For traditional spent fuel shielding materials, due to physical and chemical defects and cost constraints, they have been unable to meet the needs. Therefore, this paper carries out the first discussion on the application and performance of bismuth in neutron shielding by establishing Monte Carlo simulation on the neutron flux model of shielded spent fuel. Firstly, functional fillers such as bismuth oxide, lead oxide, boron oxide, gadolinium oxide and tungsten oxide are added to the matrices to compare the shielding rates of aluminum alloy matrix and silicone rubber matrix. The shielding rate of silicone rubber mixture is higher than aluminum alloy mixture, reaching more than 56%. The optimal addition proportion of bismuth oxide and lead oxide is 30%, and the neutron radiation protection efficiency reaches 60%. Then, the mass attenuation coefficients of bismuth oxide, lead oxide, boron oxide, gadolinium oxide and tungsten oxide in silicone rubber matrix are simulated with the change of functional fillers proportion and neutron energy. This simulation result shows that the mixture with functional fillers has good shielding performance for low energy neutrons, but poor shielding effect for high energy neutrons. Finally, in order to further evaluate the possibility of replacing lead oxide with bismuth oxide as shielding material, the half-value layers and various properties of bismuth oxide and lead oxide are compared. The results show that the shielding properties of bismuth oxide and lead oxide are basically the same, and the mechanical properties, heat resistance, radiation resistance and environmental protection of bismuth oxide are better than that of lead oxide. Therefore, in the case of neutron source strengths in the range of 0.01–6 MeV and secondary gamma rays produced below 2.5 MeV, bismuth can replace lead in neutron shielding applications.
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