• Korean Journal of Materials Research
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• v.8 no.11
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• pp.1031-1037
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• 1998

To investigate the effect of cooling rate and annealing temperature on the corrosion of Zircaloy-4 and Zr-2. 5Nb alloys, autoclave corrosion tests were performed at $500^{\circ}C$ for the specimens prepared by various heat treatments. The specimens were heat-treated at $1050^{\circ}C$ for 30 minutes and cooled by ice-brine quenching, water quenching, oil quenching, air cooling, and furnace cooling. To investigate the effect of annealing temperature, the specimens were annealed at $\alpha$, ($\alpha$+$\beta$)-, and $\beta$-temperatures. It was observed from the $500^{\circ}C$ corrosion test that nodular corrosion occurred on the Zircaloy-4 alloy but did not occur on the Zr-2.5Nb alloy. The corrosion resistance of Zircaloy-4 increased with increasing the cooling rate. On the other hand, the corrosion resistance of Zr-2.5Nb decreased with increasing the cooling rate and the annealing temperature. It is suggested that corrosion resistance of Zircaloy-4 would be controlled by the distribution of Fe and Cr element in the matrix and precipitates, while that of Zr-2.5Nb alloy the niobium concentration and $\beta_{-Nb}$ phase.

• Korean Journal of Materials Research
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• v.10 no.6
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• pp.422-429
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• 2000

To investigate the effect of annealing temperature and time on the recrystallization behavior and microstructure of Zr-based alloys, the specimens of Zr-0.8Sn-0.4Nb-0.4Fe-0.2Cu, Zr-1Nb, Zircaloy-4, and unalloyed Zr were cold-worked and annealed at 400, 500, 600, 700, 800, $900^{\circ}C$ for 30 to 5000 minutes. The hardness, microstructure and precipitate of the specimens were investigated by using micro-hardness tester, optical microscope and transmission electron microscope, respectively. The recrystallization of Zr-based alloys occurred between $400^{\circ}C$ and $600^{\circ}C$. As the content of alloying elements increased, the hardness and recrystallization temperature of the alloys increased though the grain sizes after recrystallization decreased. It was supposed that the hardness of Zr-based alloy with Fe or Cu increased during recovery by the formation of Fe or Cu precipitates.

• Journal of Welding and Joining
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• v.17 no.4
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• pp.26-31
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• 1999

An attempt was made in this study to investigate the brazing characteristics of Zr-Be binary amorphous alloys for the development of a new brazing filler metal for joining Zircaloy-4 nuclear fuel cladding tubes. This study was also aimed at the feasibility study of rapidly solidified amorphous alloys to substitute the conventional physical vapor-deposited(PVD) metallic beryllium. The $Zr_{1-x}Be_{x}$($0.3\leq$x$\leq0.5$) binary amorphous alloys were produced in the ribbon form by the melt-spinning method. It was confirmed by x-ray diffraction that the ribbons were amorphous. The amorphous. the amorphous alloys were used to join bearing pads on Zircaloy-4 nuclear fuel cladding tubes. Using Zr-Be amorphous alloys as filler metals, it was found that the reduction in the tube wall thickness caused by erosion was prevented. Especially, in the case of using $Zr_{0.65}Be_{0.35}$ and $Zr_{0.7}Be_{0.3}$ amorphousalloys, the smooth and spherical primary $\alpha$-Zr particles appeared in the brazed layer, which was the most desirable microstructure from the corrosion-resistance standpoint.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.10 no.4
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• pp.273-280
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• 2012

The electrochemical behaviors of 10 g-scale fresh and oxidized Zircaloy-4 cladding hulls were examined in $500^{\circ}C$ LiCl-KCl molten salts to confirm the feasibility of the electrorefining process for the treatment of hull wastes. In the results of measuring the potential-current response using a stainless steel basket filled with oxidized Zircaloy-4 hull specimens, the oxidation peak of Zr appears to be at -0.7 to -0.8 V vs. Ag/AgCl, which is similar to that of fresh Zircaloy-4 hulls, while the oxidation current is found to be much smaller than that of fresh Zircaloy-4 hulls. These results are congruent with the outcome of current-time curves at -0.78 V and of measuring the change in the average weight and thickness after the electrochemical dissolution process. Although the oxide layer on the surface affects the uniformity and rate of dissolution by decreasing the conductivity of Zircaloy-4 hulls, electrochemical dissolution is considered to occur owing to the defect of the surface and phase properties of the Zr oxide layer.

