铜基片静态气液界面腐蚀规律的实验

doi:10.16085/j.issn.1000-6613.2020-0775

摘要/Abstract

摘要：

气液两相界面腐蚀广泛存在于日常工业中。因气液相界面存在不稳定特性，迄今对于相界面处腐蚀的研究多针对不断变化的界面位置附近，分析一段时间内的累积腐蚀效果。本文向液相内注入一定体积的气泡，维持气液界面在金属铜壁面的稳定以及气液相界面和液相主体浓度近似恒定；在含不同Cl^-浓度的溶液中，通过电化学方法对比有无相界面的腐蚀规律，并根据数据深入分析相界面处的腐蚀机理。结果表明：引入气液界面导致铜试样腐蚀电位升高、腐蚀电流增大，腐蚀更严重；气液界面处由于引入微观界面能差腐蚀、宏观氧浓差电池腐蚀的作用显著增大了试样的腐蚀电流，使得在整个溶液浓度范围内含界面的铜腐蚀电流均高于不含界面的腐蚀电流，同时在铜表面留下清晰的界面腐蚀线；通过对界面腐蚀电流的剥离，包含液相主体腐蚀部分时无论有无界面的铜腐蚀速率均随Cl^-浓度的升高呈现先增大后减小的趋势，而去除液相部分影响的单独界面腐蚀电流则随Cl^-浓度升高而增大。

关键词: 气液, 界面腐蚀, 双膜理论, 扩散, 电化学

Abstract:

The air-liquid interface corrosion widely exists in daily industries. Because of the instability of the air-liquid interface, most research on the interface corrosion is aimed at analyzing the cumulative corrosion effect near the changing interface position for a period of time. In experimenting, a fixed volume bubble was injected into the under surface of copper sample to maintain the stability of the air-liquid interface and the constant ion concentration. By comparing the corrosion data of interface/no-interface samples in different concentration of NaCl solution, the interface corrosion mechanism was proposed. The results show that the corrosion potential and corrosion current of the copper with air-liquid interface are increased. At the air-liquid interface, the corrosion current of the sample is significantly increased by the micro-interface energy difference corrosion and macro-oxygen concentration difference battery corrosion, and therefore the corrosion rates of samples with interface are bigger than those without interface in the whole concentration range. Meanwhile a clearly visible interface corrosion line on samples is left. The interface corrosion rate is extracted by the analysis of experimental data. The results show that the total corrosion rate increases firstly and then decreases, but the interface corrosion rate monotonically increases with the increase of solution concentration.

Key words: air-liquid, interface corrosion, double-film theory, diffusion, electrochemistry

中图分类号:

TK121

陈宏霞, 刘霖, 李林涵. 铜基片静态气液界面腐蚀规律的实验[J]. 化工进展, 2021, 40(3): 1292-1299.

CHEN Hongxia, LIU Lin, LI Linhan. Experimental study of the static air-liquid interface corrosion on copper[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1292-1299.

