高性能铝青铜合金的制备及其腐蚀与磨损性能研究进展

基金项目

泰州市科技支撑计划项目(TS202403); 江苏省“六大人才高峰”项目(XCL-265)资助

中图分类号:

TG146.1+1

文献标识码:

A

作者简介

万浩(1989—),男,江苏泰州人,博士,副教授,研究方向:工程材料制备及失效分析,E-mail:wanhao@tzu.edu.cn

流转信息

收稿日期 : 2025-06-06

修订日期 : 2025-07-17

引文格式

万浩,陈悦,张修旷,蔡安琦,吴国荣,杨婉婷. 高性能铝青铜合金的制备及其腐蚀与磨损性能研究进展[J]. 铜业工程,2026(1):59-75.

Research Progress on Preparation of High-performance Aluminum Bronze Alloys and Their Corrosion and Wear Properties

Citations

WAN Hao,CHEN Yue,ZHANG Xiukuang,CAI Anqi,WU Guorong,YANG Wanting. Research progress on preparation of high-performance aluminum bronze alloys and their corrosion and wear properties[J]. Copper Engineering,2026(1):59-75.

铜业工程    第1期    59-75
doi10.3969/j.issn.1009-3842.2026.01.006
材料制备与加工工程(Material Preparation and Process Engineering)

高性能铝青铜合金的制备及其腐蚀与磨损性能研究进展

  • 万浩
  • 陈悦
  • 张修旷
  • 蔡安琦
  • 吴国荣
  • 杨婉婷
泰州学院机电工程学院江苏 泰州 225300

作者简介

万浩(1989—),男,江苏泰州人,博士,副教授,研究方向:工程材料制备及失效分析,E-mail:wanhao@tzu.edu.cn

基金项目

泰州市科技支撑计划项目(TS202403); 江苏省“六大人才高峰”项目(XCL-265)资助

中图分类号:

TG146.1+1

文献标识码:

A

流转信息

收稿日期 : 2025-06-06     修订日期 : 2025-07-17     

引文格式

万浩,陈悦,张修旷,蔡安琦,吴国荣,杨婉婷. 高性能铝青铜合金的制备及其腐蚀与磨损性能研究进展[J]. 铜业工程,2026(1):59-75.

摘要

铝青铜合金是在铜中添加主要合金元素铝以及镍、铁等其他合金元素所形成的一类青铜合金。铝青铜合金具有良好的力学性能、耐磨性能和耐蚀性能,常作为齿轮、阀门、螺旋桨等零件材料,在工程领域得到广泛应用。工业技术的快速发展,对铝青铜的各项性能提出了更高要求。传统铸态铝青铜由于铸造缺陷的存在以及复杂的多相结构,在特定的服役环境下易出现失效行为,需根据服役条件的要求,有针对性地对合金的组成、微观结构和性能进行优化与改进。本文围绕铝青铜合金的微观结构特征,制备工艺以及力学、腐蚀和磨损性能之间的内在联系,综述了近年来利用合金化处理、热处理、增材制造、表面改性处理等工艺制备高性能铝青铜的研究进展,重点总结与分析了不同工艺条件下铝青铜的耐蚀性能和摩擦磨损性能,并对其后续研究方向进行了展望。

关键词

铝青铜;显微组织;力学性能;腐蚀性能;磨损性能;

Research Progress on Preparation of High-performance Aluminum Bronze Alloys and Their Corrosion and Wear Properties

  • WAN Hao
  • CHEN Yue
  • ZHANG Xiukuang
  • CAI Anqi
  • WU Guorong
  • YANG Wanting
School of Mechanical and Electrical EngineeringTaizhou UniversityTaizhou 225300China

Citations

WAN Hao,CHEN Yue,ZHANG Xiukuang,CAI Anqi,WU Guorong,YANG Wanting. Research progress on preparation of high-performance aluminum bronze alloys and their corrosion and wear properties[J]. Copper Engineering,2026(1):59-75.

Abstract

Aluminum bronze alloys are a type of bronze alloy formed by mainly adding aluminum to copper, along with other alloying elements such as nickel and iron. Aluminum bronze alloys feature excellent mechanical properties, wear resistance and corrosion resistance, and are widely used as gears, valves and propellers. With rapid advancement of industrial technology, increasingly stringent requirements are being imposed on various properties of aluminum bronze. For traditional as-cast aluminum bronze, the presence of casting defects combined with complex multiphase structure makes it susceptible to failure under specific service conditions. The composition, microstructure, and properties of the alloy should be systematically optimized and improved in a targeted manner to meet specific requirements of service conditions. This paper investigated intrinsic relationship among preparation process, microstructural characteristics, as well as mechanical, corrosion, and wear properties of aluminum bronze alloys. It provided a comprehensive review of recent advancements in the development of high-performance aluminum bronzes through alloying, heat treatment, additive manufacturing, surface modification, and other processes. Corrosion resistance and friction-wear resistance of aluminum bronze under various technological conditions were systematically summarized and analyzed before potential future research directions were outlined.

Keywords

aluminum bronze;microstructure;mechanical property;corrosion property;wear property;



铝青铜是利用Al,Ni等元素与Cu合金化得到的一类青铜合金,不但具有优良的铸造性能、力学性能、抗蚀性能和耐磨性能,其价格相较锡青铜、铍青铜等更为便宜,因而在机械制造、海洋工程等领域应用广泛  张钢,李敬勇,刘健,等. 热处理对CMT电弧增材制造铝青铜组织及力学性能的影响[J]. 塑性工程学报,2025,32(2):213-221.
 YI X N,MA A L,ZHENG Y G,et al. Elucidating different selective corrosion behavior of two typical marine aluminum bronze alloys from the perspective of constituent phases[J]. Corrosion Science,2024,235:112167.
 MORSHED-BEHBAHANI K,BISHOP D P,NASIRI A. A review of the corrosion behavior of conventional and additively manufactured nickel–aluminum bronze (NAB) alloys:current status and future challenges[J]. Materials Horizons,2023,10(12):5391-5435.
1-3
。根据添加合金元素的数量,可将铝青铜分为二元简单铝青铜和多元复杂铝青铜两种。向Cu中加入Al元素得到Cu-Al二元合金即为简单铝青铜,在此基础上继续添加Ni,Fe和Mn等其他合金元素,则可获得性能更为优异的多元复杂铝青铜。随着工业技术的不断发展,为满足实际工况对合金提出的更为严苛的性能要求,复杂多元铝青铜受到科研工作者更广泛的关注和更深入的研究  XU C,PENG Y,CHEN L Y,et al. Tailoring microstructure via heat treatment to improve the corrosion resistance of directed energy deposited nickel-aluminum bronze alloy[J]. Journal of Materials Research and Technology,2023,25:5210-5226.
 SHAIK M A,GOLLA B R. Microstructure,mechanical and wear property correlation of Al bronze alloys[J]. Powder Metallurgy,2023,66(1):54-63.
 MA S,LI X,YANG X B,et al. Effect of annealing temperature on microstructure and properties of a heavy warm rolled nickel aluminum bronze alloy[J]. Metallurgical and Materials Transactions A,2023,54(1):293-311.
4-6

