CN116448854A - Method for testing dissimilar metal galvanic corrosion behavior under damaged organic coating - Google Patents
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- 238000005260 corrosion Methods 0.000 title claims abstract description 41
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 31
- 230000007797 corrosion Effects 0.000 title claims abstract description 28
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 238000012360 testing method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000005259 measurement Methods 0.000 claims description 6
- 238000010998 test method Methods 0.000 abstract description 6
- 239000013535 sea water Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910000975 Carbon steel Inorganic materials 0.000 description 10
- 239000010962 carbon steel Substances 0.000 description 10
- 229910000570 Cupronickel Inorganic materials 0.000 description 9
- 229910045601 alloy Inorganic materials 0.000 description 9
- 239000000956 alloy Substances 0.000 description 9
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 4
- 229920006334 epoxy coating Polymers 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- ATLAQRSQSGOMOU-UHFFFAOYSA-N niobium platinum Chemical compound [Nb].[Pt] ATLAQRSQSGOMOU-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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Abstract
Description
技术领域technical field
本发明涉及一种破损有机涂层下异种金属电偶腐蚀行为试验方法，属于海洋材料腐蚀领域。The invention relates to a test method for galvanic corrosion behavior of dissimilar metals under damaged organic coatings, belonging to the field of marine material corrosion.
背景技术Background technique
在苛刻的海洋腐蚀环境中，由于结构功能的要求，大型海洋工程（如海上石油钻井平台、跨海大桥、船舶等）的机械结构系统中通常会采用不同的材料，而这些材料在海水或潮湿的海洋大气中会发生不同程度的电偶腐蚀，这给海洋工程设备的服役安全性造成了巨大威胁。因此，研究海洋结构物金属材料的电偶腐蚀可为设计选材和腐蚀防护提供基础数据和技术基础，具有重要的理论意义和经济价值。In the harsh marine corrosion environment, due to the requirements of structural functions, different materials are usually used in the mechanical structure systems of large-scale offshore projects (such as offshore oil drilling platforms, cross-sea bridges, ships, etc.), and these materials are exposed to seawater or humidity. Different degrees of galvanic corrosion will occur in the marine atmosphere, which poses a huge threat to the service safety of marine engineering equipment. Therefore, the study of galvanic corrosion of metal materials in marine structures can provide basic data and technical basis for design material selection and corrosion protection, which has important theoretical significance and economic value.
涂覆有机涂层是防止金属腐蚀的最常见方法之一，有机涂层通过物理屏蔽作用来阻止金属基体与腐蚀介质的接触，从而阻止腐蚀电化学反应的发生。而据我们所知，目前关于有机涂层下异种金属对在模拟海水环境中的腐蚀行为的研究相对较少。并且对于涂层下电偶腐蚀行为的研究大多采用失重测量和极化曲线等一些传统方法，但是这些研究方法无法获得对于涂层下电偶腐蚀行为极其重要的局部电化学信息。而且，现有的片状电极只能获得电极表面平均化信息，而不能获得电极局部电化学信息。Applying an organic coating is one of the most common methods to prevent metal corrosion. The organic coating prevents the contact between the metal substrate and the corrosive medium through physical shielding, thereby preventing the occurrence of corrosive electrochemical reactions. However, to the best of our knowledge, there are relatively few studies on the corrosion behavior of dissimilar metal pairs under organic coatings in simulated seawater environments. And most of the research on the galvanic corrosion behavior under the coating adopts some traditional methods such as weight loss measurement and polarization curve, but these research methods cannot obtain the local electrochemical information that is extremely important for the galvanic corrosion behavior under the coating. Moreover, the existing sheet electrodes can only obtain the averaged information of the electrode surface, but cannot obtain the local electrochemical information of the electrode.
发明内容Contents of the invention
为解决现有技术中的上述问题，本发明提供一种破损有机涂层下异种金属电偶腐蚀行为试验方法。In order to solve the above-mentioned problems in the prior art, the present invention provides a method for testing the galvanic corrosion behavior of dissimilar metals under damaged organic coatings.
