70Cu-30Ni合金管FeSO<sub>4</sub>预成膜及冲刷腐蚀行为分析

doi:10.11902/1005.4537.2022.156

中国腐蚀与防护学报

2023, Vol. 43

Issue (3): 561-568 CSTR: 32134.14.1005.4537.2022.156 DOI: 10.11902/1005.4537.2022.156

研究报告

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70Cu-30Ni合金管FeSO₄预成膜及冲刷腐蚀行为分析

杨新宇¹^,², 李祯¹, 段体岗¹(

), 黄国胜¹, 马力¹, 刘峰¹, 姜丹¹

^1.中国船舶集团有限公司第七二五研究所海洋腐蚀与防护重点实验室青岛 266237
^2.哈尔滨工程大学材料科学与化学工程学院哈尔滨 150001

Erosion Corrosion Behavior in Flowing Seawater for 70Cu-30Ni Alloy Pipelines with Chemical Conversion Film Preformed in Flowing FeSO₄ Solution

YANG Xinyu¹^,², LI Zhen¹, DUAN Tigang¹(

), HUANG Guosheng¹, MA Li¹, LIU Feng¹, JIANG Dan¹

^1.State Key Laboratory for Marine Corrosion and Protection, Luoyang Ship Material Research Institute, Qingdao 266237, China
^2.College of Material Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China

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摘要:

通过动态FeSO₄溶液冲刷在70Cu-30Ni合金管内壁形成稳定的FeSO₄预成膜层，并通过不同速率的动态海水冲刷试验，研究预成膜层的耐海水冲刷腐蚀行为。FeSO₄预成膜实验结果显示，在200 mg/L FeSO₄溶液0.5 m/s流速下经历4 d冲刷，70Cu-30Ni合金管内壁形成一层淡黄色金属光泽膜层，随着时间增加，膜层颜色加深，厚度增加；30 d时，会形成底层NiO-Ni(OH)₂层，中间层Cu₂O-FeOOH致密层和表层Fe₂O₃-FeOOH疏松层的复合膜层。3个月周期的动态海水冲刷腐蚀试验结果显示，经历动态海水冲刷后，0.5和1.5 m/s低冲刷流速下试样的预成膜层保存较完整，仅出现轻微疏松层减薄现象；2.5 m/s高冲刷流速条件下，预成膜膜层局部位置存在疏松层剥离现象。XPS分析显示，高冲刷流速下，耐蚀膜层中Ni含量略有增加，Cu₂O在Cu组分中的含量增加，FeOOH含量在Fe组分中增加。电化学测试显示，随着冲刷流速的增加，预成膜层的电荷传递阻抗逐渐减小，由0.5 m/s状态下的2.28×10⁵ Ω·cm²，减小到2.5 m/s时的6.51×10⁴ Ω·cm²。70Cu-30Ni合金管FeSO₄预成膜层组成为NiO-Ni(OH)₂/Cu₂O-FeOOH/Fe₂O₃；随着冲刷速率的增加，合金管局部腐蚀现象更加显著。

关键词 ： 70Cu-30Ni合金管, FeSO₄预成膜, Cu₂O-FeOOH耐蚀膜层, 长周期冲刷腐蚀

Abstract：

A pre-chemical conversion film on the inner walls of 70Cu-30Ni alloy pipeline was first prepared with a flowing FeSO₄ solution, and then of which the erosion corrosion behavior in flowing seawater of various speeds was investigated by means of seawater circulation loop. The result showed that a chemical conversion film is obtained during the immersing- and flushing-process of the 200 mg/L FeSO₄ solution in conditions: flowing speed 0.5 m/s, pH 6.0, at 25 °C for 30 d, which is a composite film composed of an inner layer of NiO-Ni(OH)₂, a compact middle layer of Cu₂O-FeOOH and a loose outer layer of Fe₂O₃-FeOOH. Long-term seawater erosion corrosion test results showed that being suffered from flowing sea water of 0.5 and 1.5 m/s, the chemical conversion film covered pipe lines display relative sound anticorrosion performance with only slightly thinning of the top loose layer of the film, while with the increasing seawater flowing rate up to 2.5 m/s the loose layer on top of the conversion film is significantly thinned with locally spalling off, thus exposing the compact middle layer underneath. XPS analysis results showed that the chemical conversion films had been suffered from erosion corrosion of high-speed flowing seawater display higher amount of Ni, Cu₂O and FeOOH on the conversion film surface. Electrochemical impedance results showed that the charge transfer resistances of the chemical conversion films varied in the following descending order: from 2.28×10⁵ Ω·cm², 8.77×10⁴ Ω·cm² to 6.51×10⁴ Ω·cm², after being subjected to erosion-corrosion test by seawater of flowing speeds of 0.5, 1.5 to 2.5 m/s, respectively.