由于复杂多元铝青铜合金的组成元素较多,在冷却过程中会析出不同的相,因而其室温组织由多种相构成  MISHRA M K,RAO A G,TRIPATHI A,et al. On the microstructure and mechanical behavior of as-cast,wire-arc,and laser additively manufactured nickel-aluminum-bronze alloy[J]. Metallography,Microstructure,and Analysis,2025,14(3):476-481.
7
。这些组成相的成分、尺寸、分布、形貌等特征,共同决定铝青铜合金的综合性能。根据服役条件,选择适当的工艺方法,从合金成分、温度、冷却速率等方面,对铝青铜合金显微组织特征进行调控,可获得理想的组织结构以及相匹配的优异性能。基于此,本文重点围绕近年来科研工作者以提升铝青铜合金性能为目的所开展的工作,综述了利用合金化处理  寿德荣,邓正华,张朝阳. 添加铁元素对Cu-10Al-4Ni粉末冶金合金组织和性能的影响[J]. 机械工程材料,2023,47(8):18-22.
8
、热处理  MA S,YANG X B,FU L M,et al. Achieving high strength-ductility synergy in nickel aluminum bronze alloy via a quenching-aging-tempering heat treatment[J]. Materials Letters,2023,333:133661.
9
、增材制造  XU C,PENG Y,CHEN L Y,et al. Corrosion behavior of wire-arc additive manufactured and as-cast Ni-Al bronze in 3.5 wt% NaCl solution[J]. Corrosion Science,2023,215:111048.
10
以及表面改性处理  IVANOV K V,CHESNOKOV A E,SMIRNOV A V. Application of high current pulsed electron beam irradiation to smoothing of cold spray aluminum bronze coating[J]. Vacuum,2022,197:110780.
11
等工艺方法优化铝青铜微观结构,进而改善力学性能、腐蚀性能以及磨损性能等方面所取得的研究进展,指出了目前仍然存在的不足,并对其后续研究方向进行了展望。

1     铝青铜合金的平衡相图及其显微组织

图1(a)为Cu-Al二元相图Al侧部分,可见Al含量低于7.4%的二元简单铝青铜合金,其在室温下为α单相组织  DHARMENDRA C,RICE K P,AMIRKHIZ B S,et al. Atom probe tomography study of κ-phases in additively manufactured nickel aluminum bronze in as-built and heat-treated conditions[J]. Materials & Design,2021,202:109541.
12
。α相是一种具有较好塑性的Cu基固溶体[面心立方(fcc)结构]。Al含量高于7.4%的合金 在高温时还会出现Cu3Al基的β相[体心立方(bcc)结构]。在缓冷条件下,β相会发生共析分解反应形成层片状的α+γ2相,其中γ2相是一种以Cu4Al9为基的硬脆相。尤其是以网状形式出现的γ2相,会提高合金的脆性,需要抑制其产生。虽然可以加快冷却速率使 β相发生马氏体转变形成β'相,但这一方法不适用于较大的铸件。专家学者在二元简单铝青铜的基础上加入Ni,Fe等元素后发现,共析反应产物转变为α+κ相,在改善合金的微观组织的同时还能提高其综合性能,并据此开发出多元复杂铝青铜合金。

图1     (a)Cu-Al合金相图;(b)Ni和Fe质量分数各5%的Cu-Al-Ni-Fe合金相图;(c)铸态镍铝青铜Cu-9Al-4Ni-4Fe-1Mn合金中不同κ相的扫描电镜(SEM)图像;(d)铸态镍铝青铜的EBSD反极图
Fig. 1     (a) Binary Cu-Al phase diagram;(b) Cu-Al-Ni-Fe phase diagram at 5% Ni and 5% Fe;(c) SEM image of cast nickel-aluminum bronze (NAB) Cu-9Al-4Ni-4Fe-1Mn showing various κ-phases  DHARMENDRA C,RICE K P,AMIRKHIZ B S,et al. Atom probe tomography study of κ-phases in additively manufactured nickel aluminum bronze in as-built and heat-treated conditions[J]. Materials & Design,2021,202:109541.
12
;(d) EBSD inverse pole figure map of cast NAB  CAI X,YANG M M,WANG S,et al. Experimental investigations on corrosion behavior and antibacterial property of nickel-aluminum bronze fabricated through wire-arc additive manufacturing (WAAM)[J]. Corrosion Science, 2023,214:111040.
15

多元复杂铝青铜合金的典型微观组织主要由α相、β'相和κ相构成[图1(b)  DHARMENDRA C,RICE K P,AMIRKHIZ B S,et al. Atom probe tomography study of κ-phases in additively manufactured nickel aluminum bronze in as-built and heat-treated conditions[J]. Materials & Design,2021,202:109541.
12
。适量的β'相可以提高合金的强度及耐磨性能,但对韧性和耐蚀性能具有负面影响。κ相是铝青铜合金中的主要强化相。根据κ相的形成温度、组成、形貌及分布,又可将其分为κ相,κ相,κ相和κ相等不同类型  HASAN F,JAHANAFROOZ A,LORIMER G W,et al. The morphology,crystallography,and chemistry of phases in as-cast nickel-aluminum bronze[J]. Metallurgical Transactions A,1982,13:1337-1345.
13
。在平衡冷却条件下,随着温度降至约1040,930和820 ℃时会分别形成κ相,κ相和κ相,κ相会在随后的冷却过程中析出。κ相通常以花瓣状形貌出现在α相晶粒内部,其尺寸可达数十微米,如图1(c)所示  DHARMENDRA C,RICE K P,AMIRKHIZ B S,et al. Atom probe tomography study of κ-phases in additively manufactured nickel aluminum bronze in as-built and heat-treated conditions[J]. Materials & Design,2021,202:109541.
12
。κ相并非单相组织,而是由无序的富Fe固溶体(bcc结构)、Fe3Al(DO3结构)和FeAl(B2结构)等构成。因而,κ相的形成还需要合金中有较高的Fe含量,且高于Ni含量  ZHAO B J,LV Y T,DING Y,et al. The grain refinement mechanisms of various phases in shot-peened nickel-aluminum bronze (NAB) alloy[J]. Materials Characterization,2018,144:77-85.
14
。Fe3Al基的κ相往往呈球形,其尺寸相较κ相要小,常伴随κ相出现于晶界或α/β'相界处。κ相呈薄片状,为β相共析分解的产物,是NiAl基的金属间化合物,具有B2结构。因此,添加Ni元素的合金中才会形成κ相,在不含Ni的合金中,β相则会共析分解为α+γ2相。κ相是弥散分布于α相中的具有微纳尺寸的小颗粒,其晶体结构与κ相相同。图1(d)为铸态镍铝青铜的电子背散射衍射(EBSD)反极图  CAI X,YANG M M,WANG S,et al. Experimental investigations on corrosion behavior and antibacterial property of nickel-aluminum bronze fabricated through wire-arc additive manufacturing (WAAM)[J]. Corrosion Science, 2023,214:111040.
15

图2为亚共析镍铝青铜Cu-11Al-6Ni-5Fe-1Mn在平衡结晶过程中的相转变示意图,Pisarek  PISAREK B P. Model of Cu-Al-Fe-Ni bronze crystallization[J]. Archives of Foundry Engineering,2013,13(3):72-79.
16
利用差热分析法测得不同的相转变温度,并将这一过程分为Ⅰ~Ⅷ阶段进行了详细分析。阶段Ⅰ~Ⅲ呈现了合金熔体中随温度降低逐渐结晶出β相固溶体的过程。继续冷却至阶段Ⅳ,κ相将在β相相界及内部的富Fe区域形核与长大。在阶段Ⅴ的冷却过程中,大部分的β相会转变为α相,残留的少量β相为富Al相。 α相中富Ni的区域会在阶段Ⅵ析出片状或板条状的κ相。此后,因为温度的进一步降低也降低了Fe元素在α相中的溶解度,所以在阶段Ⅶ,α相中会析出富铁的κ相。在阶段Ⅷ,当温度过冷至共析转变温度以下时,残余的β相会发生共析转变形成α+γ2相。不过,现代镍铝青铜由于Al含量较低,将不会形成γ2相。在快速冷却条件下,会形成β'马氏体组织,而在缓慢冷却条件下,则形成α+κ相。

图2     Cu-11Al-6Ni-5Fe-1Mn亚共析铝青铜平衡结晶过程中的相转变示意图
Fig. 2     Schematic diagram of phase transformation during equilibrium crystallization process of a hypoeutectoid Cu-11Al-6Ni-5Fe-1Mn aluminum bronze  PISAREK B P. Model of Cu-Al-Fe-Ni bronze crystallization[J]. Archives of Foundry Engineering,2013,13(3):72-79.
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2     铝青铜合金的性能调控及其强韧化

2.1     合金化方法

通过对铝青铜合金中元素的种类、含量等进行优化,调控合金的微观结构,可提升铝青铜合金力学性能、腐蚀性能、磨损性能等,满足特定工况条件。下面将分析讨论不同合金元素对铝青铜合金性能的影响。

