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This paper investigated the electromagnetic shielding properties and the mechanisms of tricalcium silicate (C3S) paste with three water-cement (W/C) ratios after long-term curing. The C3S pastes with three W/C ratios were tested by XRD and other tests for the qualitative and quantitative analysis of the individual phases. The electromagnetic shielding properties and electromagnetic parameters of the specimens were obtained using the waveguide method. Finally, the microscopic mechanism of the variation of electromagnetic shielding properties of C3S paste affected by the W/C ratio was dissected based on the individual phases. The results show that the volume fraction of pore, calcium silicate hydrate (C-S-H) gel, calcium hydroxide (CH), and calcite (CaCO3) in the specimen increases with the rise of the W/C ratio, and the unhydrated C3S decreases; the electromagnetic shielding of the paste specimen increases; the complex relative permittivity gradually increases. The mechanism of the W/C ratio affecting the electromagnetic shielding performance of C3S paste is that, on the one hand, both the volume fraction of C-S-H and the relative permittivity in the solid phase, which have the greatest influence on the electromagnetic shielding performance, gradually increase with the increase of W/C ratio. On the other hand, as the W/C ratio increases, the volume fraction and area fraction of the mesopores in the specimen increase, which increases the internal loss of electromagnetic waves.
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