图/表 10

参考文献 33

1	周威, 花飞, 龚朝兵, 等.污水汽提装置富氨气系统腐蚀原因及对策[J]. 石油化工腐蚀与防护, 2013(1): 40-43.
	ZHOU W, HUA F, GONG C B, et al. Causes of corrosion of ammonia-rich gas system in sewage stripping unit and countermeasures[J]. Corrosion and Protectionin Petrochemical Industry, 2013(1): 40-43.
2	LUCKOW P, BAR-COHEN A, RODGERS P, et al. Energy efficient polymers for gas-liquid heat exchangers[J]. Journal of Energy Resources Technology, 2010, 132(2): 021001-021009.
3	DAS G, CHOWDHURY S G, RAY A K, et al. Turbine blade failure in a thermal power plant[J]. Engineering Failure Analysis, 2003, 10(1): 85-91.
4	郑云萍, 刘奇, 张峰, 等.气井井下的腐蚀监测技术[J].腐蚀与防护, 2013, 34(4): 355-358.
	ZHENG Y P, LIU Q, ZHANG F, et al. Downhole corrosion monitoring technology of gas well[J]. Corrosion and Protection, 2013, 34(4): 355-358.
5	OSSAI C I, BEREKET G, GU C, et al. Advances in asset management techniques: an overview of corrosion mechanisms and mitigation strategies for oil and gas pipelines[J].International Scholarly Research Notices Corrosion, 2012, 2012: 570143.
6	SOYAMA H. Corrosion behavior of pressure vessel steel exposed to residual bubbles after cavitation bubble collapse[J]. Corrosion, 2011, 67(2): 1-8.
7	LUO S Z, ZHENG Y G, LI M C, et al. Effect of cavitation on corrosion behavior of 20SiMn low-alloy steel in 3% sodium chloride solution[J]. Corrosion, 2003, 59(7): 597-605.
8	YONG X, HOU C, WU J J, et al. Cavitation corrosion of anodized aluminum alloy in 3.5% NaCl solution[J]. Corrosion, 2011, 67(4): 450031-450036.
9	陈亚林, 张伟, 王伟, 等. WBE技术研究水线区Q235碳钢腐蚀[J]. 中国腐蚀与防护学报, 2014, 34(5): 451-458.
	CHEN Y L, ZHANG W, WANG W, et al. Evaluation of water-line area corrosion for Q235 steel by WBE technique[J]. Journal of Chinese Society for Corrosion and Protection, 2014, 34(5): 451-458.
10	邢佩, 卢琳, 李晓刚.丝束电极技术研究海洋高强用E690钢水线腐蚀[C]//中国腐蚀与防护学会, 北京: 北京丰盈环蚀技术有限公司, 2015: 2-6, 9.
	XING P, LU L, LI X G. Study on water line corrosion of E690 ocean platform steels using WBE technique[C]//Chinese Society for Corrosion and Protection, Beijing, China: Beijing Fengying Ring Corrosion Technology Company, 2015: 2-6, 9.
11	LI X J, CONG H B, GUI F, et al. Development of liquid-air-interface corrosion of steel in nitrate solutions[J]. Corrosion, 2014, 70(3): 230-246.
12	EBARA R, TANAKA F, KAWASAKI M. Sulfuric acid dew pointcorrosion in waste heat boiler tube for copper smelting furnace[J].Engineering Failure Analysis, 2013, 33: 29-36.
13	DING Q, TANG X F, YANG Z G. Failure analysis on abnormalcorrosion of economizer tubes in a waste heat boiler[J]. Engineering Failure Analysis, 2017, 73: 129-138.
14	GOU W, ZHANG H, LI H, et al. Effects of silica sand on synergistic erosion caused by cavitation abrasion and corrosion[J]. Wear, 2018, 412: 120-126.
15	朱道峰, 宋玉, 陈小平, 等.腐蚀垢层对海洋天然气管道CO₂腐蚀过程的影响[J]. 腐蚀与防护, 2019, 40(9): 633-637.
	ZHU D F, SONG Y, CHEN X P, et al. Influence of corrosion scale on CO₂ corrosion of marine gas pipeline[J]. Corrosion and Protection, 2019, 40(9): 633-637.
16	ZHANG Z, WANG Z, LIU H, et al. Experimental study on bubble and droplet entrainment in vertical churn and annular flows and their relationship[J]. Chemical Engineering Science, 2019, 206: 387-400.
17	CHEN Y, ZHANG W, DING J, et al. Research on water-line corrosion of carbon steel by wire beam electrode technique[C]//EDP Sciences, MATEC Web of Conferences, Wuhan, 2016: 14-19.
18	LI S X, TEAGUE M T, DOLL G L, et al. Interfacial corrosion of copper in concentrated chloride solution and the formation of copper hydroxychloride[J]. Corrosion Science, 2018, 141: 243-254.
19	LIU X Q, LIU Z L, HU J D, et al. Influence of Cr content on corrosion behaviour of tube pile steel in half-immersion environment[J].Transactions of the Indian Institute of Metals, 2018, 71(1): 209-218.
20	REFAIT P, GROLLEAU A M, JEANNIN M, et al. Corrosion of mild steel at the seawater/sediments interface: mechanisms and kinetics[J].Corrosion Science, 2018, 130: 76-84.
21	XU W, ZHANG B, YANG L, et al. Liquid-air interface corrosion of A537 steel in high level liquid radioactive waste simulant in a sealed container[J]. Journal of the Electrochemical Society, 2019, 166(2): 33-41.
22	WEI W, SUN F, SHI Y, et al. Theoretical prediction of acid dew point and safe operating temperature of heat exchangers for coal-fired power plants[J]. Applied Thermal Engineering, 2017, 123: 782-790.
23	ISLAM M, POJTANABUNTOENG T, GUBNER R. Condensation corrosion of carbon steel at low to moderate surface temperature and iron carbonate precipitation kinetics[J]. Corrosion Science, 2016, 111: 139-150.
24	FENG J K. Principle and calculation of the boiler[M]. Beijing: Science Press, 2003: 371-379.
25	LI X, WU Z, ZHANG L, et al. An updated acid dew point temperature estimation method for air-firing and oxy-fuel combustion processes[J].Fuel Processing Technology, 2016, 154: 204-209.
26	陈衡, 潘佩媛, 赵钦新, 等. 燃煤工业锅炉黏性积灰和露点腐蚀耦合机理[J]. 化工学报, 2017, 68(12): 4774-4783.
	CHEN H, PAN P Y, ZHAO Q X, et al. Coupling mechanism of viscose ash deposition and dew point corrosion in industrial coal-fired boiler[J]. CIESC Journal, 2017, 68(12): 4774-4783.
27	林翠, 肖志阳. 碳钢在NaCl薄液膜下的电化学腐蚀行为[J].腐蚀与防护, 2014, 35(4): 316-320.
	LIN C, XIAO Z Y. Electrochemical corrosion behavior of carbon steel under thin electrolyte layer containing NaCl[J]. Corrosion and Protection, 2014, 35(4): 316-320.
28	张雪. 利用阵列电极研究水线腐蚀的机理[D]. 青岛: 中国海洋大学, 2013.
	ZHANG X. Study on the mechanism of carbon steel under water-line with wire beam electrode method[D]. Qingdao: Ocean University of China, 2013.
29	胡杰珍. 海洋环境跃变区碳钢腐蚀行为与机理研究[D].北京: 北京科技大学, 2016.
	HU J Z. Research of the corrosion behavior and mechanism of metal in the juncture area of marine environment[D]. Beijing: University of Science and Technology Beijing, 2016.
30	马友光, 余国琮. 气液相际传质的理论研究[J].天津大学学报, 1998, 31(4): 506-510.
	MA Y G, YU G Z. Thetheoretical studies of interphase mass transfer[J]. Journal of the Tianjin University, 1998, 31(4): 506-510.
31	毛志红. 气液界面特性的分子动力学模拟研究[D].杭州: 中国计量学院, 2014.
	MAO Z H. Characteristics of gas-liquid interface using molecular dynamics simulation[D]. Hangzhou: China Jiliang University, 2014.
32	翁永基, 赵海燕. 用丝束电极（WBE）评价不锈钢在NaCl溶液中点蚀敏感性[J]. 中国腐蚀与防护学报, 2003, 23(6): 326-329.
	WENG Y J, ZHAO H Y. Evaluation of pitting sensitivity of stainless steel in NaCl solutions by means of wire beam electrodes (WBE)[J]. Journal of Chinese Society for Corrosion and Protection, 2003, 23(6): 326-329.
33	王志武, 原素芳. 黄铜腐蚀速度与Cl^-浓度的关系[J].材料保护, 2004(10): 50-51, 66.
	WANG Z W, YUAN S F. Relation between corrosion rate of brass and concentration of chloridion[J]. Journal of Materials Protection, 2004(10): 50-51, 66.

