陶瓷颗粒增强铜基复合材料制备方法及性能调控研究进展

基金项目

陕西省青年科技新星项目(2025ZC-KJXX-58)资助

中图分类号:

TB331TU512.1

文献标识码:

A

作者简介

李鹏远(1998—),男,山东菏泽人,博士研究生,研究方向:金属基复合材料,E-mail:lipengyuan1998@163.com

通信作者

张洪梅,教授,E-mail:zhanghm@bit.edu.cn

流转信息

收稿日期 : 2025-09-27

修订日期 : 2025-11-23

引文格式

李鹏远,徐俊杰,张洪梅. 陶瓷颗粒增强铜基复合材料制备方法及性能调控研究进展[J]. 铜业工程,2026(2):27-42.

Fabrication Methods and Performance Regulation of Ceramic Particle Reinforced Copper Matrix Composites

Citations

LI Pengyuan,XU Junjie,ZHANG Hongmei. Fabrication methods and performance regulation of ceramic particle reinforced copper matrix composites [J]. Copper Engineering,2026(2):27-42.

铜业工程    第2期    27-42
doi10.3969/j.issn.1009-3842.2026.02.004
材料制备与加工工程(Material Preparation and Process Engineering)

陶瓷颗粒增强铜基复合材料制备方法及性能调控研究进展

  • 李鹏远 1
  • 徐俊杰 2
  • 张洪梅 1
1.北京理工大学 材料学院北京 100081
2.西安稀有金属材料研究院有限公司陕西 西安 710016

作者简介

李鹏远(1998—),男,山东菏泽人,博士研究生,研究方向:金属基复合材料,E-mail:lipengyuan1998@163.com

通信作者

张洪梅,教授,E-mail:zhanghm@bit.edu.cn

基金项目

陕西省青年科技新星项目(2025ZC-KJXX-58)资助

中图分类号:

TB331TU512.1

文献标识码:

A

流转信息

收稿日期 : 2025-09-27     修订日期 : 2025-11-23     

引文格式

李鹏远,徐俊杰,张洪梅. 陶瓷颗粒增强铜基复合材料制备方法及性能调控研究进展[J]. 铜业工程,2026(2):27-42.

摘要

陶瓷颗粒增强铜基复合材料具有优异的综合性能,在电子封装、航空航天、轨道交通等领域展现出广阔的应用前景。在铜基复合材料中引入陶瓷颗粒,不仅能显著提升铜基体的强度、硬度和耐磨性,同时可在较大程度上保持其优异的导电性和导热性。近年来,随着先进制备技术和表征手段的发展,人们对陶瓷颗粒与铜基体之间界面结构和相互作用机制的认识不断深入。目前的研究重点在于优化制备工艺参数,以及合理设计增强相的类型与分布特征,以最大限度发挥陶瓷颗粒在铜基体中的强化效果。本文系统综述了陶瓷颗粒增强铜基复合材料的制备方法(内氧化法、机械合金化法、反应喷射沉积法、粉末冶金法、增材制造法、搅拌铸造法),分析了陶瓷颗粒特性(种类、含量、粒径、界面结合)对复合材料性能的影响,并阐述了复合材料的导电机制及强化机制。最后,针对现有研究的不足,对未来研究的重点方向与发展趋势进行了展望,以期为高性能陶瓷颗粒增强铜基复合材料的进一步开发和实际应用提供参考。

关键词

铜基复合材料;陶瓷颗粒;制备方法;力学性能;电学性能;

Fabrication Methods and Performance Regulation of Ceramic Particle Reinforced Copper Matrix Composites

  • LI Pengyuan 1
  • XU Junjie 2
  • ZHANG Hongmei 1
1.School of Materials Science & EngineeringBeijing Institute of TechnologyBeijing 100081China
2.Xi'an Rare Metal Materials Institute Co.,Ltd.Xi'an 710016China

Citations

LI Pengyuan,XU Junjie,ZHANG Hongmei. Fabrication methods and performance regulation of ceramic particle reinforced copper matrix composites [J]. Copper Engineering,2026(2):27-42.

Abstract

Ceramic particle reinforced copper matrix composites have demonstrated broad application prospects in fields such as electronic packaging, aerospace, and rail transportation owing to their outstanding comprehensive properties. Incorporation of ceramic particles not only significantly enhances strength, hardness, and wear resistance of the copper matrix but also largely preserves its excellent electrical and thermal conductivity. In recent years, with the continuous advancement of fabrication technologies and characterization techniques, understanding of interfacial structures and interaction mechanisms between ceramic particles and the copper matrix has deepened considerably. Current research efforts mainly focus on precisely optimizing processing parameters and rationally designing the type and distribution characteristics of the reinforcing phases to maximize strengthening effects of ceramic particles within the copper matrix. Therefore, this review systematically summarized fabrication methods (internal oxidation, mechanical alloying, reactive spray deposition, powder metallurgy, additive manufacturing, stirring casting) of ceramic particle reinforced copper matrix composites. Influence of ceramic particle characteristics (type, content, particle size, interface bonding) on composite performance was analyzed. Electrical conduction and strengthening mechanisms were elucidated. Finally, existing challenges and future research directions were discussed, aiming to provide valuable insights for the further development and practical application of high-performance ceramic particle reinforced copper matrix composites.

Keywords

copper matrix composite;ceramic particle;fabrication method;mechanical property;electrical property;



铜以其优异的导电性、导热性及良好的加工性能,在航空航天、信号传输、轨道交通和电子封装等领域具有广泛的应用  LI C G,XIE Y H,ZHOU D S,et al. A novel way for fabricating ultrafine grained Cu-4.5 vol% Al2O3 composite with high strength and electrical conductivity[J]. Materials Characterization,2019,155:109775.
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 李明洋,常永勤. 铁钛多元微合金化对CuCrZr合金组织和性能的影响[J]. 铜业工程,2023(1):12-18.
1-3
。然而,纯铜强度和耐磨性较低,难以满足苛刻的服役条件  ZHAN Y Z,ZHANG G D. The effect of interfacial modifying on the mechanical and wear properties of SiCp/Cu composites[J]. Materials Letters,2003,57(29):4583-4591.
4
。为克服这些局限性,研究者们常在铜基体中添加陶瓷颗粒制备弥散强化型铜基复合材料,以显著提高基体强度,同时尽量保持其良好的导电导热性能  HAN T L,HOU C,ZHAO Z,et al. W-Cu composites with excellent comprehensive properties[J]. Composites Part B:Engineering,2022,233:109664.
 CHENG M,ZHANG S R,LIU Z F,et al. In-situ synthesis of TiB2 particulate reinforced copper matrix composites with ultrasonic vibration treatment[J]. Materials Letters,2023,335:133823.
 彭九庆,张斯若,李广龙,等. 超声处理时间对Cu-Zr-ZrB2复合材料组织与性能的影响[J]. 铜业工程,2025(3):72-82.
5-7

陶瓷颗粒增强铜基复合材料的性能与制备工艺,增强相种类、含量、粒径以及界面结合状态等因素密切相关。近年来,随着材料设计理论和制备技术的不断发展,铜基复合材料的性能调控研究取得显著突破。例如:通过优化制备工艺,可以实现增强相在铜基体中的理想分布,并获得良好的界面结合  HAN L,WANG J,CHEN Y Y,et al. Fabrication and mechanical properties of WC nanoparticle dispersion-strengthened copper[J]. Materials Science and Engineering:A,2021,817:141274.
 XIANG S Q,DU X J,LIANG Y H,et al. Optimizing phase interface of titanium carbide-reinforced copper matrix composites fabricated by electropulsing-assisted flash sintering[J]. Materials Science and Engineering:A,2021,819:141506.
8-9
; 而通过调控陶瓷颗粒的种类、含量和尺寸,可以平衡材料的强度与导电性,满足不同应用场景的需求  罗文伯,曹宇,胡继林,等. 烧结温度与添加剂对氧化铝基复相陶瓷的理化性能及其显微结构的影响[J]. 江西化工,2025,41(1):97-101.
 ŞAP S,TURGUT A,UZUN M. Investigation of microstructure and mechanical properties of Cu/Ti-B-SiCp hybrid composites[J]. Ceramics International,2021,47(21):29919-29929.
 刘洋赈,李恒青,马春宇,等. TiB2含量对石墨-TiB2混杂增强铜基材料组织与力学性能的影响[J]. 铜业工程,2025(5):35-41.
10-12
。此外,深入理解陶瓷颗粒增强铜基复合材料的导电机制和强化机制,对于材料的设计与性能优化至关重要。尽管已有大量研究关注铜基复合材料的制备与性能优化,但如何实现增强相的理想分布、改善陶瓷颗粒与铜基体的界面结合,从而协同提升复合材料的强度与导电性,仍需进一步探索。