破损有机涂层下异种金属电偶腐蚀行为试验方法，采用如下试验装置，所述试验装置包括电脑排线1、丝束电极2、参比电极4、辅助电极5、电解池6和铁架台7，其中，丝束电极2由若干个相互绝缘的异种金属电极丝混合组成，丝束电极2一端通过电脑排线1与外部电源连接，另一端为丝束电极暴露面3，丝束电极暴露面3均匀涂覆有防腐蚀涂层，且防腐蚀涂层上制有破损点，电解池6置于铁架台7上，电解池6内置有电解液，铁架台7固定的丝束电极2涂覆有防腐蚀涂层的一端、参比电极4、辅助电极5均浸入电解液中；The test method for the galvanic corrosion behavior of dissimilar metals under damaged organic coatings adopts the following test device, which includes a computer cable 1, a wire bundle electrode 2, a reference electrode 4, an auxiliary electrode 5, an electrolytic cell 6 and an iron stand 7 , wherein, the tow electrode 2 is composed of several mutually insulated dissimilar metal electrode wires, one end of the tow electrode 2 is connected to the external power supply through the computer cable 1, and the other end is the exposed surface 3 of the tow electrode, and the exposed surface of the tow electrode 3 Evenly coated with an anti-corrosion coating, and the anti-corrosion coating is made with damaged points, the electrolytic cell 6 is placed on the iron stand 7, the electrolytic cell 6 is built with electrolyte, and the wire bundle electrode 2 fixed on the iron stand 7 is coated One end with an anti-corrosion coating, the reference electrode 4 and the auxiliary electrode 5 are all immersed in the electrolyte;
并且，包括如下步骤：And, including the following steps:
（1）将丝束电极2浸泡在电解液中，按照周期对丝束电极2进行电位和电流分布测试，(1) Soak the wire bundle electrode 2 in the electrolyte, and test the potential and current distribution of the wire bundle electrode 2 according to the cycle,
（2）电位分布测试时，所有电极丝彼此断开，依次测量单根电极丝相对于参比电极4的腐蚀电位；(2) During the potential distribution test, all electrode wires are disconnected from each other, and the corrosion potential of a single electrode wire relative to the reference electrode 4 is measured sequentially;
电流分布测量时，单根电极丝彼此断开，测量单根电极丝与其他相互连接的电极丝之间的电偶电流。In the current distribution measurement, the single electrode wires are disconnected from each other, and the galvanic current between a single electrode wire and other interconnected electrode wires is measured.
根据实验要求的不同，可对丝束电极2表面防腐蚀涂层不同位置进行破损，例如，在异种电极丝的表面、同种电极丝距交界线距离以及交界处等位置，以研究不同位置破损时的腐蚀规律。According to different experimental requirements, different positions of the anti-corrosion coating on the surface of wire bundle electrode 2 can be damaged, for example, on the surface of different electrode wires, the distance between the same type of electrode wire and the junction line, and the junction, etc., to study damage at different positions time corrosion law.
本发明的破损有机涂层下异种金属电偶腐蚀行为试验方法能够获得破损涂层下异种金属电偶腐蚀过程中的局部电化学信息，以及浸泡过程中涂层失效与电偶腐蚀电化学参数的相关性信息，进而解决了片状电极只能获得电极表面平均化信息，而不能获得电极局部电化学信息的缺点，有效监测电偶腐蚀。The test method for galvanic corrosion behavior of dissimilar metals under damaged organic coatings of the present invention can obtain local electrochemical information in the galvanic corrosion process of dissimilar metals under damaged coatings, and the relationship between coating failure and electrochemical parameters of galvanic corrosion during immersion Correlation information, and then solve the problem that the sheet electrode can only obtain the averaged information of the electrode surface, but cannot obtain the local electrochemical information of the electrode, and effectively monitor the galvanic corrosion.
附图说明Description of drawings
图1为本发明破损有机涂层下异种金属电偶腐蚀行为试验装置示意图。Fig. 1 is a schematic diagram of a test device for galvanic corrosion behavior of dissimilar metals under a damaged organic coating according to the present invention.
图2为本发明丝束电极2平面示意图。FIG. 2 is a schematic plan view of the filament electrode 2 of the present invention.
图3为本发明丝束电极2的实际应用状态图。FIG. 3 is a diagram of the actual application state of the filament electrode 2 of the present invention.
图4为本发明破损涂层后丝束电极2的实际应用状态图。Fig. 4 is a diagram of the actual application state of the filament electrode 2 after the damaged coating of the present invention.
图5为丝束电极浸泡24 h后的电流密度分布图。Fig. 5 is the current density distribution diagram of the wire bundle electrode soaked for 24 h.
图6为丝束电极浸泡24 h后碳钢与铜镍合金区域涂层的EIS响应图。Fig. 6 is the EIS response diagram of the carbon steel and copper-nickel alloy area coating after the wire bundle electrode was soaked for 24 h.
图7为丝束电极浸泡330 h后的形貌图。Fig. 7 is the topography of the wire bundle electrode soaked for 330 h.
其中，1-电脑排线，2-丝束电极，3-丝束电极暴露面，4-参比电极，5-辅助电极，6-电解池，7-铁架台。Among them, 1-computer cable, 2-wire electrode, 3-exposed surface of wire electrode, 4-reference electrode, 5-auxiliary electrode, 6-electrolytic cell, 7-iron stand.