Key words： 70Cu-30Ni alloy pipeline ferrous sulfate preforming film anticorrosive Cu₂O-FeOOH composite film long-term erosion corrosion

收稿日期: 2022-05-19 32134.14.1005.4537.2022.156

ZTFLH:

TG174.4

通讯作者: 段体岗，E-mail：duantigang@sunrui.net，研究方向为腐蚀防护

Corresponding author: DUAN Tigang, E-mail: duantigang@sunrui.net

作者简介: 杨新宇，男，1996年生，硕士生

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引用本文:

杨新宇, 李祯, 段体岗, 黄国胜, 马力, 刘峰, 姜丹. 70Cu-30Ni合金管FeSO₄预成膜及冲刷腐蚀行为分析[J]. 中国腐蚀与防护学报, 2023, 43(3): 561-568.
YANG Xinyu, LI Zhen, DUAN Tigang, HUANG Guosheng, MA Li, LIU Feng, JIANG Dan. Erosion Corrosion Behavior in Flowing Seawater for 70Cu-30Ni Alloy Pipelines with Chemical Conversion Film Preformed in Flowing FeSO₄ Solution. Journal of Chinese Society for Corrosion and protection, 2023, 43(3): 561-568.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2022.156 或 https://www.jcscp.org/CN/Y2023/V43/I3/561