基于此,本文系统综述了陶瓷颗粒增强铜基复合材料的研究进展,讨论了常用制备方法的优缺点,归纳了增强相对复合材料力学性能和导电性能的影响,并总结了陶瓷颗粒增强铜基复合材料的导电机制与强化机制。最后对现有问题与未来发展方向进行了总结与展望,以期为高性能铜基复合材料的设计与应用提供参考。

1     铜基复合材料的制备方法

铜基复合材料的综合性能很大程度上取决于其制备工艺。成功制备高性能铜基复合材料需满足两大关键条件:1)增强相的有效引入与合理分布; 2)基体与增强相间形成稳定且强结合的界面。不同制备工艺会影响复合材料内各组分之间的结合和分布,因此即使采用相同原料,不同工艺制备的复合材料微观组织与性能也存在较大的差异。目前,一系列成熟的制备技术已被成功应用于研发高性能铜基复合材料,主要包括:内氧化法、机械合金化法、反应喷射沉积法、粉末冶金法、增材制造法以及搅拌铸造法等。

1.1     内氧化法

内氧化法是一种在制备过程中,氧化剂在金属内部优先氧化活泼组元,生成相应氧化物颗粒的工艺方法。由于氧化物颗粒从基体中直接生成,常与基体存在一定的位向关系,有效克服了增强相与金属基体结合力弱的缺点  DONG Y,WANG X K,XIE Y H,et al. Tunable microstructures and tensile mechanical properties of oxide-dispersion-strengthened Cu by extrusion and secondary processing[J]. Journal of Alloys and Compounds,2020,812:152112.
13
。然而,内氧化法仍存在若干亟待改进的问题,例如:工艺流程繁琐,制备过程复杂; 氧化过程稳定性较差,导致产品质量难以控制; 表层与心部氧化速率不同导致颗粒尺寸存在差异,造成材料的组织与力学性能不均匀等。典型的内氧化法制备铜基复合材料工艺流程如图1所示,包括如下步骤:合金粉末制备→合金粉末与氧源粉末混合→内氧化过程→去除多余的氧→还原烧结→热挤压、冷拉拔变形加工  FENG X W,ZHANG D P,FENG B,et al. Microstructure and properties of Cu-0.4 wt.% Al2O3 composites fabricated by hot extrusion and cold drawing[J]. Journal of Materials Engineering and Performance,2022,31(2):1241-1249.
14

图1     内氧化法制备铜基复合材料工艺流程示意图
Fig. 1     Schematic diagram of process flow of preparing copper matrix composites by the internal oxidation method  FENG X W,ZHANG D P,FENG B,et al. Microstructure and properties of Cu-0.4 wt.% Al2O3 composites fabricated by hot extrusion and cold drawing[J]. Journal of Materials Engineering and Performance,2022,31(2):1241-1249.
14

李美霞等  LEE J,JUNG J Y,LEE E S,et al. Microstructure and properties of titanium boride dispersed Cu alloys fabricated by spray forming[J]. Materials Science and Engineering:A,2000,277(1):274-283.
15
以水雾化Cu-Al合金粉末为原料,Cu2O粉末和氮气为介质,通过内氧化工艺成功制备出Al2O3弥散强化铜基复合材料。研究结果显示,内氧化过程中形成的纳米级Al2O3颗粒其平均尺寸约为6 nm,颗粒间距为30~50 nm。所得挤压态棒材电导率可达87%IACS,软化温度高达850 ℃;此外,直径为25 mm的挤压态棒材无需热处理即可直接冷拉拔至直径为1 mm细丝,其抗拉强度可达680 MPa。

1.2     机械合金化法

机械合金化法通过高能球磨工艺,使铜粉与增强相在固态条件下经历反复冷焊与断裂,实现原子级的均匀混合,生成具有纳米晶或非晶结构的复合粉末,随后经烧结得到铜基复合材料。该方法可制备纳米相增强铜基复合材料,显著提高铜基体强度、硬度及高温稳定性,但球磨过程易引入杂质(如Fe,O),需严格控制球磨时间与气氛以避免粉末氧化。后续烧结时,纳米颗粒易团聚,需优化工艺参数以确保均匀性。马冰等  马冰,王宏博,菱沼良光,等. 原位反应制备Cu-Y2O3弥散强化铜中机械合金化进程[J]. 金属功能材料,2023,30(6):1-9.
16
采用机械合金化结合热等静压工艺制备了Y2O3/Cu复合材料,研究结果表明,Y元素与CuO在反应过程中可生成弥散分布的Y2O3颗粒,其含量基本不受机械合金化阶段的影响。在机械合金化初期,粉末经历碾压、撕裂与冷焊作用,铜基体晶格发生收缩。随着球磨时间延长,部分Fe杂质被引入铜基体中,进一步提升了材料的硬度。

1.3     反应喷射沉积法

反应喷射沉积法是一种将液态金属雾化为微小液滴,并在其飞行或沉积过程中与外加反应物接触发生化学反应,原位生成弥散分布的增强相颗粒,然后制备铜基复合材料的技术,其原理如图2所示  LEE J,JUNG J Y,LEE E S,et al. Microstructure and properties of titanium boride dispersed Cu alloys fabricated by spray forming[J]. Materials Science and Engineering:A,2000,277(1):274-283.
17
。该方法在铜基复合材料的制备中展现出诸多优势,例如:增强相可在沉积过程中原位生成,均匀分布于基体中,有效避免团聚现象; 同时,增强相的存在能够抑制晶粒长大,从而显著提升材料的力学性能。此外,反应喷射沉积具有沉积速率快、工艺参数调节范围广等特点,适用于多种增强体系的快速合成,并具备近净成形能力。尽管如此,该技术仍存在局限性,如:沉积层易产生孔隙、致密度较低,需结合热压或其他致密化处理以优化性能; 同时,其工艺过程控制复杂,对设备条件要求较高,限制了其大规模工业化应用。Lee等  LEE J,JUNG J Y,LEE E S,et al. Microstructure and properties of titanium boride dispersed Cu alloys fabricated by spray forming[J]. Materials Science and Engineering:A,2000,277(1):274-283.
17
采用喷射沉积法制备TiB2/Cu复合材料时发现,生成的TiB2在铜熔体中出现粗化、团聚等现象,显著降低了材料的综合性能。而郭明星  郭明星. 纳米弥散强化铜合金短流程制备方法及其相关基础问题研究[D]. 长沙:中南大学,2008.
18
使用改进后的喷射沉积工艺,即双束熔体原位反应-快速凝固法,使增强相在喷射过程中原位生成并均匀分布,显著改善了复合材料的整体性能。

图2     反应喷射沉积法装置示意图
Fig. 2     Schematic diagram of the reactive spray deposition device  LEE J,JUNG J Y,LEE E S,et al. Microstructure and properties of titanium boride dispersed Cu alloys fabricated by spray forming[J]. Materials Science and Engineering:A,2000,277(1):274-283.
17

1.4     粉末冶金法

粉末冶金法是一种先将铜基体粉末与增强相粉末充分混合,经冷压或热压方式压制成坯体,再通过烧结及后续的塑性加工,获得致密铜基复合材料的工艺方法。其典型工艺流程为:混合→压制(冷压或热压)→烧结→后续加工(如轧制、挤压或拉拔)等。作为制备金属基复合材料的常用方法之一,粉末冶金法具有设备要求低、工艺成熟、可灵活调控增强相类型和体积分数等优点,但也存在成本较高、增强相与基体界面结合强度有限等缺点。为改善界面结合,可采用化学镀或物理气相沉积在增强相表面预镀过渡层再进行烧结,以提升复合材料性能。高希瑞等  高希瑞,李恒青,韦江,等. 烧结温度对车用石墨-TiB2增强铜基复合材料组织与性能的影响[J]. 材料热处理学报,2024,45(5):32-39.
19
通过真空热压烧结技术成功制备了石墨和TiB2混杂增强相的铜基复合材料。研究结果显示:在烧结过程中,原始粉末之间未发生化学反应,两种增强相在铜基体中均匀弥散,未出现明显的团聚现象。随着烧结温度的升高,复合材料的致密度和显微硬度先增大后减小,摩擦系数与磨损率先下降后上升,而电导率始终下降。

