Core-shell composites, Fe3O4@C, with 500 nm Fe3O4 microspheres as cores have been successfully prepared through in situ polymerization of phenolic resin on the Fe3O4 surface and subsequent high-temperature carbonization. The thickness of carbon shell, from 20 to 70 nm, can be well controlled by modulating the weight ratio of resorcinol and Fe3O4 microspheres. Carbothermic reduction has not been triggered at present conditions, thus the crystalline phase and magnetic property of Fe3O4 micropsheres can be well preserved during the carbonization process. Although carbon shells display amorphous nature, Raman spectra reveal that the presence of Fe3O4 micropsheres can promote their graphitization degree to a certain extent. Coating Fe3O4 microspheres with carbon shells will not only increase the complex permittivity but also improve characteristic impedance, leading to multiple relaxation processes in these composites, thus the microwave absorption properties of these composites are greatly enhanced. Very interestingly, a critical thickness of carbon shells leads to an unusual dielectric behavior of the core-shell structure, which endows these composites with strong reflection loss, especially in the high frequency range. By considering good chemical homogeneity and microwave absorption, we believe the as-fabricated Fe3O4@C composites can be promising candidates as highly effective microwave absorbers.
A novel MOF derivation method is used to prepare Fe/C nanocubes, which are constructed by a cubic framework of amorphous carbon decorated uniformly by Fe@graphitic carbon nanoparticles for microwave absorption.
Highly uniform core-shell composites, polypyrrole@polyaniline (PPy@PANI), have been successfully constructed by directing the polymerization of aniline on the surface of PPy microspheres. The thickness of PANI shells, from 30 to 120 nm, can be well controlled by modulating the weight ratio of aniline and PPy microspheres. PPy microspheres with abundant carbonyl groups have very strong affinity to the conjugated chains of PANI, which is responsible for the spontaneous formation of uniform core-shell microstructures. However, the strong affinity between PPy microspheres and PANI shells does not promote the diffusion or reassembly of two kinds of conjugated chains. Coating PPy microspheres with PANI shells increases the complex permittivity and creates the mechanism of interfacial polarization, where the latter plays an important role in increasing the dielectric loss of PPy@PANI composites. With a proper thickness of PANI shells, the moderate dielectric loss will produce well matched characteristic impedance, so that the microwave absorption properties of these composites can be greatly enhanced. Although PPy@PANI composites herein consume the incident electromagnetic wave by absolute dielectric loss, their performances are still superior or comparable to most PANI-based composites ever reported, indicating that they can be taken as a new kind of promising lightweight microwave absorbers. More importantly, microwave absorption of PPy@PANI composites can be simply modulated not only by the thickness of the absorbers, but also the shell thickness to satisfy the applications in different frequency bands.
By supplying inorganic ferrite nanoparticles of different morphologies as nucleation sites, PANI/ferrite nanocomposites with novel coralloid structures were synthesized successfully through a simple, conventional, and inexpensive one-step in situ polymerization method without the aid of any surfactant, organic dopant, or template. As shown by XRD, FT-IR and UV-vis, there is no obvious chemical interaction between PANI and BaFe 12 O 19 (BF) nanoparticles; that is, ferrite nanoparticles served only as the nucleation centers for the growth of PANI nanofibers, whereas the nanoparticles have an effect in reducing the diameters of the produced PANI nanofibers. PANI/BF nanocomposites are hard magnetic properties with alternative electrical conductivities and magnetic properties. The reflection loss of BF nanoparticles in 2-18 GHz was essentially enhanced upon PANI coating, and the frequency relating to maximum reflection loss shifts to a higher value with the increase in BF content because of the higher anisotropy field. With controllable electrical, magnetic, and electromagnetic properties, the prepared nanocomposites may have potential applications in chemical sensors, gas separation, catalysis, microwave absorbing, and magnetoelectric devices.
Composites consisting of Fe(3)O(4) microspheres (FMS) and polyaniline (PANI), FMS/PANI, have been successfully prepared through a two-step oxidative polymerization of aniline monomers in the presence of Fe(3)O(4) microspheres. In our two-step polymerization technique, Fe(3+) and ammonium persulfate (APS) are used as the oxidants in each step. It is discovered that the two-step oxidative process plays a dominant role in the morphology of these composites: aniline oligomers oxidized by Fe(3+) are mainly produced in the first stage, and "egg-like" PANI aggregates are obtained in the second stage. It can be found that embedding Fe(3)O(4) microspheres in the polymer matrixes will not only modulate the complex permittivity but also produce magnetic resonance and loss in the composites. Therefore, the characteristic impedance and reflection loss of these composites are greatly improved. Especially, the composite with equal amount of FMS and PANI, FMS/PANI(50), displays very strong reflection loss over a wide frequency range that can be manipulated by the absorber thickness. More importantly, the composites prepared from the two-step chemical oxidative polymerization using hierarchical magnetic materials have better microwave absorption and environmental stability as compared with those composites from Fe(3)O(4) nanoparticles, one-step oxidative polymerization, and physical mixture. We believe the two-step oxidative polymerization technique can be a novel route for the design and preparation of lightweight and highly effective microwave absorbers in the future.
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