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石墨烯负载铜增强铜基块体复合材料制备及其性能

冯俊俊 张会 李亚鹏 段瑾瑜 刘禹 蒲卓林

冯俊俊, 张会, 李亚鹏, 等. 石墨烯负载铜增强铜基块体复合材料制备及其性能[J]. 复合材料学报, 2022, 40(0): 1-14
引用本文: 冯俊俊, 张会, 李亚鹏, 等. 石墨烯负载铜增强铜基块体复合材料制备及其性能[J]. 复合材料学报, 2022, 40(0): 1-14
Junjun FENG, Hui ZHANG, Yapeng LI, Jinyu DUAN, Yu LIU, Zhuolin PU. Preparation and properties of graphene-supported copper reinforced copper matrix bulk composites[J]. Acta Materiae Compositae Sinica.
Citation: Junjun FENG, Hui ZHANG, Yapeng LI, Jinyu DUAN, Yu LIU, Zhuolin PU. Preparation and properties of graphene-supported copper reinforced copper matrix bulk composites[J]. Acta Materiae Compositae Sinica.

石墨烯负载铜增强铜基块体复合材料制备及其性能

基金项目: 陕西省科技厅工业攻关项目资助(2019GY-184,2021GY-222)
详细信息
    通讯作者:

    张会,博士,硕士生导师,研究方向为材料成形工艺  E-mail: zhanghui_shaanxi@163.com

    李亚鹏,博士,硕士生导师,研究方向为复合材料制备 E-mail:liyp1984@126.com

  • 中图分类号: TB331;TG113.11

Preparation and properties of graphene-supported copper reinforced copper matrix bulk composites

  • 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、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,可能是因为还原过程中,氧化石墨烯中含氧官能团没有彻底还原,同时也有可能是因为石墨烯因有缺陷的产生和团聚现象造成的。

     

  • 图  1  石墨烯负载铜复合粉体(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

    图  2  Cu-rGO/Cu块体复合材料制备过程及工艺图

    Figure  2.  The preparation process and process diagram of the graphene-supported copper reinforced Cu matrix composite materials

    图  3  Cu-rGO复合粉体XRD图谱

    Figure  3.  XRD patterns of the graphene-supported copper composite powders samples

    图  4  GO的C1s的分峰拟合图

    Figure  4.  Fitting diagram of C1s peaks of GO

    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.  The graphene-supported copper composite powder XPS detection:(a) Full spectrum; (b) Cu2p (b), O1s(c), C1s(d) peak fit

    图  6  Cu-rGO复合粉体SEM照片、粒径统计图及能谱图

    Figure  6.  SEM images、particle size distribution statistics and energy spectrum of the graphene-supported copper composite powders

    图  7  2wt%Cu-rGO复合粉体与纳米铜粉混合后混合粉体SEM照片及粒径统计图

    Figure  7.  2wt% the graphene-supported copper composite powder mixed with nano-copper powder SEM image and particle size distribution statistics

    图  8  不同增强相含量铜基块体复合材料XRD图谱

    Figure  8.  XRD patterns of Cu matrix bulk composite materials with different the reinforcing phase contents samples

    图  9  纯铜和添加不同增强相含量铜基块体复合材料金相照片:(a)纯铜;(b)2wt%Cu-rGO/Cu块体复合材料;(c)2.5wt%Cu-rGO/Cu块体复合材料;(d)3wt%Cu-rGO/Cu块体复合材料;(e)3.5wt%Cu-rGO/Cu块体复合材料;(f)4wt%Cu-rGO/Cu块体复合材料;(g)5wt%Cu-rGO/Cu块体复合材料

    Figure  9.  Gold image of pure copper and Cu matrix bulk composite materials with different the reinforcing phase contents:(a) pure copper,(b)2wt%Cu-rGO/Cu bulk composites;(c)2.5wt% Cu-rGO/Cu bulk composites;(d)3wt% Cu-rGO/Cu bulk composites;(e)3.5wt% Cu-rGO/Cu bulk composites;(f)4wt%Cu-rGO/Cu bulk composites;(g)5wt%Cu-rGO/Cu bulk composites

    图  10  (a)Cu-rGO/Cu块体复合材料SEM图;(b)Cu-rGO/Cu块体复合材料能谱图;(c)Cu-rGO/Cu块体复合材料拉曼检测图谱

    Figure  10.  (a)SEM of the graphene-supported copper reinforced Cu matrix bulk composite materials;(b)The energy spectrum of the graphene-supported copper reinforced Cu matrix composite materials;(c)Raman detection of the graphene-supported copper reinforced Cu matrix composite materials

    图  11  2wt% Cu-rGO/Cu块体复合材料TEM图:(a)微区全貌图;(b)图(a)中红色框放大图;(c)图(b)中红色框高分辨图;(d)~(e)图(c)中选区高分辨图;(f)~(g)选区电子衍射图;(a1)~(a2)是(a)中紫色框的EDS-mapping图

    Figure  11.  TEM diagram of 2wt% the graphene-supported copper reinforced Cu matrix bulk composite materials;(a) microgravity map; (b) the red box enlargement in figure (a); (c) The high-resolution figure of the red box in figure (b); (d) ~ (e) in the high-resolution map of the constituency in figure (c); (f) ~ (g) the electron diffraction map of the selection; (a1) ~ (a2) the EDS-mapping diagram of the purple box in (a)

    图  12  不同增强相含量铜基块体复合材料的致密度

    Figure  12.  The density of Cu matrix composite materials with different the reinforcing phase contents

    图  13  不同增强相含量铜基块体复合材料的导电率Fig.13 The conductivity of Cu matrix composite materials with different the reinforcing phase contents

    图  14  不同增强相含量铜基块体复合材料的硬度

    Figure  14.  The hardness of Cu matrix composite materials with different the reinforcing phase contents

    表  1  (111)晶面测试或计算数据

    Table  1.   (111) Crystal surface test or calculated data

    Composite sample/wt.%0.02.02.53.03.54.05.0
    d/nm0.2100.2090.2090.2100.2070.2080.210
    2θ/(°)43.243.343.343.243.743.443.2
    B1/2/(rad×103)3.924.013.923.914.304.233.95
    D/nm38373838343537
    Notes: d is interpianar spacing; 2θ is diffraction angle; B1/2 is half-height and width; D is the size of the grain.
    下载: 导出CSV

    表  2  铜基块体复合材料能谱分析结果

    Table  2.   The energy spectrum analysis of Cu matrix bulk composite materials

    ElementWeight percentage/wt.%Atompercentage/at.%
    Ck24.0662.63
    Cuk75.9437.37
    Total100.00100.00
    下载: 导出CSV
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  • 收稿日期:  2021-11-30
  • 录用日期:  2022-02-28
  • 修回日期:  2022-01-25
  • 网络出版日期:  2022-03-19

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