Preparation and properties of graphene-supported copper reinforced copper matrix bulk composites
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摘要: 石墨烯具有独特的二维结构及性能已成为金属基复合材料制备过程中理想的增强相备选材料之一。而铜因具有良好的导热性、导电性和化学稳定性已被广泛应用到电子产品中，但其存在机械强度低、硬度低等缺点成为其应用亟需解决的瓶颈问题。目前，将石墨烯和铜基材料进行结合，虽然在一定程度上可以改善铜基材料的的综合性能。但由于石墨烯易产生团聚，石墨烯与铜之间的润湿性差，使其两者难以形成良好的界面结合，进而导致复合材料的性能变差。因此，为了解决上述问题，本文通过化学还原法在石墨烯上负载铜粒子对石墨烯进行改性处理，成功制备了石墨烯负载铜复合粉体(Cu-rGO)，并将其作为增强相，与纳米铜粉混合，运用放电等离子烧结(SPS)工艺制备了石墨烯负载铜增强铜基块体复合材料(Cu-rGO/Cu)，研究Cu-rGO复合粉体含量对铜基体组织和性能的影响。研究发现，在50 mg氧化石墨烯(GO)和200 mg硫酸铜(CuSO4·5H2O)时，获得Cu-rGO复合粉体中还原氧化石墨烯较薄且分布均匀。同时结合TEM结构分析发现铜基体与增强相接触界面紧密，且增强相的引入可以有效地细化块体复合材料的晶粒。另外，随着增强相含量的递增，硬度呈现先增加后减小，尤其在含量为2wt%时，硬度提高17.6%。但其导电率和致密度呈现出下降趋势，可能是还原过程中，氧化石墨烯中含氧官能团没有彻底还原，同时也有可能是石墨烯因有缺陷的产生和团聚现象造成的。Abstract: Graphene has a unique two-dimensional structure and properties, which has become one of the ideal reinforcement phase candidates in the preparation of metal matrix composites. Copper has been widely used in electronic products because of its good thermal conductivity, electrical conductivity and chemical stability. But its shortcomings, such as low mechanical strength and low hardness have become a bottleneck problem that need to be solved urgently. At present, the combination of graphene and copper can improve the comprehensive properties of copper matrix materials to a certain extent. However, because graphene is easy to agglomerate and the wettability between graphene and copper is poor, it is difficult to form a good interface between graphene and copper, which leads to the deterioration of the properties of the composites. Therefore, in order to solve the above problem, by chemical reduction method, graphene was modified by reinforcing copper particles on graphene. Finally, the graphene-supported copper composite powder (Cu-rGO) was successfully prepared. Then it was selected the reinforcement phase and mixed with nano-copper powder, and the graphene-supported copper reinforced Cu matrix bulk composite materials (Cu-rGO/Cu) was prepared by the spark plasma sintering (SPS). The effect of the graphene-supported copper composite powder content on the microstructure and properties of copper matrix was studied. The results show that the reduced graphene oxide in the obtained graphene-supported copper composite powder is relatively thin and uniformly distributed with the mass of GO about 50 mg and CuSO4·5H2O about 200 mg. Meanwhile, combined with the TEM structure analysis, it is observed that the contact interface between the copper matrix and the reinforcing phase is close, and the introduction of the reinforcing phase can effectively refine the crystal grains of the bulk composite material. In addition, with the increase of the content of reinforced phase, the hardness first increases and then decreases. Especially, when the content is 2wt%, the hardness increases by 17.6%. However, its conductivity and density show a downward trend, which is due to that the oxygen-containing functional groups in the graphene oxide are not completely reduced during the reduction process, and it may be due to the occurrence of defects and agglomeration of the graphene.
