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Materials 2019, 12(13), 2206; https://doi.org/10.3390/ma12132206
A New Broadband and Strong Absorption Performance FeCO3/RGO Microwave Absorption Nanocomposites
National Key Laboratory for Remanufacturing, Academy of Army Armored Forces, Beijing 100072, China
Authors to whom correspondence should be addressed.
Received: 30 May 2019 / Accepted: 5 July 2019 / Published: 9 July 2019
A novel composite of FeCO3 nanoparticles, which are wrapped with reduced graphene oxide (RGO), is fabricated using a facile one-spot solvothermal method. The composite consists of a substrate of RGO and FeCO3 nanoparticles that are embedded in the RGO layers. The experimental results for the FeCO3/RGO composite reveal a minimum refection loss (−44.5 dB) at 11.9 GHz when the thickness reaches 2.4 mm. The effective bandwidth is 7.9 GHz between 10.1 and 18 GHz when the refection loss was below −10 dB. Compared to GO and RGO, this type of composite shows better microwave absorption thanks to improved impedance matching. Overall, this thin and lightweight FeCO3/RGO composite is a promising candidate for absorbers that require both strong and broad absorption.
Keywords:FeCO3/RGO; solvothermal method; formation mechanism; microwave absorption properties
Because of the ubiquity of electronic devices, electromagnetic radiation, and, in particular, signal interference have become a global problem [1,2,3]. As a result, big efforts have been made to reduce electromagnetic pollution and other related problems. One promising approach is the use of high-performance microwave absorbing materials (MAMs). Graphene, a relatively new carbon-based material, has excellent properties such as high electron mobility, high permittivity and a high specific surface area, which can dampen electromagnetic waves effectively using polarization relaxation [4,5,6,7]. However, pure graphene can reflect most of the electromagnetic waves, resulting in being unsuitable for MAM due to their poor impedance matching.
Fortunately, it is possible through to combine graphene with magnetic materials to overcome this problem [8,9]. Most of the related studies are focused on soft magnetic materials, which have high magnetic loss due to natural resonance, and they can produce better results as compounded with graphene. For example, Cui et al.  prepared a hollow Fe3O4@RGO composite by a facile route. The minimum reflection loss is −41.89 dB at 6.7 GHz. In the range of 1–4 mm, the reflection loss of nanocomposite thickness is less than −10 dB at 3.4 GHz to 13.6 GHz. Wang et al.  loaded MnFe2O4 nanoparticles on RGO sheets by one-step hydrothermal method. The minimum reflection loss of MnFe2O4/RGO is −32.8 dB at 8.2 GHz with the thickness of 3.5 mm, and the absorption bandwidth with the reflection loss below-10 dB is up to 4.8 GHz (from 7.2 to 12 GHz). Feng et al.  synthesized ZnFe2O4@SiO2@RGO core-shell microspheres by “coating-coating” method. The minimum reflection loss of the sample with a thickness of 2.8 mm can reach −43.9 dB at 13.9 GHz. In recent years, the composite of paramagnetic FeCO3 and RGO has shown great brilliance in the field of batteries due to its excellent electrochemical properties [13,14,15]. However, as far as we know, the microwave absorption properties of FeCO3/RGO, especially its magnetic loss characteristic spectrum, have not been investigated.
Therefore, FeCO3/RGO composites were synthesized using a one-pot solvothermal method. To reveal the microwave absorption mechanism of the FeCO3/RGO composite, the frequency dependence of both complex permittivity and the reflection-loss formation were studied and compared with GO and RGO. The outcome of this study can aid the development of light-weight and broadband electromagnetic-wave absorbers.
10.8 g FeCl3·6H2O, 7.2 g urea, 5 g PVP and 1.2 g nano-iron powder were added into a 400 mL graphene-oxide slurry (purchased from Qitaihe Baotailong New Materials Co., Ltd. (Qitaihe, China) Containing GO 3.3 mg/mL). The mixture was dispersed, aided by ultrasonic treatment for 30 min, to form a homogeneous solution, and subsequently put into a 500 mL Teflon-lined stainless-steel autoclave, where it was kept at 200 °C for 12 h. After cooling to room temperature, the reaction products were washed with deionized water and alcohol, three times. Finally, the reaction products were dried in a vacuum furnace at 60 °C for 24 h.
