碳纳米材料增强铜基复合材料性能的研究进展

基金项目

国家自然科学基金资助项目(52304382); 江西省教育厅青年基金资助项目(GJJ2200878); 云南省新材料制备与加工重点实验室创新课题(2024KF08)资助

中图分类号:

TB333

文献标识码:

A

作者简介

陈源森(2001—),男,贵州安顺人,硕士研究生,研究方向:铜基复合材料,E-mail:chenyuans813@163.com

通信作者

赵文敏,副教授,E-mail:zhaowenmin@jxust.edu.cn

流转信息

收稿日期 : 2025-04-21

修订日期 : 2026-03-17

引文格式

陈源森,李一坤,沈龙飞,赵文敏,魏民国,徐俊华. 碳纳米材料增强铜基复合材料性能的研究进展[J]. 铜业工程,2026(2):43-54.

Recent Research Progress on Properties of Carbon Nanomaterials Enhanced Copper-based Composites

Citations

CHEN Yuansen,LI Yikun,SHEN Longfei,ZHAO Wenmin,WEI Minguo,XU Junhua. Recent research progress on properties of carbon nanomaterials enhanced copper-based composites [J]. Copper Engineering,2026(2):43-54.

铜业工程    第2期    43-54
doi10.3969/j.issn.1009-3842.2026.02.005
材料制备与加工工程(Material Preparation and Process Engineering)

碳纳米材料增强铜基复合材料性能的研究进展

  • 陈源森 1
  • 李一坤 1
  • 沈龙飞 1
  • 赵文敏 1,2
  • 魏民国 1
  • 徐俊华 1
1.江西理工大学 材料科学与工程学院江西 赣州 341000
2.昆明理工大学云南省新材料制备与加工重点实验室云南 昆明 650093

作者简介

陈源森(2001—),男,贵州安顺人,硕士研究生,研究方向:铜基复合材料,E-mail:chenyuans813@163.com

通信作者

赵文敏,副教授,E-mail:zhaowenmin@jxust.edu.cn

基金项目

国家自然科学基金资助项目(52304382); 江西省教育厅青年基金资助项目(GJJ2200878); 云南省新材料制备与加工重点实验室创新课题(2024KF08)资助

中图分类号:

TB333

文献标识码:

A

流转信息

收稿日期 : 2025-04-21     修订日期 : 2026-03-17     

引文格式

陈源森,李一坤,沈龙飞,赵文敏,魏民国,徐俊华. 碳纳米材料增强铜基复合材料性能的研究进展[J]. 铜业工程,2026(2):43-54.

摘要

目前,铜(Cu)基复合材料已广泛应用于各个领域。随着科技的进步发展,高性能材料的需求不断提升,高强高导Cu基复合材料已成为当前的研究重点。碳纳米材料(carbon nano-materials,CNMs),因其本身的优异性能可作为Cu基复合材料的增强相被广泛研究。本文主要分析了三类具有代表性的CNMs/Cu基复合材料进行深入研究分析:碳纳米管(carbon nanotube,CNT)/Cu、石墨烯(graphene,GR)/Cu和碳化聚合物点(carbonized polymer dot,CPD)/Cu。CNT、GR作为增强相时普遍存在易团聚、与Cu界面结合差等问题,从而导致复合材料性能下降;而CPD在高温下结构不稳定,且较难表征。针对此类材料的研究难点和痛点,从材料本身的结构、性能出发,分别对其异同性进行分析探讨,研究以其作为增强相增强铜基复合材料的制备方法,以及材料的力学性能、电学性能和强化机制,为之后以CMNs增强铜基复合材料的制备及性能研究提供思路,以突破现有的技术瓶颈,最终实现铜基复合材料高强高导的可控制备。

关键词

铜基复合材料;碳纳米管;石墨烯;碳化聚合物点;力学性能;电学性能;

Recent Research Progress on Properties of Carbon Nanomaterials Enhanced Copper-based Composites

  • CHEN Yuansen 1
  • LI Yikun 1
  • SHEN Longfei 1
  • ZHAO Wenmin 1,2
  • WEI Minguo 1
  • XU Junhua 1
1.School of Materials Science and EngineeringJiangxi University of Science and TechnologyGanzhou 341000China
2.Engineering Center of Advanced Materials Forming & Manufacture of Yunnan ProvinceKunming University of Science and TechnologyKunming 650093China

Citations

CHEN Yuansen,LI Yikun,SHEN Longfei,ZHAO Wenmin,WEI Minguo,XU Junhua. Recent research progress on properties of carbon nanomaterials enhanced copper-based composites [J]. Copper Engineering,2026(2):43-54.

Abstract

Currently, copper-based composites have been widely applied in various fields. With advancement of science and technology and continuous improvement of material requirements, preparation of copper-based composites with high strength and high conductivity has become a current research focus. Carbon nanomaterials (CNMs), due to their excellent properties, have been widely studied by researchers as reinforcing phases in copper-based composites. This paper demonstranted an in-depth study and analysis of three representative CNMs/Cu composites: carbon nanotube (CNT)/Cu, graphene (GR)/Cu, and carbonized polymer dot (CPD)/Cu. When these three CNMs are used as reinforcing phases, they generally have problems such as prone to agglomeration and poor interface bonding with Cu, which leads to a decline in the performance of the composites. Focusing on research difficulties and disadvantages of such materials, similarities and differences in performance of each composite were analyzed and discussed based on intrinsic structural characteristics of the materials. Preparation methods, mechanical properties, electrical properties, and strengthening mechanisms of copper-based composites reinforced by introduced phases were studied. This provided inspirational ideas on preparation and performance research of copper-based composites reinforced by CNMs, breaking through the existing technical bottlenecks and realizing controllable preparation of copper-based composites with high strength and high conductivity.

