具有“层中层”结构的Zr/[Al(Si)N/CrN]涂层制备及其在海水环境中腐蚀磨损特性

doi:10.11902/1005.4537.2021.184

中国腐蚀与防护学报

2022, Vol. 42

Issue (3): 345-357 DOI: 10.11902/1005.4537.2021.184

中国腐蚀与防护学会杰出青年学术成就奖论文专栏

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具有“层中层”结构的Zr/[Al(Si)N/CrN]涂层制备及其在海水环境中腐蚀磨损特性

王永欣¹(

), 汪艺璇¹, 陈春林², 李祥², 贺南开¹, 李金龙¹

^1.中国科学院宁波材料技术与工程研究所中国科学院海洋新材料与应用技术重点实验室浙江省海洋材料与防护技术重点实验室宁波 315201
^2.中国科学院金属研究所沈阳材料科学国家研究中心沈阳 110016

Preparation of Zr/[Al(Si)N/CrN] Coatings of Stratified Structure and Their Corrosion-wear Performance in Artificial Seawater

WANG Yongxin¹(

), WANG Yixuan¹, CHEN Chunlin², LI Xiang², HE Nankai¹, LI Jinlong¹

^1.Zhejiang Key Laboratory of Marine Materials and Protection Technology, Key Laboratory of Marine New Materials and Related Technology, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
^2.Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

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摘要:

采用多弧离子镀技术制备了不同调制比的交替多元多层Zr/CrAlSiN复合涂层，通过交替沉积与间歇性接近不同靶材相结合的方法获得了Zr/[Al(Si)N/CrN] “层中层”结构，并对复合涂层的力学性能、无腐蚀时的摩擦磨损性能、无摩擦磨损时的腐蚀性能及海水环境中的腐蚀磨损性能进行了研究。结果表明：该结构设计对涂层生长缺陷具有明显的抑制和修复作用；随着CrAlSiN层厚度比例增大，调制比为1∶6时Zr/[Al(Si)N/CrN]涂层的综合力学性能最佳；由于CrAlSiN层具有多层Al(Si)N/CrN结构，增加CrAlSiN层厚度比例增加了复合涂层横向界面，从而提升了涂层腐蚀性环境中的阻隔作用，因此CrAlSiN层厚度比例的增加既可以提升无摩擦磨损时涂层的耐腐蚀性能，又可提升涂层摩擦开动后的耐腐蚀性能，并进一步降低涂层腐蚀和磨损的相互促进作用；当调制比为1∶6和1∶8时，Zr/[Al(Si)N/CrN]涂层在海水环境中展现出了较好的抗腐蚀磨损性能。

关键词 ： Zr/[Al(Si)N/CrN]涂层, “层中层”结构, 海水环境, 腐蚀磨损特性

Abstract：

Composite coatings of Zr/CrAlSiN composed of multi-elements and multi-layers were fabricated by multi-arc ion plating technique. The coatings Zr/[Al(Si)N/CrN] with stratified structure were obtained by the combination of alternatively depositing selected targe materials on substrates and intermittently moving substrates close to specific targets. Then their mechanical property, friction, and wear performance in the absence of corrosion, corrosion performance in the absence of friction and wear, and corrosion-wear performance in artificial seawater, were systematically investigated. The results showed that the prepared coatings with the desired stratified structure could inhibit the growth defects and even repair the formed defects of the coatings obviously. With the increase of thickness ratio of the CrAlSiN layer, the best comprehensive mechanical property of the Zr/[Al(Si)N/CrN] coating would achieve, when the modulation ratio is 1:6. Since the CrAlSiN layer is also of a multilayered Al(Si)N/CrN structure, thus increasing the thickness ratio of the CrAlSiN layer may result in the increment of lateral interface of the composite coating, thereby improving the barrier effect of the coating in the corrosive environment. Accordingly, the increase in the thickness ratio of the CrAlSiN layer could improve either the corrosion resistance in the absence of friction and wear or the corrosion resistance of the coating, while friction was activated, and further reduced the mutual promotion of corrosion and wear. When the modulation ratio was 1:6 and 1:8, the Zr/[Al (Si) N/CrN] coating exhibited better anti-corrosion and wear properties in the artificial seawater.