The morphology, structure, surface elements, and the electromagnetic parameters were analyzed using SEM, TEM, XRD, XPS, and VNA, field emission scanning electron microscopy (FE-SEM, Nava Nano FE-SEM450/650, Eindhoven, Netherlands), transmission electron microscopy (TEM, LI-BRA200, Oberkochen, German), X-ray diffraction (XRD, D/MAX-2500PC, Rigaku, Tokyo, Japan), X-ray photoelectron spectroscopy (XPS, PHI5300, Ulvac-Phi, Tokyo, Japan), and Vector network analyzer (VNA, PNA-N5244A, AGILENT, Santa Clara, CA, USA),respectively. The electromagnetic parameters of the measured samples were prepared by mixing the products (60%) with molten paraffin wax (40%) and placing them into a toroidal mold (Φin = 3 mm, Φout = 7 mm) with a thickness of 2.0–3.0 mm. The test software (AGILENT, Santa Clara, CA, USA) is 85071 and the calibration part is 85050D. Before the test, the permittivity of air was measured as an evaluation of the calibration effect.
3. Results and Discussion
Figure 1a shows the XRD patterns of GO, RGO, and the FeCO3/RGO composite. There is a broad peak at 13.4° in GO (pattern a), which corresponds to the (001) reflection of GO . The broad peak at 25.2° and the disappearance of the peak at 13.4° (pattern b) indicate that GO was reduced to RGO. The XRD patterns of the FeCO3/RGO composite (pattern c) show that all the diffraction peaks match JCPS No.29-0696, which confirms that the FeCO3/RGO composite was indeed obtained. The disappearance of the RGO peaks in FeCO3/RGO  due to the uniform distribution of FeCO3 particles between graphene layers (Figure 2), which prevents the interlayer aggregation of RGO sheets, causes the diffraction intensity, i.e., the RGO peak, to be much smaller than for FeCO3.
The XPS survey spectrum of FeCO3/RGO (Figure 1b) shows that the composite consists of Fe, O, C, and N. Four peaks were detected (284.4 eV, 285.8 eV, 287.7 eV, 289.2 eV) in C1s spectrum (Figure 1c), which correspond to C=C/C–C, C–O, C=O, and FeCO3 , respectively. As shown in Figure 1d (Fe2p), two peaks appear at 710.1 eV and 723.4 eV, which correspond to Fe2p3/2 and Fe2p1/2. Furthermore, a satellite peak of Fe2p3/2 appears at 714.1 eV . These characteristic peaks confirm the presence of FeCO3/RGO. The formation of FeCO3 can be derived from the following chemical equations:
Figure 2 shows the SEM, TEM, and HRTEM images of FeCO3/RGO. Polyhedron-like FeCO3 nanoparticles with a diameter of 20~40 nm were evenly embedded in layers of lamellar RGO. The formation of FeCO3 can be also proved by Figure 2c, and the space between two lattice fringes is 0.279 nm, corresponding to (104) plane of FeCO3. During the reduction process, the uniform distributions of nanoparticles in the RGO layers can prevent GO from agglomerating and the formation of a FeCO3-RGO conductive network, which might help facilitate dielectric loss.
Figure 3 shows the frequency-dependent electromagnetic properties of GO, RGO, and FeCO3/RGO between 2 and 18 GHz. Figure 3a,b illustrate the associated real (ε′) and imaginary (ε″) complex permittivity. The values of ε′ show the same trend, ε′ decreases with increasing frequency. Furthermore, the ε′ of FeCO3/RGO is higher than for both GO and RGO due to the enhanced polarization characteristics. Also, the ε″ of FeCO3/RGO is larger than for both GO and RGO due to higher conductivity . Figure 3c,d depict the real (μ′) and imaginary (μ″) complex permeability of the composites. The complex permeability of GO and RGO varies similarly with frequency, indicating that there is little effect of the reduction reaction on the magnetic properties of GO. However, the observed trend for FeCO3/RGO is different from GO and RGO. The complex permeability of FeCO3/RGO varies greatly between 10 GHz and 16 GHz because the magnetic FeCO3 nanoparticles can produce natural resonance loss and exchange resonance loss (due to size effect, surface effect, and spin wave excitation) [20,21,22,23].