Keywords

copper-based composite;carbon nanotube;graphene;carbonized polymer dot;mechanical property;electrical property;



在现代工业中,材料科学的进步是推动各领域创新发展的关键力量。纯铜(Cu)具有优良的导电性能、耐磨蚀性能及工艺性能  李强,王茜. 高强高导铜合金的强化技术研究与展望[J]. 热加工工艺,2009,38(16):8-11.
1
,然而,高磨损率、低硬度限制了Cu及其合金材料在高应力、高磨损等领域的应用  LI Y L,WANG Q,WANG S J. A review on enhancement of mechanical and tribological properties of polymer composites reinforced by carbon nanotubes and graphene sheet:Molecular dynamics simulations[J]. Composites Part B:Engineering,2019,160:348-361.
 GUIDERDONI C,ESTOURNÈS C,PEIGNEY A,et al. The preparation of double-walled carbon nanotube/Cu composites by spark plasma sintering,and their hardness and friction properties[J]. Carbon,2011,49(13):4535-4543.
 孙海影,高文嫱,陈华,等. 铜基刹车摩擦片的制备及性能研究[J]. 粉末冶金工业,2023,33(4):49-53.
2-4
。随着科技的飞速发展,各行业对材料性能的要求不断提升,传统的单一材料往往难以满足如今复杂多变的应用场景需求。因此,综合性能优异且应用场景更加广阔的复合材料逐渐成为科学研究的焦点。Cu基复合材料将Cu良好的导电性、导热性与其他增强相的优异性能(如高强度、高硬度、耐磨性等)相结合,实现性能的优势互补,为复杂场景的高性能需求提供了有效途径。

碳作为自然界中储量最丰富且最早被发现的元素之一,长期以来广泛应用于各个领域。随着科学研究的不断深入,碳的新型结构相继被发现并得以成功合成,例如碳纳米管(carbon nanotube,CNT)、石墨烯(graphene,GR)以及碳化聚合物点(carbonized polymer dot,CPD)等。碳纳米材料(carbon nano-materials,CNMs) 因优异的物理和化学性能可作为Cu基复合材料的理想增强体,有望提升Cu复合材料的力学、耐摩擦、抗腐蚀、耐高温氧化和导电、导热性能,可应用于服役条件苛刻的领域  陆瑶瑶. 分级结构WO3-TiO2-CNFs纳米复合材料的制备及其光催化性能研究[J]. 江西化工,2024,40(2):42-48.
 赵炜康,朱学宏,夏莉红,等.粉末法制备碳纳米管增强铜基复合材料及性能研究[J].矿冶工程,2018,38(3):132-135,139.
 SHU S C,LI Y H,YAN Z C,et al. Graphene-reinforced copper matrix composites as electrical contacts[J]. ACS Applied Nano Materials,2024,7(8):8685-8691.
 李滋阳,王思佳,邓文举. 陶瓷颗粒增强金属基复合材料研究进展[J]. 轻工科技,2021,37(4):41-44.
5-8

不同形态和结构的CNMs具有不同特性,因而在增强复合材料时所表现出的强化效果也存在显著差异。本文将CNMs分为CNT,GR和CPD三类进行分析和探讨,并以此为基础介绍不同CNMs/Cu基复合材料在合成、力学和电导率方面的最新研究进展,为设计具有高强度、高电导率和高伸长率的CNMs/Cu基复合材料提供新的思路。

1     Cu基复合材料与CNMs

1.1     Cu基复合材料

Cu基复合材料是以Cu或Cu合金作为基体,通过引入颗粒、纤维或晶须等一种或多种增强相,并采用特定制备工艺复合而成的功能性材料。这种复合材料不仅继承了Cu基体优异的导电性、导热性、耐腐蚀性以及加工性能,还通过增强相的加入,显著提升了材料的强度、硬度、耐磨性及高温性能,从而成为功能复合材料领域的重要组成部分。近几年,Cu基复合材料主要应用于电力传输、新能源设备、航空航天、轨道交通等关键领域。但Cu基复合材料由于制备工艺复杂、成本高、增强相和基体界面融合性差、易团聚,无法应用于大规模的工业生产中  王一同,邹存磊,李长鸣,等. 高性能铜基复合材料研究进展[J]. 复合材料学报,2023,40(10):5542-5553.
9
,所以选择合适的增强相解决这些难题成了目前研究人员的首要目标。

1.2     CNMs

CNMs独特的原子结构与纳米尺度下的特殊效应相互作用,赋予这些材料诸多卓越的性能,从而成为材料科学研究的焦点  CHOUDHARY N,HWANG S,CHOI W. Carbon nanomaterials:a review[M]. Handbook of nanomaterials properties. Berlin,Heidelberg:Springer,2014:709-769.
10
。通过引入第二相,能够在基体与增强相之间产生协同效应,实现“1+1>2”的效果,并且具有较高的设计自由度,这激发了研究人员不断探索的热情。而CNMs的分散问题和界面问题一直是研究重点和难点,研究人员已尝试采用如表面涂层、基体合金化、喷雾热解等多种方法加以解决。

本文将目前常用于改善Cu基复合材料的CNMs分为CNT,GR和CPD(如图1所示),并逐一分析这三种材料在增强Cu基复合材料性能方面存在的问题以及解决的方法。

图1     碳纳米材料结构示意图
Fig. 1     Schematic diagram of carbon nanomaterials structure  RATIVA-PARADA W,NILUFAR S. Nanocarbon-infused metal matrix composites:a review[J]. JOM,2023,75(9):4009-4023.
 OZYURT D,AL KOBAISI M,HOCKING R K,et al. Properties,synthesis,and applications of carbon dots:a review[J]. Carbon Trends,2023,12:100276.
11-12

1.2.1     碳纳米管(CNT)