具体实施方式Detailed ways
下面结合附图和具体实施例进一步说明本发明的技术方案。The technical solutions of the present invention will be further described below in conjunction with the accompanying drawings and specific embodiments.
实施例1Example 1
破损有机涂层下异种金属电偶腐蚀行为试验方法，采用如下试验装置，如图1所示，所述试验装置包括电脑排线1、丝束电极2、参比电极4、辅助电极5、电解池6和铁架台7，其中，丝束电极2由若干个相互绝缘的异种金属电极丝混合组成，丝束电极2一端通过电脑排线1与外部电源连接，另一端为丝束电极暴露面3，丝束电极暴露面3均匀涂覆有防腐蚀涂层，且防腐蚀涂层上制有破损点，电解池6置于铁架台7上，电解池6内置有电解液，铁架台7固定的丝束电极2涂覆有防腐蚀涂层的一端、参比电极4、辅助电极5均浸入电解液中；The test method for the galvanic corrosion behavior of dissimilar metals under damaged organic coatings adopts the following test device, as shown in Figure 1. The test device includes a computer cable 1, a wire bundle electrode 2, a reference electrode 4, an auxiliary electrode 5, an electrolytic The pool 6 and the iron stand 7, wherein the tow electrode 2 is composed of several mutually insulated heterogeneous metal electrode wires, one end of the tow electrode 2 is connected to an external power supply through a computer cable 1, and the other end is the exposed surface 3 of the tow electrode , the exposed surface 3 of the tow electrode is uniformly coated with an anti-corrosion coating, and the anti-corrosion coating is formed with damaged points, the electrolytic cell 6 is placed on the iron stand 7, the electrolytic cell 6 is built with electrolyte, and the iron stand 7 is fixed One end of the wire beam electrode 2 coated with an anti-corrosion coating, the reference electrode 4, and the auxiliary electrode 5 are all immersed in the electrolyte;
并且，包括如下步骤：And, including the following steps:
（1）将丝束电极2浸泡在电解液中，按照周期对丝束电极2进行电位和电流分布测试，(1) Soak the wire bundle electrode 2 in the electrolyte, and test the potential and current distribution of the wire bundle electrode 2 according to the cycle,
（2）在电位分布测试时，所有电极丝彼此断开，依次测量单根电极丝相对于参比电极4的腐蚀电位；(2) During the potential distribution test, all electrode wires are disconnected from each other, and the corrosion potential of a single electrode wire relative to the reference electrode 4 is measured sequentially;
在电流分布测量时，单根电极丝彼此断开，测量单根电极丝与其他相互连接的电极丝之间的电偶电流。In the current distribution measurement, the single electrode wires are disconnected from each other, and the galvanic current between a single electrode wire and other interconnected electrode wires is measured.
如图2和图3所示，本实施例涉及的丝束电极2的异种金属电极丝材料为Q235碳钢和B10铜镍合金，每根电极丝直径为1.5 mm，用环氧树脂将50根碳钢丝和50根铜镍合金丝密封成10×10矩阵。每根电极丝之间的间隔为1 mm并使其彼此绝缘。根据100根电极丝在丝束电极2中的具体位置，对其依次编号，其中1#-50#电极为碳钢电极，51#-100#电极为铜镍合金电极。丝束电极2样品表面用800# SiC水磨砂纸进行打磨，然后依次用去离子水和无水乙醇清洗。As shown in Fig. 2 and Fig. 3, the dissimilar metal electrode wire materials of the wire bundle electrode 2 involved in this embodiment are Q235 carbon steel and B10 copper-nickel alloy, and the diameter of each electrode wire is 1.5 mm, and 50 electrode wires are coated with epoxy resin. Carbon steel wire and 50 copper-nickel alloy wires are sealed into a 10×10 matrix. Each electrode wire is spaced 1 mm apart and insulated from each other. According to the specific position of the 100 electrode wires in the wire bundle electrode 2, they are numbered sequentially, wherein the 1 # -50 # electrodes are carbon steel electrodes, and the 51 # -100 # electrodes are copper-nickel alloy electrodes. The surface of the wire bundle electrode 2 sample was polished with 800 # SiC water abrasive paper, and then cleaned with deionized water and absolute ethanol in sequence.
如图4所示，使用厚度为150 μm的涂布棒一次性地将环氧涂层涂覆在丝束电极2表面，使得丝束电极2表面不同区域的涂层厚度一致。然后环氧涂料在室温下固化7天后，根据ISO 15184-2012测试方法测得其硬度达到HB，表明该环氧涂料已完全固化。待涂层完全固化后，测得涂层厚度为100 ± 5 μm，并且将碳钢区域的45#电极表面涂层完全去除，以满足实验在异种电极交界处破损涂层的要求。As shown in Figure 4, the epoxy coating was coated on the surface of the wire electrode 2 at one time using a coating rod with a thickness of 150 μm, so that the thickness of the coating in different regions of the surface of the wire electrode 2 was consistent. Then, after the epoxy coating was cured at room temperature for 7 days, its hardness measured according to the ISO 15184-2012 test method reached HB, indicating that the epoxy coating had been completely cured. After the coating was completely cured, the thickness of the coating was measured to be 100 ± 5 μm, and the surface coating of the 45 # electrode in the carbon steel area was completely removed to meet the requirements of the experiment for the damaged coating at the junction of different electrodes.
