• Journal of Korea Foundry Society
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• v.34 no.3
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• pp.94-99
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• 2014

A commercially used Zr-based amorphous alloy was recycled and the effects of introducing carbon during recycling on the glass forming ability and mechanical properties of the alloy were investigated. The initial carbon content used in this study was 229ppm. The carbon content was gradually increased as the number of recycling iterations was increased and after the $4^{th}$ recycling it rapidly increased. As return scrap was recycled, polygonal particles precipitated, and they were identified as ZrC. The amount of the precipitates also increased with recycling. Tg, Tx and ${\Delta}T$ of the base alloy were 615 K, 696 K and 81 Kr respectively and they changed to 634 K, 706 K and 72 K after the $10^{th}$ recycling. The decrease of the ${\Delta}T$ value indicates deterioration of the glass forming ability. Hardness was not changed during three iterations of recycling but after the $4^{th}$ recycling it significantly increased. This is ascribed to an increase of amount of the hard particles, namely ZrC.

• 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.

• Journal of Korea Foundry Society
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• v.35 no.4
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• pp.75-79
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• 2015

Commercial Zr-based amorphous alloy was recycled and oxygen was introduced during the recycling process. The oxygen content can have a great effect on the glass forming ability and the mechanical properties of the alloy. Therefore, it was closely examined. The initial oxygen content in the raw material was 1,244 ppm. It was increased to 3,789 ppm in the alloy after ten recycling processes. As the recycling processes were repeated, the oxygen content increased. Specifically, after four recycling processes, it increased sharply as compared to that after three recycling processes. After ten recycling processes, the glass transition temperature (Tg) increased from 613 K to 634 K and the crystallization temperature (Tx) increased from 696 K to 706 K. On the other hand, the super-cooled liquid region (${\Delta}T=Tx-Tg$) decreased slightly from 83 K to 72 K while the reduced glass transition temperature (Trg = Tg/Tm) was 0.63, remaining constant even when the oxygen content was increased. These results indicated that the increased oxygen content deteriorated the glass forming ability. The bending strength as determined in a three-point bending test showed a sharp decrease from 3,055 to 2,062 MPa as the oxygen content was increased from 1,244 ppm to 3,789 ppm; the extension was also decreased from 3.02 to 1.74 mm. These findings meant that the alloy became brittle.

• Resources Recycling
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• v.21 no.6
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• pp.32-38
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• 2012

In this study, direct reduction of $ZrO_2$ using liquid calcium was investigated. The influence of molar ratio of Ca and $ZrO_2$, reaction time and temperature on the reduction behavior of $ZrO_2$ was studied. Experiments were conducted in a closed stainless steel chamber under Ar atmosphere during 5 to 60 minutes. Most of the $ZrO_2$ was reduced to Zr in 5 minutes at 1223 K and 3 Ca/$ZrO_2$ molar ratio. The minimum oxygen content in reduced metal Zr was obtained about 0.66 wt% at 1373 K after 30 minutes and 4 Ca/$ZrO_2$ molar ratio. The morphology of zirconium powder obtained was highly affected by the reaction temperature and reaction time.

• Resources Recycling
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• v.20 no.6
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• pp.56-62
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• 2011

Zirconium is used in nuclear reactors as a structural material due to its excellent corrosion resistance and to low neutron crosssection. Variation in the distribution and solubility of Zr(IV) with solution pH was obtained. Distribution of Zr(IV) containing species in HCl and $HNO_3$ solution was analyzed by considering the complex formation of Zr(IV) species with the anion of the inorganic acid. Bromley interaction parameter between $ZrO^{2+}$ and nitrate ion was estimated by using the reported data on the solvent extraction of Zr(IV) by Cyanex272 from $HNO_3$ solution. This Bromley parameter can be utilized in calculating extraction isotherm of Zr(IV) and in predicting the separation factor between Zr(IV) and Hf(IV).

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.19 no.2
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• pp.271-278
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• 2021

In this study, a chlorination technique for recycling Li₂ZrO₃, a reaction product of ZrO₂-assisted rinsing process, was investigated to minimize the generation of secondary radioactive pyroprocessing waste. It was found that the reaction temperature was a key parameter that determined the reaction rate and maximum conversion ratio. In the temperature range of 400-600℃, an increase in the reaction temperature resulted in a profound increase in the reaction rate. Hence, according to the experimental results, a reaction temperature of at least 450℃ was proposed to ensure a Li₂ZrO₃ conversion ratio that exceeded 80% within 8 h of the reaction time. The activation energy was found to be 102 ± 2 kJ·mol^-1·K^-1 between 450 and 500℃. The formation of LiCl and ZrO₂ as reaction products was confirmed by X-ray diffraction analysis. The experimental results obtained at various total flow rates revealed that the overall reaction rate depends on the Cl₂ mass transfer rate in the experimental condition. The results of this study prove that the chlorination technique provides a solution to minimize the amount of radioactive waste generated during the ZrO₂-assisted rinsing process.

• 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.