pH值、温度和盐度对B30铜镍合金在海水中成膜的影响

doi:10.11902/1005.4537.2022.199

中国腐蚀与防护学报

2023, Vol. 43

Issue (3): 481-493 CSTR: 32134.14.1005.4537.2022.199 DOI: 10.11902/1005.4537.2022.199

研究报告

本期目录 | 过刊浏览

pH值、温度和盐度对B30铜镍合金在海水中成膜的影响

陈翰林¹, 马力², 黄国胜², 杜敏¹(

)

^1.中国海洋大学化学化工学院海洋化学理论与工程技术教育部重点实验室青岛 266100
^2.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

Effects of pH Value, Temperature and Salinity on Film Formation of B30 Cu-Ni Alloy in Seawater

CHEN Hanlin¹, MA Li², HUANG Guosheng², DU Min¹(

)

^1.Key Laboratory of Marine Chemistry Theory and Technology, Ministry of Education, College of Chemistry and Chemical Engineering, Ocean University of China, Qingdao 266100, China
^2.State Key Laboratory for Marine Corrosion and Protection, Luoyang Ship Material Research Institute (LSMRI), Qingdao 266237, China

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摘要:

对B30铜镍合金在海水中成膜的影响因素进行研究，确定最佳成膜条件，从而抑制B30铜镍合金在使用过程中发生点蚀等严重腐蚀损坏现象。采用电化学阻抗谱 (EIS)、X射线光电子能谱 (XPS) 和激光共聚焦显微镜 (CLSM) 等方法研究了海水的pH、温度以及盐度对B30铜镍合金成膜的影响。在pH为6.6~9.8的海水中，随着pH值的增大，膜层致密性、完整性及保护性呈现先变好再变差的趋势；温度在2~36 ℃的范围内，随着海水中温度的提高，膜层呈现先变差再变好的趋势；盐度在20~36的范围内，随着盐度的提高，膜层呈现先变差再变好的趋势。pH以及盐度对B30铜镍合金的腐蚀影响较大。综合试样的腐蚀状况以及膜层测试，B30铜镍合金在盐度为20的海水中表面形成的膜层最为致密。

关键词 ： B30铜镍合金, 成膜, pH, 温度, 盐度

Abstract：

The effect of pH value, temperature and salinity of seawater on the film formation of B30 Cu-Ni alloy were studied by EIS, XPS and CLSM. The results showed that with the increase of pH value within the range of 6.6-9.8, the film quality first became better and then worse; with the increase of the temperature within the range of 2-36 ℃, the quality of the film became worse first and then better; with the increase of salinity within the range of 20-36, the quality of the film became worse first and then better. The pH and salinity had a strong influence on the corrosion of B30 copper nickel alloy. Therefore, considering comprehensively the corrosion morphology of the alloy and the quality of the corresponding film formed on the surface, can produce the most compact and effective passivation film can be produced on the surface of B30 Cu-Ni alloy in the seawater with salinity of 20.

Key words： B30 copper nickel alloy film formation pH temperature salinity

收稿日期: 2022-06-19 32134.14.1005.4537.2022.199

ZTFLH:

TG174

基金资助:国家自然科学基金(U1706221)

通讯作者: 杜敏，E-mail：ssdm99@ouc.edu.cn，研究方向为海洋腐蚀与防护技术

Corresponding author: DU Min, E-mail: ssdm99@ouc.edu.cn

作者简介: 陈翰林，男，1997年生，硕士生

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引用本文:

陈翰林, 马力, 黄国胜, 杜敏. pH值、温度和盐度对B30铜镍合金在海水中成膜的影响[J]. 中国腐蚀与防护学报, 2023, 43(3): 481-493.
CHEN Hanlin, MA Li, HUANG Guosheng, DU Min. Effects of pH Value, Temperature and Salinity on Film Formation of B30 Cu-Ni Alloy in Seawater. Journal of Chinese Society for Corrosion and protection, 2023, 43(3): 481-493.