As well known, reflection loss (RL) can assess and characterize microwave absorption performance. According to the transmission line model, RL of a metal-backed microwave absorption layer can be calculated by the following formulas :
Here, Zin is the input impedance of the absorber, Z0 is the impedance of free space (Z0 is generally 1), εr and μr are the complex permittivity and permeability, c is the speed of light in vacuum, d is the thickness of the absorber, and f is the microwave frequency. 3D theoretical RL plots of the composites are shown in Figure 4a–c. It can be observed that with the reduction of GO and the introduction of FeCO3, the microwave absorption properties improves significantly. FeCO3/RGO nanocomposites show excellent microwave absorption properties as the thickness between 2 mm and 3 mm. RL curves of composites versus frequency is shown in Figure 4d. RL(min) appears in X and Ku band as thickness in the range of 2–3 mm and shifts to lower frequency with increasing thickness. When the thickness is 2.4 mm, FeCO3/RGO shows optimal microwave absorption and reaches a RL(min) of −44.5 dB, while the corresponding bandwidth is less than −10 dB is 7.9 GHz (10.1~18 GHz). It is noteworthy that the effective bandwidth of FeCO3/RGO can reach up to 6 GHz and keep steadily when the thickness is 2~3 mm. Table 1 lists some reported microwave absorption composites of soft magnetic based material, graphene-based material, and FeCO3/RGO composite prepared in this work. Notably, FeCO3/RGO composite not only displays a promising negative RL value, but also has a wide effective absorption bandwidth due to the good impedance matching.
The FeCO3/RGO composite produced and investigated in this study is a novel material with excellent microwave absorption. The composite can not only effectively facilitate electromagnetic loss but also improve impedance matching. Specifically, the refection loss at 11.9 GHz, when the composite thickness is 2.4 mm, reaching a minimum of −44.5 dB, and the effective bandwidth is 7.9 GHz (from 10.1 to 18 GHz). In addition, we observed very stable broad characteristics for a thickness range of 2–3 mm. Because of the good properties mentioned above, this composite is can be regarded as an excellent microwave absorber with the potential for many commercial applications.
W.H., S.W., Y.W. and B.X. designed the experiments, W.H., Y.L. and Y.H. performed the experiments, W.H. and B.W. analyzed the data, W.H., B.W. and Y.W. wrote the paper, B.X. provided theoretical direction.
This research was funded by the National Natural Science Foundation of China, grant number 51675533 and 51701238.
Conflicts of Interest
The authors declare no conflict of interest.
- Zhang, X.J.; Wang, G.S.; Cao, W.Q.; Wei, Y.Z.; Liang, J.F.; Guo, L.; Cao, M.S. Enhanced microwave absorption property of reduced graphene oxide (RGO)-MnFe2O4 nanocomposites and polyvinylidene fluoride. ACS Appl. Mater. Interfaces 2014, 6, 7471. [Google Scholar] [CrossRef]
- Radoń, A.; Włodarczyk, P. Influence of water on the dielectric properties, electrical conductivity and microwave absorption properties of amorphous yellow dextrin. Cellulose 2019, 26, 2987–2998. [Google Scholar] [CrossRef]
- Mohammadkhani, F.; Montazer, M.; Latifi, M. Microwave absorption characterization and wettability of magnetic nano iron oxide/recycled PET nanofibers web. J. Text. Inst. 2019, 110, 989–999. [Google Scholar] [CrossRef]
- Plyushch, A.; Zhai, T.; Xia, H.; Santillo, C.; Verdolotti, L.; Lavorgna, M.; Kuzhir, P. Ultra-Light reduced graphene oxide based aerogel/foam absorber of microwave radiation. Materials 2019, 12, 213. [Google Scholar] [CrossRef] [PubMed]