1)Al元素的作用。对于Al含量低于7.4%的铝青铜,其室温组织通常只有α相。因此,此时的合金具有良好的韧性和塑性,但强度和硬度值较低。当Al含量高于7.4%时,合金中会出现β相,其所占比例会随Al含量的升高而增大。β相是一种高温相,会在降温过程中通过共析分解形成α+γ2相。值得注意的是,在海水、氯化物溶液等腐蚀介质中,γ2相会成为阳极且先被腐蚀,使合金出现脱Al腐蚀现象。

2)Ni元素的作用。在铝青铜中添加Ni元素有利于提高其机械性能及耐蚀性能等  BARR C,PATERAS A,MOLOTNIKOV A,et al. Effect of composition on the tensile and corrosion performance of nickel aluminium bronze produced via laser powder bed fusion[J]. Additive Manufacturing,2022,54:102771.
17
。Ni元素不但可以促进共析点向高Al方向偏移,还能提高共析转变的温度,增大α相区的同时减小β相区的范围。另外,改变Ni元素添加量还会带来α相的形貌变化,如无Ni或Ni含量较低时,α相呈针状,而当Ni含量为3%时,α相则呈片状。Ni元素在α相中有一定的固溶度,过量的Ni则会析出富Ni 的κ相。通常是通过同时添加等量的Ni和Fe元素来避免γ2相的生成。其中,Ni加入量控制在1%~6%。

3)Fe元素的作用。少量的Fe元素可以细化铝青铜晶粒,提高合金的力学性能和耐磨性能  MICAH B,TERNGU A. Physical and mechanical characterization of aluminum bronze (Cu-10% Al) alloy doped with Fe[J]. ATBU Journal of Science,Technology and Education,2024,9(1):450-458.
 JIN F,YIN T Y,ZHANG S,et al. Effect of Ni and Fe elements on microstructure and high temperature oxidation behavior of laser cladding aluminum bronze coating[J]. Materials Chemistry and Physics,2023,297:127383.
18-19
。另外,Fe元素还可以减缓铝青铜中原子的扩散速度,扩大α相区并增加β相稳定性,降低共析转变温度,有利于减轻“缓冷脆性”现象。由于Fe在α相中的固溶度很低,尽管超出固溶的部分Fe可以与其他合金元素形成富Fe的κ相,但过量的Fe则会形成针状的FeAl3,降低合金的力学性能及耐蚀性能。因此,铝青铜合金中的Fe元素加入量通常不超过5%。

4)Mn元素的作用。在铝青铜中加入Mn元素可以稳定β相区,降低共析转变温度,延缓共析转变  李雨蔚,肖来荣,章玮,等. 不同Mn含量的铝青铜合金组织与性能[J]. 稀有金属,2017,41(9):985-991.
20
。Mn元素可以改善铝青铜的力学性能、耐蚀性能以及冷热塑性加工性能,其含量通常在1%~2.5%,高含量时可达11%~14.5%。

5)其他合金元素的作用。在铝青铜中,添加Zn元素有扩大α相区范围的作用。少量的Zn会以合金化的形式强化合金,但过量添加则会造成严重的塑性损失  DZIUBINA A V,MAZORCHUK V F,UZLOV K I,et al. Chemical composition improvement of aluminum-iron bronze industrial casting[J]. Bulletin of Prydniprovs'ka State Academy of Civil Engineering and Architecture,2020(3):57-62.
21
。而且,Zn还会减少富Fe硬质相颗粒的数量,所以Zn含量通常控制在0.3%~1.0%。添加少量的Si元素可以提高铝青铜合金机械性能以及耐磨性能  THONGYOTHEE C,CHAREONVILISIRI S. A study on the influence of silicon content on wear and mechanical properties of cast nickel-aluminum bronze[J]. Engineering,Technology & Applied Science Research,2024,14(6):18316-18323.
22
。Si元素在α相有一定的固溶度,但为避免形成复杂的脆性相,造成合金力学性能降低,其加入量通常不超过0.2%。少量的Cr元素可以细化铝青铜的显微组织,提高其力学性能  张富强,龙飞,浦娟,等. Cr含量对铝青铜熔覆涂层组织及性能的影响[J]. 精密成形工程,2025,17(3):58-66.
23
。此外,Cr还能在退火过程中抑制铝青铜晶粒的粗化,并起到提高退火铝青铜硬度的作用。

2.2     其他强韧化方法

在利用合金化来提升铝青铜性能的同时,研究者们还结合热处理、增材制造、表面改性等来进一步强韧化铝青铜合金。例如,孙业成等  孙业成,王超宁,孔见. Cr微合金化铸态铝青铜合金组织与性能研究[J]. 有色金属工程,2021,11(1):17-26.
24
在对高锰铝青铜进行Cr合金化的同时,利用热处理来提高合金的综合力学性能。结果发现,在进行0.1%~0.5%的Cr合金化处理以及(300~500) ℃×(1~3) h保温的样品中,添加0.3%Cr并经300 ℃保温2 h的合金具有最佳的综合力学性能,其抗拉强度、显微硬度和延伸率分别为821 MPa,227HV0.5和15.1%。吕海波等  吕海波,索忠源,姜峰,等. Fe基非晶合金对QAl9-4铝青铜组织和力学性能的影响[J]. 特种铸造及有色合金,2020,40(11):1298-1301.
25
利用工业纯Fe和铁基非晶合金Fe-13Si-9B分别对QAl9-4铝青铜进行合金化处理,并对其微观结构和力学性能进行了研究。结果表明,Si和B元素的添加可为合金带来组织细化效果以及基体强化作用。尽管得到的两种合金的铸态组织均由α+β'+κ相组成,但加入铁基非晶合金的铝青铜合金则形成了更为细小和均匀的组织,并获得了更为优异的综合力学性能。赵玲等  赵玲,刘光磊,张思源,等. 固溶时效深冷复合处理对ZCuAl10Fe3Mn2合金微观组织和热疲劳性能的影响[J]. 材料工程,2019,47(12):63-70.
26
则研究了T6、深冷处理以及T6+深冷处理对ZCuAl10Fe3Mn2合金微观结构、力学性能和热疲劳性能的影响。结果发现,相较于其他两种处理方式,T6+深冷处理可以更有效地细化和均匀化α相,进而提高合金的综合力学性能和热疲劳性能。

增材制造是一种通过逐层堆叠材料的方法来获得块体或零件的制造技术,可以有效提高材料的致密性及组织均匀性  郑富凯,韩光达,张思雨,等. 铜合金在增材制造领域的研究进展[J]. 铜业工程,2025(2):110-129.
27
。电弧、电子束和激光是增材制造过程中的常用热源,与传统制造方法如铸造相比,增材制造可以获得更快的冷却速率。通过工艺参数优化、微观结构调控、合金性能提升的方式,可使增材制造铝青铜满足服役条件的要求。电弧增材制造(WAAM)铝青铜的微观结构仍由α相和各种κ相构成,加工时的中等冷却速率相比铸造方法更快,这使得显微结构变得更为细小  ORZOLEK S M,SEMPLE J K,FISHER C R. Influence of processing on the microstructure of nickel aluminum bronze (NAB)[J]. Additive Manufacturing,2022,56:102859.
28
。刘缙等  刘缙,王克鸿,徐程,等. 电弧增材镍铝青铜的组织与性能[J]. 焊接学报,2024,45(8):103-109.
29
发现WAAM技术可以改善镍铝青铜的组织并提高其力学性能。对比铸态和WAAM合金显微组织可知,WAAM工艺可以抑制合金中κ相的析出,促进β'相向α+κ相的转变,在有效细化显微组织的同时可均匀化合金中的元素分布,如图3所示,这也使得WAAM工艺所制备铝青铜合金的抗拉强度和延伸率比铸态合金分别提高了28.4%和90%。

