Cr含量对Cu合金表面Ni/Ni-Cr/Ni-Cr-Al-Si膜层耐蚀性的影响

doi:10.11902/1005.4537.2021.173

中国腐蚀与防护学报

2022, Vol. 42

Issue (4): 638-646 DOI: 10.11902/1005.4537.2021.173

研究报告

本期目录 | 过刊浏览

Cr含量对Cu合金表面Ni/Ni-Cr/Ni-Cr-Al-Si膜层耐蚀性的影响

温佳源¹, 宋贵宏¹(

), 韦小园², 赵鑫¹, 吴玉胜¹, 杜昊²(

), 贺春林³

^1.沈阳工业大学材料科学与工程学院沈阳 110870
^2.广东腐蚀科学与技术创新研究院广州 510530
^3.沈阳大学辽宁省先进材料重点实验室沈阳 110044

Influence of Cr Content on Corrosion Resistance of Composite Ni/Ni-Cr/Ni-Cr-Al-Si Films on Cu

WEN Jiayuan¹, SONG Guihong¹(

), WEI Xiaoyuan², ZHAO Xin¹, WU Yusheng¹, DU Hao²(

), HE Chunlin³

^1.School of Material Science and Technology, Shenyang University of Technology, Shenyang 110870, China
^2.Institute of Corrosion Science and Technology, Guangzhou 510530, China
^3.Liaoning Province Key Laboratory of Advanced Materials, Shenyang University, Shenyang 110044, China

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摘要:

为了解决Cu合金在海水中的腐蚀问题,促进Cu合金部件在海洋工程装备和设施中的应用,采用电镀与磁控溅射相结合的方法,首先在Cu衬底上电镀Ni层,随后在Ni层上溅射沉积Ni-Cr合金薄膜,最后在Ni-Cr层上再溅射沉积不同Cr含量的Ni-Cr-Al-Si合金薄膜,获得Ni/Ni-Cr/Ni-Cr-Al-Si梯度复合膜层,并研究了该梯度复合膜层的结构与腐蚀性能。结果表明：在海水中,Cr含量为43.05%的梯度复合膜层 (S2样品),其低频端阻抗值、容抗弧半径、最大相位角、电荷转移电阻R_f和腐蚀电位最大,表明其耐腐蚀性能最好。在所研究的范围内,梯度膜层的Ni-Cr-Al-Si表层中[Al]/[Cr]原子比率越大,其耐腐蚀性越好。梯度复合膜层的腐蚀过程主要为点蚀,膜层表面团簇的界面处是点蚀的中心。适当Cr含量的Ni/Ni-Cr/Ni-Cr-Al-Si梯度复合膜层具有很好的耐海水腐蚀和导热能力,适合作为海水中使用的Cu换热器表面的防护涂层。

关键词 ： Ni/Ni-Cr/Ni-Cr-Al-Si复合膜层, 耐腐蚀性, Cr含量, 电化学阻抗谱, 阳极极化曲线

Abstract：

In order to enhance the corrosion resistance of Cu alloy to meet the requirements for their application in marine engineering equipment and facilities, a gradient composite coatings Ni/Ni-Cr/Ni-Cr-Al-Si were prepared on Cu plate by step-wise processes, i.e. firstly electrodeposited Ni film and then magnetron sputtered Ni-Cr alloy films and Ni-Cr-Al-Si alloy films in sequence. The structure and corrosion characteristics of the Ni/Ni-Cr/Ni-Cr-Al-Si gradient composite coatings with different Cr contents were characterized by means of X-ray diffractometer and electrochemical impedance spectroscope (EIS). The results show that among others, the gradient composite coating (S2 sample) with Cr content of 43.05% has the highest corrosion resistance, namely the highest low frequency impedance, capacitance arc radius, maximum phase angle, charge transfer resistance R_f and corrosion potential. The higher the atomic ratio of Al/Cr in the deposited Ni-Cr-Al-Si films is, the better the corrosive resistance of the deposited composite coating is. The corrosion process of the deposited gradient composite coating is mainly pitting corrosion, and the interface of the clusters on the surface of the films is the center of pitting corrosion. The Ni/Ni-Cr/Ni-Cr-Al-Si gradient composite coating with appropriate Cr content has good corrosion resistance in seawater and thermal conductivity, thus it is suitable as a protective coating for heat exchangers made of Cu alloys used in seawater.