1.5     增材制造法

增材制造技术起源于1986年,该技术能够直接依据计算机辅助设计(CAD)模型,无需模具或其他中间加工步骤,通过逐层堆积材料的方式制造三维部件  CHEN L Y,QIN P,ZHANG L N,et al. An overview of additively manufactured metal matrix composites:preparation,performance,and challenge[J]. International Journal of Extreme Manufacturing,2024,6(5):052006.
20
。与传统制造方法相比,该技术突破了复杂几何形状难以加工的限制,显著提高了设计自由度,并可大幅减少后续加工需求,有效降低材料浪费和能源消耗。在金属基复合材料制造方面,增材制造技术展现出独特的优势。其增强相的引入方式主要有两种:第一种是预混法,即通过球磨或机械混合等方式,将增强相与金属基体粉末预先混合均匀,从而保证在增材制造过程中原料的均匀性,使增强相均匀分布而不发生团聚; 第二种是通过粉末送料系统将增强相与基体粉末同步送入加工区域,经热源熔融后形成复合材料。这种方法可以通过精确调节送粉速率来控制增强相与基体粉末的质量比例,进而实现梯度金属基复合材料的制备。此外,在部分原位合成工艺中,增强相通过熔池内的冶金反应生成。通过激光功率、扫描速度等工艺参数的协同优化,可调控熔池热力学条件,从而抑制基体与增强相之间的有害界面反应,获得良好的增强相形貌与分布。然而,铜的高反射率和高热导率导致激光吸收率低、熔池不稳定,工艺参数窗口较窄,易出现气孔、裂纹等缺陷  LIU Y G,ZHANG J Q,NIU R M,et al. Manufacturing of high strength and high conductivity copper with laser powder bed fusion[J]. Nature Communications,2024,15(1):1283.
21
; 同时,增强相在高温熔池中的分布控制、界面反应及团聚问题仍是技术难点。为解决上述问题,研究者通过优化激光参数、采用涂层粉末、引入辅助合金元素等手段改善成形质量和复合效果。Wang等  WANG G,ZHANG Y,LIU J,et al. Dispersion hardening using amorphous nanoparticles deployed via additive manufacturing[J]. Nature Communications,2025,16(1):3589.
22
采用激光粉末床熔融技术,首次在铜基体中均匀引入高密度非晶硼碳化物纳米颗粒(平均粒径约47 nm,体积分数高达12%),这些非晶纳米颗粒可以缓解局部应力集中,同时在拉伸变形过程中产生自硬化效应,从而增强应变硬化能力并促进均匀的塑性变形。这种方法制备的铜基复合材料抗拉强度超1 GPa,延伸率达10%,性能显著优于传统晶体增强相材料。

1.6     搅拌铸造法

搅拌铸造法通过叶轮机械搅拌或磁场搅拌等外场作用,将增强相加入熔融态的金属液中,最后浇入铸型中得到复合材料,其基本原理如图3所示  THANDALAM S K,RAMANATHAN S,SUNDARRAJAN S. Synthesis, microstructural and mechanical properties of ex situ zircon particles (ZrSiO4) reinforced Metal Matrix Composites (MMCs):a review[J]. Journal of Materials Research and Technology,2015,4(3):333-347.
23
。该工艺方法可以用来生产复杂零件且能实现大规模化、产业化,具有工艺周期短、设备简单、制作成本低、容易操作等优点。但由于增强相与铜熔体间存在显著的密度差异以及较差的界面润湿性,实际应用中常出现增强相上浮偏聚和局部团聚等问题。要使增强相均匀分布在熔体中,就要合理控制熔体的熔炼温度、凝固速度以及搅拌参数。Wang等  WANG T M,ZOU C L,CHEN Z N,et al. In situ synthesis of TiB2 particulate reinforced copper matrix composite with a rotating magnetic field[J]. Materials & Design (1980—2015),2015,65:280-288.
24
在制备原位TiB2颗粒增强铜基复合材料时,通过施加旋转磁场,有效改善了TiB2颗粒在铸造过程中的分散。实验结果表明,在Cu-TiB2复合材料凝固过程中施加旋转磁场,有利于TiB2颗粒均匀分布,铸造态Cu-1%TiB2(质量分数)样品的力学性能得到显著改善:当磁场电流从0增大到60 A时,样品抗拉强度由177 MPa提高到206 MPa; 维氏硬度由84HV提高到123HV。

图3     机械搅拌铸造法制备金属基复合材料原理图
Fig. 3     Schematic diagram of stir casting technique for fabrication of metal matrix composites  WANG T M,ZOU C L,CHEN Z N,et al. In situ synthesis of TiB2 particulate reinforced copper matrix composite with a rotating magnetic field[J]. Materials & Design (1980—2015),2015,65:280-288.
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2     陶瓷增强相的种类

理想的增强相应具备以下条件  冯江. 颗粒晶须混杂增强铜基复合材料电性能和力学性能研究[D]. 西安:西安理工大学,2022.
25
:1)具有高的强度、硬度等力学性能; 2)热力学和化学稳定性好,在高温下增强相不因聚集长大或分解导致强度和传导性能降低; 3)增强相与基体具有良好的润湿性,同时增强相与基体之间不会发生使性能降低的化学反应。陶瓷颗粒因其高硬度、高熔点、优异的热稳定性及耐磨性,成为铜基复合材料的理想增强相。从材料成分体系来看,常见的陶瓷增强相主要包括:氧化物陶瓷、碳化物陶瓷以及硼化物陶瓷。这些陶瓷颗粒因其独特的物理化学特性,在铜基复合材料领域得到广泛研究和应用。