- Chen, Y.; Ma, S.Q.; Li, X.; Zhao, X.; Cheng, X.W.; Liu, J. Preparation and microwave absorption properties of microsheets VO2 (M). J. Alloys Compd. 2019, 791, 307–315. [Google Scholar] [CrossRef]
- Li, Y.; Li, D.; Yang, J.; Luo, H.; Chen, F.; Wang, X.; Gong, R. Enhanced microwave absorption and surface wave attenuation properties of Co0.5Ni0.5Fe2O4 fibers/reduced graphene oxide composites. Materials 2018, 11, 508. [Google Scholar]
- Meng, F.B.; Wang, H.G.; Huang, F.; Guo, Y.F.; Wang, Z.Y.; Hui, D.; Zhou, Z.W. Graphene-based microwave absorbing composites: A review and prospective. Compos. Part B Eng. 2018, 137, 260–277. [Google Scholar] [CrossRef]
- Chen, C.; Xi, J.B.; Zhou, E.Z.; Peng, L.; Chen, Z.C.; Gao, C. Porous graphene microflowers for high-performance microwave absorption. Nano Micro Lett. 2018, 10, 26. [Google Scholar] [CrossRef] [PubMed]
- Yang, Z.W.; Wang, Y.Z.; Xiong, G.Y.; Li, D.; Li, Q.; Ma, C.; Guo, R.; Luo, H. Facile synthesis of ZnFe2O4/reduced graphene oxide nanohybrids for enhanced microwave absorption properties. Mater. Res. Bull. 2014, 61, 292–297. [Google Scholar] [CrossRef]
- Cui, G.Z.; Liu, Y.L.; Zhou, W.; Lv, X.L.; Hu, J.N.; Zhang, G.Y.; Gu, G.X. Excellent microwave absorption properties derived from the synthesis of hollow Fe3O4@reduced graphite oxide (RGO) nanocomposites. Nanomaterials 2019, 9, 141. [Google Scholar] [CrossRef]
- Wang, Y.; Wu, X.M.; Zhang, W.Z.; Huang, S. One-pot synthesis of MnFe2O4 nanoparticles-decorated reduced graphene oxide for enhanced microwave absorption properties. Mater. Technol. 2016, 32, 32–37. [Google Scholar] [CrossRef]
- Feng, J.T.; Hou, Y.H.; Wang, Y.C.; Li, L.C. Synthesis of hierarchical ZnFe2O4@SiO2@RGO core-shell microspheres for enhanced electromagnetic wave absorption. ACS Appl. Mater. Interfaces 2017, 9, 14103–14111. [Google Scholar] [CrossRef] [PubMed]
- Zhang, C.C.; Cai, X.; Xu, D.H.; Chen, W.Y.; Fang, Y.P.; Yu, X.Y. Mn doped FeCO3/reduced graphene composite as anode material for high performance lithium-ion batteries. Appl. Surf. Sci. 2018, 428, 73–81. [Google Scholar] [CrossRef]
- Gu, X.; Yan, C.L.; Yan, L.T.; Cao, L.; Niu, F.E.; Liu, D.D.; Dai, P.C.; Li, L.J.; Yang, J.; Zhao, X.B. Carbonates (bicarbonates)/reduced graphene oxide as anode materials for sodium-ion batteries. J. Mater. Chem. A. 2017, 5, 24645–24650. [Google Scholar] [CrossRef]
- Xu, D.H.; Liu, W.J.; Zhang, C.C.; Cai, X.; Chen, W.Y.; Fang, Y.P.; Yu, X.Y. Monodispersed FeCO3 nanorods anchored on reduced graphene oxide as mesoporous composite anode for high-performance lithium-ion batteries. J. Power Sources 2017, 364, 359–366. [Google Scholar] [CrossRef]
- He, J.Z.; Zheng, Q.C.; Sun, X.; Jin, C.S.; Xi, W.X.; Mao, S.C. Axiolitic ZnO rods wrapped with reduced graphene oxide: Fabrication, microstructure and highly efficient microwave absorption. Mater. Lett. 2019, 241, 14–17. [Google Scholar] [CrossRef]
- Moussa, H.; Girot, E.; Mozet, K.; Alem, H.; Medjahdi, G.; Schneider, R. ZnO rods/reduced graphene oxide composites prepared via a solvothermal reaction for efficient sunlight-driven photocatalysis. Appl. Catal. B Environ. 2016, 185, 11–21. [Google Scholar] [CrossRef]
- Heuer, J.K.; Stubbins, J. An XPS characterization of FeCO3 films from CO2 corrosion. Corros. Sci. 1999, 41, 1231–1243. [Google Scholar] [CrossRef]