自1991年Iijima发现碳纳米管(CNT)以来,CNT就因其独特的性能应用于各种环境  IIJIMA S. Helical microtubules of graphitic carbon[J]. Nature,1991,354(6348):56-58.
13
。CNT由C原子sp2杂化形成,根据石墨片的层数不同,可将其分为单壁CNT (SWCNTs)和多壁CNT (MWCNTs)  KASEEM M,HAMAD K,KO Y G. Fabrication and materials properties of polystyrene/carbon nanotube (PS/CNT) composites:a review[J]. European Polymer Journal,2016,79:36-62.
14
。目前制备CNT的方法有电弧放电、激光烧蚀和化学气相沉积等。其中,化学气相沉积是获得CNT被广泛使用的方法之一。该工艺通常涉及金属催化剂与碳氢化合物在高温下的反应。近年来,碳纳米管(CNT)具有超高弹性模量(1.34 TPa)、高强度(可达200 GPa)、独特电子性能(电容约109 A/cm2)、高导热系数[6600 W/(m·K)],以及高比表面积和低密度等优点,是金属基复合材料增强增韧和实现功能化的理想材料  LI Z Y,LIU H R,LI Y. Study on mechanical properties of carbon nanotube reinforced composites[J]. Polymers,2023,15(16):3362.
 JAYATHILAKA W A D M,CHINNAPPAN A,RAMAKRISHNA S. A review of properties influencing the conductivity of CNT/Cu composites and their applications in wearable/flexible electronics[J]. Journal of Materials Chemistry C,2017,5(36):9209-9237.
15-16

1.2.2     石墨烯(GR)

GR是由单层碳原子紧密堆积形成的二维蜂窝状结构  NOVOSELOV K S,GEIM A K,MOROZOV S V,et al. Electric field effect in atomically thin carbon films[J]. Science,2004,306(5696):666-669.
17
,在物理、化学和机械性能等方面都有良好的性能表现。GR有着极高的柔韧性,能够进行大幅度的弯曲和变形,并且载流子迁移率比硅高100倍[2×105 cm2/(V·s)]。GR导热性能极佳,远超Cu和金刚石,热导率高达5300 W/(m·K),强度高(110 GPa),比表面积大(2630 m2/g)  HUANG X,QI X Y,BOEY F,et al. Graphene-based composites[J]. Chemical Society Reviews,2012,41(2):666-686.
 GEIM A K. Graphene:status and prospects[J]. Science,2009,324(5934):1530-1534.
 程莹莹. 碳纳米材料及其应用研究进展[J]. 现代塑料加工应用,2024,36(4):44-47.
18-20
。这些优异性能使得GR在近年来的研究和应用中受到极大关注。GR的合成方法主要有机械剥离法、化学气相沉积法(CVD)、氧化还原法、电化学法等。

1.2.3     碳化聚合物点(CPD)

碳化聚合物点(CPD)是CNMs系列的一种新型材料,具有独特聚合物/碳杂化结构。与传统碳点(如石墨烯量子点GQD、碳量子点CQD和碳纳米点CND等)不同,CPD不仅有传统碳点(CD)的光学特性,还具有聚合物的结构特性和功能特性  李若晨. 荧光碳量子点及其明胶复合材料的制备及应用[D]. 保定:河北大学,2023.
21
。CPD的合成主要采用自下而上的方法,通常包括溶剂热法、微波辅助合成法和水热法等  LEE K,PARK E,LEE H A,et al. Phenolic condensation and facilitation of fluorescent carbon dot formation:a mechanism study[J]. Nanoscale,2017,9(43):16596-16601.
22
。它的基体和表面存在丰富的环氧、羟基和羧基,有利于电子转移和其在极性溶剂中均匀分散  XIA C L,ZHU S J,FENG T L,et al. Evolution and synthesis of carbon dots:from carbon dots to carbonized polymer dots[J]. Advanced Science,2019,6(23):1901316.
 LI S,LI L,TU H Y,et al. The development of carbon dots:From the perspective of materials chemistry[J]. Materials Today,2021,51:188-207.
23-24

2     CNMs/Cu复合材料

2.1     CNT/Cu复合材料

CNT具有优异的力学、电学和热学性能,但制备CNT/Cu复合材料过程中仍然面临两个主要挑战:一是由于CNT存在强大的范德华力,并且具有较高比表面积,所以在复合材料加工过程中往往发生团聚,导致其表面能降低从而难以在Cu基体中分散均匀; 二是CNT与Cu基体的润湿性较差,难以形成牢固的界面结合  TJONG S C. Recent progress in the development and properties of novel metal matrix nanocomposites reinforced with carbon nanotubes and graphene nanosheets[J]. Materials Science and Engineering:R:Reports,2013,74(10):281-350.
25

近年来,研究人员通过表面处理、杂化结构设计和制备工艺优化等,改善CNT在Cu基体中的分散性以及与Cu的界面结合,使CNT/Cu复合材料的力学性能和电学性能均得到显著提升。