Key words： Ni/Ni-Cr/Ni-Cr-Al-Si gradient composite film corrosion resistance Cr content electrochemical impedance spectrum anodic polarization curve

收稿日期: 2021-07-19

ZTFLH:

TQ150.6

基金资助:国家自然科学基金(51772193);兴辽英才计划(XLYC2008014)

通讯作者: 宋贵宏,杜昊 E-mail: songgh@sut.edu.cn;hdu@icost.ac.cn

Corresponding author: SONG Guihong,DU Hao E-mail: songgh@sut.edu.cn;hdu@icost.ac.cn

作者简介: 温佳源,女,1997年生,硕士生

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引用本文:

温佳源, 宋贵宏, 韦小园, 赵鑫, 吴玉胜, 杜昊, 贺春林. Cr含量对Cu合金表面Ni/Ni-Cr/Ni-Cr-Al-Si膜层耐蚀性的影响[J]. 中国腐蚀与防护学报, 2022, 42(4): 638-646.
Jiayuan WEN, Guihong SONG, Xiaoyuan WEI, Xin ZHAO, Yusheng WU, Hao DU, Chunlin HE. Influence of Cr Content on Corrosion Resistance of Composite Ni/Ni-Cr/Ni-Cr-Al-Si Films on Cu. Journal of Chinese Society for Corrosion and protection, 2022, 42(4): 638-646.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2021.173 或 https://www.jcscp.org/CN/Y2022/V42/I4/638