图3     铸态和WAAM镍铝青铜显微组织的光学显微镜(OM)、SEM图像及元素分布图:(a,c)铸态;(b,d)WAAM
Fig. 3     OM images,SEM images and EDS mapping images of (a,c) cast and (b,d) WAAM NAB  刘缙,王克鸿,徐程,等. 电弧增材镍铝青铜的组织与性能[J]. 焊接学报,2024,45(8):103-109.
29

激光或电子束基增材制造具有更快的冷却速率,所获得铝青铜合金的微观结构主要由β'马氏体和纳米级κ相组成  ORZOLEK S M,SEMPLE J K,FISHER C R. Influence of processing on the microstructure of nickel aluminum bronze (NAB)[J]. Additive Manufacturing,2022,56:102859.
28
。与铸态合金相比,激光或电子束基增材铝青铜的屈服强度可以提高60%~100%,但也会造成延伸率的降低(<30%)。Han等  HAN C J,ZOU Y J,HU G L,et al. Effect of process parameters on microstructure and mechanical properties of a nickel-aluminum-bronze alloy fabricated by laser powder bed fusion[J]. Journal of Central South University, 2024,31(8):2944-2960.
30
通过控制激光粉末床熔融(LPBF)打印镍铝青铜过程中的激光功率、扫描速度等工艺参数,一方面提高了合金的致密度,另一方面通过影响LPBF打印凝固过程中的相转变以及相构成(图4),进而改善镍铝青铜的力学性能。在激光功率为350 W、扫描速度为800 mm/s时,由于针状马氏体得到细化且数量增多,合金获得最大的显微硬度(386HV)和抗拉强度(671 MPa)。

图4     LPBF打印镍铝青铜过程中的微观结构演化示意图:(a)初始阶段;(b)中间阶段;(c)最终阶段
Fig. 4     Schematic diagram of microstructure evolution of LPBF-printed NAB:(a) Initial stage;(b) Middle stage;(c)Terminal stage  HAN C J,ZOU Y J,HU G L,et al. Effect of process parameters on microstructure and mechanical properties of a nickel-aluminum-bronze alloy fabricated by laser powder bed fusion[J]. Journal of Central South University, 2024,31(8):2944-2960.
30

对铝青铜合金进行表面改性处理,优化表层微观结构,提高合金的使用性能,近年来也获得越来越多的关注。铝青铜的表面改性方法主要包括:表面搅拌摩擦加工  ZANGENE D,KAYVANDARIAN F,KHODABAKHSHI F,et al. Nickel-aluminum bronze (NAB) alloy design under two-steps casting and submerged friction stir processing[J]. Materials Science and Engineering:A,2024,890:145960.
 LI Y,LIAN Y,SUN Y J. Comparison of cavitation erosion behaviors between the as-cast and friction stir processed Ni–Al bronze in distilled water and artificial seawater[J]. Journal of Materials Research and Technology,2021,13:906-918.
31-32
、激光表面处理  杨杰,贺春林,孙宇海漩,等. 铜合金表面激光熔覆技术的研究现状[J]. 材料保护,2022,55(11):133-141,177.
 GUO N,GAO Y,GAO Y K,et al. Microstructure and properties of in-situ nickel-aluminum bronze coating by underwater wire-feed laser cladding[J]. Journal of Materials Research and Technology,2023,25:6459-6471.
 GAO Y,YANG W Y,HUANG Z Z,et al. Effects of residual stress and surface roughness on the fatigue life of nickel aluminium bronze alloy under laser shock peening[J]. Engineering Fracture Mechanics,2021,244:107524.
 QIN Z B,XIA D H,ZHANG Y W,et al. Microstructure modification and improving corrosion resistance of laser surface quenched nickel–aluminum bronze alloy[J]. Corrosion Science,2020,174:108744.
33-36
、表面喷涂  佘定君. 直升机传动系统用铝青铜-聚苯酯涂层磨损性能研究[J]. 材料研究与应用,2024,18(4):662-667.
 WAN S M,CUI X F,JIN Q W,et al. Microstructure and properties of cold sprayed aluminum bronze coating on MBLS10A-200 magnesium-lithium alloy[J]. Materials Chemistry and Physics,2022,281:125832.
 史周琨,徐丽萍,张吉阜,等. 超音速火焰喷涂铝青铜涂层微动磨损行为[J]. 表面技术,2021,50(11):226-232,278.
 王荣城,王文宇,殷凤仕,等. 铜及其合金表面涂层技术与增材制造技术研究进展[J]. 材料导报,2021,35(19):19142-19152.
37-40
、电沉积  ZHANG Y,LI L,WANG X M,et al. Experimental study on aluminum bronze coating fabricated by electro-spark deposition with subsequent ultrasonic surface rolling[J]. Surface and Coatings Technology,2021,426:127772.
41
、微弧氧化  MENG X Z,ZHU L Y,LI Y Y,et al. The influence of ultrasonic vibration on micro-arc oxidation behaviour of manganese aluminium bronze[J]. Journal of Materials Research and Technology,2024,33:758-772.
42
等。表面搅拌摩擦加工基于搅拌摩擦焊技术发展而来,可以在细化和均匀化表层组织的同时消除铸造缺陷,提高合金的综合性能。激光表面处理可以对样品的表层材料进行重熔、合金化及表面淬火等,通过改变表层微观结构来达到调控性能的目的。相关的激光表面改性研究  杨杰,贺春林,孙宇海漩,等. 铜合金表面激光熔覆技术的研究现状[J]. 材料保护,2022,55(11):133-141,177.
 GUO N,GAO Y,GAO Y K,et al. Microstructure and properties of in-situ nickel-aluminum bronze coating by underwater wire-feed laser cladding[J]. Journal of Materials Research and Technology,2023,25:6459-6471.
 GAO Y,YANG W Y,HUANG Z Z,et al. Effects of residual stress and surface roughness on the fatigue life of nickel aluminium bronze alloy under laser shock peening[J]. Engineering Fracture Mechanics,2021,244:107524.
 QIN Z B,XIA D H,ZHANG Y W,et al. Microstructure modification and improving corrosion resistance of laser surface quenched nickel–aluminum bronze alloy[J]. Corrosion Science,2020,174:108744.
33-36
,如激光熔覆、激光冲击强化和激光淬火等,一直是近年来的研究热点。

3     铝青铜合金的耐蚀性能

简单铝青铜合金中加入Ni,Fe和Mn等合金元素形成的多元复杂铝青铜,具有良好的力学性能,同时在海洋服役环境下也具有较好的耐蚀性能,在海洋装备领域应用广泛。然而,多元复杂铝青铜中的多相构成以及海洋环境的复杂性,使其在服役过程中面临选相腐蚀、空化腐蚀(空蚀)等诸多挑战,相关的腐蚀行为研究已成为当前关注的焦点。李慧琳等  李慧琳,宋亓宁,张根元,等. 螺旋桨用铜合金在3.5% NaCl溶液中的空蚀和冲蚀行为[J]. 腐蚀与防护,2022,43(7):74-80,86.
43
对比研究了锰黄铜、锰铝青铜和镍铝青铜3种铜合金在3.5%NaCl溶液中的空蚀和冲蚀损伤行为,发现镍铝青铜的抗空蚀和冲蚀性能最为优异。因此,本小节主要对海洋工程中应用最为广泛的含Ni的铝青铜合金腐蚀行为、机理等进行分析。