1)针对分散性问题。Yang等  YANG P,YOU X,YI J H,et al. Simultaneous achievement of high strength,excellent ductility,and good electrical conductivity in carbon nanotube/copper composites[J]. Journal of Alloys and Compounds,2018,752:431-439.
26
采用湿法混合球磨加放电等离子烧结(SPS)的方法,使得CNT能够均匀分散在Cu基体中,如图2所示。制备的CNT/Cu复合材料抗拉强度达280 MPa、延伸率达41.7%、导电率达91.6%IACS。Zhang等  ZHANG W W,YOU X,FANG D,et al. Influence of acid-treated time of carbon nanotubes on mechanical property in carbon nanotubes reinforced copper matrix composites[J]. Diamond and Related Materials,2020,109:108069.
27
在形成CNT/Cu复合材料之前,采用浓硝酸和硫酸的混合物氧化CNT,去除其表面存在的无定形碳和金属杂质,提高CNT与Cu基体之间的黏附力。此过程使CNT更具反应活性,改善了CNT与Cu基体的结合,使得CNT得以均匀分散。实验结果显示,CNT/Cu复合材料的拉伸强度比纯Cu提高了46%。Shuai等  SHUAI J,XIONG L Q,ZHU L,et al. Enhanced strength and excellent transport properties of a superaligned carbon nanotubes reinforced copper matrix laminar composite[J]. Composites Part A:Applied Science and Manufacturing,2016,88:148-155.
28
设计一种高度有序、定向排列的连续CNT薄膜(SACNT)用来增强Cu基复合材料,结果改善了CNT的分散性并提高了导电性能,制备的Cu/SACNT复合材料与相同实验条件下的纯Cu相比,机械强度和载流量均得到显著提高。当SACNTs的体积分数为1.04%时,复合材料的拉伸强度、屈服强度和载流量可达到最大值,分别提高了48.5%,94.9%和32%。康建立等  康建立,李家俊,赵乃勤. 碳纳米管增强铜基复合材料的制备[A]. 中国机械工程学会热处理学会.第九次全国热处理大会论文集(一). 天津:天津大学材料科学与工程学院,2007:370-373.
29
采用原位合成法制备CNT/Cu复合材料,硬度提高了38%,导电率只降低了1.74%。其中催化剂的加入,能有效提高CNT的表面特性,有利于其在Cu基体中的分散,但在Cu表面生长CNT时,部分催化剂在高温下扩散到Cu基体中而降低活性  崔童,杜善豪,钱高祥,等. 原位合成颗粒增强铜基复合材料的研究进展[J]. 铜业工程,2024(2):131-138.
 张运娜,贾磊,周永欣,等. 粉末冶金制备碳纳米管增强铜基复合材料研究进展[J]. 中南大学学报(自然科学版),2024,55(8):3165-3179.
30-31
。为了解决这个问题,Zheng等  ZHENG R,LI S F,ZHANG L,et al. In-situ synthesis of high-quality carbon nanotubes on Cu powder by constructing an Al2O3 barrier layer[J]. Materials Letters,2023,350:134930.
32
在Cu粉表面预涂致密的Al2O3涂层,以促进CNT的原位生长,防止催化剂的扩散和失活,使得CNT的分散性进一步提高。

图2     (a)CNT/Cu复合材料工艺流程示意图; (b)CNT/Cu复合粉末SEM图; (c)三种CNT/Cu复合材料的导电率和相对密度; (d)三种CNT/Cu复合材料的应力-应变图
Fig. 2     (a) Schematic diagram of process flow for CNT/Cu composite materials; (b) SEM images of CNT/Cu composite powder; (c) Electrical conductivity and relative density of different CNT/Cu composites; (d) Stress-strain diagram of different CNT/Cu composites  YANG P,YOU X,YI J H,et al. Simultaneous achievement of high strength,excellent ductility,and good electrical conductivity in carbon nanotube/copper composites[J]. Journal of Alloys and Compounds,2018,752:431-439.
26

2)针对界面优化问题。Cai等  CAI X L,WANG Z Y,YANG C J,et al. Fabrication of CNTs reinforced copper composite powders by electrochemical co-deposition[J]. Integrated Ferroelectrics,2019,201(1):249-257.
33
采用电化学共沉积法改善界面结合。研究发现,在制备过程中CNT会分散在电镀液中,而Cu离子会沉积在CNT上,使得制备出的复合材料具有高CNT负载量,并且CNT和Cu基体之间形成良好的界面结合。Li等  LI L B,BAO R,YI J H,et al. Preparation of CNT/Cu nano composite powder with uniform dispersion and strong interface bonding by SP method[J]. Powder Technology,2018,325:107-112.
34
采用喷雾热解法(SP)制备CNT/Cu复合粉末,研究发现SP工艺不仅可以提高CNT的结构完整性和纯度,获得分散均匀的CNT,还可以促进CNT与Cu颗粒之间的界面结合。随后,李澜波等  李澜波. 喷雾热解法制备碳纳米管增强铜基复合材料及其烧结性能研究[D]. 昆明:昆明理工大学,2017.
35
采用SP法制备CNT/Cu复合材料,研究发现制备的复合材料力学性能比纯Cu好,其中质量分数为0.5%时性能最佳,抗拉强度、屈服强度分别为232 MPa和146 MPa,硬度最高为162HV。基体合金化是提高界面结合的又一重要途径,Feng等  FENG J Q,TAO J M,LIU Y C,et al. Optimization of the mechanical properties of CNTs/Cu composite by regulating the size of interfacial TiC[J]. Ceramics International,2022,48(18):26716-26724.
36
采用分子级共混法在CNT上沉积Cu,然后在CNT/Cu复合粉末中引入Ti粉末,通过热压烧结,获得了具有界面相TiC的CNTs/Cu复合材料,发现TiC@CNTs/Cu复合材料的屈服强度为324 MPa,比纯Cu提高了175.8%,抗拉强度为364 MPa,比纯Cu高了58.0%。研究人员对SWCNTs纳米晶铜复合模型进行研究时,发现引入Ni原子后,增强了CNT与Cu基体之间的界面键合,并减少了界面处的空位。结果表明,通过在CNT和具有纳米级Ni颗粒的Cu基体之间形成强界面,可以大大提高CNT/Cu复合材料的综合性能  ZHANG Y K,LIU Y C,ZHAO Q,et al. Molecular dynamics study of the interface fine structure and mechanical properties of Ni@SWCNT/Cu nanocrystalline composite materials[J]. Materials Science and Engineering:A,2024,901:146523.
 WANG D,YAN A,LIU Y C,et al. Interfacial bonding improvement through nickel decoration on carbon nanotubes in carbon nanotubes/Cu composite foams reinforced copper matrix composites[J]. Nanomaterials,2022,12(15):2548.
37-38
。由此,Ya等  YA B,MENG F Q,XU Y,et al. Enhancing the mechanical properties of copper matrix composites through nickel-grafted carbon nanotubes prepared by molecular-level mixing and self-reduction methods[J]. Journal of Alloys and Compounds,2025,1020:179546.
39
提出了一种纳米管表面接枝Ni颗粒制备碳纳米管镍粉(CNT-Ni)的新方法。采用分子级共混法结合自还原法制备了表面接枝Ni颗粒的CNT,再通过机械球磨和热压制备出CNT-Ni/Cu复合材料。如图3所示,与纯Cu样品相比,CNT含量为0.1%的CNT-Ni/Cu复合材料在保持高导电性的同时,可以显著细化晶粒并改善其综合性能,并且含0.1%CNT的CNT-Ni/Cu复合材料硬度达到85.2HV,导电率达到94.1%IACS,拉伸率达到18.4%,拉伸强度达到232.6 MPa。