2.1     氧化物陶瓷

氧化物弥散强化铜基复合材料具有出色的综合力学性能。这类材料不仅具有优异的常温和高温强度,还保持了良好的电导率和热导率,因此在微波管构件、电接触元件、电子器件连接部件等多个工业领域得到广泛应用  李美霞, 罗骥, 郭志猛, 等. 高塑高强纳米Al2O3-Cu复合材料的组织与性能[J]. 材料热处理学报, 2010, 31(04): 14-17.
15
。在氧化物颗粒中,Al2O3是最常用的弥散强化相,因其价格低廉、来源广泛,吸引了大量研究者对Al2O3/Cu复合材料进行研究。20世纪70年代,美国SCM公司率先运用粉末冶金技术成功开发出Al2O3弥散强化铜合金系列产品。该系列材料涵盖C15715,C15725及C15760三种牌号,测试数据显示,它们的抗拉强度依次超过500,600和620 MPa,同时抗高温软化温度均高于600 ℃,远高于传统铜合金(通常低于400 ℃)。基于这些优异性能,该系列合金被认为是电阻焊电极的理想材料,并已在汽车车身制造中得到应用  吴浩,甘雪萍. 喷雾干燥法制备Cu-Al2O3复合粉末及其复合材料的组织与性能[J]. 粉末冶金材料科学与工程,2023,28(1):74-82.
26
。Gao等  GAO S J,WANG Q S,GUO H,et al. Simultaneously enhanced strength and ductility of Cu matrix composites by incorporating Al2O3 aerogel particles[J]. Materials Science and Engineering:A,2024,916:147313.
27
利用Al2O3气凝胶颗粒Al2O3(A)p作为增强相,通过粉末冶金法制备了高性能铜基复合材料,如图4所示。研究表明:经球磨分散与致密化处理后,纳米级Al2O3(A)p均匀分布在基体内,且部分Al2O3(A)p分布在基体晶粒内部并形成半共格界面。含0.5% Al2O3(A)p(质量分数)的复合材料展现出470 MPa的高抗拉强度与10%的断裂延伸率,同时保持92%IACS的高电导率。与相同工艺制备的纯铜相比,该复合材料实现了强度与均匀延伸率的同步提升。与Al2O3陶瓷颗粒相比,具有更高熔点和更低生成焓的Y2O3具有更优异的热稳定性,且其特有的类萤石结构,能够与铜基体形成良好共格关系的相界面,有利于复合材料综合性能的提升  MA B,HISHINUMA Y,NOTO H,et al. Effect of different Y components on optimization of dispersive Y2O3 particles in ODS-Cu[J]. Journal of Nuclear Materials,2022,571:154016.
 宋文龙,谢小凯,王翔,等. 球磨转速对Cu-Y2O3复合材料组织及性能的影响[J]. 江西冶金,2025,45(3):174,177-184.
28-29
。Chen等  CHEN Y L,ZHANG X H,HUANG F,et al. Microstructure and properties of Y2O3/Cu composites fabricated by a novel liquid phase in situ reactive synthesis process[J]. Ceramics International,2022,48(21):31273-31280.
30
采用液相原位反应法成功制备了不同Y2O3含量的Cu-Y2O3复合材料,如图5所示,并对其硬度、电导率和拉伸性能进行了研究。结果表明,铜基体中的Y2O3纳米颗粒平均尺寸为5.0 nm且分布较为均匀,立方相Y2O3与铜基体呈共格关系,即(422)Y2O3//(1¯11)Cu和[011¯]Y2O3//[11¯2]Cu。Cu-Y2O3复合材料的硬度和强度随Y2O3体积分数的增加而显著提升。当Y2O3体积分数为10%时,材料的硬度达到115HV,较纯铜提高了192.0%,其抗拉强度也提升了168.2%。然而,较高的增强相含量会导致Y2O3颗粒出现轻微团聚,使材料的电导率有所降低。ZrO2的密度、热膨胀系数都与铜较为接近,同时也具有较好的热稳定性,因此是铜基复合材料中较为理想的增强相  高晶,郑冀,李群英,等. 纳米氧化锆增强铜基复合材料[J]. 金属热处理,2006,31(1):40-42.
31
。Adel Fathy以Cu(NO32和ZrOCl2为原料,通过原位反应法制备了Cu-ZrO2复合材料  FATHY A. Investigation on microstructure and properties of Cu-ZrO2 nanocomposites synthesized by in situ processing[J]. Materials Letters,2018,213:95-99.
32
。结果表明,ZrO2纳米颗粒均匀地分布在铜基体中,粒径约为45 nm。由于高硬度的纳米ZrO2颗粒弥散分布在铜基体中,在塑性变形时起到阻碍位错运动的作用,使Cu-ZrO2复合材料的显微硬度随着ZrO2含量的增加而增加。但是其热导率从370.8降低到101.3 W/(m·K),这种负面影响可归因于以下两个因素:一是ZrO2陶瓷颗粒本身导热性能较差; 二是复合材料中孔隙率随ZrO2含量增加而升高,未完全烧结的陶瓷颗粒之间的孔隙阻碍了热传导路径  WEBER L,TAVANGAR R. On the influence of active element content on the thermal conductivity and thermal expansion of Cu-X (X=Cr,B) diamond composites[J]. Scripta Materialia,2007,57(11):988-991.
33
。刘玉浩等  刘玉浩,陈旭洲,王子杰,等. 热压烧结Cu-ZrO2合金的组织调控与性能研究[J]. 核聚变与等离子体物理,2025,45(3):249-256.
34
通过引入匀质、低熔点的Cu-Zr非晶粉作为原料,在较低温度与压力下实现了ZrO2弥散增强ODS-Cu材料的烧结制备,获得了界面结合较好的ZrO2颗粒弥散强化铜合金。在此基础上,通过轧制和热处理工艺,对Cu-ZrO2合金烧结坯的组织进行调控,轧制86%+475 ℃×1 h退火态样品,其室温屈服和抗拉强度分别为213 MPa和282 MPa,拉伸应变为20.2%; 其450 ℃下的屈服和抗拉强度分别为125和159 MPa,拉伸应变为23.2%,室温电导率为87%IACS。

图4     (a) Al2O3(A)p/Cu复合材料的制备工艺示意图; (b) Al2O3(A)p/Cu复合材料的工程应力-应变曲线; (c)屈服强度、抗拉强度、延伸率和电导率的柱状图
Fig. 4     (a) Schematic diagram of fabrication process of Al2O3(A)p/Cu composites; (b) Engineering stress-strain curves of Al2O3(A)p/Cu composites; (c) Histogram of yield strength,ultimate tensile strength,elongation and electrical conductivity  GAO S J,WANG Q S,GUO H,et al. Simultaneously enhanced strength and ductility of Cu matrix composites by incorporating Al2O3 aerogel particles[J]. Materials Science and Engineering:A,2024,916:147313.
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2.2     碳化物陶瓷

碳化物陶瓷是铜基复合材料中另一类常用的增强相,具有硬度高、熔点高、与铜基体润湿性好等优点。常见的碳化物颗粒主要有SiC,WC和TiC等。SiC中Si和C原子之间的化学键以共价键为主,键能高且稳定,因而SiC具有优异的物理性能和稳定的化学性能。此外,SiC具有硬度高、弹性模量高、热膨胀系数低、导热性好等优点,是铜基复合材料中一种理想的增强相  AKBARPOUR M R,GAZANI F,MOUSA MIRABAD H,et al. Recent advances in processing,and mechanical,thermal and electrical properties of Cu-SiC metal matrix composites prepared by powder metallurgy[J]. Progress in Materials Science,2023,140:101191.
35
。Akbarpour等  AKBARPOUR M R,SALAHI E,HESARI F A,et al. Microstructural development and mechanical properties of nanostructured copper reinforced with SiC nanoparticles[J]. Materials Science and Engineering:A,2013,568:33-39.
36
采用高能机械球磨和热压技术制备了SiC/Cu复合材料,压缩试验表明,Cu-2%SiC (体积分数)复合材料屈服强度达到了(630±12) MPa,与相同工艺制备的纯铜相比提升了24.8%。Moustafa等  MOUSTAFA E B,TAHA M A. Evaluation of the microstructure,thermal and mechanical properties of Cu/SiC nanocomposites fabricated by mechanical alloying[J]. International Journal of Minerals,Metallurgy and Materials,2021,28(3):475-486.
37
通过机械合金化的方法制备了纳米SiC增强铜基复合材料(质量分数分别为0%,1%,2%,4%,8%),所制备复合材料的热膨胀系数小于Cu基体的热膨胀系数,随着SiC添加量的增加,铜基体晶粒明显细化,导电性能略有降低。WC颗粒的添加可以改善铜材料的硬度与耐磨性,常用来制备耐磨材料。例如Zhou等  ZHOU K C,PEI H L,XIAO J K,et al. Micro-scratch behavior of WC particle-reinforced copper matrix composites[J]. Rare Metals,2022,41(7):2337-2342.
38
以电解铜粉(粒径<25 μm)和碳化钨粉(粒径<1 μm)为原料,采用粉末冶金法制备了Cu-WC复合材料,并在1~4 N载荷下进行了微观划痕实验,系统研究了法向载荷与WC含量对复合材料摩擦学行为的影响。结果表明,WC颗粒的引入能够显著提高材料的硬度和抗划伤能力,从而改善其整体耐磨性能。随着外加载荷的增大,复合材料的穿透深度和残余深度呈近似线性上升趋势,而提高WC含量则使其降低; 摩擦系数随着载荷增大而升高,但随着WC含量的增加呈现下降趋势,表明WC的添加能有效提升材料的耐磨性能。由于碳化钛具有密度低、弹性模量高、硬度大、熔点高以及热稳定性好等特性,将其作为增强相引入铜基复合材料中,能够有效提升基体材料的抗拉强度和耐磨性能。宋丹等  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
采用直接熔炼法原位制备了质量分数为1% TiC的铜基复合材料。研究结果表明,TiC颗粒在铜基体中分布均匀,且与基体之间形成了良好的界面结合。所制备的Cu-1% TiC复合材料抗拉强度提升至258.5 MPa,优于纯铜,这主要归因于TiC作为硬质增强相发挥了弥散强化作用。此外,原位生成的TiC颗粒在凝固过程中可作为异质形核位点,有效细化晶粒,优化复合材料的微观组织。然而,复合材料的电导率有所下降,从重熔态纯铜的94.5%IACS降低至76.5%IACS,其原因是TiC颗粒本身以及铸造过程中产生的气孔、缩孔和杂质等缺陷增强了电子的散射,从而影响了材料的导电性能。李月英等  李月英,倪慨宇,祝夫文. TiC颗粒增强铜基复合材料的研究[J]. 粉末冶金技术,2018,36(2):106-110.
40
以电解铜粉和TiC粉末为原料,通过粉末冶金工艺成功合成了TiC/Cu复合材料。表征结果显示,TiC颗粒在铜基体中分布较为均匀,仅有少量团聚现象,且与基体界面结合良好。性能测试表明,提高TiC含量可有效提升复合材料硬度,但会导致其致密度与电导率下降。在磨损性能方面,当TiC质量分数达到15%时,材料表现出最佳的耐磨性,与纯铜相比,铜基复合材料的摩擦系数显著下降,主要磨损机制为磨粒磨损。