3.1     静态腐蚀性能

在静态海水腐蚀条件下,选相腐蚀是镍铝青铜最常发生的一种腐蚀形式。这是因为镍铝青铜中不同相之间存在电势值差异(EβEα>EκⅢ>EκⅣ>EκⅡ>EκⅠ),而电势低的物相会充当阳极先被腐蚀  NAKHAIE D,DAVOODI A,IMANI A. The role of constituent phases on corrosion initiation of NiAl bronze in acidic media studied by SEM–EDS,AFM and SKPFM[J]. Corrosion Science,2014,80:104-110.
44
。不过,中性溶液中的腐蚀试验表明,κ相会因为其表面所形成Al2O3膜的保护,使其周围的α相先被腐蚀。而在酸性溶液环境下,κ相则会因为表面形成的腐蚀产物膜不稳定使其暴露在腐蚀溶液中,此时κ相将作为阳极而先被腐蚀。可见,镍铝青铜的选相腐蚀不仅与其相组成有关,还与腐蚀介质的pH值以及钝化膜的稳定性有关。姚联等  姚联,刘生发,王振,等. 风电用CuAl10Fe2铝青铜套筒的显微组织与性能[J]. 特种铸造及有色合金,2023,43(5):664-669.
45
在离心铸造工艺条件下通过合理添加Ni,Fe和Mn元素,在避免γ2相形成的同时,调控了CuAl10Fe2合金中α,β和κ相组成比例,进而提高了合金的强韧性和耐蚀性能。拉伸及硬度测试得出的抗拉强度、伸长率和布氏硬度分别约为613 MPa,33%和137 HBW,在3.5%NaCl溶液中测得的腐蚀电位、腐蚀电流密度和腐蚀速率分别为–0.303 V,0.66 A/cm2和8.94 μm/a。Song等  SONG Q N,LI H L,ZHANG H N,et al. Correlation between microstructure and corrosion and cavitation erosion behaviors of nickel aluminum bronze[J]. Transactions of Nonferrous Metals Society of China,2022,32(9):2948-2964.
46
对比研究了铸态、退火态、正火态、淬火态和淬火+时效态5种镍铝青铜在3.5%NaCl溶液中的腐蚀行为,其耐蚀性能从高到低依次为:淬火态>淬火+时效态>正火态>铸态>退火态。淬火态合金耐蚀性能最好是因为其表面所形成的腐蚀产物膜保护性最好,而退火使β'相发生共析反应在合金中形成最多的共析体,造成严重的选相腐蚀,导致退火态合金的耐蚀性能最差。景媛等  景媛,黄晓飞,杨荣,等. 铝含量对镍铝青铜合金耐盐水腐蚀的影响[J]. 腐蚀与防护,2020,41(11):43-49.
47
研究了Al含量为5%~13%镍铝青铜在NaCl溶液中耐蚀性能,发现过低或过高的Al含量都会对合金的耐蚀性能造成影响,其中Al含量为9%的镍铝青铜耐蚀性能最佳。这是因为,较低的Al含量不利于样品表面形成致密氧化物保护膜,从而降低对Cl侵蚀基体时的保护作用; 而较高的Al含量则会导致合金在实验过程中出现脱Al腐蚀,这也会降低合金的耐蚀性能。

3.2     空化腐蚀性能

在实际海洋环境工况下,运行中的镍铝青铜件如螺旋桨、叶片等还会受到空蚀所带来的材料表面损伤  徐林,胡强,刘俊伟,等. 海洋环境用含Ni耐蚀铜合金研究现状及展望[J]. 铜业工程,2022(6):1-6.
48
。空蚀的起因是流体局部压力降低至其饱和蒸汽压之下时所形成的空泡  张赪栋,刘斌,石泽耀,等. 镍铝青铜合金海水腐蚀行为研究进展[J]. 中国腐蚀与防护学报,2022,42(1):25-33.
49
。这些空泡在溃灭后会释放极高能量密度的微射流和冲击波,对合金表面反复施加极高的瞬间载荷(数百MPa至数十GPa),造成材料的变形和质量损失  杨睿,田野,刘奕,等. 空蚀测试及耐空蚀材料研究现状[J]. 中国表面工程,2024,37(6):164-204.
50
。在空蚀过程中,κ/α相界周围较软的α相会被选择性腐蚀,形成较大的空洞或凹坑  WANG L X,LIU K,LI J,et al. A review on corrosion behavior and surface modification technology of nickel aluminum bronze alloys:current research and prospects[J]. Advanced Engineering Materials,2025,27(1):2401779.
51
。空蚀裂纹会从这些空洞或凹坑底部萌生,经过基体α相并沿着κ相界扩展,进而导致材料的剥落和质量损失。

研究表明,铝青铜合金的微观结构对其腐蚀性能影响显著。通过成分优化设计  SONG S L,LI D G,CHEN D R,et al. The role of Ti in cavitation erosion and corrosion behaviours of NAB alloy in 3.5% NaCl solution[J]. Journal of Alloys and Compounds,2022,919:165728.
52
、热处理  QIN Z B,ZHANG Q,LUO Q,et al. Microstructure design to improve the corrosion and cavitation corrosion resistance of a nickel-aluminum bronze[J]. Corrosion Science,2018,139:255-266.
53
、增材制造  刘明泽,周礼龙,左鹏程,等.增材制造镍铝青铜合金的制备与腐蚀行为研究进展[J]. 铜业工程,2024(1):54-66.
54
、表面改性  SONG Q N,TONG Y,LI H L,et al. Corrosion and cavitation erosion resistance enhancement of cast Ni–Al bronze by laser surface melting[J]. Journal of Iron and Steel Research International,2022,29:359-369.
 ZHAI W Z,LI J J,ZHOU R H,et al. Improved corrosion resistance of nickel-aluminum bronze by electron beam powder bed fusion[J]. Materials Chemistry and Physics,2023,296:127225.
55-56
等技术来调控微观结构以及改善材料整体或表面层机械性能,是提高合金抗空蚀性能的有效方法。相较于优化成分设计、热处理等常规手段而言,增材制造技术利用其快速非平衡凝固特性来优化合金组织,提高机械和耐蚀性能  BARR C,PATERAS A,MOLOTNIKOV A,et al. Effect of composition on the tensile and corrosion performance of nickel aluminium bronze produced via laser powder bed fusion[J]. Additive Manufacturing,2022,54:102771.
17
 CAI X,YANG M M,LI S J,et al. Comparative analysis of cavitation erosion behavior in wire-arc directed energy deposition and cast nickel-aluminum bronze alloys[J]. Ultrasonics Sonochemistry,2025,113:107235.
57
,是目前关注的热点之一。例如,Cai等  CAI X,YANG M M,LI S J,et al. Comparative analysis of cavitation erosion behavior in wire-arc directed energy deposition and cast nickel-aluminum bronze alloys[J]. Ultrasonics Sonochemistry,2025,113:107235.
57
发现电弧定向能量沉积(DED)镍铝青铜在人工海水和去离子水中的抗空蚀性能均优于铸态合金。图5为两种样品在不同时间空化侵蚀后的质量损失。可见,经过相同时间的空化侵蚀,DED合金的累积质量损失率和质量损失率始终低于铸态合金。Xu等  XU C,PENG Y,CHEN L Y,et al. Advanced cavitation erosion-corrosion resistance of nickel-aluminum bronze prepared by directed energy deposition[J]. Corrosion Science, 2024,231:111982.
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认为DED技术可以显著细化合金晶粒,高的冷却速率不但避免了大尺寸κI相的析出,还降低了其他析出κ相的尺寸和数量。更均匀的显微组织减轻了DED样品中的选相腐蚀,并表现出均匀腐蚀行为。另外,DED提高了样品表层的残余应力水平,有助于在空化侵蚀过程中抵抗沿层间界面疲劳裂纹的形成和扩展。图6为铸态和DED镍铝青铜在蒸馏水和NaCl溶液中的空化侵蚀原理图  XU C,PENG Y,CHEN L Y,et al. Advanced cavitation erosion-corrosion resistance of nickel-aluminum bronze prepared by directed energy deposition[J]. Corrosion Science, 2024,231:111982.
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。相较于铸态样品,DED样品不管是面对蒸馏水中的空化侵蚀,还是面对NaCl溶液中的空化侵蚀-腐蚀耦合作用,其表现都更为优异。