Key words： Zr/[Al (Si) N/CrN] coating stratified structure seawater environment corrosion-wear performance

收稿日期: 2021-08-02

ZTFLH:

TG172

基金资助:浙江省重点研发计划(2020C03102);中国科学院战略性先导科技专项 (A类)(XDA13040602);宁波市科技创新;2025重大专项(2018B10028);中国科学院青年创新促进会(2018336)

通讯作者: 王永欣 E-mail: yxwang@nimte.ac.cn

Corresponding author: WANG Yongxin E-mail: yxwang@nimte.ac.cn

作者简介: 王永欣，男，1982年生，博士，研究员

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引用本文:

王永欣, 汪艺璇, 陈春林, 李祥, 贺南开, 李金龙. 具有“层中层”结构的Zr/[Al(Si)N/CrN]涂层制备及其在海水环境中腐蚀磨损特性[J]. 中国腐蚀与防护学报, 2022, 42(3): 345-357.
Yongxin WANG, Yixuan WANG, Chunlin CHEN, Xiang LI, Nankai HE, Jinlong LI. Preparation of Zr/[Al(Si)N/CrN] Coatings of Stratified Structure and Their Corrosion-wear Performance in Artificial Seawater. Journal of Chinese Society for Corrosion and protection, 2022, 42(3): 345-357.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.184 或 https://www.jcscp.org/CN/Y2022/V42/I3/345

表1 不同调制比Zr/CrAlSiN多层涂层沉积时间及循环次数参数

图1 不同调制比多层Zr/CrAlSiN涂层的截面形貌和表面形貌

图2 多层涂层中生长缺陷的修复

图3 不同调制比多层Zr/CrAlSiN涂层的XRD图谱

图4 调制比为1:1多层Zr/CrAlSiN涂层的HRTEM图

图5 多层Zr/CrAlSiN涂层硬度和弹性模量

表2 不同调制比多层Zr/CrAlSiN涂层硬度、弹性模量和硬弹比

图6 不同调制比多层Zr/CrAlSiN涂层划痕测试声发射信号

图7 不同调制比多层Zr/CrAlSiN涂层的划痕形貌

图8 不同调制比多层Zr/CrAlSiN涂层摩擦曲线

图9 不同调制比多层Zr/CrAlSiN涂层摩擦系数、磨损率及磨损形貌

图10 不同调制比多层Zr/CrAlSiN涂层的极化曲线

表3 不同调制比多层Zr/CrAlSiN涂层的电化学数据

图11 不同调制比多层Zr/CrAlSiN涂层的EIS曲线及模拟电路

Ratio	R_S / Ω·cm²	Q_c-Y₀ / μF·cm^-2	n_c	R_c / Ω·cm²	Q_dl-Y₀ / μF·cm^-2	n_dl	R_ct / Ω·cm²	χ²×10^-5
1:1	21.02	37.03	0.80	8.49 $×$ 10^-1	32.41	0.93	2.43 $×$ 10⁵	0.9852
1:2	21.97	10.04	0.93	2.67 $×$ 10³	5.07	0.61	6.81 $×$ 10⁵	1.971
1:4	23.06	27.88	0.92	9.13 $×$ 10²	2.48	0.92	3.63 $×$ 10⁶	1.972
1:6	23.00	30.55	0.90	2.22 $×$ 10³	1.54	1.00	1.45 $×$ 10⁶	2.18
1:8	22.86	26.40	0.92	1.10 $×$ 10³	28.65	0.93	4.00 $×$ 10⁶	1.399

表4 交替多层Zr/CrAlSiN涂层等效电路图拟合参数

表5 不同调制比多层Zr/CrAlSiN涂层摩擦条件下电化学数据

图12 不同调制比多层Zr/CrAlSiN涂层在摩擦条件下的极化曲线

图13 不同调制比多层Zr/CrAlSiN涂层在人工海水中的开路电位和摩擦系数

图14 不同调制比Zr/CrAlSiN涂层在人工海水中的摩擦系数、磨损率及磨损形貌

图15 不同调制比多层Zr/CrAlSiN涂层磨痕形貌图

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