图5     (a,b) SPS烧结后Cu-7% Y2O3的TEM形貌; (c) 图(a)中的高分辨率图像; (d) Y2O3体积分数对Cu-Y2O3复合材料硬度和电导率的影响; (e)不同Y2O3含量的Cu-Y2O3样品的工程应力-应变曲线
Fig. 5     (a,b) TEM morphologies of Cu-7% Y2O3 after SPS sintering; (c) High resolution transmission electron microscopy image in (a); (d) Influence of volume fraction of Y2O3 content on hardness and electrical conductivity of Cu-Y2O3 composites; (e) Engineering stress-strain curves of Cu-Y2O3 samples with various Y2O3 contents  CHEN Y L,ZHANG X H,HUANG F,et al. Microstructure and properties of Y2O3/Cu composites fabricated by a novel liquid phase in situ reactive synthesis process[J]. Ceramics International,2022,48(21):31273-31280.
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2.3     硼化物陶瓷

在铜基复合材料体系中,TiB2和ZrB2是两类典型的硼化物陶瓷增强相。其中,TiB2的热膨胀系数约为7.8×10−6 K−1,与多数金属材料的热膨胀系数较为接近,表现出良好的物理相容性。此外,B-B共价键和B-Ti离子键的强结合决定了TiB2晶体高强度、高熔点等一系列特性,因此TiB2在铜基复合材料的开发与应用中表现出巨大的潜力  纪嘉明,周飞,李忠华,等. TiB2和ZrB2晶体结构与性能的电子理论研究[J]. 中国有色金属学报,2000(3):358-360.
41
。Wang等  WANG Y F,WANG C G,MA C Y,et al. A novel method enabling in-situ additive manufactured TiB2/Cu composite with high performance[J]. Journal of Materials Research and Technology,2025,36:4893-4897.
42
采用选择性激光熔化技术制备的TiB2/Cu复合材料综合性能优异,电导率高达80.8%IACS的同时,抗拉强度达到了346 MPa。Chen等  CHEN D,JIANG Y H,LI Y F,et al. In situ TiB2/Cu composites fabricated by spray deposition using solid-liquid and liquid-liquid reactions[J]. Transactions of Nonferrous Metals Society of China,2020,30(7):1849-1856.
43
基于固-液与液-液反应喷射沉积技术,并结合后续的冷轧与退火处理,成功制备了原位TiB2颗粒增强铜基复合材料。研究表明,液-液反应中的原位反应更彻底,液-液反应喷射沉积法(401 MPa,83.5%IACS)制备的TiB2/Cu复合材料的综合性能优于固-液反应喷射沉积法(520 MPa,20.2%IACS)。ZrB2陶瓷颗粒具备高熔点、高硬度以及高弹性模量等优异特性,同时与铜熔体之间的润湿性较好,界面润湿角较小,有利于形成稳定的界面结合。作为增强相,ZrB2可以显著提升铜基体的强度、硬度及耐磨性能,因此被视为强化铜基复合材料的理想候选材料之一  SAUNDERS T,TATARKO P,GRASSO S,et al. Effectiveness of boria welding flux in improving the wettability of ZrB2 in contact with molten Cu[J]. Journal of the European Ceramic Society,2018,38(12):4198-4202.
 RADKLAOCHOTSATAIN N,NIYOMWAS S,CHANADEE T. Zirconium diboride-mullite composite form mineral:Combustion synthesis,consolidation,characterizations and properties[J]. Ceramics International,2020,46(11,Part B):18842-18850.
 PASSERONE A,MUOLO M L,NOVAKOVIC R,et al. Liquid metal/ceramic interactions in the (Cu,Ag,Au)/ZrB2 systems[J]. Journal of the European Ceramic Society,2007,27(10):3277-3285.
44-46
。柳青等  柳青,陈俊浩,丁海民,等. 原位合成ZrB2增强铜基复合材料的组织及性能与制备温度的关系[J]. 材料热处理学报,2022,43(4):10-19.
47
采用熔铸法在铜熔体中实现了ZrB2颗粒的原位生成,用于制备ZrB2增强铜基复合材料。研究发现:ZrB2颗粒的形貌与制备温度密切相关。当温度从1150 ℃升至1250 ℃时,颗粒由尺寸约0.5 μm的不规则片状逐渐转变为超过5 μm的板状结构,复合材料的硬度和导电率均随温度上升而逐渐降低; 在1150 ℃时,材料表现出最佳的综合性能,硬度达到最高值105.4HV0.5,电导率为454.3 S/cm。Li等  LI C,SHI J,LI B,et al. Interfacial characteristics,electrical conductivity,mechanical performance,and tribology behavior of ZrB2/Cu composites[J]. Materials & Design,2025,256:114366.
48
通过放电等离子烧结制备了ZrB2/Cu复合材料,并对其压缩性能、耐磨性和电导率进行了研究。实验结果表明,ZrB2颗粒的引入提高了Cu基体的硬度,但电导率有所降低。Cu-20%ZrB2(质量分数)复合材料的电导率和硬度分别为20.18%IACS和231.64HV,复合材料的压缩强度随着增强相含量的增加先提高后下降,连续摩擦层提供的润滑特性和ZrB2微纳米颗粒的支撑作用是增强铜基复合材料减摩抗磨性能的主要原因。

3     陶瓷增强相特性对铜基复合材料的影响

陶瓷增强相的种类繁多,其含量、粒径以及界面结合状态共同影响载荷传递的有效性、塑性变形的协同性及损伤萌生与扩展的主导机制,从而决定力学性能的强化上限。与此同时,这些因素也深刻影响电子传输行为:通过调控界面电阻以及导电通道的连续性,重塑复合材料的电学响应。基于此,本章将系统探讨这些关键特性的影响规律。