图5     铸态和电弧定向能沉积镍铝青铜在不同空化侵蚀时间下的质量损失:在人工海水中的(a)累积质量损失,(b)累积质量损失率;在去离子水中的(c)累积质量损失率,(d)累积质量损失率
Fig. 5     Mass loss of cast and wire-arc DED NAB after different cavitation erosion (CE) time:(a) Cumulative mass loss and (b) cumulative mass loss rate in artificial seawater;(c) Cumulative mass loss and (d) cumulative mass loss rate in deionized water  CAI X,YANG M M,LI S J,et al. Comparative analysis of cavitation erosion behavior in wire-arc directed energy deposition and cast nickel-aluminum bronze alloys[J]. Ultrasonics Sonochemistry,2025,113:107235.
57
图6     (a)铸态和(b)DED镍铝青铜的空化侵蚀及空化侵蚀-腐蚀耦合机理示意图: (a1,b1)蒸馏水;(a2,b2)3.5%NaCl溶液
Fig. 6     Schematic diagram of cavitation erosion and cavitation erosion-corrosion coupling mechanisms of (a) as-cast and (b) DED NABs: (a1,b1) Distilled water;(a2,b2) 3.5%NaCl solution  XU C,PENG Y,CHEN L Y,et al. Advanced cavitation erosion-corrosion resistance of nickel-aluminum bronze prepared by directed energy deposition[J]. Corrosion Science, 2024,231:111982.
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此外,不同表面改性技术条件下铝青铜合金的抗腐蚀性能研究近来也备受关注,图7为镍铝青铜中常见的腐蚀行为及表面改性强化技术  WANG L X,LIU K,LI J,et al. A review on corrosion behavior and surface modification technology of nickel aluminum bronze alloys:current research and prospects[J]. Advanced Engineering Materials,2025,27(1):2401779.
51
。Zeng等  ZENG S Q,HU S B,CHENG G K. Effect of shot peening on surface characterization and cavitation resistance of nickel aluminum bronze[J]. Materials Today Communications,2022,33:104767.
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利用喷丸处理(SP)在镍铝青铜中构建由细晶区、变形亚晶区和基体组成的多层结构(图8),通过强化表层材料来提高其抗空蚀性能。Yao等  YAO C L,HE S S,LEE K Y,et al. Microstructural transformation and corrosion–cavitation behavior of ultrasonic nanocrystal surface modified nickel aluminum bronze (NAB)[J]. Materials Today Communications,2024,40:109697.
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对镍铝青铜进行了超声纳米晶表面改性(UNSM),通过获得细化且分布相对均匀、弥散的多相结构以及增加表层硬度,提高其抗空蚀性能。从图9可以发现,尽管UNSM处理前后样品表面都观察到了深坑、凹坑和裂缝等缺陷,但UNSM处理样品表面的损伤程度显然更轻。

图7     镍铝青铜中常见的腐蚀行为及常用的表面强化技术
Fig. 7     Common corrosion behaviors and surface strengthening technology of NAB  WANG L X,LIU K,LI J,et al. A review on corrosion behavior and surface modification technology of nickel aluminum bronze alloys:current research and prospects[J]. Advanced Engineering Materials,2025,27(1):2401779.
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图8     喷丸处理镍铝青铜的微观结构示意图
Fig. 8     Schematic illustration of microstructural of SP NAB  ZENG S Q,HU S B,CHENG G K. Effect of shot peening on surface characterization and cavitation resistance of nickel aluminum bronze[J]. Materials Today Communications,2022,33:104767.
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图9     在3.5%NaCl溶液中空蚀4 h后,(a,b)UNSM处理前和(c,d)处理后的样品表面形貌
Fig. 9     Surface morphology of samples (a,b) before and (c,d) after UNSM treatment post cavitation erosion for 4 h in 3.5%NaCl solution  YAO C L,HE S S,LEE K Y,et al. Microstructural transformation and corrosion–cavitation behavior of ultrasonic nanocrystal surface modified nickel aluminum bronze (NAB)[J]. Materials Today Communications,2024,40:109697.
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张弘扬等  张弘扬,廉影,李阳,等. 水下搅拌摩擦加工对铸态镍铝青铜空蚀行为的影响[J]. 焊接,2024(4):28-34,39.
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利用水下搅拌摩擦加工技术对铸态镍铝青铜进行表面改性处理,并对处理前后样品在蒸馏水和人工海水中的空蚀行为进行了研究。处理起到了细化晶粒以及弥散化κ相的作用,合金的平均显微硬度提高至400HV,约为铸态样品的2倍。在蒸馏水和人工海水中空蚀18 h后,水下搅拌摩擦样品的质量损伤分别为2.55和4.85 mg,约为铸态样品质量损伤的50%和44%,表现出更为优异的抗空蚀性能。Zeng等  ZENG S Q,TIAN J J,HU S B,et al. Effect of laser surface melting on microstructure evolution and cavitation behavior of nickel aluminum bronze[J]. Transactions of Nonferrous Metals Society of China, 2023,33(7):2090-2109.
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利用功率为3 kW和扫描速度为10 mm/s的激光对镍铝青铜进行表面熔凝处理,得益于该过程所起到的细晶强化、位错强化和析出相强化协同作用以及均匀组织所带来的消除选相腐蚀作用,进而提高了合金的耐蚀性能和抗空蚀性能。

由上可见,随着海洋工程领域的不断发展,在增材制造、表面改性技术等工艺条件下,铝青铜合金的耐海洋环境腐蚀研究备受关注。不过,不同工艺参数对腐蚀行为的影响规律以及内在腐蚀机理研究还有待深入。

4     铝青铜合金的摩擦磨损性能

铝青铜合金软质基体+硬质相的微观结构,使其成为一种优异的耐磨材料,主要用于制造面对摩擦磨损工况的零部件,如蜗轮、蜗杆、轴承等。因此,铝青铜除耐蚀性能之外,其摩擦磨损性能也备受科研工作者关注  CAI X, YANG M M, QIAO Y X, et al. Experimental investigation on wear resistance and corrosion behavior of nickel-aluminum bronze alloy fabricated by wire-arc additive manufacturing[J]. Journal of Materials Research and Technology, 2023, 26: 5801-5815.
 LIU X H,HUANG D Y,YAN C H,et al. Multi-directional forging and aging treatment effects on friction and wear characterization of aluminium-bronze alloy[J]. Materials Characterization,2020,167:110511.
 ÖZTÜRK S,SÜNBÜL S E,METOĞLU A,et al. Improvement of microstructure,tribology and corrosion characteristics of nickel-aluminum bronze by P/M method[J]. Tribology International,2020,151:106519.
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。随着科学技术的飞速发展,迫切需要进一步提高铝青铜的综合机械性能及耐磨性能。基于此,国内外学者进行了大量的研究,主要集中在以下几个方面:1)不同工况条件下合金的耐磨性能分析,例如载荷、时间、温度等参数对铝青铜合金耐磨性能的影响  万浩,司乃潮,刘光磊,等. 稀土对新型多元铝青铜磨损行为的影响[J]. 稀土,2015,36(4):81-87.
 SHI Z K,XU L P,DENG C M,et al. Effects of frequency on the fretting wear behavior of aluminum bronze coatings[J]. Surface and Coatings Technology,2023,457:129306.
 李辉,闫金顺. QAl10-4-4铝青铜高温干摩擦磨损特性研究与参数优化[J]. 特种铸造及有色合金,2022,42(2):190-194.
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; 2)合金组成的优化设计,例如通过微合金化处理  万浩,司乃潮,李萌,等. 稀土对CuAl9Fe4Ni4Mn2合金性能的影响[J]. 稀土,2015,36(3):27-32.
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、制备铝青铜基复合材料  金孔杰,胡铮,谈辉,等. 铝青铜-Ti3AlC2复合材料摩擦学性能与工程耐冲击性能研究[J]. 摩擦学学报(中英文),2025,45(1):35-45.
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、设计新的铜基合金  柏伟,张爱军,孟军虎,等. (CuMnNi)100-xAlx高熵铜合金的显微组织、力学与摩擦学性能研究[J]. 摩擦学学报,2021,41(5):609-618.
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等提高耐磨性能; 3)通过热处理工艺  DU Y,DONG Y H,MA S,et al. Insight into the tribological behavior of the dual-phase nickel aluminum bronze alloy by multiscale characterization[J]. Wear,2024,556:205530.
 杨晨星,李付伟,刘汇河,等. 固溶时效处理对QAl10-3-1.5合金力学及摩擦磨损性能的影响[J]. 轴承,2025(1):76-81.
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或新的合金制备工艺  吕海波,刘祥玲,索忠源,等. 大功率超声处理对铸态QAl9-4铝青铜组织与性能的影响[J]. 铸造,2020,69(11):1162-1166.
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,优化合金显微组织的构成,增强其摩擦磨损抗性; 4)表面改性,例如利用超声表面滚压  YE H,CHEN A M,LIU S Z,et al. Effect of ultrasonic surface rolling process on the surface properties of QAl10-3-1.5 aluminum bronze alloy[J]. Surface and Coatings Technology,2022,433:128126.
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、表面织构构建  王梦娇,胡新政,刘焜,等. 激光微织构排布方式对铝青铜摩擦学性能影响研究[J]. 摩擦学学报(中英文),2025,45(9):1317-1330.
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、激光熔覆  LI Z Y,YAN H,ZHANG P L,et al. Improving surface resistance to wear and corrosion of nickel-aluminum bronze by laser-clad TaC/Co-based alloy composite coatings[J]. Surface and Coatings Technology,2021,405:126592.
 WANG G C,YANG X H,GENG J Y,et al. Effect of Al0.3CoFeNi content on microstructure,corrosion resistance,and friction performance of aluminium bronze coatings[J]. Surfaces and Interfaces,2025,56:105748.
 YIN T Y,ZHANG S,WANG Z Y,et al. Effect of laser energy density on microstructural evolution and wear resistance of modified aluminum bronze coatings fabricated by laser cladding[J]. Materials Chemistry and Physics,2022,285:126191.
 LIU H T,ZHAO Q Q,DAI Y L,et al. Enhancing corrosion and wear resistance of nickel–aluminum bronze through laser-cladded amorphous-crystalline composite coating[J]. Smart Materials in Manufacturing,2024,2:100046.
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等技术强化表层材料,从而达到降低磨损的目的。

