摘要
[Background and purposes]In recent years,there has been growing attention in academia and industry on the development of high-performance electromagnetic wave(EMW)absorbing materials.However,creating lightweight broadband absorbers remains a challenge in terms of practical applications.EMW absorbing materials primarily rely on the magnetic loss of magnetic materials and/or the dielectric loss of dielectric materials to convert EMW energy into thermal energy for dissipation.Among various magnetic materials,Fe_(3)O_(4) plays an irreplaceable role in EMW absorption due to its high saturation magnetization,low cost and compatible dielectric loss in the gigahertz frequency range.Nevertheless,the high density,large matching thickness and narrow absorption bandwidth of Fe_(3)O_(4) pose significant challenges for practical applications.In contrast,one-dimensional(1D)structures not only retain the characteristic properties of lightweight,chemical stability and high dielectric loss,but also exhibit anisotropic structures and large aspect ratios.Additionally,researchers have found that the minimum reflection loss(RL)of hollow carbon materials with mesopores is nearly four times that of non-porous hollow carbon materials and nine times that of dense carbon materials.According to Maxwell's EMW theory,composites consisting of Fe_(3)O_(4) and one-dimensional(1D)mesoporous carbon materials can leverage their respective advantages by optimizing the composition and structure of the composites to balance u,and Er,thereby enhancing EMW absorption performance.Additionally,numerous studies have demonstrated that composites composed of multi-component heterostructures significantly enhance the EAB.This enhancement is primarily ascribed to the numerous interface polarization losses generated by the additional heterostructure interfaces,which also improve the overall impedance matching of the composites.In this study,we leverage the advantages of magnetic/carbon composites,one-dimensional(1D)mesoporous carbon and multi-component heterostructures to prepare a composite of 1D mesoporous carbon-coated manganese oxide(Mn_(3)O_(4) and MnO,denoted as Mn_(x)O_(y))embedded with Fe_(3)0_(4) nanoparticles(Mn_(x)O_(y)/C@Fe_(3)O_(4)).This composite was synthesized and its formation mechanism and microstructure were analyzed in detail.At the same time,the influence of this Mn_(x)O_(y)/C@Fe_(3)O_(4) structure on EMW properties and absorbing performance was further discussed.[Methods]Firstly,MnO_(2) nanowires were synthesized by using a simple hydrothermal method.Then,the MnO_(2) nanowires served as templates for the synthesis of MnO_(2)/PDA@Fe^(3+)composites through the in-situ polymerization of dopamine and Fe^(3+)adsorption.Finally,1D mesoporous carbon-coated manganese oxide composite embedded with Fe_(3)O_(4) nanoparticles(Mn_(x)O_(y)/C@Fe_(3)O_(4))composites were obtained after heat treatment at 550℃ in N_(2).The crystal structure of the samples was analyzed using X-ray diffractometer with Cu Ka irradiation.Scanning electron microscopy(SEM)and high-resolution transmission electron microscopy(TEM)were used to observe microstructure and morphology of the samples.Nitrogen sorption measurements were obtained at 77 K on a Quantachrome surface area and pore size analyzer to measure the specific surface area and pore size distribution.XPS analysis was performed on X-ray photoelectron spectrometer with monochromatic Al Ka radiation.Magnetization curves of the samples were recorded with a Quantum Design physical property measurement system(PPMS-9)at room temperature.The electromagnetic parameters of the Mn_(x)O_(y)/C@Fe_(3)O_(4) composites were measured using an Agilent N5230C network analyzer in the frequency range of 2-18 GHz.For electromagentic testing,the Mn,Oy/C@Fe34 composites and paraffin wax were mixed at 50°C according to the mass ratio of 15 wt.%,20 wt.%and 25 wt.%,and pressed in a special mold to make coaxial rings(inner diameter=3.04 mm,outer diameter-7 mm),which were denoted as S-1,S-2 and S-3,respectively.