目的 赋予防腐涂层环境响应性的同时,提高涂层的主动防腐性能和耐久性。方法 将没食子酸（GA）负载于介孔分子筛（MCM-41）上,在其表面包覆聚乙烯亚胺（PEI）和聚对苯乙烯磺酸钠（PSS）形成GA@MCM-41/PEI/PSS防腐增效组份。通过X射线衍射,扫描电子显微镜等分析增效组份的结构、形貌、元素组成和PEI/PSS表面包覆状态。分别用热分析法和紫外光谱法探究缓蚀剂在载体中的负载率和不同pH下缓蚀剂的控制释放特性。将防腐增效组份掺入水性环氧涂料（EP）中并涂敷于碳钢上形成防腐涂层,采用电化学和耐盐雾测试,评价涂层对碳钢的主动防腐性能。结果 缓蚀剂在MCM-41载体中的负载率为26%（质量分数）,防腐增效组份在酸、碱性条件下能够对缓蚀剂控制释放。掺加0.4%（质量分数）的GA@MCM-41/PEI /PSS-EP涂层在3.5%（质量分数）NaCl溶液中浸泡28 d后,低频阻抗值依然维持在6.35×108 Ω·cm2以上;具有最低的双电层电容CPEdl;并且涂层腐蚀电流密度降至0.32 μA/m2,说明涂层与基体结合紧密具有优异的阻隔性能和极化作用。复合涂层在盐水中浸泡21 d后呈现比14 d更高的低频阻抗值和阻抗半径,并且盐雾试验10 d后涂层表面无腐蚀迹象,划痕处有钝化层出现,表明涂层对碳钢具有主动防护性能。MD模拟分析表明,GA分子与碳钢Fe原子之间产生了化学吸附作用。结论 制备的GA@MCM-41/PEI/PSS涂层具有环境响应性、优异的防腐耐久性和主动防护作用。
Abstract
An environmentally responsive anti-corrosion coating can release corrosion inhibitors upon the invasion of corrosive media and actively repair itself to prevent the propagation of corrosion. However, the direct addition of corrosion inhibitors to coatings often results in a substantial release within a short period, which is detrimental to the long-term corrosion resistance of the coating. Encapsulating the corrosion inhibitor within a carrier to form microcapsules will enable the controlled release of the inhibitor in response to the stimulation of the corrosion environment, thereby forming an environmentally responsive anti-corrosion enhancement component to improve the durability of the composite coating.
In this work, GA corrosion inhibitor was loaded into mesoporous molecular sieve MCM-41, coating polyelectrolyte PEI and PSS by electrostatic adsorption, and preparing GA@MCM-41/PEI/PSS anti-corrosion and efficiency-enhancing components. The structure, morphology, elemental composition, and surface coating state of PEI/PSS of the GA@MCM-41/PEI/PSS were analyzed by means of X-ray diffraction and scanning electron microscopy. The loading rate of the corrosion inhibitor in the carrier and the controlled release characteristics of the inhibitor at different pH levels were obtained through thermal analysis and ultraviolet spectroscopy, respectively. The anti-corrosion enhancement component was incorporated into a water-based epoxy coating (EP) and applied to carbon steel to form a protective coating. The active anti-corrosion performance and durability of the coating on carbon steel were evaluated through electrochemical impedance spectroscopy, polarization curves, and salt spray resistance tests. The loading rate of the corrosion inhibitor in the MCM-41 carrier was 26wt.%, and the anti-corrosion enhancement component was capable of accelerating the controlled release of the inhibitor to a certain extent under both acidic and alkaline conditions. After immersion in a 3.5% NaCl solution for 28 days, the low-frequency impedance value of the coating with 0.4wt.% GA@MCM-41/PEI/PSS-EP still remained above 6.35×108 Ω·cm2 which was three orders of magnitude higher than that of the control EP coating. Following accelerated corrosion, the coating potential shifted significantly in the positive direction, and the corrosion current density decreased to 0.32 μA/m2. Additionally, the coating exhibited the highest coating resistance and the lowest double-layer capacitance (CPEdl), indicating that the coating had a tight bond with the carbon steel substrate and exhibited excellent barrier properties. Furthermore, the composite coating exhibited a higher low-frequency impedance and a larger impedance radius after 21 days of immersion in saline solution compared to that after 14 days. Additionally, after 10 days of salt spray testing, the coating surface showed almost no signs of corrosion, and a passivation layer appeared at the scratches, indicating that the coating provided excellent active anti-corrosion protection for carbon steel. MD simulation analysis revealed that a strong chemical adsorption interaction occurred between GA molecules and Fe atoms of carbon steel. Stimulated by changes in the pH of the corrosive environment, the controlled release of the corrosion inhibitor by GA@MCM-41/PEI/PSS-EP, the filling effect of nanoscale materials, and the barrier properties of the coating synergistically enhanced the corrosion resistance of the protective coating. In conclusion, the prepared GA@MCM-41/ PEI/PSS coating exhibits environmental responsiveness, outstanding anti-corrosion durability, and active protective effects.
