Study on preparation and absorption properties of ZnO-graphene-TPU/PLA composites
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摘要: 开发轻质、高效的吸波复合材料是解决电磁污染问题的重要途径之一。本文采用两步法制备ZnO-石墨烯-热塑性聚氨酯弹性体橡胶 (TPU)/聚乳酸 (PLA)吸波复合材料，通过XRD、拉曼光谱、SEM和矢量网络分析仪分别对复合材料的物相结构、微观形貌和电磁特性进行表征，并研究不同ZnO/石墨烯吸波剂组合对复合材料吸波性能的影响，揭示ZnO和石墨烯协同吸波机制。研究结果表明：随着ZnO含量的增加，吸波效果先增强后减弱。适量的ZnO分散在基体中，使复合材料的缺陷程度增加，这丰富了异质界面，增强了界面极化和偶极极化，进而改善了复合材料的吸波性能。当ZnO添加量仅为2wt%时吸波效果最佳，在5.6 mm厚度下，其最小反射损耗为−49.2 dB，有效吸收带宽为2.0 GHz。优异的吸波效果源于良好的阻抗匹配和界面极化损耗、偶极极化损耗、电导损耗之间的协同作用。此外相比化学法制备的吸波材料，ZnO-石墨烯-TPU/PLA复合材料的制备过程简单环保，吸波剂组分可调，轻质高效可规模化生产，有望用于复杂吸波结构制造。Abstract: Developing light-weight and high-efficiency absorbing composite materials is one of the important ways to solve the electromagnetic pollution. In this paper, ZnO-graphene (GR)/polylactic acid (PLA)/thermoplastic polyurethane (TPU) composite materials were prepared by a two-step method and the phase structure, micromorphology and electromagnetic characteristics of the composite were characterized by XRD, Raman spectroscopy, SEM and vector network analyzer. The effects of different combinations of ZnO/GR on the microwave absorbing properties of the composites were studied, and the synergistic mechanism was revealed. The results show that with the increase of the content of ZnO, the microwave absorbing effect increases at first and then decreases. Proper amount of ZnO dispersed in the matrix increases the defects of the composites enriching the heterogeneous interface, enhancing the interface polarization and dipolarization, and improving the microwave absorbing properties of the composites. When the content of ZnO is 2wt% , at 5.6 mm thickness, the minimum reflection loss is −49.2 dB and the effective absorption bandwidth is 2.0 GHz meaning the best absorption efficiency. The excellent absorbing effect is attributed to the good impedance matching and the synergy among the interface polarization loss, the dipolarization loss and the conductivity loss. In addition, the preparation process of ZnO-GR/PLA/TPU composite is simple and environment-friendly, and the component of absorbing agent can be adjusted which is expected to be used in the manufacturing of complex absorption structures.
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Keywords:
- composites /
- graphene /
- ZnO /
- electromagnetic wave absorbing properties /
- impedance matching
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图 2 (a) ZnO-GR-TPU/PLA复合线材；(b) 同轴环
Figure 2. (a) ZnO-GR-TPU/PLA composite filaments; (b) Coaxial rings
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图 3 ZnO-GR-TPU/PLA复合材料XRD图谱(a)和拉曼光谱(b)
Figure 3. XRD patterns (a) and Raman spectra (b) of the ZnO-GR-TPU/PLA composites
ID/IG—Intensity ratio of peak D to peak G
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图 4 ZnO-GR-TPU/PLA复合粉末的SEM图像：(a) ZN0；(b) ZN2；(c) ZN4；(d) ZN6；(e) ZN8
Figure 4. SEM images of ZnO-GR-TPU/PLA composite powder: (a) ZN0; (b) ZN2; (c) ZN4; (d) ZN6; (e) ZN8