链接本文:

https://www.jcscp.org/CN/10.11902/1005.4537.2022.199 或 https://www.jcscp.org/CN/Y2023/V43/I3/481

图1 B30铜镍合金在不同pH海水中的OCP图

图2 B30铜镍合金在不同pH值海水中的EIS图

图3 B30铜镍合金在海水中电化学阻抗拟合等效电路图

表1 B30铜镍合金在不同pH的海水中浸泡不同时间的EIS的拟合数据

图4 B30铜镍合金在不同pH值海水中浸泡20 d后表面的XPS分析结果

表2 B30铜镍合金在不同pH海水中浸泡20 d后表面XPS的拟合结果

图5 B30铜镍合金在不同pH海水中浸泡20 d后表面的激光共聚焦显微图像

图6 B30铜镍合金在不同温度海水中的OCP图

图7 B30铜镍合金在不同温度海水中的电化学阻抗图

表3 B30铜镍合金在不同温度海水中的电化学阻抗拟合数据

图8 B30铜镍合金在不同温度海水中浸泡20 d后表面的XPS图谱

表4 B30铜镍合金在不同温度海水中浸泡20 d后表面成膜物质及其含量

图9 B30铜镍合金在不同温度海水中浸泡20 d后表面的激光共聚焦显微镜图

图10 B30铜镍合金在不同盐度海水中的OCP

图11 B30铜镍合金在不同盐度海水中的EIS图

表5 B30铜镍合金在不同盐度的海水中的电化学阻抗拟合数据

图12 B30铜镍合金在不同盐度海水中浸泡20 d后表面的XPS图

表6 B30铜镍合金在不同盐度海水中浸泡20 d的XPS图拟合结果

图13 B30铜镍合金在不同盐度海水中浸泡20 d后表面的激光共聚焦显微镜图

图14 B30铜镍合金在不同海水中的相位角-45°所对应的频率值

表7 B30铜镍合金在不同条件的海水中的相位角-45°所对应的频率值

图15 B30铜镍合金在不同海水中的腐蚀电流密度图

表8 B30铜镍合金在不同条件的海水中的腐蚀电流密度

1	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
2	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
3	Wang Y Z, Beccaria A M, Poggi G. The effect of temperature on the corrosion behaviour of a 70/30 Cu-Ni commercial alloy in seawater [J]. Corros. Sci., 1994, 36: 1277 doi: 10.1016/0010-938X(94)90181-3
4	Cheng D B, Guo Y, Liu X H, et al. Studies on corrosion and protection of heat exchange tubes of B30 copper-nickel alloy [J]. Dev. Appl. Mater., 2020, 35(1): 84
4	程德彬, 郭悦, 刘雪辉等. B30铜镍合金换热管腐蚀与防护研究进展 [J]. 材料开发与应用, 2020, 35(1): 84
5	Li Y X, Ives M B, Coley K S, et al. Corrosion of nickel-containing stainless steel in concentrated sulphuric acid [J]. Corros. Sci., 2004, 46: 1969 doi: 10.1016/j.corsci.2003.10.017
6	Glover T J. Copper-Nickel alloy for the construction of ship and boat hulls [J]. Br. Corros. J., 1982, 17: 155 doi: 10.1179/000705982798274228
7	Alfantazi A M, Ahmed T M, Tromans D. Corrosion behavior of copper alloys in chloride media [J]. Mater. Des., 2009, 30: 2425 doi: 10.1016/j.matdes.2008.10.015
8	Mansfeld F, Liu G, Xiao H, et al. The corrosion behavior of copper alloys, stainless steels and titanium in seawater [J]. Corros. Sci., 1994, 36: 2063 doi: 10.1016/0010-938X(94)90008-6
9	Lin L Y, Liu S F, Zhu X L. Seawater-corrosion-induced intergranular precipitation in Cu-Ni alloy [J]. J. Chin. Soc. Corros. Prot., 1997, 17(1): 1
9	林乐耘, 刘少峰, 朱小龙. 海水腐蚀导致铜镍合金的沿晶析出 [J]. 中国腐蚀与防护学报, 1997, 17(1): 1
10	Ravindranath K, Tanoli N, Gopal H. Failure investigation of brass heat exchanger tube [J]. Eng. Failure Anal., 2012, 26: 332 doi: 10.1016/j.engfailanal.2012.07.018
11	Yan Y M, Lin L Y, Zhu X L. Effect of residual stress on corrosion resistance of copper tube BFe30-1-1 in 3.5%NaCl [J]. J. Chin. Soc. Corros. Prot., 1994, 14(1): 59
11	严宇民, 林乐耘, 朱小龙. 残余应力对BFe30-1-1铜管耐蚀性能的影响 [J]. 中国腐蚀与防护学报, 1994, 14(1): 59
12	Admiraal L, Ijsseling F P, Kolster B H, et al. Influence of temperature on corrosion product film formation on CuNi10Fe in the low temperature range: Part 2: studies on corrosion product film formation and properties in relation to microstructure and iron content [J]. Br. Corros. J., 1986, 21: 33 doi: 10.1179/000705986798272451