实验过程：experiment procedure:
将丝束电极2浸泡在3.5 wt.% NaCl溶液中，温度为25 ℃。Soak the filament electrode 2 in 3.5 wt.% NaCl solution at 25 °C.
分别测量浸泡时间为0.5 h，2 h，6 h, 12 h, 24 h时的电位电流分布，之后每隔12 h测量一次，每次测量完后，丝束电极2中的所有电极丝都连接在一起，以使电子自由流动。丝束电极浸泡24 h后的电流密度分布如图5所示。Measure the potential and current distribution when the soaking time is 0.5 h, 2 h, 6 h, 12 h, and 24 h, and then measure it every 12 h. After each measurement, all the electrode wires in the wire bundle electrode 2 are connected together so that electrons can flow freely. The current density distribution of the wire bundle electrode after soaking for 24 h is shown in Fig. 5.
分别对浸泡时间为0.5 h，24 h时碳钢、铜镍合金区域涂层进行电化学阻抗谱测量，以对比分析碳钢、铜镍合金区域涂层阻抗模型的变化特征。测试过程如下：电化学阻抗谱测量是在恒电位控制下于开路电势下进行的，正弦波信号幅值为20 mV，测试频率范围为105~10-2 Hz。电解池6采用经典的三电极体系，丝束电极2作为工作电极，饱和甘汞电极作为参比电极4，铂铌丝作为辅助电极5。分别将45#电极以外的49根碳钢丝和50根铜镍合金丝偶合在一起，然后进行电化学阻抗谱进行测量，获得碳钢区域和铜镍合金区域的电化学阻抗谱。丝束电极浸泡24 h后碳钢与铜镍合金区域涂层的EIS响应如图6所示。Electrochemical impedance spectroscopy was measured for carbon steel and copper-nickel alloy regional coatings at 0.5 h and 24 h soaking time, respectively, to compare and analyze the change characteristics of the impedance models of carbon steel and copper-nickel alloy regional coatings. The test process is as follows: the electrochemical impedance spectroscopy measurement is carried out under the constant potential control at the open circuit potential, the amplitude of the sine wave signal is 20 mV, and the test frequency range is 10 5 ~10 -2 Hz. The electrolytic cell 6 adopts a classic three-electrode system, the wire beam electrode 2 is used as the working electrode, the saturated calomel electrode is used as the reference electrode 4 , and the platinum-niobium wire is used as the auxiliary electrode 5 . 49 carbon steel wires and 50 copper-nickel alloy wires other than the 45 # electrode were coupled together, and then measured by electrochemical impedance spectroscopy to obtain electrochemical impedance spectroscopy in the carbon steel area and the copper-nickel alloy area. The EIS response of the carbon steel and copper-nickel alloy area coating after the wire bundle electrode was soaked for 24 h is shown in Fig. 6.
每次浸泡周期结束后，分别使用数码相机和体式显微镜对丝束电极表面的宏观和微观形貌演变进行跟踪拍摄。丝束电极浸泡330 h后的形貌图如图7所示。After each immersion cycle, digital cameras and stereo microscopes were used to track and photograph the evolution of the macroscopic and microscopic topography of the wire electrode surface. The topography of the wire bundle electrode after soaking for 330 h is shown in Fig. 7.
本发明的方法能够获得浸泡过程中涂层失效与电偶腐蚀电化学参数的相关性信息，有效监测电偶腐蚀，解决了片状电极只能获得电极表面平均化信息，而不能获得电极局部电化学信息的缺陷。The method of the present invention can obtain the correlation information between coating failure and electrochemical parameters of galvanic corrosion during the immersion process, effectively monitor galvanic corrosion, and solve the problem that sheet electrodes can only obtain averaged information on the electrode surface, but cannot obtain local electrode corrosion information. Defects in chemical information.
以上详细描述了本发明的优选实施方式，但是，本发明并不限于上述实施方式中的具体细节。在本发明的技术构思范围内，可以对本发明的技术方案进行多种等同变换，这些等同变换均属于本发明的保护范围。Preferred embodiments of the present invention have been described in detail above, however, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various equivalent transformations can be made to the technical solutions of the present invention, and these equivalent transformations all belong to the protection scope of the present invention.
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