• Proceedings of the Korean Radioactive Waste Society Conference
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• 2009.11a
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• pp.177-177
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• 2009

사용후 핵연료의 건식처리 시 핵연료 다발을 절단하여 voloxidation 즉 휘발산화처리를 하면 고온에 의해 분리가 가능한 핵분열생성물의 분리와 우라늄의 산화에 의한 부피팽창으로 핵연료가 쪼개져서 입도가 작아지고 또한 핵연료가 피복재에서 쉽게 박리되게 된다. 그 결과 폐기물 처리 시에 발열핵종으로 폐기물의 저준위화시에 분리가 요망되는 Cs-137이 분리되는 장점이 있어 습식 재처리에 있어서도 바람직하다. 건식처리에 있어서는 voloxidation 으로 처리된 피복재에는 금속 지르코늄에 불순물로 함유된 우라늄의 의한 방사화 생성물과 피복재 표변에 부착/침투한 방사화 생성물이 방사능을 갖게 된다. 이러한 부착된 TRU 잔류물은 통상 1% 미만으로 알파핵종의 방사능이 원자로에서 배출시에는 고준위 기준치의 약 100배 수준이었다가 30년 냉각후에는 약 1/10 수준으로 저준위화 된다. 지르코늄 금속중에 불순물로 함유된 우라늄의 방사화로 생기는 방사능은 고준위 기준치의 10% 를 넘지 않아서 피복재의 저준위화시에 고려할 필요가 없다. 발생열은 방출시에 고준위 기준치의 약 30 배 수준에서 5년 냉각후에는 기준치 미만이 되며 30년후에는 1/8000 정도로 저준위화 된다. 사용후 핵연료를 습시처리시에 발생하는 고준위 폐기물 중 약 1/4 가 피복재 (hull) 임을 고려하면 피복재의 저준위화는 사용후 연료의 건식처리에 있어서도 필수적인 과정이다. 특히 미국의 고준위 폐기물 처분장 Yucca Mt.의 포기와 우리의 고준위 폐기불 처분장이 공론화되는 싯점에서 저준위화는 매우 필요한 기술이다. 피복재는 방사성 물질의 침투두께가 0.01mm 미만이 대부분으로 저준위화에는 표면제염에 의한 저준위화가 주로 연구되어왔다. 표면제염에 의한 저준화는 이온 빔, laser에 의한 방법, dry ice 분사에 의한 방법이 시도되었다. 염소기체를 이용하여 지르코늄의 산화막을 제거하고자 하였으나 이 산화막이 안정적이어서 표변의 연마, 아크릴 칼의 사용, 표면을 눌러서 처리하는 등 전처리하여서 염소기체 반응에 의한 표면제거 실험이 가장 효과적임이 실험적 결과이었다. 이러한 전처리로 방사능을 1/100 수준으로 낮춘다고 하더라도 지르코늄 금속중에 불순물로 함유된 우라늄의 방사화에 의해 중저준위 폐기물의 범주에서 벗어나지 않으므로 재활용에는 제한이 있다. 또한 전처리(표면제염)하여 분리되는 고준위는 다른 고준위 염폐기물과 함께 처리하여 발열 핵종을 제거하면 중저준위화가 가능하다. 저준위화 된 hull폐기물에는 지르코늄 금속에 불순물로서 함유되어있는 우라늄에 의한 방사능을 갖는데 이들의 제거나 분리는 지르코늄 합금 피복재 원료물질에 불순물로 함유하는 우라늄의 함량을 낮추는 것과 유사한 문제이다. 현재까지 지르코늄합금 피복재에 우라늄이 불순물로 함유된 것을 사용함으로 원자로내에서 방사화되어서 방사능을 갖게 되는 것은 피할 수가 없다. 따라서 저준위화 처리된 피복재는 장기 보관으로 방사능을 감쇠시켜서 재활용하도록 한다. 처리 방법으로는 초고압 압축저장, 시멘트 고화, 합성암석에 의한 고화법 등으로 장기간 보관 후에 금속으로서 재활용한다.

