Nd-doped ZrSiO4 Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability

doi:10.15541/jim20220775

Abstract

Abstract:

In contrast to conventional solid-phase sintering, molten salt method can provide a fast mass transfer and nucleation process at lower temperatures which has potential to synthesize the ceramic solid solution for immobilization of high-level nuclear waste (HLW). In this work, Nd-doped zircon (ZrSiO₄) ceramics (Zr_1-_xNd_xSiO_4-_x_/2(0≤x≤0.1)) were prepared by the molten salt synthesis(MSS) at different sintering temperatures (1100, 1200, 1300, 1400, 1500 ℃) for different sintering time (3, 6, 9, 12, and 15 h). Chemical stability of Nd-doped zircon ceramics in simulated geological disposal environment was studied by static leaching test (PCT). Zr_1-_xNd_xSiO_4-_x_/2 was synthesized by the molten salt method under the optimum molar ratio of molten salt to oxide at 10:1, sintering temperature at 1200 ℃ and sintering time of 6 h with the solid solution of Nd in ZrSiO₄ being increased to 8% (in mol). The MSS can reduce the synthetic temperature, shorten the sintering time and save the solid solution. The immobilizing mechanism of ZrSiO₄ ceramics for trivalent actinide nuclides is lattice immobilizing. Experimental results show that the normalized leaching rate (LR_Nd) of Nd is as low as ~10^-5g·m^-2·d^-1. ZrSiO₄ ceramics have no phase evolution before and after leaching, suggesting good structural stability. TLeaching model consolidates that Nd leaching is due to dissolution of the ceramic surface layer. Data from this study show that MSS is a promising method to synthesize ceramics solid solution.

Key words: immobilization, zircon, molten salt, chemical stability

CLC Number:

TQ174

LIU Jian, WANG Lingkun, XU Baoliang, ZHAO Qian, WANG Yaoxuan, DING Yi, ZHANG Shengtai, DUAN Tao. Nd-doped ZrSiO₄ Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability[J]. Journal of Inorganic Materials, 2023, 38(8): 910-916.

Figures/Tables 12

Fig. 1 Synthetic schematic of Nd-doped ZrSiO4 by MSS

Fig. 2 XRD patterns of ZrSiO4 synthesized by MSS at different temperatures (1100, 1200, 1300, 1400, and 1500 ℃)

Fig. 3 XRD patterns of ZrSiO4 synthesized by MSS at 1200 ℃ for different time (3, 6, 9, 12, and 15 h)

Fig. 4 XRD patterns of ZrSiO4 synthesized by MSS with different molar ratios of molten salt to oxide (1200 ℃/6 h)

Fig. 5 Mechanism of ZrSiO4 ceramics synthesis by MSS

Fig. 6 XRD patterns of Zr1-xNdxSiO4-x/2 (0≤x≤0.1) synthesized by MSS at 1200 ℃ for 6 h

Fig. 7 Variation of lattice volume of Zr1-xNdxSiO4-x/2 (0≤x≤0.1) in contrast to Nd content

Fig. 8 Micromorphologies and correponding particle size distributions of Zr1-xNdxSiO4-x/2 (a) ZrSiO4; (b) Zr0.98Nd0.02SiO3.99; (c)Zr0.92Nd0.08SiO3.96; (d) Correponding particle size distribution

Fig. 9 Normalized leaching rate of Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10)

Fig. 10 Logarithmic relationship of ${{B}_{\text{Nd}}}$ on the time of contact with leaching solution

Fig. 11 XRD patterns of Zr1-xNdxSiO4-x/2 (0.02≤x≤0.10) after leaching for 42 d

Fig. 12 SEM images of Zr1-xNdxSiO4-x/2 (x=0.02, 0.08) after leaching for 42 d

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Nd-doped ZrSiO₄ Ceramics: Synthesis in Molten Salt at Low Temperature, Phase Evolution and Chemical Stability

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