In Korea, borated stainless steel (BSS) is used as a storage rack in spent fuel pools (SFP) to maintain the nuclear criticality of spent fuels. As the number of nuclear power plants and the corresponding amount of spent fuels increased, the density in SFP storage rack also increased. In this regard, maintaining subcriticality of spent nuclear fuels became an issue and BSS was selected as the structural material and neutron absorber for high density storage rack. Since it is difficult to replace the storage rack, corrosion resistance and neutron absorbency are required for long period. BSS is based on stainless steel 304 and is specified in the ASTM A887-89 standard depending on the boron concentration from 304B (0.20-0.29% B) to 304B7 (1.75-2.25% B). Due to the low solubility of boron in austenitic stainless steel, metallic borides such as (Fe, Cr) 2B are formed as a secondary phase. Metallic borides could cause Cr depletion near it, which could decrease the corrosion resistance of the material. In this paper, the long-term corrosion behavior of BSS and its oxide microstructures are investigated through accelerated corrosion experiment in simulated SFP conditions. Because the corrosion rate of austenitic stainless steel is known to be dependent on the Arrhenius equation, a function of temperature, the corrosion experiment is conducted by increasing the experimental temperature. Detail microstructural analysis is conducted using a scanning electron microscope, transmission electron microscope and energy dispersive spectrometer. After oxidation, a hematite structure oxide film is formed, and pitting corrosion occurs on the surface of specimens. Most of the pitting corrosion is found at the substrate surface because the corrosion resistance of the substrate, which has low Cr content, is relatively low. Also, the oxidation reaction of B in the secondary phase has the lowest Gibbs free energy compared to other elements. Furthermore, oxidation of Cr has low Gibbs free energy, which means that oxidation of B and Cr could be faster than other elements. Thus, the long-term corrosion might affect the boron content and the neutron absorption ability of the material. Using boron’s high cross-section for neutrons, the neutron absorption performance of BSS was evaluated through neutron transmission tests. The effect of the corrosion behavior of BSS on its neutron absorption performance was investigated. Samples simulated to undergo up to 60 years of degradation before corrosion through accelerated corrosion testing did not show significant changes in the neutron shielding ability before and after corrosion. This can be explained in relation to the corrosion behavior of BSS. Boron was only leached out from the secondary phase exposed on the surface, and this oxidized secondary phase corresponds to about 0.17% of the volume of the total secondary phase. This can be seen as a very small proportion compared to the total boron content and is not expected to have a significant impact on neutron absorption performance.
In Korea, borated stainless steel (BSS) is used as spent fuel pool (SFP) storage rack to maintain nuclear criticality of spent fuels. As number of nuclear power plants and corresponding number of spent fuels increased, density in SFP storage rack also increased. In this regard, maintain subcriticality of spent nuclear fuels was raised as an issue and BSS was selected as structural material and neutron absorber for high density storage rack. Because it is difficult to replace storage rack, corrosion resistance and neutron absorbency are required for long period. BSS is based on stainless steel 304 and it is specified in the ASTM A887-89 standard depending on the boron concentration from 304B (0.20-0.29% B) to 304B7 (1.75-2.25% B). Due to low solubility of boron in austenitic stainless steel, metallic borides such as (Fe, Cr)2B are formed as secondary phase metallic borides could make Cr depletion near it which could decrease the corrosion resistance of material. In this paper, long-term corrosion behavior of BSS and its oxide microstructures are investigated through accelerated corrosion experiment in simulated SFP condition. Because corrosion rate of austenitic stainless steel is known to be dependent on the Arrhenius equation, a function of temperature, corrosion experiment is conducted by increasing the experimental temperature. Detail microstructural analysis was conducted with scanning electron microscope, transmission electron microscope and energy dispersive spectrometer. After oxidation, hematite structure oxide film is formed and pitting corrosions occur on the surface of specimens. Most of pitting corrosions are found at the substrate surface because corrosion resistance of substrate, which has low Cr content, is relatively low. Also, oxidation reaction of B in the secondary phase has the lowest Gibbs free energy compared to other elements. Furthermore, oxidation of Cr has low Gibbs free energy which means that oxidation of B and Cr could be faster than other elements. Thus, the long-term corrosion might affect to boron content and the neutron absorption ability of the material.
The effect of oxidation time on the characteristics and mechanical properties of spent nuclear fuel cladding was investigated using Raman spectroscopy, tube rupture test, and tensile test. As oxidation time increased, the Raman peak associated with the tetragonal zirconium oxide phase diminished and merged with the Raman peak associated with the monoclinic zirconium oxide phase near 333 cm−1. Additionally, the other tetragonal zirconium oxide phase peak at 380 cm−1 decreased after 100 d of oxidation, whereas the zirconium monoclinic oxide peak became the dominant peak. The oxidation time had no effect on the tube rupture pressure of the oxidized zirconium alloy tube. However, the yield and tensile stresses of the oxidized nuclear fuel cladding tube decreased after 100 d of oxidation. The results of the scanning electron microscopy and transmission electron microscopy were represented with the in-situ Raman analysis result for the oxide characteristics generated on the cladding of spent nuclear fuel.
W-10 wt% Ti alloys that have a homogeneous microstructure are prepared by thermal decomposition of WO3-TiH2 powder mixtures and spark plasma sintering. The reduction and dehydrogenation behavior of WO3 and TiH2 are analyzed by temperature programmed reduction and a thermogravimetric method, respectively. The X-ray diffraction analysis of the powder mixture, heat-treated in an argon atmosphere, shows W- oxides and TiO2 peaks. Conversely, the powder mixtures heated in a hydrogen atmosphere are composed of W, WO2 and TiO2 phases at 600 ℃ and W and W-rich β phases at 800 ℃. The densified specimen by spark plasma sintering at 1500 ℃ in a vacuum using hydrogen-reduced WO3-TiH2 powder mixtures shows a Vickers hardness value of 4.6 GPa and a homogeneous microstructure with pure W, β and Ti phases. The phase evolution dependent on the atmosphere and temperature is explained by the thermal decomposition and reaction behavior of WO3 and TiH2.