13	Hack H P. Role of the corrosion product film in the corrosion protection Cu-Ni alloys in saltwater [D]. Dissertation of Pennsylvania State University, 1987
14	Zhang Z, Yao L A, Gan F X. The effect of surface film on electrochemical behavior of Cu-Ni-Alloy [J]. J. Chin. Soc. Corros. Prot., 1987, 7: 143
14	张哲, 姚禄安, 甘复兴. 铜镍合金表面膜对其电化学行为的影响 [J]. 中国腐蚀与防护学报, 1987, 7: 143
15	Bai M M, Bai Z H, Jiang L, et al. Corrosion behavior of H62 brass alloy/TC4 titanium alloy welded specimens [J]. J. Chin. Soc. Corros. Prot., 2020, 40: 159
15	白苗苗, 白子恒, 蒋立等. H62黄铜/TC4钛合金焊接件腐蚀行为研究 [J]. 中国腐蚀与防护学报, 2020, 40: 159 doi: 10.11902/1005.4537.2019.012
16	Efird K D. Potential-pH diagrams for 90-10 and 70-30 Cu-Ni in sea water [J]. Corrosion, 1975, 31: 77 doi: 10.5006/0010-9312-31.3.77
17	Syrett B C, Macdonald D D, Wing S S. Corrosion of copper-nickel alloys in sea water polluted with sulfide and sulfide oxidation products [J]. Corrosion, 1979, 35: 409 doi: 10.5006/0010-9312-35.9.409
18	Chi C Y, Xu L K, Lin C G, et al. Influence of pH on electrochemical behavior of 70/30 Cu-Ni alloy [J]. Equip. Environ. Eng., 2009, 6(3): 38
18	迟长云, 许立坤, 蔺存国等. pH值变化对B30铜镍合金腐蚀电化学行为的影响 [J]. 装备环境工程, 2009, 6(3): 38
19	Chi C Y, Li N, Xue J J, et al. Effect of temperature on electrochemical behavior of B30 Cu-Ni alloy in seawater [J]. Corros. Prot., 2009, 30: 772
19	迟长云, 李宁, 薛建军等. 温度对B30铜镍合金在海水中电化学行为的影响 [J]. 腐蚀与防护, 2009, 30: 772
20	Zhu X L, Lin L Y, Xu J, et al. Review of corrosion product films of Cu-Ni alloys in seawater [J]. Mater. Sci. Technol., 1997, 5(2): 21
20	朱小龙, 林乐耘, 徐杰等. Cu-Ni合金海水蚀产物膜研究进展 [J]. 材料科学与工艺, 1997, 5(2): 21
21	Ekerenam O O, Ma A L, Zheng Y G, et al. Evolution of the corrosion product film and its effect on the erosion-corrosion behavior of two commercial 90Cu-10Ni tubes in seawater [J]. Acta Metall. Sin. (Engl. Lett), 2018, 31: 1148 doi: 10.1007/s40195-018-0745-1
22	Chi C Y, Li N, Xue J J, et al. Electrochemical behavior of B30 Cu-Ni alloy in seawater [J]. Mater. Prot., 2009, 42(8): 19
22	迟长云, 李宁, 薛建军等. B30铜镍合金在海水中的电化学行为 [J]. 材料保护, 2009, 42(8): 19
23	Li H J, Yang X Q, Zhou Z Q. Analysis of factors affecting the corrosion of copper alloys [J]. Electr. Power Environ. Prot., 1995, 11(2): 45
23	李海舰, 杨小琴, 周宗权. 影响铜合金腐蚀的因素分析 [J]. 电力环境保护, 1995, 11(2): 45
24	Xu Q J, Ding M R, Chen Z C, et al. Electrochemical studies of inhibition effects for B30 Cu-Ni alloy corrosion in simulated water [J]. J. Shanghai Univ. Electr. Power, 2006, 22: 229
24	徐群杰, 丁茂荣, 陈子超等. 模拟水中B30铜镍合金耐蚀性的电化学研究 [J]. 上海电力学院学报, 2006, 22: 229
25	Zhu X L, Lin L Y, Lei T Q. Review on corrosion behaviors of Cu Ni alloys in seawater [J]. Corros. Sci. Prot. Technol., 1997, 9(1): 48
25	朱小龙, 林乐耘, 雷廷权. Cu-Ni合金海水腐蚀行为研究进展 [J]. 腐蚀科学与防护技术, 1997, 9(1): 48