表1 制备的Ni/Ni-Cr/Ni-Cr-Al-Si梯度复合膜层的化学成分

图1 S2样品的SEM-EDS面扫描

图2 不同Cr含量的Ni/Ni-Cr/Ni-Cr-Al-Si复合膜层的XRD图谱及晶格常数与Cr含量的关系

图3 不同Cr含量的Ni/Ni-Cr/Ni-Cr-Al-Si梯度复合膜层的表面形貌。

图4 不同Cr含量的Ni/Ni-Cr/Ni-Cr-Al-Si梯度复合膜层的截面形貌

图5 梯度复合膜层的电化学阻抗谱及样品最大阻抗值与Cr含量的关系

图6 梯度复合膜层试样的EIS图及最大相位角与Cr含量的关系

图7 梯度复合膜层模拟腐蚀反应的等效电路图

表2 复合膜层等效电路及标准腐蚀参数的EIS数据

图8 复合膜层试样的阳极极化曲线

图9 复合膜层腐蚀后的表面形貌

1	Dong C L, Bai X Q, Yan X P, et al. Research status and advances on tribological study of materials under ocean environment [J]. Tribology, 2013, 33: 311
1	董从林, 白秀琴, 严新平等. 海洋环境下的材料摩擦学研究进展与展望 [J]. 摩擦学学报, 2013, 33: 311
2	Lin Z H, Ming N X, He C, et al. Effect of hydrostatic pressure on corrosion behavior of X70 steel in simulated sea water [J]. J. Chin. Soc. Corros. Prot., 2021, 41: 307
2	林朝晖, 明南希, 何川等. 静水压力对X70钢在海洋环境中腐蚀行为影响研究 [J]. 中国腐蚀与防护学报, 2021, 41: 307
3	Li G Q, Li G F, Wang J Q, et al. Microbiologically influenced corrosion mechanism and protection of offshore pipelines [J]. J. Chin. Soc. Corros. Prot., 2021, 41: 429
3	李光泉, 李广芳, 王俊强等. 临海管道微生物腐蚀损伤机制与防护 [J]. 中国腐蚀与防护学报, 2021, 41: 429
4	Ye Y W, Wang Y X, Ma X L, et al. Tribocorrosion behaviors of multilayer PVD DLC coated 304L stainless steel in seawater [J]. Diam. Relat. Mater., 2017, 79: 70 doi: 10.1016/j.diamond.2017.09.002
5	Liang G, Zhu S, Wang W Y, et al. Research status and development trend of aluminum alloy anticorrosion technology [J]. Mater. Rep., 2020, 34(Z2): 1429
5	梁广, 朱胜, 王文宇等. 铝合金腐蚀防护技术研究现状及发展趋势 [J]. 材料导报, 2020, 34(Z2): 1429
6	Ren X Y. Study on the preparation and catalytic performance of corrosion-resistant composite metal materials [J]. World Nonferr. Met., 2019, (20): 191
6	任显赟. 耐腐蚀复合金属材料的制备与催化性能研究 [J]. 世界有色金属, 2019, (20): 191
7	Xia Q Q, Zhu T, Xu Y. Analysis of structural corrosion allowance requirement standards for naval ship [J]. Ship Standard. Eng., 2020, 53(5): 6
7	夏齐强, 朱韬, 徐忆. 舰船结构腐蚀余量要求标准分析 [J]. 船舶标准化工程师, 2020, 53(5): 6
8	Jiang Z, Zhang C H, Du J, et al. A pipeline was protected by impressed current cathodic protection and sacrificial anode external corrosion factors and control measures [J]. Total Corros. Control, 2021, 35(4): 105
8	蒋志, 张昌会, 杜涓等. 某采用外加电流阴极保护与牺牲阳极联合保护管线外腐蚀因素及控制措施 [J]. 全面腐蚀控制, 2021, 35(4): 105
9	Yan H J. Study on preparation technology and properties of Ni-Cr-Al-Si-Y₂O₃-B alloy system [D]. Nanning: Guangxi University, 2018
9	闫海居. Ni-Cr-Al-Si-Y₂O₃-B合金体系的制备工艺及性能研究[D]. 南宁: 广西大学, 2018
10	Chen M F, Sun J S, You C, et al. Effect of chromium and silicon on microstructure and corrosion resistance of Ni-based superalloy [J]. J. Tianjin Inst. Technol., 2000, 16(1): 6
10	陈民芳, 孙家枢, 由臣等. 铬、硅含量对镍基高温合金组织及耐蚀性的影响 [J]. 天津理工学院学报, 2000, 16(1): 6
11	Singh H, Kalsi S B S, Sidhu T S, et al. Microstructure of Ni-Cr-based coating for corrosive conditions [J]. J. Therm. Spray. Technnol., 2019, 28: 1420
12	Firouzi-Nerbin H, Nasirpouri F, Moslehifard E. Pulse electrodeposition and corrosion properties of nanocrystalline nickel-chromium alloy coatings on copper substrate [J]. J. Alloy. Compd., 2020, 822: 153712 doi: 10.1016/j.jallcom.2020.153712
13	Tseng Y T, Lin J C, Jang J S C, et al. Three-dimensional amorphous Ni-Cr alloy printing by electrochemical additive manufacturing [J]. ACS. Appl. Electron. Mater., 2020, 2: 3538 doi: 10.1021/acsaelm.0c00570