3.1     陶瓷颗粒含量对复合材料的影响

在陶瓷颗粒增强铜基复合材料中,陶瓷颗粒的含量对复合材料的最终性能起着关键作用,此处主要对复合材料的抗拉强度、延伸率及电导率进行讨论。图6(a,b)展示了不同类型的增强相对复合材料抗拉强度和塑性的影响  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
 ZOU C L,CHEN Z N,KANG H J,et al. Study of enhanced dry sliding wear behavior and mechanical properties of Cu-TiB2 composites fabricated by in situ casting process[J]. Wear,2017,392-393:118-125.
 ZHANG X D,JIANG Y H,CAO F,et al. Hybrid effect on mechanical properties and high-temperature performance of copper matrix composite reinforced with micro-nano dual-scale particles[J]. Journal of Materials Science & Technology,2024,172:94-103.
 JIANG C,LIU Z K,QIN D,et al. Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method[J]. Materials Today Communications,2024,39:108983.
 HAN L,LIU Z,YU L M,et al. Effect of WC nanoparticles on the thermal stability and mechanical performance of dispersion-reinforced Cu composites[J]. Scripta Materialia,2023,222:115030.
49-52
。分析可知,在适量范围内,复合材料的强度随着陶瓷颗粒含量的增加而增加,但塑性会降低。这是由于在Cu基体中引入的陶瓷颗粒作为非均相形核位点,会细化基体晶粒,铜基体与陶瓷颗粒之间的变形失配会在颗粒周围产生高密度的位错,从而提升复合材料强度  ZHANG S R,KANG H J,WANG Z C,et al. Microstructure and properties of dual-scale particulate reinforced copper matrix composites with superior comprehensive properties[J]. Journal of Alloys and Compounds,2021,860:157888.
 AHMADIAN H,FOULY A,ZHOU T F,et al. Investigating the valence balance of adding Nano SiC and MWCNTs on the improvement properties of copper composite using mechanical alloying and SPS techniques[J]. Diamond and Related Materials,2024,145:111113.
53-54
。从塑性变形角度来看,增强相通过影响变形过程中的位错运动、应力-应变分布等来影响复合材料的塑性。当颗粒体积分数较高时,颗粒引起的内应力明显增加,导致塑性变形早期便萌生裂纹  ZHANG X X,YUAN Y L,ZHAO S Q,et al. Microstructure stability,softening temperature and strengthening mechanism of pure copper,CuCrZr and Cu-Al2O3 up to 1000 ℃[J]. Nuclear Materials and Energy,2022,30:101123.
 姜伊辉,张兴德,石浩,等. 先进导电铜基复合材料设计与制备研究进展[J]. 金属学报,2026,62(2):289-308.
55-56
。此外,范涛等  范涛,丁翔祺,段春媚,等. 原位合成低含量SiC-Cu复合材料的导电和拉伸性能研究[J]. 粉末冶金技术,2018,36(2):96-99.
57
和Zhang等  ZHANG X K,LEI Q,LIU B,et al. Enhanced softening resistance and mechanical properties of Mo2C particle-reinforced Cu-matrix composites[J]. Composite Structures,2023,305:116503.
58
的研究表明,增强相含量过高易引发颗粒团聚,显著降低复合材料的强度和塑性。图6(c)展示了不同类型的增强相对复合材料电导率的影响  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
 ZOU C L,CHEN Z N,KANG H J,et al. Study of enhanced dry sliding wear behavior and mechanical properties of Cu-TiB2 composites fabricated by in situ casting process[J]. Wear,2017,392-393:118-125.
 ZHANG X D,JIANG Y H,CAO F,et al. Hybrid effect on mechanical properties and high-temperature performance of copper matrix composite reinforced with micro-nano dual-scale particles[J]. Journal of Materials Science & Technology,2024,172:94-103.
 JIANG C,LIU Z K,QIN D,et al. Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method[J]. Materials Today Communications,2024,39:108983.
49-51
 EFE G C,ALTINSOY I,YENER T,et al. Characterization of cemented Cu matrix composites reinforced with SiC[J]. Vacuum,2010,85(5):643-647.
59
。随着陶瓷增强相含量的增加,复合材料电导率呈下降趋势。由于自由电子决定了材料的导电性能,任何阻碍或散射自由电子的因素都会导致电阻升高。与金属不同,陶瓷颗粒中自由电子与原子核间的相互作用较强,导致电子迁移率极低,因此其电导率较低。此外,陶瓷颗粒的引入导致铜基体产生晶格畸变,阻碍自由电子的运动,还会提高基体位错密度、晶界面积和整体孔隙率。这些因素均会导致电子散射现象,所以与纯铜相比,铜基复合材料电导率会有所下降  AKBARPOUR M R,GAZANI F,MOUSA MIRABAD H,et al. Recent advances in processing,and mechanical,thermal and electrical properties of Cu-SiC metal matrix composites prepared by powder metallurgy[J]. Progress in Materials Science,2023,140:101191.
35
。综上所述,制备铜基复合材料时需要对增强相的含量进行合理选择。

图6     陶瓷增强相含量与(a)抗拉强度,(b)延伸率和(c)电导率的关系
Fig. 6     Relationship between content of ceramic reinforcement phase and (a) tensile strength  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
 ZOU C L,CHEN Z N,KANG H J,et al. Study of enhanced dry sliding wear behavior and mechanical properties of Cu-TiB2 composites fabricated by in situ casting process[J]. Wear,2017,392-393:118-125.
 ZHANG X D,JIANG Y H,CAO F,et al. Hybrid effect on mechanical properties and high-temperature performance of copper matrix composite reinforced with micro-nano dual-scale particles[J]. Journal of Materials Science & Technology,2024,172:94-103.
 JIANG C,LIU Z K,QIN D,et al. Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method[J]. Materials Today Communications,2024,39:108983.
 HAN L,LIU Z,YU L M,et al. Effect of WC nanoparticles on the thermal stability and mechanical performance of dispersion-reinforced Cu composites[J]. Scripta Materialia,2023,222:115030.
49-52
,(b) elongation  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
 ZOU C L,CHEN Z N,KANG H J,et al. Study of enhanced dry sliding wear behavior and mechanical properties of Cu-TiB2 composites fabricated by in situ casting process[J]. Wear,2017,392-393:118-125.
 ZHANG X D,JIANG Y H,CAO F,et al. Hybrid effect on mechanical properties and high-temperature performance of copper matrix composite reinforced with micro-nano dual-scale particles[J]. Journal of Materials Science & Technology,2024,172:94-103.
 JIANG C,LIU Z K,QIN D,et al. Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method[J]. Materials Today Communications,2024,39:108983.
 HAN L,LIU Z,YU L M,et al. Effect of WC nanoparticles on the thermal stability and mechanical performance of dispersion-reinforced Cu composites[J]. Scripta Materialia,2023,222:115030.
49-52
,and (c) electrical conductivity  宋丹,葛熔熔,陈建清,等. 原位合成TiC弥散强化铜合金工艺与性能[J]. 热加工工艺,2019,48(22):38-41.
39
 ZOU C L,CHEN Z N,KANG H J,et al. Study of enhanced dry sliding wear behavior and mechanical properties of Cu-TiB2 composites fabricated by in situ casting process[J]. Wear,2017,392-393:118-125.
 ZHANG X D,JIANG Y H,CAO F,et al. Hybrid effect on mechanical properties and high-temperature performance of copper matrix composite reinforced with micro-nano dual-scale particles[J]. Journal of Materials Science & Technology,2024,172:94-103.
 JIANG C,LIU Z K,QIN D,et al. Preparation and microstructure of Cu-Al2O3 composites by a novel supercritical water liquid phase in-situ reaction method[J]. Materials Today Communications,2024,39:108983.
49-51
 EFE G C,ALTINSOY I,YENER T,et al. Characterization of cemented Cu matrix composites reinforced with SiC[J]. Vacuum,2010,85(5):643-647.
59