图3     (a)CNT-Ni/Cu复合材料工艺流程示意图; (b)CNT-Ni/Cu复合材料拉伸断裂机制示意图; (c)CNT-Ni复合粉末与Ni颗粒的透射电镜; (d)纯铜和CNT-Ni/Cu 复合材料的应力-应变曲线
Fig. 3     (a) Schematic diagram of process flow for CNT-Ni/Cu composite materials; (b) Schematic diagram of tensile fracture mechanism of CNT-Ni/Cu composites; (c) Transmission electron microscopy images of CNT-Ni composite powder and Ni particles; (d) Stress-strain curves of pure copper and CNT-Ni/Cu composites  YA B,MENG F Q,XU Y,et al. Enhancing the mechanical properties of copper matrix composites through nickel-grafted carbon nanotubes prepared by molecular-level mixing and self-reduction methods[J]. Journal of Alloys and Compounds,2025,1020:179546.
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2.2     GR/Cu复合材料

与CNT/Cu复合材料相比,GR/Cu复合材料在制备过程中也存在几个难以解决的问题:1)GR在Cu基体中的分散性较差,易发生团聚现象,形成微米级聚集体,导致复合材料内部产生应力集中和缺陷; 2)GR与Cu基体之间的界面相容性较差,界面结合强度不足,不仅限制了应力传递效率,还会引起显著的电子散射效应; 3)在复合材料制备过程中,GR的二维结构易受机械损伤和热效应影响,其优异的力学性能和电学性能难以完整保留。针对这些问题,研究人员进行了大量研究。

1)针对分散性问题。GR在Cu基体中的弥散分布使其以孤立片层或小团聚的形式随机分散在Cu基体中,其在Cu基体中被连续强化形成的三维结构可以克服GR层之间的范德华力,有效防止石墨烯薄片的自排列,从而解决GR在复合材料中的分散问题  HUANG J R,ZHANG Y B,YANG X,et al. Achieving excellent physico-mechanical properties of Cu matrix composites by incorporating a low content of a three-dimensional graphene network[J]. Composites Part A:Applied Science and Manufacturing,2024,184:108246.
 NAN N,LI J M,ZHANG X,et al. Achieving excellent thermal stability in continuous three-dimensional graphene network reinforced copper matrix composites[J]. Carbon,2023,212:118153.
40-41
。段涛等  段涛,金利华,梁明,等. 石墨烯化学镀铜及增强铜基复合块材的制备[J]. 材料导报,2022,36(S2):308-311.
42
采用化学镀结合球磨的方法制备GR/Cu复合材料,化学镀改善了GR与Cu界面之间的浸润性,再通过球磨进一步提高GR在Cu基体中的分散性。研究结果表明,GR/Cu复合材料的硬度达到104HV,相较于纯Cu提高了1.6倍,导电率达90%IACS。冯俊俊等  冯俊俊. 改性石墨烯增强铜基块体复合材料的制备及性能研究[D]. 汉中:陕西理工大学,2023.
43
则采用表面改性技术制备GR/Cu复合材料,在GR的层间和表面负载金属纳米粒子,防止GR团聚并均匀分散在Cu基体中。研究发现,当增强相含量为0.5%时,复合材料的硬度比纯Cu提高了62.1%,抗拉强度提高了61%,导电率为88%IACS。

2)针对界面优化问题。蒋宇乾等  蒋宇乾,张翔,赵乃勤,等. 石墨烯增强铜基复合材料的界面调控及其性能研究进展[J]. 中国材料进展,2023,42(12):959-973,984.
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研究发现,GR与Cu基体间的界面特性是决定复合材料综合性能的关键因素,直接影响增强相与基体间的载荷传递效率和能量耗散机制。Yang等  YANG Z,ZHANG M,JIANG L,et al. Reinforcing or weakening determined by the interfacial nanostructures in graphene reinforced copper matrix composites[J]. Diamond and Related Materials,2024,141:110664.
45
使用分子动力学模拟方法,研究纳米结构与各种GR/Cu复合材料演化机制之间的内在关系。研究发现,GR/Cu复合材料界面的增强取决于其纳米结构。在压缩载荷下,带有GR/Cu{100}的界面比GR/Cu{111}和GR/Cu{110}界面更容易发生塑性变形。GR可以在GR/Cu{100}界面润滑原子迁移,但在GR/Cu{111}和 Cu{110}界面则会阻碍这一过程。Chen等  CHEN Y K,ZHANG X,LIU E Z,et al. Fabrication of in-situ grown graphene reinforced Cu matrix composites[J]. Scientific Reports,2016,6:19363.
46
采用原位合成法在片状Cu粉末上原位生长GR,这不仅使GR均匀分散在Cu基体上,还显著促进了界面键结合。所制备质量分数为0.95%的GR/Cu复合材料表现出244 MPa的屈服强度和274 MPa的拉伸强度,分别比纯Cu提高了177%和27.4%。董龙龙等  董龙龙,李亮,霍望图,等. 一种改善石墨烯铜基复合材料界面结合强度的方法:CN111979438A[P]. 2020-11-24.
47
则开发了一种改善GR/Cu复合材料的方法。该方法通过粉末冶金技术引入钨粉在Cu基体与GR的界面处原位形成非连续的WxCy纳米颗粒或纳米层,将GR与Cu基体紧紧连接起来,把Cu基体与GR之间原来的非润湿性物理结合界面改善成为润湿性化学反应结合界面,提高了GR与Cu基体之间的界面结合强度,增强了复合材料的力学性能。