14	Demir M, Kanca E, Karahan İ H. Characterization of electrodeposited Ni-Cr/hBN composite coatings [J]. J. Alloy. Compd., 2020, 844: 155511 doi: 10.1016/j.jallcom.2020.155511
15	Hou W, Ding Y H, Li J Z, et al. Research on process of hard chromium electroplating with trivalent chromium sulfate electrolyte [J]. New Technol. New Process, 2013, (11): 89
15	侯蔚, 丁运虎, 李家柱等. 硫酸盐体系三价铬硬铬电镀工艺研究 [J]. 新技术新工艺, 2013, (11): 89
16	Wang W Q, Li Y Q, Li X, et al. Microstructures and properties of Ni-Cr-B-Si alloy powders prepared by selective laser melting [J]. Mater. Rep., 2020, 34(2): 2077
16	王文权, 李雅倩, 李欣等. 选区激光熔化制备Ni-Cr-B-Si合金粉末的微观组织与性能 [J]. 材料导报, 2020, 34(2): 2077
17	Guo X H, Shen J, Liu S, et al. The corrosion behavior of Ni-Cr-Al alloys exposed to mixed oxidizing-carburizing atmospheres at 800 ℃ [J]. Corros. Sci., 2020, 176: 108877 doi: 10.1016/j.corsci.2020.108877
18	Li Y R, Lin Y, Tao B W. Electronic Materials [M]. Beijing: Tsinghua University Press, 2013
18	李言荣, 林媛, 陶伯万. 电子材料 [M]. 北京: 清华大学出版社, 2013
19	Xie M Y, Wang C, Zhang P Y, et al. Effects of composite strengthening on microstructure and mechanical property of K403 aluminized alloy [J]. China Surf. Eng., 2018, 31(1): 26
19	谢孟芸, 汪诚, 张佩宇等. 复合强化对渗铝K403合金组织和力学性能的影响 [J]. 中国表面工程, 2018, 31(1): 26
20	Greeff A P, Louw C W, Swart H C. The oxidation of industrial FeCrMo steel [J]. Corros. Sci., 2000, 42: 1725 doi: 10.1016/S0010-938X(00)00026-3
21	Liu H L, Teng X Y, Wang Z F, et al. Oxidation resistance of Fe-Cr-Ni-N heat-resistance steel [J]. Foundry Technol., 2001, (6): 55
21	刘含莲, 滕新营, 王执福等. Fe-Cr-Ni-N高温耐热钢的抗氧化性研究 [J]. 铸造技术, 2001, (6): 55
22	Cho B, Choi E, Chung S, et al. A novel Cr₂O₃ thin film on stainless steel with high sorption resistance [J]. Surf. Sci., 1999, 439: L799 doi: 10.1016/S0039-6028(99)00815-8
23	Song G H, Lou Z, Xiong G L, et al. Preparation, structure and performance of Ti/TiN multilayer film on surface of copper alloy [J]. J. Shenyang Univer. Technol., 2012, 34: 391
23	宋贵宏, 娄茁, 熊光连等. 铜合金表面Ti/TiN多层膜的制备、结构及其性能 [J]. 沈阳工业大学学报, 2012, 34: 391
24	Yang H Y, Chen Q S, Zhang R Q, et al. Effect of deposition temperature on microstructures and properties of FeCrAl coating prepared by magnetron sputtering [J]. Nucl. Power Eng., 2020, 41(suppl.1) : 200
24	杨红艳, 陈青松, 张瑞谦等. 沉积温度对磁控溅射制备FeCrAl涂层微观结构及性能的影响 [J]. 核动力工程, 2020, 41(): 200
25	Cao Z Q, Yu L, Zhang K. Effect of Al addition on high temperature oxidation behavior of Cu-Ni-Cr alloy [J]. Rare Met. Mater. Eng., 2013, 42: 2149
25	曹中秋, 于龙, 张轲. 添加Al对Cu-Ni-Cr合金高温氧化行为的影响 [J]. 稀有金属材料与工程, 2013, 42: 2149
26	Huang Y, Lu S Q, Zheng H Z. Effect of Al on high temperature oxidation resistance of Cr-20Nb alloy [J]. J. Aeronaut. Mater., 2009, 29(6): 8
26	黄毅, 鲁世强, 郑海忠. 合金元素Al对Cr-20Nb合金高温抗氧化性能的影响 [J]. 航空材料学报, 2009, 29(6): 8
27	Xian X B, Wang Q F, Liu K Z, et al. Corrosion behavior of the vacuum cathodic Arc, deposited TiN/Ti coatings [J]. Rare Met. Mater. Eng., 2005, 34: 1774
27	鲜晓斌, 王庆富, 刘柯钊等. 阴极电弧离子沉积TiN/Ti镀层腐蚀特性 [J]. 稀有金属材料与工程, 2005, 34(11): 1774
28	Roach M, Parsell D, Gardner S, et al. Correlation of corrosion andsurface analyses for Ni-Cr alloys [J]. Crit. Rev. Biomed. Eng., 1998, (26): 391
29	Song G H, Jin T, Xiong Y, et al. Deposition of the Ti/TiN multilayer films on Cu filament [J]. Vacuum, 2011, 48(4): 61
29	宋贵宏, 金弢, 熊焰等. Cu丝上沉积Ti/TiN多层膜的研究 [J]. 真空, 2011, 48(4): 61

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