• Corrosion Science and Technology
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• v.2 no.6
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• pp.253-259
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• 2003

Zirconium based alloys have been extensively used as a cladding material for fuel rods in nuclear reactors, due to their low thermal neutron absorption cross-section, excellent corrosion resistance and good mechanical properties at high temperatures. However, a cladding material for fuel rods in nuclear reactors was contact water during long time at high-temperature, so it is necessary to improve the wear and corrosion resistance of the fuel cladding, At ambient environment, there are few data or paper on the characteristic of corrosion in chloride solution and acidic solution. The specimens used in this work are pure Zr and Zircaloy-4. Zircaloy-4 is a specific zirconium-based alloy containing, on a weight percent basis, 1.4% Sn, 0.2% Fe, 0.1% Cr. Pitting corrosion resistance of two alloys by ASTM G48 is higher than that of electrochemical method. Passive film formed on Zircaloy-4 is mainly composed of $ZrO_2$, metallic Sn, and iron species regardless of formation environments. Also, passive film formed on Zr alloys shows n-type semiconductic property on the base of Mott-Schottky plot.

• Proceedings of the Korean Nuclear Society Conference
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• 2002.05a
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• pp.255-255
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• 2002

• 한국전자현미경학회:학술대회논문집
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• 2005.11a
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• pp.68-73
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• 2005

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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• v.11 no.1
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• pp.55-61
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• 2013

The recovery of Zr from Zircaloy-4 (Zry-4) cladding hulls using a chlorination method was demonstrated for complete conversion of Zr into $ZrCl_4$. A chlorination reaction was performed by reacting Zry-4 hulls for 8 h under a 70 cc/min $Cl_2$ + 70 cc/min Ar flow at $380^{\circ}C$. The initial weight of the reactant (51.7 g) decreased to 0.49 g after 8 h of operation, which is only 0.95wt% of the initial weight. The weight of the total reaction products was 121.7 g with a high Zr purity of 99.80wt%. Fe and Sn were identified as major (0.18wt%) and minor (0.02wt%) impurities of the reaction products, respectively. It was also shown that Zr exhibited a high recovery ratio of 96.95wt% with a relatively small experimental loss of 2.34wt%. Observation of the reaction residues revealed that the chlorination reaction was dominant along the longitudinal direction, and surface oxide layers remained as reaction residues. The high purity and recovery ratio of Zr proposed the feasibility of the chlorination technique as an effective hull waste treatment method.

• Journal of the Korea Academia-Industrial cooperation Society
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• v.7 no.2
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• pp.113-119
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• 2006

Brazing is an important manufacturing process in the fabrication of Heavy Water Reactor fuel rods, in which bearing and spacer pads are joined to Zircaloy-4 cladding tubes. The physical vapor deposition(PVD) technique is currently used to deposit metallic Be on the surfaces of pads as a filler metal. Amorphous Zr-Be binary alloys which are manufactured by rapid solidification process are under developing to substitute the conventional PVD-Be coating. In the present study, brazed joint with PVD and amorphous alloys of $Zr_{1-x}Be_{x}(0.3{\le}x{\le}0.5)$ as filler metals are compared by mechanism, microstructure and hardness. The thickness of brazed joint with amorphous alloys became much smaller than that of PVD-Be. The erosion of base metal did not occur in the brazed joint with amorphous alloys. The brazing mechanism for PVD-Be seems to be Be diffusion into Zr-4 with capillary action resulting from eutectic reaction while that for amorphous alloys are associated with the liquid phase formation in the brazed joint. The brazed joint microstructure with PVD-Be consists of dendrite while that with amorphous alloys is globular. The $Zr_{0.7}Be_{0.3}$ alloy shows the smooth interface with little erosion in the base metal and is recommended a most suitable brazing filler metal for Zircaloy-4.

• Nuclear Engineering and Technology
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• v.52 no.9
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• pp.2054-2063
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• 2020

The high-temperature oxidation behavior of ZrSi₂ used as a coating material for nuclear fuel cladding was investigated for developing accident-tolerant fuel cladding of light water reactors. Bulk ZrSi₂ samples were prepared by spark plasma sintering. In situ X-ray diffraction was conducted in air at 900, 1000, and 1100 ℃ for 20 h. The microstructures of the samples before and after oxidation were examined by scanning electron microscopy and transmission electron microscopy. The results showed that the oxide layer of zirconium silicide exhibited a layer-by-layer structure of crystalline ZrO₂ and amorphous SiO₂, and the high-temperature oxidation resistance was superior to that of Zircaloy-4 owing to the SiO₂ layer formed. ZrSi₂ was coated on the Zircaloy-4 tube surface using laser 3D printing, and the coated tube was oxidized for 2000 s at 1200 ℃ under a vapor/argon mixture atmosphere. The outer surface of the coated tube was hardly oxidized (10-30 ㎛), while the inner surface of the uncoated tube was significantly oxidized to approximately 300 ㎛.