Research progress of anticorrosive coatings on concrete surface
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摘要: 混凝土是典型的非均质多孔材料，易受到环境中侵蚀离子介质的侵蚀，导致混凝土及其内部钢筋腐蚀，进而影响混凝土结构的性能并缩短其使用寿命。在众多防护措施中，采用表面防腐涂料是防止混凝土腐蚀、延长其结构服役寿命的最经济有效方法。基于此，本文系统总结了四类混凝土表面防腐涂料：表面成膜型、孔隙封闭型、疏水浸渍型和多功能表面处理型。探讨了每种涂料防护机制、防腐性能及存在的问题与不足。其中，重点分析了不同改性方式对混凝土表面防腐涂料增强效果的影响：有机/无机复合涂料能实现优势互补，显著提升涂料整体性能；有机硅和有机氟的低极性使改性后聚合物的表面能降低，从而显著提升涂料疏水性和耐化学稳定性；添加纳米颗粒能改善涂料力学性能和耐久性；构建特殊纳米结构能改善纳米颗粒团聚性，提高涂料疏水性能。展望未来，高效、安全、低成本、适用性强的混凝土表面防腐涂料是研究的重点，尤其是水性防护涂料与可再生材料的结合、纳米复合改性新型涂料以及自修复涂料等。Abstract: Concrete, a typical heterogeneous porous material, is susceptible to the erosion of ionic media in the environment. This erosion leads to the corrosion of concrete and its internal steel bars, consequently affecting the performance of concrete structures and shortening their service life. Among various protective measures, the application of surface anti-corrosion coatings stands out as the most economical and effective method to prevent concrete corrosion and extend the service life of concrete structures. This paper systematically summarizes four types of concrete surface anti-corrosion coatings: surface film-forming, pore-sealing, hydrophobic impregnation, and multi-functional surface treatment coatings. The protection mechanism, corrosion resistance, and existing problems and shortcomings of each coating are discussed. The influence of different modification methods on the enhancement effect of anti-corrosion coatings on concrete surfaces is analyzed emphatically: organic/inorganic composite coatings can achieve complementary advantages and significantly improve the overall performance of coatings. The low polarity of organic silicon and organic fluorine reduces the surface energy of the modified polymer, thereby significantly improving the hydrophobicity and chemical stability of the coating. Adding nanoparticles can improve the mechanical properties and durability of coatings. The construction of special nanostructures can improve the agglomeration of nanoparticles and enhance the hydrophobicity of coatings. Looking forward, the focus of research is on developing efficient, safe, low-cost, and adaptable concrete surface anti-corrosion coatings. This includes exploring the combination of waterborne protective coatings and renewable materials, nano-composite modified new coatings and self-healing coatings.
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图 7 (a) 水泥的水化反应；(b) 改性体系中聚丙烯酸酯乳液的水解；(c) 聚丙烯酸酯乳液与水泥的交联反应；(d) 聚丙烯酸酯乳胶改性水泥体系中通过化学反应得到的交联网络结构[67]
Figure 7. (a) The hydration reactions of cement; (b) The hydrolysis of polyacrylate latex in the modified system; (c) The crosslinking reaction between polyacrylate latex and cement; (d) The cross-linked network structure which was obtained by chemical reactions in the polyacrylate latex-modified cement system[67]
图 10 纳米SiO2对混凝土表面形貌和力学性能的强化机制：(a) 仅存在微粗糙度，磨损会破坏微观粗糙度；(b) 机械磨损微峰，亲水性水泥基材料将暴露；(c) 表面由具有纳米粗糙度的机械强化微凸块组成[63]
Figure 10. Strengthening mechanism of nano-silica on surface morphology and mechanical properties of concrete: (a) only microroughness is present, abrasion will destroy the micro-scale roughness; (b) mechanical abrasion wears off the micro peaks, hydrophilic cement-based material will be exposed; (c) the surface consists of mechanically strengthened micro-bumps with nano-roughness on them[63]
表 1 混凝土表面防腐有机涂料的性能
Table 1. Performance of organic anticorrosive coating on concrete surface
Organic coatings Curing mechanism Advantage Disadvantage Epoxy Resin[7, 33-35] 
Excellent hardness;
Easy curing;
Good wear resistance;
Good corrosion resistance;Weak UV resistance;
Easy to age;
High brittleness;