3)针对结构损伤问题。Hwang等  HWANG J,YOON T,JIN S H,et al. Enhanced mechanical properties of graphene/copper nanocomposites using a molecular‐level mixing process[J]. Advanced Materials,2013,25(46):6724-6729.
48
采用分子级共混法成功将GR分散到Cu基体中。此方法可有效修复GR的结构损伤,防止GR在范德华力作用下发生团聚,还能有效改善GR与金属基体之间的接触界面  樊家兴,戴佺民,成传晖,等. 石墨烯/铜复合材料性能调控方法研究进展[J]. 金属功能材料,2025,32(1):50-58.
49
,制备的GR/Cu复合材料弹性模量达到131 GPa,屈服强度达到284 MPa。戴丹等  戴丹,杨科,叶辰,等. 化学气相沉积石墨烯/铜合金制备与导电、耐磨性能研究[J]. 铜业工程,2023(4):78-84.
50
采用CVD法实现了在Cu粉表面原位生长GR。此方法可在微观尺度上实现GR与Cu粉的均匀混合,避免传统混合方法中GR的结构破损和团聚,有效提升电导率和力学性能  姜庆伟,林惠志,丁云航,等. 石墨烯和碳纳米管增强铜基复合材料的研究进展[J]. 铜业工程,2024(5):63-78.
51
。所制备的复合材料摩擦系数降低到0.46,与纯Cu相比降低了38.7%。Li等  LI X H,YAN S J,CHEN X,et al. Microstructure and mechanical properties of graphene-reinforced copper matrix composites prepared by in-situ CVD,ball-milling,and spark plasma sintering[J]. Journal of Alloys and Compounds,2020,834:155182.
52
通过CVD法结合球磨和SPS,成功合成了GR/Cu复合材料。研究结果显示,GR/Cu复合材料的屈服强度和拉伸强度与纯铜相比分别提高了136.6%和16.7%。Gao等  GAO Z S,ZUO T T,WANG M,et al. In-situ graphene enhanced copper wire:A novel electrical material with simultaneously high electrical conductivity and high strength[J]. Carbon,2022,186:303-312.
53
利用真空热压技术在Cu中原位生长高质量GR。研究发现,GR沿晶界的原位形成不仅有效地解决了团聚问题,还确保了GR的结构完整性,从而提高了Cu基体与GR之间的界面连通性。分析认为,原位形成的GR可作为电子的传递通道,使得复合材料具有高导电率(94.85%IACS)和高强度(516 MPa)。

2.3     CPD/Cu复合材料

近几年,关于CPD/Cu复合材料的研究一直是一个比较热门的话题。CPD因具有GR和CNT一样的结构特性,所以也具有与GR和CNT一样良好的力学和电学性能。并且CPD含有丰富的表面官能团,这使得其在调和Cu基复合材料强度和导电率的不相容特性方面具有独特的潜力。进一步通过CPD的官能化和表面钝化,然后再通过合适的方法可以有效解决其在Cu基体中的分散问题  HE Y,YI J H,LIU L,et al. Insights on the electrical conductivity enhancement mechanisms of carbon polymer dots (CPDs) reinforced Cu composites[J]. Diamond and Related Materials,2024,150:111674.
 ZHAO W M,BAO R,YI J H,et al. Influence of carbonized polymer dot (CPD) structure on mechanical and electrical properties of copper matrix composite[J]. Materials Characterization,2021,181:111463.
54-55

Zhao等  ZHAO W M,BAO R,YI J H,et al. Improving mechanical and thermal property of pure copper matrix simultaneously by carbonized polymer dots (CPD) cluster reinforcement[J]. Materials Science and Engineering:A,2021,805:140573.
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采用分子级共混法结合SPS制备了CPD/Cu复合材料,发现CPD能很好地分散在Cu晶粒界面处,热导率从305 W/(m·K)提高到360 W/(m·K),且对力学性能方面无任何不利影响。Bao等  ZHAO W M,BAO R,YI J H,et al. Achieving a better mechanical enhancing effect of carbonized polymer dots than carbon nanotubes and graphene in copper matrix[J]. Composites Communications,2021,28:100906.
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采用球磨与SPS相结合来制备CPD/Cu复合材料,研究发现,纳米CPD球能均匀地分散在复合材料中,并且清晰的壳结构能与Cu基体完美结合,所制备的CPD/Cu复合材料具有312.1 MPa的高抗拉强度和34.3%的伸长率。除此之外,Xu等  XU J H,ZHAO W M,LI S Y,et al. Effect of structure of carbonized polymer dot on the mechanical and electrical properties of copper matrix composites[J]. Metals,2022,12(10):1701.
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采用热处理CPD(h-CPD)用于制备CNT/Cu复合材料,探究h-CPD/Cu复合材料的力学性能、导电性、微观组织以及导电机制,并与以相同方法制备的CPD/Cu复合材料进行了详细比较。实验结果发现,CPD的官能团和聚合物链在热处理过程中分解,削弱了复合材料的机械和电气性能,这表明CPD结构完整性对复合材料至关重要。为了全面了解CPD尺寸对其在Cu晶粒内空间分布的重要性,Li等  LI Z J,LIU L,BAO R,et al. High strength-tough and super-dispersed carbonized polymer dots reinforced copper composites fabricated by ultrasonic spray pyrolysis[J]. Carbon,2024,230:119649.
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采用超声波喷雾热解最大限度地消除CPD团聚,实现均匀的晶内分布,其最大抗拉强度、导热系数和导电率分别为470 MPa,390 W/(m·K)和93.2%IACS,这种短流程工艺制备方法以及性能之间的良好结合为Cu复合材料的工程设计提供了新的策略。而为了将CPD的性能优点进一步提高,Zhang等  ZHANG W F,LIU L,BAO R,et al. Enhancing the mechanical and electrical conductivity of copper matrix composites through grafting carbonized polymer dots (CPD) onto carbon nanotube surfaces[J]. Diamond and Related Materials,2023,137:110147.
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将CPD与CNT用于协同增强,使得CNT的分散性得到改善。首先通过一步合成法得到CPD-CNT增强材料,再通过球磨与烧结的方法制备CPD-CNT/Cu复合材料。研究结果显示,制备的复合材料具有优异的力学性能,屈服强度高达269 MPa,拉伸强度高达308 MPa,同时延展性也达到43%,并且复合材料的导电率保持在高水平(95.3%IACS)。Li等  LI Z J,YOU X,LIU L,et al. Attaining the strength-plasticity-electricity balance of carbon nanotube/Cu composites through combining the intragranular carbonized polymer dots distribution[J]. Journal of Materials Research and Technology,2023,27:3339-3348.
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则采用喷雾热解和混合球磨将多维杂化增强材料、CNT和CPD掺入Cu基体中,结果如图4所示,CNT-CPD/Cu复合材料的伸长率和抗拉强度分别达到19.8%和411 MPa,分别比CNT/Cu复合材料高46.6%和39.3%,具有优异的强度-延展性协同作用。同时,CNT-CPD/Cu复合材料的导电率(96.5%IACS)远优于CNT/Cu(86.7%IACS)。

