This study investigates the electric polarization, including direct current (DC) and alternating current (AC), and electromagnetic interference (EMI) shielding capabilities within the microwave range (2.5–3.9 GHz) of cross-ply continuous carbon fiber-reinforced polymer (CFRP) composites, constructed by stacking prepreg composites. The DC conductivity of CFRP was evaluated using a multimeter, while the AC relative permittivity was measured with electronic test equipment (LCR meter). To describe the relationship between shielding effectiveness and polarization behavior, the EMI shielding of CFRP was assessed using the waveguide method, presenting a quantitative description of this relationship for the first time. Results indicate a decrease in DC conductivity with increasing specimen thickness due to increasing defects. Conversely, AC permittivity increases with specimen thickness, attributed to a rise in charged carriers and associated carrier-atom interactions. Skin depth δ, at a given thickness, follows a trend of initial decrease and subsequent increase with rising frequency; at a given frequency, it increases with decreasing specimen thickness. The interaction between CFRP and radiation is primarily reflective, with the reflection coefficient being much higher than the absorption coefficient across the frequency range, escalating with specimen thickness. Shielding effectiveness (SET) and absorption loss (SEA) display an initial increase followed by a decrease with rising frequency, whereas reflection loss (SER) sees a slight increase. For the smallest thickness, SEA per unit thickness exceeds 3120 dB/m and 7960 dB/m using specimen and carbon thickness, respectively. The absorption loss predominantly arises from the interaction of the electric field with electric dipoles formed by carrier-atom interaction at defects.
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