关键词
环境响应性 /
缓蚀剂没食子酸 /
控制释放 /
主动防护 /
防腐耐久性
Key words
environmental responsiveness /
corrosion inhibitor gallic acid /
controlled release /
active protection /
corrosion resistance and durability
{{custom_sec.title}}
{{custom_sec.title}}
{{custom_sec.content}}
参考文献
[1] 李微, 孙涛, 柏国伟, 等. 钢在高温CO2环境中氧化渗碳腐蚀机理及其涂层防护研究进展[J]. 中国表面工程, 2024, 37(2): 72-90.
LI W, SUN T, BO G W, et al.Research Progress on the Mechanism of Oxidative Carburization Corrosion and Coating Protection of Steels Served at High-Temperature CO2 Environment[J]. China Surface Engineering, 2024, 37(2): 72-90.
[2] ZHANG X M, CHEN Z Y, LUO H F, et al.Corrosion Resistances of Metallic Materials in Environments Containing Chloride Ions: A Review[J]. Transactions of Nonferrous Metals Society of China, 2022, 32(2): 377-410.
[3] ALJIBORI H, AL-AMIERY A, ISAHAK W N R. Advancements in Corrosion Prevention Techniques[J]. Journal of Bio-and Tribo-Corrosion, 2024, 10(4): 78.
[4] LI J X, ZHU Z Y, LI Z W, et al.Progress of Research on Gallic Acid in Corrosion Inhibition and Rust Removal Protection of Metals[J]. Anti-Corrosion Methods and Materials, 2023, 70(6): 478-489.
[5] SESIA R, SPRIANO S, SANGERMANO M, et al.Natural Polyphenols and the Corrosion Protection of Steel: Recent Advances and Future Perspectives for Green and Promising Strategies[J]. Metals, 2023, 13(6): 1070.
[6] 王朴炎, 俞嘉辉, 臧显峰, 等. 深海环境下环氧重防腐涂层的防护机理和应用研究进展[J]. 中国表面工程, 2024, 37(6): 135-145.
WANG P Y, YU J H, ZANG X F, et al.Research Progress on the Protection Mechanism and Application of Epoxy Heavy-Duty Anti-Corrosion Coatings in Deep-Sea Environments[J]. China Surface Engineering, 2024, 37(6): 135-145.
[7] BHAT S I, MOBIN M, ISLAM S, et al.Recent Advances in Anticorrosive Coatings Based on Sustainable Polymers: Challenges and Perspectives[J]. Surface and Coatings Technology, 2024, 480: 130596.
[8] ZHU H L, LIU J H, LU X M, et al.Wettability and Anticorrosion Behavior of Organic-Inorganic Hybrid Superhydrophobic Epoxy Coatings Containing Triazine Corrosion Inhibitor Loaded in Mesoporous Molecular Sieve[J]. Journal of The Institute of Chemical Engineers, 2022, 141: 104604.
[9] 刘晓艺, 尹红阳, 张青青, 等. 基于缓蚀剂负载型微纳米容器防腐涂层的研究进展[J]. 涂料工业, 2024, 54(9): 56-63.
LIU X Y, YIN H Y, ZHANG Q Q, et al.Research Progress of Anticorrosive Coating Based on Micro/Nanocontainer Loaded with Corrosion Inhibitor[J]. Paint & Coatings Industry, 2024, 54(9): 56-63.
[10] ZHANG Y F, HU C, ZHAO Z B, et al.Fabrication of BTA-Loaded Mesoporous Silica-Encapsulated ZSM-5 Molecular Sieve for Enhancing Anti-Corrosion Performance of Waterborne Epoxy Coatings[J]. Progress in Organic Coatings, 2022, 172: 107160.
[11] LIU T, MA L W, WANG X, et al.Self-Healing Corrosion Protective Coatings Based on Micro/Nanocarriers: A Review[J]. Corrosion Communications, 2021, 1: 18-25.