图4     (a)CNT-CPD/Cu复合材料的工艺流程示意图; (b)复合材料与纯铜的应力-应变曲线; (c)复合材料与纯铜的综合性能雷达图
Fig. 4     (a) Schematic diagram of process flow for CNT-CPD/Cu composites; (b) Stress-strain curves of composite materials and pure copper; (c) Radar chart of comprehensive properties of composite materials and pure copper  LI Z J,YOU X,LIU L,et al. Attaining the strength-plasticity-electricity balance of carbon nanotube/Cu composites through combining the intragranular carbonized polymer dots distribution[J]. Journal of Materials Research and Technology,2023,27:3339-3348.
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2.4     CNMs/Cu复合材料的强化机制

2.4.1     力学性能影响

一般来说,在CNMs/Cu复合材料的制备过程中会同时发生多种强化机制。1)在Cu基体中引入CNMs,会抑制复合材料烧结过程的晶界迁移,从而阻碍复合材料的晶粒长大,起到晶粒强化的作用  WANG M Y,YANG X,TAO J M,et al. Achieving high ductility in layered carbon nanotube/copper composite prepared by composite electrodeposition[J]. Diamond and Related Materials,2020,108:107992.
62
。2)CNMs/Cu复合材料的制备过程中会产生界面结合,而良好的CNMs/Cu复合材料界面能够显著提升载荷从Cu基体向CNMs传递的效率。在拉伸过程中,当载荷从Cu基体转移到CNMs时,会发生载荷转移强化,从而增强复合材料的整体强度  ZHAO W M,BAO R,YI J H,et al. Fabrication of CNT/Cu based composite with twice in-situ formation from powder preparation to sintering[J]. Materials Research Express,2019,6(9):095088.
63
。3)CNMs的加入会阻碍复合材料中位错的运动,产生奥罗万强化,从而提高强度  XIONG N,BAO R,YI J H,et al. CNTs/Cu-Ti composites fabrication through the synergistic reinforcement of CNTs and in situ generated nano-TiC particles[J]. Journal of Alloys and Compounds,2019,770:204-213.
64
。4)在烧结或热加工过程中,CNMs与Cu基体因热膨胀系数不匹配发生局部塑性变形,在CNMs周围产生较高的位错密度区域,从而阻碍位错运动  ZAREI F,SHEIBANI S. Comparative study on carbon nanotube and graphene reinforced Cu matrix nanocomposites for thermal management applications[J]. Diamond and Related Materials,2021,113:108273.
65
。5)CNMs的存在会钉扎位错,使位错在CNMs周围聚集,形成应力集中,从而阻碍位错的进一步运动,有助于提高复合材料的强度  LIU J P,FAN G L,TAN Z Q,et al. Mechanical properties and failure mechanisms at high temperature in carbon nanotube reinforced copper matrix nanolaminated composite[J]. Composites Part A:Applied Science and Manufacturing,2019,116:54-61.
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2.4.2     电导率性能影响

在金属电子传导理论框架下,理想导体中的电子传输过程是无散射的,电子能够顺畅移动而不受阻碍。然而,当电子穿越存在缺陷的晶体结构时,其运动轨迹会被散射干扰,从而产生电阻。根据马西森定则(Matthiessen's rule),CNMs/Cu复合材料的电阻主要来源于晶界、界面、位错和声子散射。1)在复合材料中,晶粒尺寸越小,晶界数量越多,晶界散射现象就越显著,对电子传输的阻碍作用也越强,进而导致电阻增大  PENG W,GAO J B,LU T W,et al. Insights into abnormal grain growth in copper thin films for reduced electrical resistivity:a quantitative multi-order-parameter phase-field study under finite element framework[J]. Acta Materialia,2023,260:119236.
67
。2)对于CNMs/Cu复合材料,CNMs与Cu的不润湿性导致界面缺陷,使电子在界面处发生散射,增加了电子传输的阻力,从而导致电阻升高  ZHENG Z,YANG A X,TAO J F,et al. Mechanical and conductive properties of Cu matrix composites reinforced by oriented carbon nanotubes with different coatings[J]. Nanomaterials,2022,12(2):266.
68
。3)声子散射是指载流子与声子的相互作用。一般来说,温度越高,声子数量越多,载流子与声子碰撞机会也越多,导致声子散射数量增加,电阻也随之增大  ZHOU Z F,HUANG Y,WEI B,et al. Compositing effects for high thermoelectric performance of Cu2Se-based materials[J]. Nature Communications,2023,14:2410.
69
。4)复合材料中产生的位错也会阻碍电子的传输,使电子在位错处发生散射,进一步引起电阻的上升  ZHANG W J,HUANG L,MI X J,et al. Researches for higher electrical conductivity copper‐based materials[J]. cMat,2024,1(1):e13.
70

