integrated inactive DEmonstration facility).

• 공업화학
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• 제10권8호
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• pp.1119-1123
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• 1999

본 연구는 용융염계에서 우라늄금속의 건식전해정련공정을 개발하기 위해서 수행되었다. 금속우라늄과 $CdCl_2$와의 반응은 약 3시간이 소요되었으며, 모든 전해전달실험에서 우라늄금속 석출물들은 음극표면에서 성장한 수지상으로 얻어졌다. 수지상의 형태는 부가전압에 따라 변화되었으며, 전류효율은 전류밀도가 증가함에 따라 감소하였다. 반응시간이 6시간 경과된 후에 석출속도는 변화하지 않았으며, 전류밀도가 $100{\sim}150mA/cm^2$이고 교반속도가 약 75 rpm일 때 최대석출속도를 얻었다. 또한, 전류효율은 음극에 있는 나선형 홈의 피치가 작을수록 증가되었다.

• Nuclear Engineering and Technology
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• 제54권2호
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• pp.644-652
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• 2022

During the pyroprocessing operation, various signals can be collected by process monitoring (PM). These signals are utilized to diagnose process states. In this study, feasibility of using PM for nuclear safeguards of electrorefining operation was examined based on the use of machine learning for detecting off-normal operations. The off-normal operation, in this study, is defined as co-deposition of key elements through reduction on cathode. The monitored process signal selected for PM was cathode potential. The necessary data were produced through electrodeposition experiments in a laboratory molten salt system. Model-based cathodic surface area data were also generated and used to support model development. Computer models for classification were developed using a series of recurrent neural network architectures. The concept of transfer learning was also employed by combining pre-training and fine-tuning to minimize data requirement for training. The resulting models were found to classify the normal and the off-normal operation states with a 95% accuracy. With the availability of more process data, the approach is expected to have higher reliability.