Weather resistance and heat resistance are affected;Acrylate[36-38] The dual-functional groups - vinyl (unsaturated double bond) and ester group (consisting of carbonyl and alkoxy), can undergo self-polymerization or copolymerization with other monomers. Excellent heat resistance and weatherability;
Good UV resistance and color retention;Limited water resistance;
Limited corrosion resistance;
Poor abrasion resistance;Polyurethane[39-42] 
Excellent abrasion resistance and adhesion;
Outstanding heat resistance;
Good weatherability and chemical resistance;High construction environment requirements;
Long curing time;
Relatively high cost;
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表 2 不同涂料体系及其防腐效率对比研究
Table 2. Comparative study of different coating systems along with their corrosion efficiencies
Anticorrosive coatings Modification methods Anticorrosion effect References cement-based coatings By introducing GO into silicone-modified polyacrylate (SPA) emulsion, polymer-modified cement-based coatings were prepared. With a 0.05% doping level of GO, the tensile strength is 3.01 MPa; the bond strength is 4.21 MPa; the 24 h water absorption rate is 4.6%; the hardness is 3 H; the Cl− corrosion potential is 3.88 Ω·cm2, and the corrosion current is 8.86×10−3 μA/cm2; after 1000 hours of UV light exposure, the loss rates of tensile strength and elongation at break are 6.85% and 33.55%, respectively.[82] Geopolymer coatings A hydrophobic emulsion was prepared using 70% deionized water, 5% water-soluble polyvinyl alcohol, and 25% hydrogen-containing silicone oil, and used to modify a geopolymer coating based on 1.1% pure acrylic emulsion. When the silicon-to-alumina ratio is 3.2, the water-to-solid ratio is 0.8, and the modulus is 1.6, the coating viscosity is 2.1 Pa·s; the hardness is 6 H; the adhesion is grade 3; and the contact angle is 147.71°. [30] Epoxy resin coatings Nano-TiO2 embedded GO nanosheets were prepared by in-situ intercalation method to modify epoxy resin. With a 0.5% doping level of GO, the bond strength is 13.75 MPa; the capillary absorption rate is 0.004 mm/min0.5; and the Cl− diffusion coefficient is 1.74×10−6 mm2/s. [76] Water-based polyurethane coatings Fluorinated nano-SiO2 incorporated into siloxane-modified hyperbranched water-based polyurethane. The contact angle is 162°, and remains close to 150° after 140 cycles of sandpaper abrasion; after immersion in acidic, alkaline, or other solutions for 144 hours, the contact angle remains greater than 150°; and the ice adhesion force at -20℃ is 21.2 kPa. [107] Cement-based permeable crystalline coatings Apply 11 types of active material solutions separately to the surface of cement mortar substrates. The water absorption rate of the TEOS-coated material is 40.44%, and the compressive strength is 57 MPa. [50] Water glass coatings Preparing waterproof coatings by activating blast furnace slag with sodium silicate modified by styrene-acrylate copolymer. Tensile strength is 2.2 MPa; elongation at break is 90.48%; flexibility is 10 mm; no leakage occurs under a pressure of 0.3 MPa for 30 minutes. [44] Hydrophobic immersion coatings Preparation of TEOS/isobutyltriethoxysilane composite emulsion by sol-gel method. After three months of exposure, the contact angle is 103.15°, and it can effectively inhibit the formation of biofilms, with a reduction of 86.6% in the capillary water absorption coefficient. [84, 87] Superhydrophobic coatings Superhydrophobic coatings were prepared by incorporating fluorinated nano-SiO2 and fly ash floating beads into polyvinyl alcohol. Contact angle is 163.4°; water absorption rates after immersion in deionized water and 3.5wt% NaCl solution for 7 days are 1.85% and 2.71%, respectively; antibacterial rate against Escherichia coli is 84.57%; and antibacterial rate against Streptococcus epidermidis is 90.43%. [95]
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