[12] 赵东. 自动防护与腐蚀预警一体化涂层材料的制备及性能研究[D]. 石家庄: 石家庄铁道大学, 2023.
ZHAO D.Preparation and Properties of Automatic Protection and Corrosion Warning Integrated Coating Materials[D]. Shijiazhuang: Shijiazhuang Tiedao University, 2023.
[13] 杜鑫, 刘湘梅, 郑奕, 等. 静电层层自组装制备聚苯乙烯微球(核)/MCM-41纳米粒子(壳)阶层结构复合微粒[J]. 化学学报, 2009, 67(5): 435-441.
DU X, LIU X M, ZHENG Y, et al.Preparation of Hierarchical Polystyrene Microsphere (Core)/MCM-41 Nanoparticle (Shell) Composite Particles via Electrostatic Layer-by-Layer Assembly[J]. Acta Chimica Sinica, 2009, 67(5): 435-441.
[14] WANG N, CHENG K Q, WU H, et al.Effect of Nano-Sized Mesoporous Silica MCM-41 and MMT on Corrosion Properties of Epoxy Coating[J]. Progress in Organic Coatings, 2012, 75(4): 386-391.
[15] FANG S, CHEN K F, YAO H R, et al.Preparation of Gallic Acid Intercalated Layered Double Hydroxide for Enhanced Corrosion Protection of Epoxy Coatings[J]. Coatings, 2023, 13(1): 128.
[16] ZHOU L B, WANG X D, ZHAO X X, et al.2-Chloromethylbenzimidazole Loaded and Polyethyleneimine/Poly (Sodium-p-Styrenesulfonate) Decorated Fumed Silica as Filler to Prepare pH Stimuli-Responsive and Self-Healing Epoxy Composite Coating[J]. Progress in Organic Coatings, 2023, 174: 107307.
[17] LI J Y, KRISHNA B A, VAN EWIJK G, et al.A Comparison of Complexation Induced Brittleness in PEI/PSS and PEI/NaPSS Single-Step Coatings[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2022, 648: 129143.
[18] BIBAK S, POURSATTAR MARJANI A, SARRESHTEHDAR ASLAHEH H.MCM-41 Supported 2-Aminothiophenol/Cu Complex as a Sustainable Nanocatalyst for Suzuki Coupling Reaction[J]. Scientific Reports, 2024, 14: 18070.
[19] GAN L H, ZHANG J, WU Y T, et al.Tailoring Polyelectrolyte Multilayer Nanofiltration Membranes by Aerosol-Assisted Printing: Insights into Membrane Formation Mechanisms[J]. Environmental Science & Technology, 2025, 59(1): 913-923.
[20] SERRANO-LOTINA A, PORTELA R, BAEZA P, et al.Zeta Potential as a Tool for Functional Materials Development[J]. Catalysis Today, 2023, 423: 113862.
[21] FADHILLAH F, KRIAA K, ALI F A A, et al. Innovative Polyelectrolyte Multilayer Nanofiltration Membrane Fabricated Through Spin-Spray Assisted Layer-by-Layer Assembly[J].Polymer Preprints, 2024, 74(1): 444-445.
[22] HOSTNIK G, TOŠOVIĆ J, ŠTUMPF S, et al. The Influence of pH on UV/Vis Spectra of Gallic and Ellagic Acid: A Combined Experimental and Computational Study[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2022, 267: 120472.
[23] GOU J F, SUN M R, MA X X, et al.Effects of Temperature and pH Value on the Morphology and Corrosion Resistance of Titanium-Containing Conversion Coating[J]. Applied Surface Science Advances, 2021, 3: 100060.
[24] TRENTIN A, PAKSERESHT A, DURAN A, et al.Electrochemical Characterization of Polymeric Coatings for Corrosion Protection: A Review of Advances and Perspectives[J]. Polymers, 2022, 14(12): 2306.
[25] 郭发扬. 典型有机污染物-矿物界面吸附机制的计算模拟[D]. 武汉: 华中农业大学, 2022.
GUO F Y.Computational Simulation of Adsorption Mechanism at Typical Organic Pollutant-mineral Interfaces[D]. Wuhan: Huazhong Agricultural University, 2022.
基金
河北省重点研发计划项目（22371201D）
PDF(15161 KB)
渝公网安备 50010702501715号 渝ICP备15012534号-3
