• 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.

• Nuclear Engineering and Technology
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• v.54 no.5
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• pp.1549-1559
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• 2022

As an accident tolerant fuel (ATF) concept, oxide dispersion strengthened Zircaloy-4 (ODS Zry-4) cladding has been developed to enhance the mechanical properties of cladding using laser processing technology. In this study, a simulation technique was established to investigate the mechanical properties and effects of Y₂O₃ particles for the ODS Zry-4. A 3D representative volume element (RVE) model was developed considering the parameters of the size, shape, distribution and volume fraction (VF) of the Y₂O₃ particles. From the 3D RVE model, the Young's modulus, coefficient of thermal expansion (CTE) and creep strain rate of the ODS Zry-4 were effectively calculated. It was observed that the VF of Y₂O₃ particles had a significant effect on the aforementioned mechanical properties. In addition, the predicted properties of ODS Zry-4 were applied to a simulation model to investigate cladding deformation under a transient condition. The ODS Zry-4 cladding showed better performance, such as a delay in large deformation compared to Zry-4 cladding, which was also found experimentally. Accordingly, it is expected that the simulation approach developed here can be efficiently employed to predict more properties and to provide useful information with which to improve ODS Zry-4.

• Bulletin of the Korean Chemical Society
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• v.28 no.8
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• pp.1341-1345
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• 2007

The surface chemistry of D2O dosed Zircaloy-4 (Zry-4) surface followed by Ar-ion bombardment and annealing was studied by means of X-ray photoelectron spectroscopy (XPS) and Ultraviolet photoelectron spectroscopy (UPS). In the XPS study, Ar-ion bombardment caused decrease of the oxygen on the surface region of Zry-4 and therefore led to change the oxidation states of the zirconium from oxide to metallic form. In addition, oxidation states of zirconium were changed to lower oxidation states of zirconium due to depopulation of oxygen on the surface region by annealing. Up to about 787 K, the bulk oxygen diffused out to the subsurface region and after this temperature, the oxygen on the surface of Zry-4 was depopulated. UPS study showed that the valence band spectrum of the D2O exposed Zry-4 exhibited a dominant peak at around 13 eV and no clear Fermi edge was detected. After stepwise Ar+ sputtering processes, the decrease of the oxygen on the surface of Zry-4 led to suppress the dominant peak around 13 eV, the peak around 9 eV and develop a new peak of the metallic Zr 4d state (20.5-21.0 eV) at the Fermi level.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1751-1755
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• 2007

The interaction of ammonium hydroxide (NH4OH) with zircaloy-4 (Zry-4) was investigated using X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) methods. In order to study the surface chemistry of NH4OH/Zry-4 system, the binding energies of N1s, O1s and Zr3d electrons were monitored. The N1s peak intensity was remarkably increased by following cycles of Ar+ sputtering of NH4OH dosed Zry-4 surface at room temperature. Because the nitrogen stayed under the subsurface region was diffused out onto the Zry-4 surface after oxygen concentration was decreased. These could be occurred after the surface oxygen was diffused into the bulk or desorbed out from the surface until Ar+ fluence was 6.0 × 1016 Ar+/cm2 then the surface was relatively atomic deficient state. The O1s peak intensity was decreased by stepwise Ar+ sputtering. After many cycles of Ar+ sputtering, the peak intensities of Zr3d peaks did not change much but the shape of the peak clearly did change. This implies that the oxidation state of zirconium was changed during stepwise Ar+ sputtering of NH4OH/Zry-4. The Zr3d peak intensity of zirconium nitride (ZrNx) increased as the intensity of N1s (from zirconium nitride) increased but the Zr3d peak intensity of zirconium oxide (ZrOx) decreased due to the depopulation of the oxygen species on the surface region. We also observed that the peak intensity of Zr4+ was nearly same after Ar+ sputtering processes but the peak intensity of metallic zirconium increased compared to that of before the sputtering process was performed.

• Proceedings of the Korean Nuclear Society Conference
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• 2001.05a
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• pp.319.1-319
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• 2001

• Proceedings of the Korean Nuclear Society Conference
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• 2002.10a
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• pp.263-263
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• 2002

• Proceedings of the Korean Nuclear Society Conference
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• 1996.05b
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• pp.739-744
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• 1996

The U solubility in the Zircaloy melt including the other investigators' result was investigated in a range of reaction temperatures from 2223k to 2473k and for the mole ratios of UO$_2$ crucible/Zircaloy-4 melt(subsequently abbreviated as UO$_2$/Zry) from 2.4 to 18.2, The U solubility in the melt increased with increasing reaction temperature and with decreasing the mole ratio of UO$_2$/Zry. An empirical correlation was obtained as functions of UO$_2$/Zry mole ratio and reaction temperature including other investigators' results. The experimental results with use of internally heated fuel element simulators were analyzed by the empirical correlation from UO$_2$ crucible experiments.

• Bulletin of the Korean Chemical Society
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• v.30 no.6
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• pp.1349-1352
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• 2009

We report the results of the surface chemistry of deuterized ethanol exposed Zircaloy-4 (Zry-4) surfaces with various amount of $C_2D_5$OD exposures at 190 K. This system was examined with Auger electron spectroscopy (AES) and temperature programmed desorption (TPD) techniques. In TPD study, $D_2$ was evolved at two different desorption temperature regions accompanying with broad desorption background. The lower temperature feature at around 520 K showed first-order desorption kinetics. The high temperature desorption peak at around 650 K shifted to lower desorption temperature as the exposure of $C_2D_5$OD increased. The Zr(MNV) Auger peak shifted about 2.5 eV from 147 eV to lower electron energy followed by 300 L of $C_2D_5$OD dosing. This implies metallic zirconium was oxidized by deuterized ethanol adsorption. After stepwise annealing of the oxidized Zry-4 sample up to 843 K, the shifted Zr(MNV) peak was gradually shifted back to metallic zirconium peak position. After the sample was heated to 843 K, the oxygen content near the Zry-4 surface was recovered to clean surface level. The concentration of carbon, however, was not recovered by annealing the sample.

• Proceedings of the Korean Vacuum Society Conference
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• 2005.08a
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• pp.70-70
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• 2005

• Proceedings of the Korean Institute of Surface Engineering Conference
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• 2000.05a
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• pp.5-5
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• 2000

In the severe accident case like LOCA, Zircaloy(Zry) claddings are oxidized not only in high temperature but also in high pressures. It is a concem whether the safety of high bum up fuels can be maintained during severe accident. The effects of steam pressure on Zry-4 oxidation, and the effect of prc-existing oxide layer on the cladding in the high temperature-high pressure oxidation of Ziy-4 were investigated. The experimental temperature range was $700-900^{\circ}C$, and the pressures were between 0.1 and l5.0MPa. Partial pressure of steam tumed out to be the important one rather than total gas pressure. The higher the steam pressure was applied, the thicker the oxide became. nle effect of st,earn pressure on the oxidation of claddings with preexisting oxide was about 40-60% less effective than that of pickled cladding. Aocelerated oxidation in highpressure slean1 seems to be originated from the formation of microcracks produced during the transformation of tetragonal zirconia to monoclinic phase. Steam pressure seems to affect the stability of tetragonal phase.