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图 5 ZnO-GR-TPU/PLA复合材料的电磁参数：(a) 复介电常数实部ε'；(b) 复介电常数虚部ε''；(c) 介电损耗角正切tanδe
Figure 5. Electromagnetic parameters of ZnO-GR-TPU/PLA composites: (a) Real part of complex permittivity ε'; (b) Imaginary part of complex permittivity ε''; (c) Dielectric loss tangent tanδe
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图 6 ZnO-GR-TPU/PLA复合材料的Colo-Colo曲线：(a) ZN0；(b) ZN2；(c) ZN4；(d) ZN6；(e) ZN8
Figure 6. Colo-Colo curves of ZnO-GR-TPU/PLA composites: (a) ZN0; (b) ZN2; (c) ZN4; (d) ZN6; (e) ZN8
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图 7 ZnO-GR-TPU/PLA复合材料的衰减常数及阻抗匹配
Figure 7. Attenuation constant and impedance matching of ZnO-GR-TPU/PLA composites
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8 ZnO-GR-TPU/PLA复合材料的反射损耗图与3D映射图：((a), (b)) ZN0；((c), (d)) ZN2；((e), (f)) ZN4；((g), (h)) ZN6；((i), (j)) ZN8
8. Reflection loss diagram and 3D mapping diagram of ZnO-GR-TPU/PLA composite materials: ((a), (b)) ZN0; ((c), (d)) ZN2; ((e), (f)) ZN4; ((g), (h)) ZN6; ((i), (j)) ZN8
RLmin—Minimal reflection loss; d—Depth; EAB—Effectively absorb bandwidth
表 1 ZnO-GR-热塑性聚氨酯弹性体橡胶(TPU)/聚乳酸(PLA)复合材料成分
Table 1 Ingredients of ZnO-GR-thermoplasticpolyurethane (TPU)/polylactic acid (PLA) composites
Sample Mass fraction/wt% ZnO GR PLA TPU ZN0 0 5 85.5 9.5 ZN2 2 5 83.7 9.3 ZN4 4 5 81.9 9.1 ZN6 6 5 80.1 8.9 ZN8 8 5 78.3 8.7 
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表 2 近期文献报道ZnO/石墨烯复合材料的吸波性能
Table 2 Recent literature reports on the absorption properties of ZnO/graphene composites
Materials Loading/wt% Matrix RLmin (Thickness) Ref. Starlike ZnO/RGO 75 Paraffin −77.50 dB (4.5 mm) [9] ZnO@RGO 75 Paraffin −44.50 dB (4.5 mm) [15] RGO@NiO/ZnO 70 PS −42.50 dB (2.15 mm) [41] GR/ZnO hollow sphere 50 Paraffin −45.05 dB (2.2 mm) [42] 3D-ZFO/GNs 50 Paraffin −34.56 dB (1.3 mm) [43] ZnO/ZnO nanocrystal@RGO foam 25 Paraffin −38.00 dB (3.2 mm) [26] RGO/ZnO-mrs 15 Paraffin −38.50 dB (2.0 mm) [44] MF/ZnO@Reduced graphene oxide 5 Paraffin −63.20 dB (4.1 mm) [33] 5wt%GR+2wt%ZnO 7 PLA −49.20 dB (5.6 mm) This work Notes: RGO—Reduced graphene oxide; ZFO—ZnFe2O4; GNs—Graphene nanosheets; mrs—Microrods; MF—Carbonized melamine foame; PS—Polystyrene.
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其他类型引用(4)
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石墨烯因其强介电损耗和高电导率等特点，可作为高性能电磁波衰减材料。为了解决单一石墨烯材料的界面阻抗失配问题，常引入其他材料作为增强其吸波性能。目前，大多数研究将磁性材料与石墨烯结合起来，以获得优异的微波吸收性能，但磁性材料的加入会大大增加吸波材料的密度，并且传统的化学制备法存在工序繁琐、产量低、难以成型等问题。
为了获得较低密度的吸波复合材料，本文在石墨烯的基础上添加了介电材料ZnO，采用球磨和熔融挤出两步法制备了可用于FDM3D打印的ZnO-石墨烯/PLA/TPU吸波复合材料。通过调节ZnO(2%~8%)含量来改善阻抗匹配进而提高吸波性能。ZnO的加入促进了复合材料的界面极化和偶极极化，实现了吸波材料低密度和强吸收。研究结果表明，当石墨烯含量为5wt%，ZnO添加量仅为2wt%时吸波效果最佳，在5.6 mm厚度下，其最小反射损耗为-49.2 dB，有效吸收带宽为2.0 GHz。同时得益于FDM3D打印的成型方法，本文所制备的复合吸波线材可打印复杂的吸波结构及器件。
5wt%GR、2wt%ZnO时吸波复合材料的反射损耗图与3D映射图
ZnO-石墨烯/PLA/TPU吸波复合材料的衰减常数图
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