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Chinese Journal of Materials Research  2018, Vol. 32 Issue (2): 119-126    DOI: 10.11901/1005.3093.2017.318
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Self-assembly of Graphene Hollow Microspheres with Wideband and Controllable Microwave Absorption Properties
Qiang ZENG1, Ping CHEN1(), Qi YU2, Dongwei XU1
1 Key Laboratory of Materials Modification by Laser, Ion and Electron Beams of Ministry of Education ＆ School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
2 Liaoning Key Laboratory of Advanced Polymer Matrix Composites, Shenyang Aerospace University, Shenyang 110136, China
Cite this article: 

Qiang ZENG, Ping CHEN, Qi YU, Dongwei XU. Self-assembly of Graphene Hollow Microspheres with Wideband and Controllable Microwave Absorption Properties. Chinese Journal of Materials Research, 2018, 32(2): 119-126.

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Abstract  

Fe3O4 nanoparticles coated hollow microspheres of reduced graphene oxide (Air@rGO€Fe3O4) were synthesized via a simple and efficient two-step method consisting of water-in-oil (W/O) emulsion technique and subsequent annealing process. The Air@rGO€Fe3O4 hollow microspheres showed good electromagnetic properties because of the coexistence of magnetic loss and dielectric loss to microwave. The microwave absorbing bandwidth (reflection loss<-10 dB) for Air@rGO€Fe3O4 of thickness in 2.8 mm (with 33.3 mass% paraffin) locates in the range of 7.5~14.7 GHz, while a minimum reflection loss -52 dB at 10.0 GHz. More interestingly, the microwave absorbing properties of the hollow microspheres can be easily controlled by tuning the ratio of the two components in the composites and the thickness of samples, and as the Fe3O4 content increase, the minimum reflection loss valve of Air@rGO €Fe3O4 microspheres move to higher frequency range. These Air@rGO€Fe3O4 hollow microspheres are great potential candidate as microwave absorbents due to their excellent properties such as wide absorbing frequency, strong absorption, low density and controllable absorbing properties.

Key words:  composite      wideband and controllable microwave absorption properties      self-assembly      Air@rGO€Fe3O4 hollow microsphere      impedance matching     
Received:  16 May 2017     
ZTFLH:  TB332  
Fund: Supported by National Defense Key Program Fundamental Research Program (No. A35201XXXXX);National Natural Science Foundation of China (No. 51303106);Key Laboratory of Materials Modification by Laser, Ion and Electron Beams of Ministry of Education (No. LABKF1502)
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Qiang ZENG
Ping CHEN
Qi YU
Dongwei XU

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https://www.cjmr.org/EN/10.11901/1005.3093.2017.318     OR     https://www.cjmr.org/EN/Y2018/V32/I2/119

Fig.1  Schematic illustration of the assembly process of Air@rGO€Fe3O4 hollow microspheres
Fig.2  Photo of vector network analyzer and coaxial test sample
Fig.3  TGA thermograms of PVA under nitrogen
Fig.4  XRD patterns of GO, Sp and S1.0
Fig.5  XPS wide scan spectra (a), C1s spectrum (b), Fe2p spectrum (d) of S1.0 and XPS C1s spectrum of graphene oxide (c)
Concentration of functional groups / %
-C-C- -C-O- -C=O -O-C=O
S1.0 86.43 13.57 0 0
Graphene oxide 46.73 38.78 12.15 2.34
Table 1  Content of the various functional groups of S1.0 and graphene oxide
Fig.6  SEM images of PVA/AAI/GO precursor (a), S1.0 (Air@rGO€Fe3O4 microspheres) (b), cross-section of S1.0 microsphere (c), TEM image of a fragment from a microsphere which has been ultrasonically decomposed (d), high magnification TEM image of the fragment (e)
Fig.7  Reflection loss of S0.5 (a), S1.0 (b), S1.5 (c) and Sp (d) at difference thickness
Samples in matrices % Min|RL|
/dB		 Thickness/mm
(RL≤-10 dB)		 Frequency range/GHz
(RL≤-10 dB)		 Refs
Air@rGO€Fe3O4 microsphere in wax 33 -52.0 2.8 7.2 This work
Silica-nickel-carbon microspheres in wax 40 -37.6 2.4 6.0 [1]
cobalt/polypyrrole in wax 30 -33.0 2.0 4.8 [2]
graphene@Fe3O4@SiO2@PANI in wax 25 -40.7 2.5 5.8 [3]
Co/carbon nanotube-
graphene in wax		 30 -65.6 2.2 10.0-13.5 [4]
NiCoP/RGO in wax 75 -17.8 1.5 6.2-9.3 [5]
CoxFe3-xO4(x=0-1) spheres in wax 75 -41.1 2.0 4.2 [6]
Fe3O4/graphene capsules in wax 30 -32.0 3.5 4.2 [7]
RGO-PPy-Co3O4 in wax 50 -43.5 3.2 6.4 [8]
Fe3O4@SiO2@RGO in wax 20 -26.6 3.0 3.6 [9]
graphene@Fe3O4@carbon@MnO2 in wax 25 -38.8 1.8 5.4 [14]
RGO-CoFe2O4/GNSs in cyanate ester resin 13 -21.8 1.2 2.8 [17]
graphene@Fe3O4@C@PANI in wax 25 -44.2 3.0 5.8 [18]
Co-doped MnO2 in wax 20 -17.5 2.0 5.2 [19]
hierarchical NiCo2O4 in wax 50 -25.5 4.0 1.8 [20]
α-Co/graphene in wax 60 -47.5 2.0 3.9 [21]
ring-shaped FeCo@
carbon fiber in wax		 20 -37.7 1.8 1.9 [22]
cobalt-cobalt oxide in wax 60 -30.5 1.7 4.7 [23]
rugby-shaped CoFe2O4 in wax 50 -34.1 2.5 2.6 [24]
Fe3O4@ZnO in wax 50 -22.7 3.5 5.9 [25]
hollow porous Ni/SnO2 in wax 50 -36.7 1.7 3.4 [26]
hollow urchinlike α-MnO2 in wax 50 -41.0 1.9 2.5 [27]
RGO/CoFe2O4 in wax 50 -42.2 2.3 5.2 [28]
Ag@Fe3O4/RGO in wax 50 -40.1 2.0 3.1 [29]
graphene@Fe3O4@carbon in wax 25 -30.1 1.8 3.4 [30]
Ni0.5Zn0.5Fe2O4 ferrite nanofiber in wax 15 -14.1 3.6 4.4 [31]
Table 2  microwave absorption performance of best microwave absorption materials reported in literatures
Samples RLmin/dB Frequency range/GHz
(RL≤-10 dB)		 The bandwidth/GHz
(RL≤-10 dB)
S0.5 -28.5 5.8~9.3 3.5
S1.0 -52 7.5~14.7 7.2
S1.5 -25.9 8.8~14.3 5.5
Sp -11.7 7.9~9.2 1.3
Table 3  Microwave absorption performance of the Air@rGO€Fe3O4 microspheres with different Fe3O4 loadings at a thickness of 2.8 mm
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