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图 1 石墨烯负载铜(Cu-rGO)复合粉体制备工艺过程图
Figure 1. Process diagram of preparation of graphene-supported copper (Cu-rGO) composite powder
rGO—Reduced graphene oxide
图 2 石墨烯负载铜增强铜基(Cu-rGO/Cu)块体复合材料制备过程及工艺图
Figure 2. Preparation process and process diagram of the graphene-supported copper reinforced Cu matrix composite materials (Cu-rGO/Cu)
图 5 Cu-rGO复合粉体XPS图谱：(a) 全谱；Cu2p (b)、O1s (c)、C1s (d) 的分峰拟合图
Figure 5. XPS patterns of graphene-supported copper composite powder: (a) Full spectrum; Cu2p (b), O1s (c), C1s (d) peak fit
图 6 Cu-rGO复合粉体SEM图像 (a)、粒径统计图 (b) 及能谱图 (c)
Figure 6. SEM image (a), particle size distribution statistic (b) and energy spectrum (c) of the graphene-supported copper composite powders
图 7 含量2wt%的Cu-rGO复合粉体与纳米铜粉混合后混合粉体SEM图像 (a) 及粒径统计图 (b)
Figure 7. Cu-rGO composite powder containing 2wt% mixed with nano-copper powder SEM image (a) and particle size distribution statistics (b)
图 8 不同增强相Cu-rGO含量的铜基块体复合材料XRD图谱
Figure 8. XRD patterns of Cu matrix bulk composite materials with different the reinforcing phase Cu-rGO contents
图 9 纯铜和添加不同增强相含量铜基块体复合材料金相图像：(a) 纯铜；Cu-rGO含量2wt% (b)、2.5wt% (c)、3wt% (d)、3.5wt% (e)、4wt% (f)、5wt% (g) 的Cu-rGO/Cu块体复合材料
Figure 9. Metallographic images of pure copper and Cu matrix bulk composite materials with different the reinforcing phase contents: (a) Pure copper; Cu-rGO/Cu bulk composites with Cu-rGO containing 2wt% (b), 2.5wt% (c), 3wt% (d), 3.5wt% (e), 4wt% (f), 5wt% (g)
图 10 Cu-rGO/Cu块体复合材料SEM图像(a)、能谱图(b)和拉曼图谱(c)
Figure 10. SEM images (a), energy spectrum (b) and Raman spectrum (c) of the graphene-supported copper reinforced Cu-rGO/Cu bulk composite
图 11 Cu-rGO含量2wt%的Cu-rGO/Cu块体复合材料TEM图像：(a) 微区全貌图；(b) 图11(a)中大方框放大图；(c) 图11(b)中方框区高分辨图；((d)、(e)) 图11(c)中选区高分辨图；((f)、(g)) 选区电子衍射图；((a1)、(a2))是图11(a)中小方框的EDS-mapping图
Figure 11. TEM images of Cu-rGO/Cu bulk composite materials with Cu-rGO content 2wt%: (a) Microgravity map; (b) Big box enlargement in Fig. 11(a); (c) High-resolution figure of the box in Fig. 11(b); ((d), (e)) High-resolution map of the constituency in Fig. 11(c); ((f), (g)) Electron diffraction map of the selection; ((a1), (a2)) EDS-mapping diagram of the small box in Fig. 11(a)
图 12 不同增强相Cu-rGO含量的Cu-rGO/Cu 块体复合材料的致密度
Figure 12. Density of Cu-rGO/Cu bulk composite with different reinforcing phase Cu-rGO contents
图 13 不同增强相Cu-rGO含量的Cu-rGO/Cu块体复合材料的导电率
Figure 13. Conductivity of Cu-rGO/Cu bulk composite with different reinforcing phase Cu-rGO contents
图 14 不同增强相Cu-rGO含量的Cu-rGO/Cu块体复合材料的硬度
Figure 14. Hardness of Cu-rGO/Cu bulk composite with different reinforcing phase Cu-rGO contents
表 1 不同增强相Cu-rGO含量的铜基块体复合材料Cu(111)晶面测试或计算数据
Table 1. Cu(111) crystal surface test or calculated data of Cu-based bulk composites with different Cu-rGO contents in reinforcement phase
Cu-rGO content/
wt%d/nm 2θ/(°) B1/2/rad D/nm 0.0 0.210 43.2 3.92×10−3 38 2.0 0.209 43.3 4.01×10−3 37 2.5 0.209 43.3 3.92×10−3 38 3.0 0.210 43.2 3.91×10−3 38 3.5 0.207 43.7 4.30×10−3 34 4.0 0.208 43.4 4.23×10−3 35 5.0 0.210 43.2 3.95×10−3 37 Notes: d—Interplanar spacing; 2θ—Diffraction angle; B1/2—Half-height and width; D—Size of the grain. 
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表 2 Cu-rGO/Cu 块体复合材料能谱分析结果
Table 2. Energy spectrum analysis of Cu-rGO/Cu bulk composite materials
Element Mass fraction/wt% Atom fraction/at% C 24.06 62.63 Cu 75.94 37.37 Total 100.00 100.00
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