图1 70Cu-30Ni合金管FeSO4预成膜不同周期形貌图

图2 70Cu-30Ni管FeSO4预成膜不同周期SEM图

图3 70Cu-30Ni合金管FeSO4预成膜层经3个月不同流速下冲刷腐蚀后的表面形貌

图4 FeSO4预成膜处理的70Cu-30Ni合金管经3个月冲刷后SEM图

图5 70Cu-30Ni合金管30 d处理形成的预成膜的XPS成分分析

图6 FeSO4预成膜70Cu-30Ni试样经3个月不同流速冲刷腐蚀后表面XPS分析结果

表1 经历3个月周期冲刷腐蚀后70Cu-30Ni FeSO4预成膜膜层试样的XPS分析结果

图7 经不同流速冲刷腐蚀后FeSO4预成膜处理的70Cu-30Ni合金管的动电位极化测试结果

图8 FeSO4预成膜处理的70Cu-30Ni合金管不同流速冲刷腐蚀后的电化学阻抗图

表2 FeSO4预成膜处理的70Cu-30Ni合金管不同流速冲刷腐蚀后电化学阻抗拟合结果

图9 70Cu-30Ni合金管FeSO4预成膜层与冲刷腐蚀膜层演变机理示意图

1	Huang L Q, Wu X W. Application of the ablate pipe in the marine seawater pipe system [J]. Ship Boat, 2011, 22(1): 40
1	黄璐琼, 武兴伟. 铜镍合金管在舰船海水管系中的应用 [J]. 船舶, 2011, 22(1): 40
2	Guo F, Yuan F S, Wang T T. Market analysis and development ideas of copper-alloy condenser tube in our country [J]. Nonferrous Met. Eng. Res., 2015, 36(5): 37
2	郭峰, 袁孚胜, 王彤彤. 我国铜合金冷凝管市场分析及发展思路 [J]. 有色冶金设计与研究, 2015, 36(5): 37
3	Lu J, Wu J Y. Review on research and application of Cu-Ni alloys [J]. Nonferrous Met. Mater. Eng., 2020, 41(3): 55
3	陆菁, 武家艳. 铜镍合金的研究及其应用综述 [J]. 有色金属材料与工程, 2020, 41(3): 55
4	Chang Q P, Chen Y Y, Song F, et al. Corrosion properties of B30 Cu-Ni alloy and 316L stainless steel in a heat pump system [J]. J. Chin. Soc. Corros. Prot., 2014, 34: 544
4	常钦鹏, 陈友媛, 宋芳等. B30铜镍合金和316L不锈钢在热泵系统中的耐腐蚀性能 [J]. 中国腐蚀与防护学报, 2014, 34: 544 doi: 10.11902/1005.4537.2013.221
5	Chen H L, Ma L, Huang G S, et al. Effect of dissolved oxygen and flow rate of seawater on film formation of B30 Cu-Ni alloy [J]. J. Chin. Soc. Corros. Prot., 2022, 42: 724
5	陈翰林, 马力, 黄国胜等. 溶解氧和流速对B30铜镍合金在海水中成膜的影响 [J]. 中国腐蚀与防护学报, 2022, 42: 724 doi: 10.11902/1005.4537.2021.260
6	Asrar N, Malik A U, Ahmad S, et al. Early failure of cupro-nickel condenser tubes in thermal desalination plant [J]. Desalination, 1998, 116: 135 doi: 10.1016/S0011-9164(98)00190-8
7	Liao Q H. The analysis on the reason of earlier corrosion invalidation of Bfe30-1-1 white brown pipe [J]. Northwest China Electr. Power, 2004, 32(4): 70
7	廖庆华. Bfe30-1-1白铜管早期腐蚀失效原因分析 [J]. 西北电力技术, 2004, 32(4): 70
8	Wang H T, Qi L M, Wang Y. Cause analysis to copper pipe corrosion of No. 3 unit condenser, Haibowan Power Plant [J]. Inner Mongolia Electr. Power, 2007, 25(): 22
8	王海涛, 祁利明, 王勇. 海勃湾发电厂3号机组凝汽器铜管腐蚀原因分析 [J]. 内蒙古电力技术, 2007, 25(): 22
9	Sang J Z, Liu K C, Wang X P, et al. Cause analysis and prevention measures on corrosion of white copper condenser tubes [J]. Turb. Technol., 2009, 51: 393
9	桑俊珍, 刘克成, 王晓攀等. 凝汽器白铜管腐蚀原因分析及防止措施 [J]. 汽轮机技术, 2009, 51: 393
10	Fang G Q, Yang H, Yang R. Comparison analysis and discussion of shell side flow and heat transfer by CFD and HTRI [J]. Dev. Appl. Mater., 2016, 31(2): 10
10	方国强, 杨辉, 杨瑞. 冷凝器传热管腐蚀失效分析 [J]. 材料开发与应用, 2016, 31(2): 10
11	Zhu X L, Lin L Y, Lei T Q. Process of formation of corrosion films on alloy 70Cu-30Ni seawater [J]. Acta Metall. Sin., 1997, 33: 1256
11	朱小龙, 林乐耘, 雷廷权. 70Cu-30Ni合金海水腐蚀产物膜形成过程 [J]. 金属学报, 1997, 33: 1256
12	Liu S F, Lin L Y. Transforming behavior of surface film of Cu-Ni alloy exposed to seawater [J]. Chin. J. Mater. Res., 1998, 12: 20
12	刘少峰, 林乐耘. Cu-Ni合金表面膜在海水中的转化行为 [J]. 材料研究学报, 1998, 12: 20