c/mol·L^-1	A_Cu/cm²	A_bubble/cm²	A_bubble/A_Cu
0.1	4	0.6483	0.1621
0.2	4	0.5428	0.1357
0.3	4	0.7339	0.1835
0.6	4	0.8992	0.2248
0.8	4	0.6150	0.1537
0.9	4	0.6342	0.1586

c/mol·L^-1	A_Cu/cm²	A_bubble/cm²	A_bubble/A_Cu
0.1	4	0.6483	0.1621
0.2	4	0.5428	0.1357
0.3	4	0.7339	0.1835
0.6	4	0.8992	0.2248
0.8	4	0.6150	0.1537
0.9	4	0.6342	0.1586

c/mol·L^-1	ΔE/V	I_interface/×10^-5A	V/mm·a^-1
0.1	0.0156	0.1964	2.2911
0.2	0.0068	0.2594	3.0260
0.3	0.0084	0.3309	3.8601
0.6	0.0107	0.4586	5.3498
0.8	0.0078	0.5132	5.9867
0.9	0.0114	0.5687	6.6341

c/mol·L^-1	ΔE/V	I_interface/×10^-5A	V/mm·a^-1
0.1	0.0156	0.1964	2.2911
0.2	0.0068	0.2594	3.0260
0.3	0.0084	0.3309	3.8601
0.6	0.0107	0.4586	5.3498
0.8	0.0078	0.5132	5.9867
0.9	0.0114	0.5687	6.6341

浓度/mol?L^-1	有无相界面	R_s/Ω·cm^-2	R_ct/Ω·cm^-2	C_dl/F·cm^-2	β（弥散系数）	Z_w/Ω·cm^-2	方差值
0.1	含界面	4.267	13.67	2.226×10^-8	1.002	5.747	0.00011358
	无界面	4.14	14.57	2.3001×10^-8	1.001	4.401	0.00005130
0.2	含界面	4.631	3.722	5.9544×10^-8	0.98897	3.806	0.00026404
	无界面	4.57	5.379	5.4566×10^-8	0.9853	4.232	0.00020466
0.3	含界面	4.426	2.831	9.6633×10^-8	0.95495	2.503	0.00022757
	无界面	4.15	2.657	8.9033×10^-8	0.98519	2.86	0.00032575