The work in this paper is dedicated to the study of wave-absorbing materials for applications in extremely harsh environmental conditions such as seawater and oil. In this paper, FeNiCrMn high-entropy alloy material with corrosion resistance and polylactic acid (PLA) material with high strength and high modulus were used to prepare more environmentally adaptable FeNiCrMn/PLA electromagnetic(EM) microwave-absorbing materials by two-step method of ball milling and melt extrusion.The physical phases, microscopic morphology, EM parameters and mechanical performance of FeCoNiCrMn/PLA composites were characterized using XRD, SEM, Vector Network Analyzer and Universal Testing Machine respectively. The microwave-absorbing properties of FeCoNiCrMn/PLA composites were investigated, and the effects of their components and micro-morphology on the microwave-absorbing and mechanical performance were discussed. The results show that when the FeCoNiCrMn content reaches 25 wt% and the thickness is 4.5 mm, the minimum reflection loss of FeCoNiCrMn/PLA composites reaches −24.58 dB, and the effective microwave-absorbing bandwidth is 2.51 Ghz. The maximum tensile strength and elongation at break of the composites could reach 23.83 MPa and 7.12 %, respectively. The microwave-absorbing ability of FeCoNiCrMn composites is mainly due to their rich EM loss mechanisms, including dielectric losses such as dipole polarization, interface polarization, defect-induced polarization, etc., as well as magnetic losses such as natural resonance, exchange resonance, and eddy current losses. Finally, the wide-angle microwave-absorbing characteristics of FeCoNiCrMn/PLA 3D-printed composites were investigated, the results showed that the composites with FeCoNiCrMn content of 25 wt% had Radar Cross Section (RCS) values lower than −10 dBm² within the microwave incidence angle of −90° < θ < −6° and 6° < θ < 90°, which indicated that the composites had wide-angle microwave-absorbing capability. The materials have microwave-absorbing properties along with a certain degree of mechanical strength, and at the same time have good environmental adaptability. The FeCoNiCrMn/PLA composite wire can be used in FDM technology to prepare structural microwave absorbers, realizing the integration of “material-design-manufacturing”, which has a broad application prospect in the field of EM microwave absorption and 3D printing.
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