不同的制备方法对CNMs/Cu复合材料的力学和导电性有着不同的影响,现收集了部分CNMs/Cu复合材料拉伸与导电性能的数据,以及相应的制备方法  WEI X,TAO J M,HU Y,et al. Enhancement of mechanical properties and conductivity in carbon nanotubes (CNTs)/Cu matrix composite by surface and intratube decoration of CNTs[J]. Materials Science and Engineering:A,2021,816:141248.
 FU S L,CHEN X H,LIU P. Preparation of CNTs/Cu composites with good electrical conductivity and excellent mechanical properties[J]. Materials Science and Engineering:A,2020,771:138656.
 SONG H Y,MAI J J,ZHANG Z Q,et al. A high strength and high electrical conductivity copper based composite enhanced by graphene and Al2O3 nanoparticles[J]. Materials Science and Engineering:A,2024,899:146432.
 YANG X H,CHENG X W,CHEN Y,et al. Microstructure and properties of copper matrix composites reinforced with Cu-doped graphene[J]. Carbon Letters,2024,34(5):1317-1327.
 CHEN Y,WANG Z,JIN G,et al. Achieving high strengthening efficiency and good balance between strength and ductility/electrical conductivity in the laminated RGO/copper composites[J]. ACS Applied Electronic Materials,2024,6(8):5903-5913.
 ZHAO W M,BAO R,YI J H. Enhancing the mechanical-electrical property simultaneously in pure copper composites by using carbonized polymer dots[J]. Journal of Materials Science,2021,56(22):12753-12763.
71-76
,如图5所示。

图5     CNMs/Cu复合材料的性能汇总图
Fig. 5     Properties summary diagram of CNMs/Cu composites

2.5     增强体材料的异同性

2.5.1     相同点

CNT,GR,CPD均为碳基材料,通过其独特的碳结构(sp2或sp3杂化)赋予Cu基复合材料更高的强度和硬度,但同时以牺牲伸长率和导电性为代价。因为CNMs与Cu基体之间的热膨胀失配会导致过渡区产生高密度的位错,阻碍电子传输。同时,CNMs的引入使Cu基体晶粒细化,晶界数量增加,导致电子传递势垒升高和平均自由路径缩短。此外,Cu与CNMs之间的界面为非润湿性,这使得Cu和C原子之间的亲和力较弱,导致复合材料界面空位增加,电子传递受阻,这些原因都能使得电导率降低。除此之外,这3种材料之间还存在一些共性问题,例如与Cu之间的界面结合较差。CNT和GR的表面惰性强,需功能化修饰(如引入官能团)改善与Cu基体的界面结合; 分散性问题也是这3种材料在关键工艺上的重点和难点。良好的分散性能可避免团聚,并与Cu基体产生更好的结合,从而更大限度地提高复合材料性能。

2.5.2     不同点

CNT,GR和CPD同为碳基材料,但它们的结构维度不同。不同结构维度在制备Cu基复合材料时表现出的性能特点也不同。CNT是一维中空的管状结构,分为单壁和多壁两种。有较大的长径比,在Cu基体中可起到类似“纤维”的增强作用,能承受较大的拉伸载荷。GR是二维平面结构,比表面积大使其与Cu基体接触面积也大,但在制备过程中会更难分散,常发生团聚。CPD具有核-壳结构,核是高度交联的聚合物或者碳原子晶格,壳是聚合物链,通常为球形或近似球形,整体为纳米级尺寸。CPD与Cu基体的结合方式与CNT和GR有所不同,因为其壳层表面存在丰富的环氧基、羟基和羧基,使得CPD具有良好的水溶性,可以进一步功能化和表面钝化,通过合适的方法可以较好地解决CPD在Cu基体中的分散问题。当GR结构发生卷曲之后,能形成CNT结构,而CPD作为碳核中的微小碳簇,不仅可以是共轭的,也可以是类金刚石结构。在透射电子显微镜下观察CPD,可以发现部分CPD呈现定型结构,而其他一些则显示出完整的晶格结构,这些晶格结构不仅可以是石墨的晶格,还可以是有序致密的聚合物框架结构。在成本方面,CNT的制备成本相对较高,高质量GR的大规模制备也面临挑战,而CPD的聚合物前驱体碳化工艺简单,成本较低,且与Cu基体复合的工艺较CNT与GR更为简便。

3     结论与展望

尽管在CNMs/Cu基复合材料的研究和应用方面取得了一定的进展,但仍然面临着诸多问题与挑战。

1)材料结构优化问题。CNMs在Cu基体中的均匀分散问题和界面结合问题尚未完全解决。这要求进一步优化制备工艺并开发新型合成方法,以提升复合材料的性能与质量。

2)性能调控问题。如何在提高力学性能的同时保持或提升电学性能,成为当前研究的重点和难点。CNMs的引入往往使导电性能下降,如何通过界面设计和结构调控,实现性能的协同优化仍需深入探索。

3)成本问题。成本控制是限制CNMs/Cu复合材料大规模应用的关键因素。CNMs的制备过程能耗高、原材料消耗大,且工艺复杂,导致其成本居高不下。同时,CVD法和电沉积等制备方法设备投资大、能耗高,导致复合材料的制造成本高。而高昂的成本限制了这类材料在民用电子、大规模能源设备等领域的推广应用。

这些现存问题严重制约了CNMs/Cu复合材料的进一步发展和广泛应用,未来需要通过跨学科合作,探索新的实验方法和技术路径,例如开发低成本的CNMs规模化制备技术、优化复合工艺以降低能耗、设计新型界面结构以提升性能等。随着研究的持续深化与技术的不断进步,CNMs/Cu复合材料有望在更多领域得到应用,进一步推动相关行业的发展。

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