Corrosion Behavior of Si3N4 Ceramic in High-temperature Molten Salt-water Vapor Environment

doi:10.15541/jim20230391

Abstract

Abstract:

Molten salt electrolysis is the key technology for dry reprocessing of spent fuel in the nuclear energy industry. High-temperature molten salt can cause severe corrosion to crucible materials used for spent fuel, so the selection of the crucible material with good resistance to high temperature and corrosion is crucial for the development of the dry reprocessing method. Si₃N₄ is considered as a promising candidate for the crucible used in dry reprocessing, primarily due to its excellent high-temperature thermal and mechanical properties. However, its resistance to high-temperature molten salts and water vapor has not been fully investigated. In this work, the corrosion behavior of Si₃N₄ in LiCl-KCl and NaCl-2CsCl molten salt under Ar atmosphere and water vapor (5%H₂O-10%O₂-85%Ar) was investigated. The results show that in argon atmosphere, Si₃N₄ undergoes slight grain boundary corrosion in LiCl-KCl molten salt, while NaCl-2CsCl molten salt presents weak corrosion on Si₃N₄. In 5%H₂O-10%O₂-85%Ar water vapor environment, LiCl-KCl molten salt prefers to attack the grain boundary phase. Si₃N₄ shows serious corrosion degradation in the NaCl-2CsCl molten salt compared with the corrosion level in argon atmosphere. The water vapor environment significantly promotes the corrosion of Si₃N₄ in the molten salt environment, while the grain boundary phase is the most susceptible site for the corrosion of Si₃N₄. In addition, no direct correlation is found between the wettability and corrosion resistance of LiCl-KCl and NaCl-2CsCl molten salts. Results of this work elucidate the mechanism of high-temperature molten salt-water vapor-induced degradation of Si₃N₄, offering guidelines for the selection of crucibles in the dry reprocessing of spent fuel.

Key words: Si₃N₄, grain boundary phase, molten salt, water vapor, dry reprocessing

CLC Number:

TQ174
F416

QIU Zihao, TIAN Zhilin, ZHENG Liya, LI Bin. Corrosion Behavior of Si₃N₄ Ceramic in High-temperature Molten Salt-water Vapor Environment[J]. Journal of Inorganic Materials, 2024, 39(3): 274-282.

Figures/Tables 20

Fig. 1 Schematic diagrams of contact angle measurement and corrosion apparatus

Fig. 2 Microstructure of Si3N4 ceramic

Fig. 3 Size distributions of (a) diameter and (b) length of Si3N4 grains

Fig. 4 Elemental distributions of Si3N4

Table 1 Composition of grain boundary phase in Si3N4

Element/(%, in atom)	N	O	Al	Si	Y
1	32.77	13.73	3.55	44.72	5.23
2	27.10	12.44	4.90	47.63	7.93

Fig. 5 Evolution of LiCl-KCl on the Si3N4 with the increase of temperature

Fig. 6 Evolution of NaCl-2CsCl on the Si3N4 with the increase of temperature

Fig. 7 Contact angles of (a) LiCl-KCl and (b) NaCl-2CsCl molten salt on Si3N4

Fig. 8 Temperature-dependent viscosity of LiCl-KCl and NaCl-2CsCl molten salts

Fig. 9 XRD patterns of Si3N4 after corrosion in LiCl-KCl and NaCl-2CsCl molten salt under Ar atmosphere for 100 h

Fig. 10 Surface microstructures of Si3N4 after corrosion in (a) LiCl-KCl and (b) NaCl-2CsCl molten salt under Ar atmosphere for 100 h

Fig. 11 EDS mappings of Si3N4 after corrosion in (a-e) LiCl-KCl and (f-k) NaCl-2CsCl molten salt under Ar atmosphere for 100 h

Fig. 12 XRD patterns of Si3N4 after corrosion in LiCl-KCl and NaCl-2CsCl molten salt under 5%H2O-10%O2-85%Ar atmosphere for 100 h

Fig. 13 Surface microstructures of Si3N4 after corrosion in (a) LiCl-KCl and (b) NaCl-2CsCl molten salt under 5%H2O-10%O2-85%Ar for 100 h

Fig. 14 Weight change of Si3N4 before and after corrosion

Fig. 15 EDS mappings of Si3N4 after corrosion in (a-e) LiCl- KCl and (f-k) NaCl-2CsCl molten salt under 5%H2O-10%O2-85%Ar for 100 h

Fig. 16 (a) Surface microstructure and (b) XRD pattern of Si3N4 after oxidation at 650 ℃ for 100 h

Fig. S1 Fracture surface of Si3N4

Fig. S2 Photos of LiCl raw powder(a) and laid for 2 h at room temperature(b)

Fig. S3 3D morphologies of the surface of (a) X1-Si3N4, (b) X2-Si3N4, (c) Y1-Si3N4, (d) Y2-Si3N4 after corrosion for 100 h

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Corrosion Behavior of Si₃N₄ Ceramic in High-temperature Molten Salt-water Vapor Environment

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