- Lu, M.M.; Cao, W.Q.; Shi, H.L.; Xiao, Y.F.; Jian, Y.; Zhi, L.H.; Hai, B.J.; Wen, Z.W.; Jie, Y.; Mao, S.C. Multi-wall carbon nanotubes decorated with ZnO nanocrystals: Mild solution-process synthesis and highly efficient microwave absorption properties at elevated temperature. J. Mater. Chem. A. 2014, 2, 10540–10547. [Google Scholar] [CrossRef]
- Acher, O.; Gourrierec, P.L.; Perrin, G.; Baclet, P.; Roblin, O. Demonstration of anisotropic composites with tuneable microwave permeability manufactured from ferromagnetic thin films. IEEE Trans. Microw. Theory Tech. 1996, 44, 674–684. [Google Scholar] [CrossRef]
- Wen, F.S.; Yi, H.B.; Qiao, L.; Zheng, H.; Zhou, D.; Li, F.S. Analyses on double resonance behavior in microwave magnetic permeability of multiwalled carbon nanotube composites containing Ni catalyst. Appl. Phys. Lett. 2008, 92, 04257. [Google Scholar] [CrossRef]
- Aharoni, A. Some Recent Developments in Micromagnetics at the Weizmann Institute of Science. J. Appl. Phys. 1959, 30, S70–S78. [Google Scholar] [CrossRef]
- Vleck, V. Concerning the theory of ferromagnetic resonance absorption. Phys. Rev. 1950, 78, 266–274. [Google Scholar] [CrossRef]
- Shu, R.W.; Zhang, G.Y.; Zhang, J.B.; Wang, X.; Wang, M.; Gan, Y.; Shi, J.J.; He, J. Synthesis and high-performance microwave absorption of reduced graphene oxide/zinc ferrite hybrid nanocomposite. Mater. Lett. 2018, 215, 229–232. [Google Scholar] [CrossRef]
- Wang, Y.P.; Peng, Z.; Jiang, W. Controlled synthesis of Fe3O4@SnO2/RGO nanocomposite for microwave absorption enhancement. Ceram. Int. 2016, 42, 10682–10689. [Google Scholar] [CrossRef]
- Zhang, Y.L.; Wang, X.X.; Cao, M.S. Confinedly implanted NiFe2O4-rGO: Cluster tailoring and highly tunable electromagnetic properties for selective-frequency microwave absorption. Nano Res. 2018, 11, 1426–1436. [Google Scholar] [CrossRef]
- Shu, R.W.; Li, W.J.; Zhou, X.; Tian, D.D.; Zhang, G.Y.; Gan, Y.; Shi, J.J.; He, J. Facile preparation and microwave absorption properties of RGO/MWCNTs/ZnFe2O4 hybrid nanocomposites. J. Alloys Compd. 2018, 743, 163–174. [Google Scholar] [CrossRef]
- Zhang, K.; Gao, X.; Zhang, Q.; Li, T.; Chen, H.; Chen, X. Preparation and microwave absorption properties of asphalt carbon coated reduced graphene oxide/magnetic CoFe2O4 hollow particles modified multi-wall carbon nanotube composites. J. Alloys Compd. 2017, 723, 912–921. [Google Scholar] [CrossRef]
- Zong, M.; Huang, Y.; Wu, H.W.; Zhao, Y.; Liu, P.B.; Wang, L. Facile preparation of RGO/Cu2O/Cu composite and its excellent microwave absorption properties. Mater. Lett. 2013, 109, 112–115. [Google Scholar] [CrossRef]
- Zhang, C.; Wang, B.C.; Xiang, J.Y.; Su, C.; Mu, C.P.; Wen, F.S.; Liu, Z.Y. Microwave Absorption Properties of CoS2 Nanocrystals Embedded into Reduced Graphene Oxide. ACS Appl. Mater. Interfaces 2017, 9, 28868–28875. [Google Scholar] [CrossRef]
Figure 1. (a) XRD patterns for graphene oxide, (GO), reduced graphene (RGO), and FeCO3/RGO; XPS spectra of FeCO3/RGO; (b) wide scan; (c) C1s spectrum; (d) Fe2p spectrum.
Figure 2. (a) SEM; (b) TEM; (c) HRTEM images of FeCO3/reduced graphene oxide (RGO).
Figure 3. (a) ε′; (b) ε″; (c) μ′; (d) μ″ for graphene oxide (GO), reduced graphene oxide (RGO), and FeCO3/RGO.
Figure 4. 3D RL plots of (a) graphene oxide (GO); (b) reduced graphene oxide (RGO) and (c) FeCO3/RGO; (d) RL curves of FeCO3/RGO with 2~3 mm.
Table 1. Microwave absorption performances of the soft magnetic material-based, graphene material-based composite compared with FeCO3/reduced graphene oxide (RGO).
|Sample||RL (dB)||Effective Bandwidth (GHz) (RL < −10 dB)||Thickness (mm)||Wt. (%)||Reference|
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