Preparation and wave absorption properties of ZnO@RGO composites
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摘要: 随着无线信息技术的飞速发展，电磁干扰问题日益突出，引起了全球的广泛关注。人体长时间暴露于电磁辐射下，会对中枢神经系统、心血管系统和视觉系统等造成不同程度的损伤。解决这一问题的关键在于开发能够吸收电磁波的材料。为了改善还原氧化石墨烯(RGO)的微波吸收性能，采用感应加热的方式成功获得四面体针状氧化锌(ZnO)，并通过简单水热法制备了不同比例的ZnO@RGO复合材料。利用SEM、XRD和Raman分别对ZnO@RGO复合材料的形貌、尺寸和结构进行了分析，并且探讨了ZnO含量和石蜡填充量对其电磁参数和吸波性能的影响。ZnO∶GO质量比为3∶1时的ZnO@RGO复合材料拥有最为优异的吸波性能(−44.5 dB; 3 mm)。电磁参数表明ZnO@RGO复合材料的衰减机制可以归结为电导损耗和极化效应。ZnO@RGO复合材料具有较低的反射损耗值和较薄的厚度，在军事隐身领域具有很大的潜力。Abstract: With the rapid development of wireless information technology, electromagnetic interference has become a prominent problem, which has attracted worldwide attention. Exposure to electromagnetic radiation for a long time will damage the central nervous system, cardiovascular system and visual system to varying degrees. The key to solving this problem is to develop materials that can absorb electromagnetic waves. In order to improve the microwave absorption properties of reduced graphene oxide (RGO), the tetrahedral needle-like ZnO was successfully obtained by induction heating, and ZnO@RGO composites with different proportions were prepared by simple hydrothermal method. The morphology, size, and phase structure of ZnO@RGO composites were analyzed by SEM, XRD and Raman. And the effects of the mass ratio of ZnO and the paraffin filling amount on the electromagnetic parameters and absorbing properties of ZnO@RGO composites were also discussed. The ZnO@RGO composite with ZnO∶GO mass ratio of 3∶1 has the best wave absorption performance (−44.5 dB; 3 mm). Electromagnetic parame-ters show that the attenuation mechanism of ZnO@RGO composites can be attributed to the conductance loss and polarization effect. ZnO@RGO composites have a low reflection loss value and thin thickness, which has great potential for military stealth.
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图 1 ZnO@RGO复合材料制备流程图
Figure 1. Sketch of the preparation of ZnO@RGO composites
RGO—Reduced graphene oxide
图 2 不同ZnO含量的ZnO@RGO复合材料的XRD图谱
Figure 2. XRD patterns of ZnO@RGO composites with different ZnO contents
图 4 不同ZnO质量比的ZnO@RGO复合材料的SEM图像
Figure 4. SEM images of ZnO@RGO composites with different ZnO mass ratios ((a) 1∶1; (b) 2∶1; (c) 3∶1; (d) 4∶1; (e) 5∶1)
图 5 不同ZnO质量比的ZnO@RGO复合材料的反射损耗
Figure 5. Reflection loss of ZnO@RGO composites with different ZnO mass ratios((a)1∶1; (b) 2∶1; (c) 3∶1; (d) 4∶1; (e) 5∶1)
图 6 不同石蜡填充量的ZnO@RGO复合材料的反射损耗
Figure 6. Reflection loss of ZnO@RGO composites with different paraffin filling contents ((a) 10wt%; (b) 15wt%; (c) 20wt%; (d) 25wt%; (e) 30wt%)
图 7 不同ZnO和RGO质量比的ZnO@RGO复合材料的相对复介电常数：(a) 介电常数实部(
$ \varepsilon ^{'} $ ); (b) 介电常数虚部($ \varepsilon ^{''}$ ); (c) 介电损耗角正切tan$ {\delta }_{\varepsilon} $ Figure 7. Relative dielectric complex constant of ZnO@RGO composites with different mass ratios of ZnO and RGO: (a) Real part of the dielectric constant (
$ \varepsilon ^{'} $ ); (b) Imaginary part of the dielectric constant ($ \varepsilon ^{''}$ ); (c) Tangent to the dielectric loss angle (tan$ {\delta }_{\varepsilon} $ )
图 8 不同石蜡填充量的ZnO@RGO复合材料的相对复介电常数：(a) 实部(
$ \varepsilon ^{'} $ ); (b) 虚部($ \varepsilon ^{''}$ ); (c) 介电损耗角正切tan$ {\delta }_{\varepsilon} $ Figure 8. Relative dielectric complex constant of ZnO@RGO composites with different paraffin filling contents: (a) Real part (
$ \mathit{\varepsilon }^{'} $ ); (b) Imaginary part ($ \varepsilon ^{''}$ ); (c) Tangent to the dielectric loss angle (tan$ {\delta }_{\varepsilon} $ )
图 9 不同质量比例ZnO@RGO 复合材料的衰减常数(a)和阻抗匹配 (b); 试样3∶1的3D反射损耗图谱(c)和四分之一波长模型(d)
Figure 9. (a) Attenuation constant of ZnO@RGO composites with different mass ratios; (b) Impedance matching; erent mass ratios; 3D Reflection loss (c) and model of a 1/4 wavelength (d) of the samples with a filling proportion of 3∶1
图 10 不同质量比例ZnO@RGO 复合材料的cole-cole曲线
Figure 10. Cole-cole curve of ZnO@RGO composites with different mass ratios ((a) 2∶1; (b) 3∶1; (c) 4∶1; (d) 5∶1)
表 1 近期文献报道的RGO基复合材料的吸波性能
Table 1. Microwave absorbing properties of RGO based composites in recent publications
Absorber Loading/wt% RL/dB Bandwidth/GHz Thickness/mm References Cocoon-like RGO 7 −29.05 5.27 2.00 [30] CeO2−RGO 50 −45.90 4.5 2.00 [31] RGO/MWCNTs/ZnFe2O4 50 −23.80 2.60 1.50 [32] MoS2/RGO 60 −67.10 5.92 1.95 [33] RGO/Ni 10 −39.03 4.30 2.00 [34] ZnO/RGO 75 −44.50 7.44 3.00 This study Notes: MWCNTs—Multiwalled carbon nanotube; RGO—Reduced graphene oxide. 
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