| 引用本文: | 俞嘉辉,安然,任建炜,王朴炎,胡慧峰,刘栓.二次掺杂聚苯胺改性玄武岩鳞片复合环氧涂层的疏水防腐性能[J].中国表面工程,2024,37(6):364~376 |
| YU Jiahui,AN Ran,REN Jianwei,WANG Puyan,HU Huifeng,LIU Shuan.Hydrophobic and Anticorrosive Properties of Secondary Doped Polyaniline-modified Basalt Flake Composite Epoxy Coatings[J].China Surface Engineering,2024,37(6):364~376 |
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| 摘要: |
| 苛刻海洋腐蚀环境下防护涂层的腐蚀失效严重威胁着海工装备的可靠运行和长寿命服役安全，传统防腐涂层在大气中的水接触角小，在苛刻海洋腐蚀环境下的长效防护性能不佳。为了提升环氧涂层在苛刻海洋腐蚀环境中的防护性能和疏水性能，采用对氨基苯甲酸（ABA）将蚀刻后的玄武岩鳞片（B）与聚苯胺（PANI）共价结合，得到玄武岩鳞片 / 聚苯胺（BP） 粉末，通过全氟十四烷酸对 BP 进行二次掺杂，得到氟化玄武岩鳞片 / 聚苯胺（FBP）复合材料。在碳钢 Q235 上制备了以 FBP 为功能填料的复合环氧涂层，该涂层具有良好的疏水性和防护性能。润湿性测试结果表明：涂层表面的接触角能达到 138.1°， 在经过 100 次往复循环摩擦后涂层水接触角仍能达到 127.4°。电化学测试结果表明：在 3.5wt.% NaCl 溶液中浸泡 20 d 后， 环氧复合氟化玄武岩鳞片 / 聚苯胺（EP / FBP）涂层具有最大的低频阻抗模量 0.654 TΩ·cm2 和最小的腐蚀电流密度 2.59 pA·cm2 。 EP / FBP 涂层优异的耐蚀性主要归因于涂层表面形成的微 / 纳结构和 B 的片层阻隔与 PANI 缓蚀作用的协同效应，该复合涂层有效降低腐蚀介质向漆膜内部的渗透速率。因此，通过利用 PANI 二次掺杂特性制备的疏水 PANI，能有效降低腐蚀介质向环氧涂层内部的渗透速率，为新型功能填料在环氧涂层中的应用提供新思路。 |
| 关键词: 疏水涂层 氟化玄武岩 环氧涂层 电化学腐蚀 |
| DOI：10.11933/j.issn.1007-9289.20231217001 |
| 分类号:TB332；TQ638 |
| 基金项目:国家重点研发计划项目（2023YFC2809901）；宁波市电力设计院有限公司科技项目（KJXM2022053）；变电站惰性气体泡沫灭火系统（IGFS）灭火关键技术研究及应用（KJKY20230277） |
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| Hydrophobic and Anticorrosive Properties of Secondary Doped Polyaniline-modified Basalt Flake Composite Epoxy Coatings |
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YU Jiahui1，AN Ran2，REN Jianwei1，WANG Puyan1，HU Huifeng1，LIU Shuan2，3
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1.Ningbo Electric Power Design Institute Co., Ltd., Ningbo 315000 , China ；2.State Grid Zhejiang Electric Power Co., Ltd.Research Institute, Hangzhou 310010 , China ；3.Key Laboratory of Advanced Marine Materials, Ningbo Institute of Materials Technology and Engineering,Chinese Academy of Sciences, Ningbo 315201 , China
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| Abstract: |
| Oceans account for 71% of the Earth’s surface area. The average depth of the ocean is approximately 3 700 m with 90% of the ocean depth exceeding 1 000 m. In addition to containing abundant mineral resources, the ocean has huge reserves of natural gas, combustible ice, and oil. Therefore, it has become the most promising strategic space for the development and utilization of natural resources on Earth. Heavy-duty anticorrosion coatings are crucial to ensure the safe service of marine engineering and equipment. The failure of anticorrosion coatings in harsh corrosive marine environments seriously threatens the reliable operation and long-term service safety of marine equipment. However, traditional anticorrosion coatings have a small water contact angle in the atmosphere and poor long-term protection performance in harsh corrosive marine environments. The presence of active epoxy groups in the molecular structure of epoxy resin allows epoxy to crosslink with various types of curing agents to form a three-dimensional network structure of polymers. Epoxy resin is typically used as the main film-forming material in marine heavy-duty anticorrosion coating systems. However, cured epoxy paint films have shortcomings such as brittleness, fatigue resistance, heat resistance, and poor impact resistance, which limit their application in harsh corrosive marine environments. The comprehensive protective performance of epoxy coatings can be improved by adding functional fillers, such as two-dimensional layered materials, hydrophobic materials, corrosion inhibitors, and functional additives. To improve the protective and hydrophobic properties of epoxy coatings, p-aminobenzoic acid (ABA) was used to covalently combine etched basalt scales (B) with polyaniline (PANI), to obtain basalt / polyaniline (BP) powder. Fluorinated basalt / polyaniline (FBP) composite materials were obtained by the secondary doping of BP with perfluorodetradecanoic acid. A composite epoxy coating was prepared with FBP as a functional filler to protect Q235 carbon steel. The coating exhibited good hydrophobicity and protective performance. The wettability test results showed that the water contact angle of the FBP functional filler can reach 147.6°, indicating that the composite coating has a higher hydrophobic performance than B, PANI, and BP filler, which are all hydrophilic. The surface contact angle of the prepared coating could reach 138.1°, and after 100 cycles of reciprocating friction, the water contact angle of the coating could still reach 127.4°. One of the most important factors for the coating to protect the metal due to its excellent barrier performance against water. Upon performing a water absorption test by soaking the coating in water, the water absorption rate of the pure EP coating was observed to reach approximately 10% after 120 h, whereas the water absorption rate of the EP / FBP coating was only 3% after 120 h, indicating that the composite coating has an excellent barrier performance against water. The electrochemical test results indicated that after 20 d immersion in a 3.5wt.% NaCl solution, the EP / FBP coating had a maximum low-frequency impedance modulus of 0.654 TΩ·cm2 and a minimum corrosion current density of 2.59 pA·cm2 . After 480 h of a simulated cycle experiment in a neutral salt spray circulation box, the EP / FBP coating did not show obvious rust on the scratches, and the other coatings exhibited different degrees of corrosion. The excellent corrosion resistance of the EP / FBP coating was mainly attributed to the micro / nanostructures formed on the surface of the composite coating and the synergistic effect of the basalt layer barrier and the corrosion inhibition of the PANI. The composite coatings effectively reduced the the penetration rate of corrosive media. In conclusion, a hydrophobic PANI functional filler was prepared using PANI secondary doping technology. The addition of FBP to epoxy resin was found to effectively reduce the penetration rate of corrosive media in the composite coating. This study provides new insights into the addition of functional fillers to epoxy coatings. |
| Key words: hydrophobic coating fluorinated basalt epoxy coating electrochemical corrosion |