3.2     陶瓷颗粒粒径对复合材料的影响

在强度方面,当陶瓷颗粒尺寸大于1 μm时,由于增强相的载荷传递作用,硬度与强度随之增加; 但如果颗粒尺寸介于0.01~1 μm之间,硬度和强度的增加主要来源于Orowan强化机制  AKBARPOUR M R,GAZANI F,MOUSA MIRABAD H,et al. Recent advances in processing,and mechanical,thermal and electrical properties of Cu-SiC metal matrix composites prepared by powder metallurgy[J]. Progress in Materials Science,2023,140:101191.
35
。更细小的颗粒在相同体积分数下颗粒数量增加、颗粒间距减小,对位错运动的阻碍更有效; 同时,更大的比表面积也有利于应力从基体向硬质颗粒传递。此外,纳米颗粒对基体晶粒生长的抑制作用更强,细晶强化进一步提高了材料的强度。然而,存在一个临界最优粒径范围,当粒径过小(尤其是纳米级)时,极高的表面能导致颗粒严重团聚,团聚体作为应力集中点和裂纹源,反而会削弱材料强度; 同时,过大的界面面积若伴随不良界面结合(如污染或脆性反应层),易成为裂纹拓展路径,损害强度。材料的导电性主要由基体中电子的迁移能力决定,但陶瓷颗粒的引入及其与基体界面处产生的电子散射效应,会阻碍电子的自由运动。当颗粒尺寸减小,其比表面积显著增加,导致界面区域增多,散射作用增强,从而进一步限制电子传输,使得复合材料的导电性降低  YAN Y F,KOU S Q,YANG H Y,et al. Ceramic particles reinforced copper matrix composites manufactured by advanced powder metallurgy:preparation,performance,and mechanisms[J]. International Journal of Extreme Manufacturing,2023,5(3):032006.
60
。赵培峰等  赵培峰,赵江辉,石红信,等. Al2O3颗粒直径对1 vol%的Al2O3/Cu基复合材料组织和性能的影响[J]. 材料热处理学报,2023,44(7):13-20.
61
采用粉末冶金法制备了不同Al2O3颗粒直径(5,10和15 μm)的1%(体积分数)Al2O3/Cu复合材料,力学性能测试实验数据显示,随着Al2O3颗粒尺寸的减小,复合材料的力学性能显著提升。当采用5 μm Al2O3颗粒时,材料展现出优良的力学性能,其屈服强度和抗拉强度分别达到90和207 MPa,较15 μm颗粒增强的复合材料分别提高了28.6%和17.6%。Liu等  LIU Y G,ZHANG J Q,NIU R M,et al. Manufacturing of high strength and high conductivity copper with laser powder bed fusion[J]. Nature Communications,2024,15(1):1283.
21
通过3D打印技术将低含量纳米LaB6颗粒引入Cu基体中,发现较低的添加量可使其接近纯Cu电导率(98.4%IACS),同时弥散分布的增强相可使复合材料强度与塑性同时得到提升,并改善其热稳定性。Efe等  CELEBI EFE G,IPEK M,ZEYTIN S,et al. An investigation of the effect of SiC particle size on Cu-SiC composites[J]. Composites Part B:Engineering,2012,43(4):1813-1822.
62
通过粉末冶金工艺成功制备了SiC/Cu复合材料,如图7所示,随着SiC颗粒尺寸的增大,复合材料的相对密度和电导率均呈现上升趋势。

图7     SiC/Cu复合材料(a)相对密度及其(b)电导率随SiC含量和颗粒尺寸变化的等高线图
Fig. 7     Contour diagram of (a) relative density and (b) electrical conductivity of SiC/Cu composites as a function of SiC content and particle size  CELEBI EFE G,IPEK M,ZEYTIN S,et al. An investigation of the effect of SiC particle size on Cu-SiC composites[J]. Composites Part B:Engineering,2012,43(4):1813-1822.
62

3.3     陶瓷颗粒与铜基体的界面结合对复合材料的影响

界面在复合材料中发挥着至关重要的作用。界面不仅是将载荷传递到增强相的主要媒介,也是硬度、导电、导热率等物理性能传递的桥梁。界面结构直接影响复合材料的微观组织及其整体性能  高苏剑. 气凝胶型陶瓷颗粒增强铜基复合材料组织与性能研究[D]. 北京:北京科技大学,2025.
63
。陶瓷颗粒与铜基体之间的界面通常分为机械结合和化学结合两类。相较于机械结合,化学结合可在界面处实现增强相与铜基体的原子级连接,更有利于提升材料的整体性能。这种结合方式不仅能促进界面区域的电子交换,还能有效降低电子在界面处的散射程度,从而改善复合材料的导电和导热能力。反之,若界面结合较弱,则易引发开裂、颗粒脱粘等问题,加速材料的损伤与失效,进而削弱陶瓷颗粒的增强作用。因此,优化陶瓷颗粒与铜基体之间的界面结合状态,是提升复合材料综合性能的关键途径之一  YAN Y F,KOU S Q,YANG H Y,et al. Ceramic particles reinforced copper matrix composites manufactured by advanced powder metallurgy:preparation,performance,and mechanisms[J]. International Journal of Extreme Manufacturing,2023,5(3):032006.
60
。Nosewicz等  NOSEWICZ S,ROMELCZYK-BAISHYA B,LUMELSKYJ D,et al. Experimental and numerical studies of micro-and macromechanical properties of modified copper-silicon carbide composites[J]. International Journal of Solids and Structures,2019,160:187-200.
64
采用等离子体气相沉积的方法在SiC颗粒上镀镍,然后通过球磨和放电等离子烧结技术制备了界面改性SiC/Cu复合材料。研究表明,镍包覆的SiC颗粒与铜基体发生化学反应,拉伸实验证实涂覆镍金属的复合材料其界面结合强度高于未经界面改性的复合材料。Chen等  CHEN G J,GUO S D,ZHANG H H,et al. The effects of active elements on adhesion strength of SiC/Cu interface in SiC reinforced Cu-based composite:a first-principles investigation[J]. Materials Today Communications,2022,31:103233.
65
基于密度泛函理论的第一性原理计算,分析了Fe,W,Zr和Ti等活性合金元素对界面结合强度的影响。结果表明,引入四种掺杂剂后,界面附着力明显改善,其中Ti表现出良好的界面强化作用。Gan等  GAN K K,GU M Y,MU G H. Effect of Fe on the properties of Cu/SiCp composite[J]. Journal of Materials Science,2008,43(4):1318-1323.
66
研究了添加Fe作为活性元素对Cu-SiC复合材料界面强化的影响,通过粉末冶金制备了Cu-SiC复合材料,并对其微观组织和性能进行了表征分析。实验结果表明,添加Fe元素能够优化复合材料界面结合状态,进而提升其力学性能与热物理性能。此外,Fe的引入还使材料的断裂机制从界面脱粘转变为基体撕裂。图8为Cu-SiC和Cu-Fe-SiC复合材料界面的TEM图像,可以看出:在没有Fe的情况下,SiC和Cu基体之间出现了一些孔洞; 然而,由于Fe的加入,SiC颗粒与铜基体具有更好的界面结合,Cu-Fe-SiC复合材料的界面未观察到孔洞。

图8     复合材料界面处的TEM图像
Fig. 8     TEM images at the interface of composites: (a) Cu-SiC; (b) Cu-Fe-SiC  GAN K K,GU M Y,MU G H. Effect of Fe on the properties of Cu/SiCp composite[J]. Journal of Materials Science,2008,43(4):1318-1323.
66

4     陶瓷颗粒增强铜基复合材料的导电机制及强化机制

4.1     导电机制

陶瓷颗粒增强铜基复合材料的电导率受多种因素控制,包括基体的电导率、增强相的化学成分、体积分数、尺寸大小等,金属材料的电阻率可以用Matthiessen定则表示  王佳睿,张翔,何春年,等. 高导电高耐热铜合金及铜基复合材料的研究现状与展望[J]. 铸造技术,2024,45(1):1-26.
67

ρ=ρt+ρD
式(1)

式中,ρt为晶格振动或声子对电子散射引起的电阻率,称为本征电阻率,依赖于温度,ρD为杂质和缺陷对电子的散射引起的电阻率,称为剩余电阻率,与温度无关。

随着温度升高,晶格原子热振动的振幅增大,导致电子在运动时与声子碰撞的概率和强度增加,从而使电子的平均自由程减小,本征电阻率增大  GAN B,LI J,GAO J J,et al. Electrical conductivity of copper under ultrahigh pressure and temperature conditions by both experiments and first-principles simulations[J]. Physical Review B,2024,109(11):115129.
68
。与温度无关部分描述了由各类缺陷引起的电阻率,可进一步分解为以下部分  BOTCHAROVA E,FREUDENBERGER J,SCHULTZ L. Mechanical and electrical properties of mechanically alloyed nanocrystalline Cu-Nb alloys[J]. Acta Materialia,2006,54(12):3333-3341.
69

ρDρfaρdlρgbρpclρp
式(2)

式中,Δρfa,Δρdl,Δρgb,Δρpcl,Δρp分别为固溶原子、位错、晶界、第二相粒子和孔隙产生的电阻率。本文主要讨论陶瓷颗粒作为增强相在铜基复合材料中的作用,鉴于其与铜基体的固溶度极低,因此忽略固溶原子产生的影响。