4.1     摩擦磨损试验条件的影响

万浩等  万浩,司乃潮,刘光磊,等. 稀土对新型多元铝青铜磨损行为的影响[J]. 稀土,2015,36(4):81-87.
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研究了不同载荷(600,900和1200 N)对含0~0.33%稀土铝青铜的耐磨性能影响后发现,含0.08%稀土的合金在3种载荷下均具有更好的耐磨性能,而未加稀土合金其磨损机理随载荷的增加有较大变化,在600,900和1200 N条件下,分别为较严重的黏着磨损、严重的疲劳磨损和严重的黏着磨损,如图10(a,c,e)所示。相比而言,含0.08%稀土的合金在这3种载荷下的主要磨损机理均为磨粒磨损,如图10(b,d,f)所示。Shi等  SHI Z K,XU L P,DENG C M,et al. Effects of frequency on the fretting wear behavior of aluminum bronze coatings[J]. Surface and Coatings Technology,2023,457:129306.
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研究了微动磨损试验频率(5~20 Hz)对高速氧燃料喷涂铝青铜涂层微动磨损性能的影响,发现随着频率从5 Hz增至20 Hz时,摩擦系数呈现先增加后降低的趋势。在5 Hz和10 Hz低频率下,涂层的磨损机制以磨粒磨损为主,并伴有剥层现象。当频率增加至15 Hz和20 Hz时,涂层的磨损机制则以黏着磨损为主,并伴随着逐渐加剧的氧化磨损。李辉等  李辉,闫金顺. QAl10-4-4铝青铜高温干摩擦磨损特性研究与参数优化[J]. 特种铸造及有色合金,2022,42(2):190-194.
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利用Box-Behnken实验设计方法研究载荷、温度和转速对QAl10-4-4铝青铜摩擦磨损特性的影响发现:在干摩擦磨损下,转速与载荷以及转速与温度的交互作用分别对合金的摩擦因素及磨损率带来显著影响。

图10     添加稀土前后铝青铜合金在不同载荷下的磨损形貌
Fig. 10     Wear morphologies of aluminum bronze alloys with and without rare earths under different loads:(a) 600 N,0;(b) 600 N,0.08%;(c) 900 N,0;(d) 900 N,0.08%;(e) 1200 N,0;(f) 1200 N,0.08%  万浩,司乃潮,刘光磊,等. 稀土对新型多元铝青铜磨损行为的影响[J]. 稀土,2015,36(4):81-87.
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4.2     组成及微观结构优化的影响

金孔杰等  金孔杰,胡铮,谈辉,等. 铝青铜-Ti3AlC2复合材料摩擦学性能与工程耐冲击性能研究[J]. 摩擦学学报(中英文),2025,45(1):35-45.
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利用球磨+烧结工艺制备出Ti3AlC2含量为7%,14%和21%的铝青铜-Ti3AlC2复合材料,发现适量添加Ti3AlC2粉末不但可以提高合金的硬度和抗压强度,还能使恶劣工况下样件中的黏着磨损现象得到改善,从而提高材料的耐磨及耐热冲击性能。柏伟等  柏伟,张爱军,孟军虎,等. (CuMnNi)100-xAlx高熵铜合金的显微组织、力学与摩擦学性能研究[J]. 摩擦学学报,2021,41(5):609-618.
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在室温干摩擦条件下对比研究(CuMnNi)100-xAlxx=0,5,10,15)高熵铜合金和C6161铝青铜的耐磨性能,发现(CuMnNi)90Al10合金的耐磨性能最为优异。这主要是因为,添加Al不但可以起到固溶强化的效果,还会诱发基体组织由韧性、塑性较好的fcc相向硬度、强度较高的bcc相转变。(CuMnNi)90Al10高熵铜合金由于形成了最佳含量的软、硬相配合组织,因而在几种合金中具有最为优异的耐磨性能。Du等  DU Y,DONG Y H,MA S,et al. Insight into the tribological behavior of the dual-phase nickel aluminum bronze alloy by multiscale characterization[J]. Wear,2024,556:205530.
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研究了C95500镍铝青铜中α/β'两相比例对其摩擦学性能的影响。实验首先在700~950 ℃下退火1 h并随后进行淬火处理,以获得不同α/β'相比例的合金。如图11所示,可见除900 ℃退火样品基体由β'相构成外,其余样品的基体均由α+β'两相构成。干摩擦试验结果表明,所有实验样品的磨损机制均以磨粒磨损为主,同时伴有剥落磨损、氧化磨损和疲劳磨损。不同的是,样品的耐磨性能会受α/β'比例及显微硬度的影响,其中双相合金的耐磨性不如单相合金。这是因为β'相比α相耐磨,磨损过程中基体由α+β'相构成的样品会出现两相间的交替磨损,导致磨损过程加速。所以,在所有样品中,900 ℃×1 h退火+淬火后基体由β'相构成的样品耐磨性能最好。杨晨星等  杨晨星,李付伟,刘汇河,等. 固溶时效处理对QAl10-3-1.5合金力学及摩擦磨损性能的影响[J]. 轴承,2025(1):76-81.
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在850 ℃×60 min水冷+550 ℃×4 h空冷条件下对挤压态QAl10-3-1.5合金进行了固溶时效处理,对热处理前后样品进行不同载荷的摩擦磨损试验发现,尽管两种合金的磨损机制均为磨粒磨损,磨面形貌以犁沟为主,但挤压态合金磨面还伴有较大的剥落坑,因而时效态合金具有更好的耐磨性能。吕海波等  吕海波,刘祥玲,索忠源,等. 大功率超声处理对铸态QAl9-4铝青铜组织与性能的影响[J]. 铸造,2020,69(11):1162-1166.
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发现大功率超声处理可以细化QAl9-4铝青铜的α相和β'相,并引起细小弥散κ相的粗化。尽管超声处理可以带来细晶强化和固溶强化效果,提高合金的抗拉强度和硬度,但较粗大的κ相在变形过程中易出现应力集中,造成裂纹萌生与开裂并导致合金塑性的降低。而且,数量较少且粗大的κ相与基体的结合相对较弱,在磨损过程中的支承作用减弱且易剥落,对合金的耐磨性能带来不利影响。