13	Hua Q. Studies on B30 copper nickel alloy corrosion product film in artificial seawater [D]. Harbin: Harbin Engineering University, 2014
13	华清. B30铜镍合金在人工海水中腐蚀产物膜的研究 [D]. 哈尔滨: 哈尔滨工程大学, 2014
14	Ma A L, Jiang S L, Zheng Y G, et al. Corrosion product film formed on the 90/10 copper-nickel tube in natural seawater: Composition/structure and formation mechanism [J]. Corros. Sci., 2015, 91: 245 doi: 10.1016/j.corsci.2014.11.028
15	Li X, Guo J K, Zhao Y. Comparison and analysis of condenser tube film quality with different film forming agent [J]. North China Electr. Power, 2006, (3): 13
15	李兴, 郭军科, 赵迎. 凝结器铜管不同成膜剂膜质的比较分析 [J]. 华北电力技术, 2006, (3): 13
16	Kang T Y, Yang S D. Application and study of FeSO₄ film for condenser copper tube [J]. Corros. Sci. Prot. Technol., 2004, 16: 57
16	康桃英, 杨尚东. 凝汽器铜管FeSO₄成膜的应用与研究 [J]. 腐蚀科学与防护技术, 2004, 16: 57
17	Chen G, Zhang Y X, Liu H B. The principles and implementation of film coating technology with ferrous sulfate to condenser brass pipes [J]. Northeast Electr. Power Technol., 2005, 26(2): 34
17	陈刚, 张羽翔, 刘宏斌. 凝汽器铜管硫酸亚铁镀膜原理与实践 [J]. 东北电力技术, 2005, 26(2): 34
18	Pearson C. Role of iron in the inhibition of corrosion of marine heat exchangers-a review [J]. Br. Corros. J., 1972, 7: 61 doi: 10.1179/000705972798323288
19	Beccaria A M, Crousier J. Influence of iron addition on corrosion layer built up on 70Cu-30Ni alloy in sea water [J]. Br. Corros. J., 1991, 26: 215 doi: 10.1179/000705991798269189
20	Hargrave R E. Unusual failures involving copper deposition in boiler tubing [J]. Corrosion, 1991, 47: 555 doi: 10.5006/1.3585292
21	Ma Q G, Xiao W, Chen S X, et al. Cathodic protection of pure iron for B10 and B30 copper alloys in simulated marine environment [J]. Corros. Prot., 2016, 37: 793
21	马启国, 肖稳, 陈散兴等. 纯铁对B10和B30铜合金在模拟海洋环境中的阴极保护 [J]. 腐蚀与防护, 2016, 37: 793
22	Shi H X. Research on Fe₂SO₄ once filming technology for copper tubes of small batch [J]. Hebei Electr. Power, 2003, 22(1): 21
22	史海象. 小批量铜管Fe₂SO₄一次成膜技术研究 [J]. 河北电力技术, 2003, 22(1): 21
23	North R F, Pryor M J. The protection of Cu by ferrous sulphate additions [J]. Corros. Sci., 1968, 8: 149 doi: 10.1016/S0010-938X(68)80197-0
24	Wang S. Research on Fe₂SO₄ once filming technology for copper tubes [J]. Inner Mongolia Sci. Technol. Econ., 2007, (5): 92
24	王栓. 铜管Fe₂SO₄一次成膜技术研究 [J]. 内蒙古科技与经济, 2007, (5): 92
25	Deng C P, Huang B Y, Yin Z M, et al. The corrosion mechanism of failure of copper-nickel condenser tubes coated by ferrisulphas [J]. Nat. Sci. J. Xiangtan Univ., 2006, 28(4): 85
25	邓楚平, 黄伯云, 尹志民等. 硫酸亚铁成膜失效的镍白铜冷凝管腐蚀机理分析 [J]. 湘潭大学自然科学学报, 2006, 28(4): 85
26	Wang Z Y, Wang P. An approach to enhancing film formation quality on copper tubes in condenser by using ferrous sulfate only at once [J]. Therm. Power Gener., 2010, 39(6): 71
26	王朝阳, 王平. 提高凝汽器铜管硫酸亚铁一次性成膜质量 [J]. 热力发电, 2010, 39(6): 71
27	Bautista B E T, Carvalho M L, Seyeux A, et al. Effect of protein adsorption on the corrosion behavior of 70Cu-30Ni alloy in artificial seawater [J]. Bioelectrochemistry, 2014, 97: 34 doi: 10.1016/j.bioelechem.2013.10.004 pmid: 24177137

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