• Resources Recycling
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• v.21 no.5
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• pp.18-30
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• 2012

Zirconium is one of the most important material used as cladding of fuel rods in nuclear reactors because of its high dimensional stability, good corrosion resistance and especially low neutron-absorbing cross section. However, Hf free nuclear grade Zr sponge is commercially produced by only three countries including USA, France and Russia. So, Zr has been thoroughly managed as a national strategic material in Korea. Most of the zirconium is used for Korean nuclear industry as nuclear fuel cladding materials manufactured from Hf free Zr alloy raw material. Also, there are some other applications such as alloying element and detonator. In this review, zirconium production and recycling technologies have been reviewed and current industrial status was also analyzed. And recent achievements in innovative reduction technologies such as electrolytic reduction process and molten oxide electrolysis were also introduced.

• 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.

• Resources Recycling
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• v.26 no.6
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• pp.3-9
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• 2017

In this study, plasma arc remelting behaviors according to arc current, arc voltage, and types of plasma gas were investigated using Kroll processed Ti sponges as anode. In the discharge pressure range of vacuum pump ($200{\sim}300kgf/cm^2$), the arc voltage did not vary greatly with the increase of discharge pressure at a given arc length. This means that the pressure in the vacuum chamber during operation hardly changes and the atmospheric pressure maintains. Under various conditions of arc currents (700~900A), the arc voltage slightly increased with arc current. The effects of anode materials and operational variables on the arc length-arc voltage relationship were compared with the results in previous studies. When the atmospheric gas changed from argon to helium, double effect of improvement on the output of the steady state was observed. The increase of output in the plasma arc device was accompanied by an increase in the melting rate of the Ti sponge and the quality of the ingot surface was also improved. The plasma arc remelting of the new scrap titanium and the old scrap zirconium alloy could result in the fabrication of an ingot with high surface quality.

• Clean Technology
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• v.19 no.3
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• pp.264-271
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• 2013

In this study, we optimized the removal condition of contaminants attached on the scrap surface to recycle the scrap generated from the Zr alloy tube manufacturing process back to the nuclear grade. The main contaminant is remnant of watersoluble cooling lubricant that is used in the pilgering manufacture during the tube production, and it is assumed to be compressed and carbonized on the surface of tube. Zirlo alloy tube of ${\phi}9.50mm$, which has high occurrence frequency of scrap, was selected as the object to be cleaned, and cleaning abilities of reagents were evaluated by measuring the characteristics of contaminants remained and by analyzing the surface of the tube after cleaning process. For evaluation of each cleaning agent, we selected two types of sodium hydroxide series and three types of potassium hydroxide series. Furthermore, to confirm dependence on tempe-rature and ultrasonic intensities, cleaning at the room temperature, $40^{\circ}C$, and $60^{\circ}C$ was conducted, and results showed that higher the cleaning temperature and higher the ultrasonic intensity, better the cleaning effect. As a result of the bare-eye inspection, while the use of sodium hydroxide provided satisfactory condition on the tube surface, the use of potassium hydroxide series provided satisfactory condition on the tube surface only when the ultrasonic intensity was over 120 W. In the cleaning effect analysis using the gravimetric method, cleaning efficiency of sodium hydroxide series was as high as 97.6% ($60^{\circ}C$, 120 W), but since the tube surface condition was poor after the use of potassium hydroxide, the gravimetric method was not appropriate. In the analytical result of surface contaminants on the tube surface, C, O, Ca, and Zr were detected, and mainly C and O dominated the proportion of contaminants. It was also found that the degree of cleaning on the tube affected the componential ratio of C and O; if the degree of cleaning is high, or if cleaning is well-conducted, the proportion of C is decreased, and the proportion of O is increased. Based on these results, optimal cleaning for application in the industry can be expected by categorizing cleaning process into three steps of Alkali cleaning, Rinsing, and Drying and by adjusting cleaning parameters in each step.