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材料研究学报  2018, Vol. 32 Issue (2): 119-126    DOI: 10.11901/1005.3093.2017.318
  研究论文 本期目录 | 过刊浏览 |
具有宽频与可控微波吸收性能的石墨烯空心微球的自组装
曾强1, 陈平1(), 于祺2, 徐东卫1
1 大连理工大学化工学院 三束材料改性教育部重点实验室 大连 116024
2 沈阳航空航天大学 辽宁省先进聚合物基复合材料重点实验室 沈阳 110136
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
引用本文:

曾强, 陈平, 于祺, 徐东卫. 具有宽频与可控微波吸收性能的石墨烯空心微球的自组装[J]. 材料研究学报, 2018, 32(2): 119-126.
Qiang ZENG, Ping CHEN, Qi YU, Dongwei XU. Self-assembly of Graphene Hollow Microspheres with Wideband and Controllable Microwave Absorption Properties[J]. Chinese Journal of Materials Research, 2018, 32(2): 119-126.

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摘要: 

用简单高效的两步法制备了一种包覆有四氧化三铁的还原石墨烯空心微球(Air@rGO€Fe3O4)。两步法包括油包水乳化技术和高温煅烧技术。Air@rGO€Fe3O4空心微球的介电损耗和磁损耗优异,使其具有良好的微波吸收性能。空心微球在石蜡中的添加量为33.3%、厚度为2.8 mm的微球在10 GHz处有最小反射率,为-52 dB,反射率小于-10 dB的频率范围为7.5~14.7 GHz。调节各成分的配比和样品厚度可控制空心微球的吸波性能。随着四氧化三铁含量的提高,微球的最小反射率的峰值位置向高频移动。Air@rGO€Fe3O4空心微球有吸收频率范围宽、吸收强度大以及吸波性能可调控等优点,使其成为具有潜在应用价值的高性能吸波材料。
关键词 ： 复合材料,  宽频与可控微波吸收性能,  自组装,  Air@rGO€Fe3O4空心微球,  阻抗匹配    
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
收稿日期: 2017-05-16     
ZTFLH:  TB332  
基金资助:国防基础科研重点项目(A35201XXXXX),国家自然科学基金(51303106),三束材料改性教育部重点实验室基金(LABKF1502)
作者简介:

作者简介 曾 强,男,1989生,博士生
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https://www.cjmr.org/CN/10.11901/1005.3093.2017.318      或      https://www.cjmr.org/CN/Y2018/V32/I2/119

图1  Air@rGO€Fe3O4空心微球的制备示意图
图2  矢量网络分析仪和同轴测试样品图
图3  在氮气保护下PVA的TGA曲线
图4  氧化石墨烯﹑Sp和S1.0的XRD谱图
图5  S1.0的XPS全谱图,C1s分峰图,Fe2p分峰图和氧化石墨烯C1s分峰图
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
表1  S1.0和氧化石墨烯各个官能团的含量
图6  PVA/AAI/GO前驱体(a)和S1.0的SEM图(b)﹑(c)以及S1.0碎片的TEM图(d)﹑(e)
图7  不同厚度的S0.5﹑S1.0﹑S1.5和Sp的反射率
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]
表2  文献中一些吸波材料的吸波性能
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
表3  Fe3O4含量不同厚度为2.8 mm的Air@rGO€Fe3O4微球的吸波性能
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