因为晶界处产生的点阵畸变会引起自由电子散射,所以晶粒细化会导致材料电导率下降  ANDREWS P V,WEST M B,ROBESON C R. The effect of grain boundaries on the electrical resistivity of polycrystalline copper and aluminium[J]. The Philosophical Magazine:A Journal of Theoretical Experimental and Applied Physics,1969,19(161):887-898.
70
,晶界和晶粒尺寸对铜电阻率的影响可以根据式(3)进行计算  NACHUM S,FLECK N A,ASHBY M F,et al. The microstructural basis for the mechanical properties and electrical resistivity of nanocrystalline Cu-Al2O3[J]. Materials Science and Engineering:A,2010,527(20):5065-5071.
71

Δρgb=23ρsgb(SV)
式(3)

式中,ρsgb为单位晶界的电阻率,SV为单位体积内晶界的面积。

对于不导电的陶瓷增强相,Δρpcl可用式(4)进行计算  SUDHARSHAN PHANI P,VISHNUKANTHAN V,SUNDARARAJAN G. Effect of heat treatment on properties of cold sprayed nanocrystalline copper alumina coatings[J]. Acta Materialia,2007,55(14):4741-4751.
72

Δρpcl=ρm3fp2(1-fp)
式(4)

式中,pm为基体的电阻率,fp为增强相的体积分数。孔隙对电阻率的影响可采用与陶瓷颗粒对电阻率影响相同的模型进行计算  SUDHARSHAN PHANI P,VISHNUKANTHAN V,SUNDARARAJAN G. Effect of heat treatment on properties of cold sprayed nanocrystalline copper alumina coatings[J]. Acta Materialia,2007,55(14):4741-4751.
72

位错密度对电阻率的影响可以通过式(5)进行计算  SUDHARSHAN PHANI P,VISHNUKANTHAN V,SUNDARARAJAN G. Effect of heat treatment on properties of cold sprayed nanocrystalline copper alumina coatings[J]. Acta Materialia,2007,55(14):4741-4751.
 SCHAFLER E,STEINER G,KORZNIKOVA E,et al. Lattice defect investigation of ECAP-Cu by means of X-ray line profile analysis,calorimetry and electrical resistometry[J]. Materials Science and Engineering:A,2005,410/411:169-173.
72-73

Δρdl=Nrdl
式(5)

式中,N为位错密度,rdl为单位位错密度对电阻率的贡献。

4.2     强化机制

陶瓷颗粒增强铜基复合材料强化机制主要有四种,即细晶强化、奥罗万(Orowan)强化、热错配强化、载荷传递强化。

1)细晶强化

增强相通过细化铜基体晶粒来提高屈服强度,这归因于细晶粒缩小了位错滑移面、减少了堆积位错数量,从而抑制了应力集中,最终使相邻晶粒的位错源更难以启动。屈服强度与晶粒大小之间的关系可用Hall-Petch公式表示,即  YAN Y F,QIU Y L,ZHANG X,et al. Tailoring the strength-conductivity combination in Cu matrix composites via in-situ TiB2 synthesis[J]. Journal of Materials Research and Technology,2025,38:62-74.
74

Δσrefine=Ky(dc-12-da-12)
式(6)

式中:Δσrefine为细晶强化对屈服强度的贡献增量; Ky为Hall-Petch常数; dc为复合材料平均晶粒尺寸; da为铜基体平均晶粒尺寸。

2)Orowan强化

Orowan强化是指位错在滑移过程中被迫绕过滑移面上的硬质颗粒,在绕过过程中,位错受阻并在颗粒周围留下位错环(图9),从而消耗更多能量,实现复合材料强度的提升。基于Ashby-Orowan模型,Orowan强化效果可由以下方程式表示  CHEN X F,TAO J M,YI J H,et al. Strengthening behavior of carbon nanotube-graphene hybrids in copper matrix composites[J]. Materials Science and Engineering:A,2018,718:427-436.
75

ΔσOrowan=0.13Gbλlnrb
式(7)

式中:ΔσOrowan为Orowan强化对屈服强度的贡献增量; G为金属基体的剪切模量; b为Burgers矢量; λ为陶瓷颗粒之间的间距; r为陶瓷颗粒平均半径。

图9     Orowan机制示意图
Fig. 9     Schematic diagram of Orowan mechanism  MAO Q Z,LIU Y F,ZHAO Y H. A review on copper alloys with high strength and high electrical conductivity[J]. Journal of Alloys and Compounds,2024,990:174456.
76

3)热错配强化

由于铜基体与陶瓷增强相的热膨胀系数存在差异,温度的变化导致基体与陶瓷颗粒发生不同的热变形,进而在陶瓷颗粒/基体界面区域诱发残余应力场,这种热失配应力会显著提高界面附近的位错密度,从而起到强化作用。其强化效果主要取决于增强相与铜基体热膨胀系数差值、颗粒的体积分数、尺寸及分布等特性。热错配引起的屈服强度增量可由式(8)表示  CHEN X F,TAO J M,YI J H,et al. Strengthening behavior of carbon nanotube-graphene hybrids in copper matrix composites[J]. Materials Science and Engineering:A,2018,718:427-436.
 MAO Q Z,LIU Y F,ZHAO Y H. A review on copper alloys with high strength and high electrical conductivity[J]. Journal of Alloys and Compounds,2024,990:174456.
 何广进,李文珍. 纳米颗粒分布对镁基复合材料强化机制的影响[J]. 复合材料学报,2013,30(2):105-110.
75-77

ΔσCTE=kGb12VpΔαΔT(1-Vp)bdp
式(8)

式中:ΔσCTE为热错配强化对屈服强度的贡献增量; k为常数; G为金属基体剪切模量; b为Burgers矢量; Δα为热膨胀系数之差; Vp为增强相的体积分数; ΔT为制备温度与室温之差; dp为颗粒的尺寸。

4)载荷传递强化

铜基复合材料在塑性变形过程中,载荷首先作用于硬度较低的铜基体,部分载荷通过铜基体与陶瓷颗粒的界面传递到硬度较高的陶瓷颗粒上,最终由铜基体和陶瓷颗粒相互协作共同承担外加的载荷  MATIN A,SANIEE F F,ABEDI H R. Microstructure and mechanical properties of Mg/SiC and AZ80/SiC nano-composites fabricated through stir casting method[J]. Materials Science and Engineering:A,2015,625:81-88.
78
。其效率高度依赖于增强颗粒与基体之间界面结合情况,以及颗粒的形状、尺寸、取向和体积分数。载荷传递引起的屈服强度增量可由下式表示  NARDONE V C,PREWO K M. On the strength of discontinuous silicon carbide reinforced aluminum composites[J]. Scripta Metallurgica,1986,20(1):43-48.
79

ΔσLT=Vpσm[(L+T)A4L]
式(9)

式中:ΔσLT为载荷传递强化对屈服强度的贡献增量,MPa; Vp为增强相颗粒体积分数; σm为铜基体的屈服强度; LT分别代表颗粒平行于和垂直于载荷方向的尺寸; A为颗粒的长径比。

当增强相为等轴状颗粒时,公式可简化为:

Δσ=0.5Vpσm
式(10)

5     总结与展望

陶瓷颗粒增强铜基复合材料在电子封装、航空航天和轨道交通等领域展现出重要应用潜力。近年来,制备工艺的不断发展及研究的不断深入,为制备性能可控的复合材料提供了多样化途径。然而,不同制备方法在增强相分布均匀性、界面结合强度、性能平衡及工业化可行性等方面仍存在局限。

当前研究的主要挑战包括:大多数高性能复合材料显著依赖复杂工艺,存在设备成本高、工艺重复性差、成品率低等问题,难以满足工业化量产需求; 陶瓷颗粒与铜基体间界面结合强度不足,易成为裂纹萌生和扩展的薄弱环节,现有界面改性技术虽能部分改善结合强度,但可能引入额外界面电阻,损害导电性能; 颗粒团聚或偏析仍较普遍,影响致密化及性能稳定性; 强度的提升往往伴随导电、导热性能下降,如何在两者间取得良好平衡仍是难点。

未来研究聚焦方向多尺度协同设计(如纳米-微米混杂增强)与界面工程优化及智能化制备技术(如机器学习辅助工艺调控),以突破强度-电导率的性能瓶颈; 构建材料制备与性能数据库,实现数据驱动的工艺参数设计与优化; 同时,探索其在极端环境下的适应性(如抗辐照、耐高温),推动该材料在核聚变、高端电子器件等领域的实用化进程。

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