N掺杂对磁控溅射Ta涂层微观结构与耐磨损性能的影响

doi:10.11900/0412.1961.2018.00136

金属学报

2019, Vol. 55

Issue (3): 308-316 DOI: 10.11900/0412.1961.2018.00136

本期目录 | 过刊浏览

N掺杂对磁控溅射Ta涂层微观结构与耐磨损性能的影响

杨莎莎^1,²,杨峰³,陈明辉⁴(

),牛云松¹,朱圣龙¹,王福会⁴

1. 中国科学院金属研究所沈阳 110016
2. 中国科学技术大学材料科学与工程学院沈阳 110016
3. 沈阳理工大学装备工程学院沈阳 110159
4. 东北大学沈阳材料科学国家研究中心东北大学联合研究分部沈阳 110819

Effect of Nitrogen Doping on Microstructure and Wear Resistance of Tantalum Coatings Deposited by Direct Current Magnetron Sputtering

Shasha YANG^1,²,Feng YANG³,Minghui CHEN⁴(

),Yunsong NIU¹,Shenglong ZHU¹,Fuhui WANG⁴

1. Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2. School of Material Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3. School of Equipment Engineering, Shenyang Ligong University, Shenyang 110159, China
4. Shenyang National Key Laboratory for Materials Science, Northeastern University, Shenyang 110819, China

引用本文:

杨莎莎,杨峰,陈明辉,牛云松,朱圣龙,王福会. N掺杂对磁控溅射Ta涂层微观结构与耐磨损性能的影响[J]. 金属学报, 2019, 55(3): 308-316.
Shasha YANG, Feng YANG, Minghui CHEN, Yunsong NIU, Shenglong ZHU, Fuhui WANG. Effect of Nitrogen Doping on Microstructure and Wear Resistance of Tantalum Coatings Deposited by Direct Current Magnetron Sputtering[J]. Acta Metall Sin, 2019, 55(3): 308-316.

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摘要:

采用磁控溅射技术，以AISI304不锈钢为基体，通过在溅射过程中引入不同流量的N₂，制备出不同程度N掺杂的Ta涂层，研究了少量N掺杂对Ta涂层微观结构、物相组成、力学及磨损性能的影响。结果表明，无N掺杂时，Ta涂层中的物相组成为α-Ta，晶粒粗大，(211)和(110)晶面竞争生长；N掺杂后涂层中的物相组成为TaN_0.1，晶粒细小并呈(110)择优取向。少量N掺杂可以显著提高Ta涂层的硬度和弹性模量，并大幅度改善其抗磨损性能。涂层硬度和弹性模量的提高与晶粒细化、N原子固溶及涂层中存在的压应力有关。N掺杂后涂层的磨损机制由磨粒磨损向黏着磨损转变。

关键词 ： Ta涂层, 磁控溅射, N掺杂, 磨损

Abstract：

Tantalum coating attracts increasing attention in heat, corrosion and wear resistant applications today because of its high melting point, immunity to chemical attack and high toughness. Recently, tantalum has been considered a desirable candidate to replace electrodeposited (ED) chromium coating which is often used as protective coating against corrosion and wear. However, the wastes associated with ED chromium contain a well-known carcinogen, i.e. hexavalent chromium, which is a hazard to environment. In comparison, thick Ta coating is regarded as a more environmental and beneficial replacement. Tantalum coating is usually obtained by magnetron sputtering. However, tantalum exhibits two distinct crystalline phases. The body-centered cubic α-phase is the common phase in bulk metal and thermodynamically stable. α-Ta with good ductility and excellent mechanical properties is welcomed in most fields. β-Ta is a metastable phase with tetragonal crystalline lattice structure. The properties of β-Ta are not as advantageous as α-Ta because it is hard and brittle. The existence of β-Ta may compromise tantalum coating in adhesion, corrosion and wear resistance, hence, finding appropriate deposition conditions to obtain pure α-phase Ta coating has attracted a lot of interests. In previous work, pure α-phase Ta coating has been deposited by direct current magnetron sputtering when substrates were located in negative glow space. In this work, nitrogen was mixed in sputtering gases to deposit Ta coating with N interstitially dissolved on stainless steel. Effect of N on microstructure, mechanical and tribological performance of Ta coating was studied. Results indicated that when no nitrogen or very low flux of N₂ (l mL/s) were introduced in gas mixtures, α-phase Ta coating with coarse grains grew and revealed strong reflections of (211) and (110) diffraction peaks. When N₂ flow rate reached to 5 mL/s, Ta coating with N interstitially dissolved was obtained and revealed grain refinement and (110) preferred orientation of TaN_0.1 phase. Compared to α-phase Ta coating, N-doped tantalum coatings displayed excellent wear resistance for their high hardness and H ³/E ² ratio (H—hardness, E—elastic modulus). The wear mechanism for α-Ta coating was abrasive wear, while that of N-doped Ta coating switched to adhesive wear.

Key words： Ta coating magnetron sputtering nitrogen doping wear

收稿日期: 2018-04-11

ZTFLH:

TG174.4

基金资助:国家重点研发计划项目(2017YFB0306100);国家自然科学基金项目(51671053);国家自然科学基金项目(51701223);装备预研教育部联合基金项目(6141A020332-004);中央高校基本科研业务费专项基金项目(N160205001)

作者简介: 杨莎莎，女，1993年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2018.00136 或 https://www.ams.org.cn/CN/Y2019/V55/I3/308

表1 Ta涂层的制备工艺参数

图1 不同Ar气以及N2流量下沉积的Ta涂层表面及断面形貌的SEM像

图2 15Ar和15Ar-5N2沉积态涂层的TEM像及选区电子衍射花样

图3 不同Ar气以及N2流量下沉积的Ta涂层XRD谱

图4 15Ar-5N2沉积态涂层Ta4f XPS结果

表2 Ta涂层的力学性能和磨损率

图5 不同Ar气以及N2流量下沉积的Ta涂层磨痕形貌的SEM像

图6 图5b中矩形区域的放大图以及EDS分析

图7 有无N元素掺杂时Ta涂层的磨损机理示意图

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