[Results]SEM images illustrate the preparation process of iD mesoporous carbon-coated manganese oxide embedded with Fe3O4 nanoparticles composites(Mn_(x)O_(y)/C@Fe_(3)O_(4)).Most of the manganese oxide(Mn,Oy)was reduced to granular after heat treatment,while the outer carbon layer remains its 1D morphology and the carbon layer is interspersed with Fe_(3)O_(4) nanoparticles.The diffraction peaks of MnO_(2) nanowires align well with the body-centered tetragonal a-MnO2.For the Mn_(x)O_(y)/C@Fe_(3)O_(4) composites,the signals of α-MnO_(2) disappears,followed by the emergence of Mn_(3)O_(4) and three prominent diffraction peaks for the cubic MnO.In addition,four weak diffraction peaks correspond to the magnetite Fe_(3)O_(4),consistent with the HRTEM results.The corresponding nitrogen adsorption-desorption isotherm and pore size distribution curve are presented to further analyze the mesoporous structure of composite.The surface composition and element valence states of the Mn_(x)O_(y)/C@Fe_(3)O_(4) composite were investigated by using XPS.The polarization relaxation processes were analyzed according to the Debye theory which describes the relationship between e'and e".Besides the polarization loss,the contribution of the conduction loss plays an important role for the overall dielectric loss.The magnetization curve of Mn_(x)O_(y)/C@Fe_(3)O_(4) exhibits typical ferromagnetic behavior.The permittivity parameter(Co),defined as Co=u"(u)^(-2)f^(-1) determine the contribution of eddy current effect to magnetic loss.The tand values are all larger than those of tand,for the three samples,indicating that the loss capacity of Mn_(x)O_(y)/C@Fe_(3)O_(4) composites is mainly derived from the dielectric loss.Although tand,is smaller,it plays an important role in improving the impedance matching of Mn_(x)O_(y)/C@Fe_(3)O_(4) composites.When the filler loading is 15 wt.%,the RL of sample S-1 is about-10.0 dB at the thickness of 1.5 mm with narrow EAB.As the filler loading increased to 20 wt.%,the RL of sample S-2 reached-62.0 dB at a thickness of 2.2 mm and the EAB was 6.4 GHz at a small thickness of 1.7 mm.When the filler loading is further increased to 25 wt.%,the microwave absorption performance of sample S3 decreased significantly with a little region of RL<-10.0 dB at the thickness of 5.0 mm.The values of[Zin/Zol of the three samples at thicknesses of 1.5-5.0 mm were calculated.Due to good impedance matching of S-2,the incident EMW can enter the material and then can be dissipated through dipole polarization loss,interface polarization loss,conduction loss,eddy current loss and natural ferromagnetic resonance loss.[Conclusions]1D Mn_(x)O_(y)/C@Fe_(3)O_(4) was synthesized via a process involving the coating of polydopamine,adsorption of Fe(ll)salts and heat treatment,using MnO_(2) nanowires as templates.The multi-component heterostructure of the Mn_(x)O_(y)/C@Fe_(3)O_(4) composite(Mn_(3)O_(4),MnO,Fe_(3)O_(4),and C)enhances the interfacial interactions between the different phases,providing increased interface polarization loss under the action of an alternating electromagnetic field.The numerous defects and terminal groups in the mesoporous carbon provide abundant dipole polarization centers.Additionally,the presence of mesopores reduces the weight of the material while increasing the multiple scattering losses of the electromagnetic waves within the material.The ID carbon structure in the matrix forms a conductive network between adjacent fibers,facilitating electron migration and transition,thereby enhancing conductive loss.The incorporation of magnetic Fe_(3)O_(4) nanoparticles introduces eddy current loss and natural ferromagnetic resonance loss,thus increasing magnetic loss.Moreover,the synergistic effect between dielectric and magnetic losses improves the impedance matching of the material,leading to excellent EMW absorption performance.
由于雷达探测频段的多样性,仅针对特定频率的强吸收吸波材料已无法满足隐身需求,如何提升有效吸收带宽(Effective Absorption Bandwidth, EAB)仍是高性能吸波材料发展亟待解决的难题。该研究提出了一种以MnO_(2)纳米线为模板,通过原位聚合多巴胺、吸附Fe盐和碳化等方法得到了附载有Fe_(3)O_(4)纳米颗粒的一维(1D)介孔碳包覆锰氧化物(Mn_(x)O_(y)、Mn_(3)O_(4)和MnO)复合材料的制备方法(Mn_(x)O_(y)/C@Fe_(3)O_(4))。结果表明,Mn_(x)O_(y)/C@Fe_(3)O_(4)复合材料的多组分异质结构(Mn_(3)O_(4)、MnO、Fe_(3)O_(4)和C)增加了不同物相的相互接触,在交变电磁场的作用下提供了更多的界面极化损耗;基体中1D碳结构两两之间形成导电网络,有利于电子的迁移和跃迁,增强了传导损耗;介孔碳中的众多缺陷和末端基团提供了大量的偶极子极化中心,增加了电磁波在材料内部的多重散射损耗,且介孔的存在减轻了材料的重量;磁性Fe_(3)O_(4)颗粒提供了涡流损耗和自然铁磁共振损耗,增加了磁损耗,并且与介电损耗的协同作用下改善了材料的阻抗匹配,使得Mn_(x)O_(y)/C@Fe_(3)O_(4)复合材料具有优异的吸波性能。Mn_(x)O_(y)/C@Fe_(3)O_(4)复合材料在填充量低至20 wt.%的情况下,厚度为2.2 mm时的反射损耗(RL)为-62.0 dB。值得注意的是,在1.7 mm的超薄厚度下EAB达到了6.4 GHz(11.4 GHz~17.8 GHz),表明该复合材料具有超轻、宽带吸收的优异吸波性能。
出处
《陶瓷学报》
北大核心
2025年第4期729-741,共13页
Journal of Ceramics
基金
National Natural Science Foundation of China (52371171, 52222106, 51971008, 52121001)
Fund of National Key Laboratory of Scattering and Radiation (Beijing Institute of Environmental Features)。
作者简介
Correspondent author:LIU Xiaofang(1982-),Female,Ph.D.,Professor.E-mail:liuxfo5@buaa.edu.cn。