26	Ismail K M, Fathi A M, Badawy W A. Electrochemical behavior of copper-nickel alloys in acidic chloride solutions [J]. Corros. Sci., 2006, 48: 1912 doi: 10.1016/j.corsci.2005.07.004
27	Zhao Y T, Li H H, Chen G Z. EIS characteristics of Cu-based alloy in seawater [J]. Mar. Sci., 2005, 29(7): 21
27	赵永韬, 李海洪, 陈光章. 铜合金在海水中电化学阻抗谱特征研究 [J]. 海洋科学, 2005, 29(7): 21
28	Zhang Z, Yao L A, Gan F X. Electrochemical behavior of Cu-Ni alloy in sodium chloride solution [J]. J. Chin. Soc. Corros. Prot., 1986, 6(2): 103
28	张哲, 姚禄安, 甘复兴. 铜镍合金B-30在氯化钠介质中的电化学行为 [J]. 中国腐蚀与防护学报, 1986, 6(2): 103
29	Barik R C, Wharton J A, Wood R J K, et al. Galvanic corrosion performance of high-strength copper-nickel alloys in seawater [J]. Corrosion, 2009, 65: 359 doi: 10.5006/1.3319141
30	Metcalfe R G, Pearce-Boltec N. Stress corrosion cracking of a copper elbow fitting [J]. Eng. Failure Anal., 2018, 90: 197 doi: 10.1016/j.engfailanal.2018.03.016
31	Milošev I, Kovačević N, Kovač J, et al. The roles of mercapto, benzene and methyl groups in the corrosion inhibition of imidazoles on copper: I. Experimental characterization [J]. Corros. Sci., 2015, 98: 107 doi: 10.1016/j.corsci.2015.05.006
32	Aben T, Tromans D. Anodic polarization behavior of copper in aqueous bromide and bromide/benzotriazole solutions [J]. J. Electrochem. Soc., 1995, 142: 398 doi: 10.1149/1.2044031
33	Ijsseling F P, Kroingman J M, Drolenga L J P. Congress on marine corrosion and fouling [C]. Spain: Barcelons, 1981: 146
34	Wang J M, Yang H D, Du M, et al. Corrosion of B10 Cu-Ni alloy in seawater polluted by high concentration of NH₄ ⁺ [J]. J. Chin. Soc. Corros. Prot., 2021, 41: 609
34	王家明, 杨昊东, 杜敏等. B10铜镍合金在高浓度NH₄ ⁺污染海水中腐蚀研究 [J]. 中国腐蚀与防护学报, 2021, 41: 609 doi: 10.11902/1005.4537.2020.222
35	Zhu X L, Li Z J, Xu J. Research progress on the formation and rupture mechanism of seawater corrosion product film of Cu-Ni alloy [J]. Chin. J. Rare Met., 1997, 21(6): 463
35	朱小龙, 李中建, 徐杰. Cu-Ni合金海水腐蚀产物膜的形成与破裂机制研究进展 [J]. 稀有金属, 1997, 21(6): 463
36	Yuan S J, Pehkonen S O. Surface characterization and corrosion behavior of 70/30 Cu-Ni alloy in pristine and sulfide-containing simulated seawater [J]. Corros. Sci., 2007, 49: 1276 doi: 10.1016/j.corsci.2006.07.003
37	Féron D. Corrosion Behaviour and Protection of Copper and Aluminium Alloys in Seawater [M]. Boca Raton: Woodhead Publishing Limited, 2007, 64, 119
38	Swartzendruber L J, Bennett L H. The effect of Fe on the corrosion rate of copper rich Cu-Ni alloys [J]. Scr. Metall., 1968, 2: 93 doi: 10.1016/0036-9748(68)90077-X
39	Khan A F, Patil A P. Combined effect of chloride and pH on corrosion resistance of Cu-10Ni alloy [J]. Trans. Indian Inst. Met., 2008, 61: 225 doi: 10.1007/s12666-008-0011-8
40	Sun T T, Li N, Xue J J, et al. Effect of environment factors on corrosion behavior of 90-10 Cu-Ni alloy in seawater [J]. Equip. Environ. Eng., 2010, 7(4): 25
40	孙婷婷, 李宁, 薛建军等. 环境因素对B10铜镍合金耐蚀性的影响 [J]. 装备环境工程, 2010, 7(4): 25

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