图11     700~950 ℃,1 h退火+淬火镍铝青铜的(a)相组成和显微硬度,(b)摩擦系数,(c)平均摩擦系数,(d)磨损失重
Fig. 11     (a) Phase fraction and microhardness,(b) friction coefficient,(c) average coefficient of friction,and (d) weight loss of NAB after annealing at 700~950 ℃ for 1 h followed by quenching  DU Y,DONG Y H,MA S,et al. Insight into the tribological behavior of the dual-phase nickel aluminum bronze alloy by multiscale characterization[J]. Wear,2024,556:205530.
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4.3     不同表面改性工艺的影响

Ye等  YE H,CHEN A M,LIU S Z,et al. Effect of ultrasonic surface rolling process on the surface properties of QAl10-3-1.5 aluminum bronze alloy[J]. Surface and Coatings Technology,2022,433:128126.
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利用超声表面滚压工艺(USRP)对QAl10-3-1.5铝青铜合金进行表层强化处理,进而改善铝青铜件的耐磨性。图12为USRP以及细化晶粒的工作原理图。由于USRP处理时样品表层材料会经受严重的塑性变形,α相被拉长,晶粒尺寸减小,β相密度增加,这使得USRP处理样品表层的微观结构整体呈细小且均匀的分布,并形成了一定厚度(430~570 μm)的硬化层。其中,压下量0.75 mm、滚压4道次的样品,具有最高显微硬度值323.04HV,相比原始样品提高了75%。此外,在进行不同压下量和滚压道次的USRP处理后,样品表面获得的最小平均粗糙度为0.0374 μm,与原始样品相比降低了约67.6%。王梦娇等  王梦娇,胡新政,刘焜,等. 激光微织构排布方式对铝青铜摩擦学性能影响研究[J]. 摩擦学学报(中英文),2025,45(9):1317-1330.
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发现,在CuAl10Fe5Ni5合金表面进行合理的织构形状和排布方式设计可以提高其摩擦学性能。在干摩擦条件下,线性排布方式的织构可以降低样品表面摩擦阻力,而交错方式排布的织构则更有利于样品耐磨性能的提高。在油润滑条件下,三角形+椭圆复合排布的织构比单一形状排布的织构,能更好地提高表面流体动压承载力,降低磨损率。另外,与线性排布方式的织构相比,交错排布方式的织构可以提高垂直于摩擦方向上的磨屑和润滑油进入织构坑中的概率,进而增强样品的耐磨性能。

图12     (a)USRP的工作原理;(b)表层微观结构细化原理示意图
Fig. 12     (a) Schematic diagram of working principle of USRP;(b) Principle of refinement of surface microstructure  YE H,CHEN A M,LIU S Z,et al. Effect of ultrasonic surface rolling process on the surface properties of QAl10-3-1.5 aluminum bronze alloy[J]. Surface and Coatings Technology,2022,433:128126.
75

Li等  LI Z Y,YAN H,ZHANG P L,et al. Improving surface resistance to wear and corrosion of nickel-aluminum bronze by laser-clad TaC/Co-based alloy composite coatings[J]. Surface and Coatings Technology,2021,405:126592.
77
通过在铝青铜表面激光熔覆TaC/Co基合金复合涂层来提高其耐磨性能。结果发现,在添加TaC为0~30%的4种熔覆涂层中,含20% TaC的复合涂层具有最高的平均显微硬度(771.7HV0.2),约为镍铝青铜基体硬度值的6.2倍。摩擦磨损试验表明,此时样品(涂层3)具有最小的平均摩擦系数和最低的磨损率,如图13所示。类似的,Wang等  WANG G C,YANG X H,GENG J Y,et al. Effect of Al0.3CoFeNi content on microstructure,corrosion resistance,and friction performance of aluminium bronze coatings[J]. Surfaces and Interfaces,2025,56:105748.
78
利用激光熔覆技术在45#钢表面制备铝青铜涂层的过程中,分别加入0,2.8%,7%和14.1%的Al0.3CoFeNi,制备出高熵合金粉末含量不同的4种复合涂层,并对比了不同涂层的摩擦学性能。其中,添加2.8%高熵合金粉末的复合涂层摩擦系数最小且磨损性能最佳。这是因为适量的Al0.3CoFeNi可以改善涂层中富铁相的分布、形貌并提高其所占比例,提高涂层的硬度和耐磨性能。Yin等  YIN T Y,ZHANG S,WANG Z Y,et al. Effect of laser energy density on microstructural evolution and wear resistance of modified aluminum bronze coatings fabricated by laser cladding[J]. Materials Chemistry and Physics,2022,285:126191.
79
研究了激光能量密度与熔覆涂层中宏观结构、微观结构、显微硬度和耐磨性之间的关系,发现通过调节激光能量密度可以提高涂层显微硬度以及降低磨损量。Liu等  LIU H T,ZHAO Q Q,DAI Y L,et al. Enhancing corrosion and wear resistance of nickel–aluminum bronze through laser-cladded amorphous-crystalline composite coating[J]. Smart Materials in Manufacturing,2024,2:100046.
80
选用Cu44Zr48Al8(原子分数)非晶粉末作为激光熔覆材料,通过在镍铝青铜表面制备非晶-晶态复合涂层来提高耐磨性能。结果表明,在5~20 mm/s激光扫描速率下,20 mm/s速率所制备的复合涂层中,非晶相体积分数最高,为68.8%,此时涂层的显微硬度和平均摩擦系数分别约为基体的4.5倍和0.5倍。

图13     激光表面熔覆前后镍铝青铜的摩擦学特性:(a)摩擦系数;(b)磨损率
Fig. 13     Tribological characteristics of NAB before and after laser surface cladding:(a) Coefficient of friction;(b) Wear rate  LI Z Y,YAN H,ZHANG P L,et al. Improving surface resistance to wear and corrosion of nickel-aluminum bronze by laser-clad TaC/Co-based alloy composite coatings[J]. Surface and Coatings Technology,2021,405:126592.
77

5     总结与展望

本文对铝青铜合金的微观结构特征以及降温过程中的组织转变进行了回顾,梳理了合金化处理、热处理、增材制造以及表面改性处理等工艺对铝青铜合金的强韧化作用,并对不同工艺条件下铝青铜耐蚀性能和摩擦磨损性能的研究进展进行了重点分析。研究发现,铝青铜性能提升的核心在于通过控制工艺参数,精准调控铝青铜合金的微观结构,以满足相关的性能要求。不过,不同工艺条件下特别是增材制造以及表面改性处理铝青铜合金的耐蚀性能以及耐磨性能还有待深入,并提出以下建议:

1)在新工艺如电弧增材制造、激光粉末床熔融等条件下制备铝青铜时因为对连续相变过程掌握仍不够透彻,需要进一步探索工艺参数变化与组织结构演化的内在联系,进而根据使用性能要求对合金的微观结构进行精准调控。

2)增材制造过程中形成的气孔及氧化夹杂缺陷会降低铝青铜合金的致密性与耐蚀性,多层沉积热积累导致的残余应力集中易造成构件的翘曲或开裂。对此,需要开发智能补偿算法实时调控热输入以及层间冷却速率,提高工艺稳定性和工程应用的可靠性。

3)在表面改性处理铝青铜合金过程中,存在均匀性差、性能协同矛盾等问题。例如,超声表面滚压处理后会导致表层残余压应力梯度的陡变,在应力集中区域易萌生疲劳裂纹。利用激光熔覆技术制备的高硬度改性层,容易在磨损过程中因韧塑性问题发生脆性剥落。对此,可以从工艺的智能调控、表层材料的梯度结构设计等方面来协调表面层耐磨性与界面可靠性的问题。

4)在不同工艺处理条件下,工艺参数对力学、腐蚀、摩擦磨损等行为的影响规律以及内在机理还有待深入研究。对此可尝试基于最新的研究成果,通过不同工艺组合使用时的互补效应来突破单一技术的局限,协同提升铝青铜合金的综合性能。

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