硅酸盐学报

硅酸盐防腐涂层多尺度改性研究进展

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李伟华 ¹^,²^,³ , 李舒婷 ¹ , 付波 ⁴ , 王晓军 ⁴ , 赵利 ⁴ , 郑海兵 ²^,³

硅酸盐学报 | 综合评述 2025,53(4): 1018-1030

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硅酸盐学报 |综合评述 2025 , 53 (4) : 1018 -1030

硅酸盐防腐涂层多尺度改性研究进展

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李伟华¹^,²^,³, 李舒婷¹, 付波⁴, 王晓军⁴, 赵利⁴, 郑海兵²^,³

作者信息

^1．华北水利水电大学土木与交通学院，郑州 450045

^2．河南省科学院化学研究所，郑州 450046

^3．河南省科学院，郑州 450046

^4．山东龙泉管业股份有限公司，山东淄博 255200

通讯作者:

郑海兵（1988—），男，博士，副研究员。

作者简介:

李伟华（1971—），女，博士，教授。

Research Progress on Multi-Scale Modification of Silicate Anti-Corrosion Coatings

Weihua LI¹^,²^,³, Shuting LI¹, Bo FU⁴, Xiaojun WANG⁴, Li ZHAO⁴, Haibing ZHENG²^,³

Affiliations

^1.School of Civil Engineering and Communication, North China University of Water Resources and Electric Power, Zhengzhou 450045, China

^2.Henan Academy of Sciences Institute of Chemistry, Zhengzhou 450046, China

^3.Henan Academy of Sciences, Zhengzhou 450046, China

^4.Shandong Longquan Pipe Industry Co., Ltd, Zibo 255200, Shandong, China

Corresponding Author:

ZHENG Haibing (1988-), male, Ph.D., Associate Professor. E-mail: zhenghaibing.ln@163.com

LI Weihua (1971-), female, Ph.D., Professor. E-mail: liweihua1928@163.com

出版时间: 2025-04-20 doi: 10.14062/j.issn.0454-5648.20240656

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摘要

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硅酸盐涂层作为一种无机涂料，具有优异的长期防腐性能、耐热性以及耐候性。与传统的有机涂层相比，其更加绿色环保，符合环保涂料发展的新趋势。然而，纯硅酸盐涂层存在脆性大、易开裂和耐水性差等问题，限制了其在实际工程中的应用。针对上述问题，本文综述了不同材料对硅酸盐涂层改性，各材料均不同程度影响涂层的综合性能。基于空间多尺度理念，将相关改性材料按宏观、介观和微观3个尺度分类概述。宏观尺度下的改性材料包括硅溶胶、磷酸铝（AlPO₄）、磷酸氢钙（CHP）等无机材料，以及有机硅化合物、有机聚合物等有机材料；介观尺度下改性材料则包括“锌”型填料、层状填料及其它金属及其氧化物等微米级改性填料；微观尺度下改性材料主要为纳米级填料，如纳米SiO₂、纳米石墨烯基填料等。介绍了不同尺度下改性材料对硅酸盐涂层性能的影响及其改性机制，最后讨论了不同尺度改性材料在当前研究中的不足之处以及未来的发展趋势。

关键词

防腐涂层 / 硅酸盐涂层 / 涂层改性 / 多尺度

Abstract

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Inorganic silicate coatings, as a type of inorganic paint, exhibit the superior long-term anti-corrosion performance, heat resistance, and weather resistance. Compared to the conventional organic coatings, inorganic silicate coatings are more environmentally friendly, aligning with the development of eco-friendly coatings. However, pure inorganic silicate coatings face some issues such as high brittleness, susceptibility to cracking, and poor water resistance, thus restricting their practical application. Extensive research has been conducted on the modification of these coatings to enhance the mechanical properties and anti-corrosion performance of inorganic silicate coatings. It is essential to review the current research on the modification of inorganic silicate coatings to accelerate progress in both research and practical applications in engineering. This review represents the modification of inorganic silicate coatings with various materials affecting the overall performance of the coatings in varying degrees. Based on a spatial multi-scale approach, the relevant modifying materials are categorized into three scales, i.e., macro-scale, meso-scale, and micro-scale.

In the macro-scale, the modifying materials include inorganic substances such as silica sol, aluminum phosphate (AlPO₄), and calcium hydrogen phosphate (CHP), while organic materials consist of organo-silicon emulsions, silane coupling agents, acrylic resins, and epoxy resins. Silica sol significantly enhances the corrosion resistance of coatings via increasing their degree of crosslinking. Phosphate compounds promote the polymerization of silanol groups by providing H⁺ ions, thereby accelerating the curing of the coatings and improving their water resistance. Organic modifiers increase the internal crosslinking density and flexibility of the coatings, while also imparting hydrophobic and self-cleaning properties, by introducing functional groups such as hydroxyl and carboxyl groups into the silicate curing process.

In the meso-scale, the modifications primarily utilize micron-sized fillers, i.e., zinc-type fillers, layered structure fillers, and other metallic and metal oxide fillers. Zinc-type fillers encompass zinc powder, zinc oxide, and zinc silicate. Layered structure fillers include mica powder, two-dimensional transition metal carbides (Ti₃C₂T_x), and layered double hydroxides (LDHs), and other metallic and metal oxide fillers comprise aluminum powder, zinc-aluminum alloy powder, mica iron oxide, titanium (Ti), and titanium oxide (TiO₂). Metal and metal oxide modified fillers enhance the anti-corrosion performance of inorganic silicate coatings through a threefold mechanism of filling, physical shielding, and electrochemical protection, which delays and prevents the penetration of corrosive media into the substrate surface. In addition, these fillers can also chemically bond with silicate matrix, thereby enhancing the adhesion and chemical stability of the coating. Layered fillers, such as mica powder, Ti₃C₂T_x, and layered double hydroxides (LDHs), provide the superior physical shielding and create a "maze effect" within the coating, which extends and convolutes the diffusion pathways of corrosive media like chloride ions and water molecules. This ultimately slows down the corrosion reactions of the substrate and improves the anti-corrosion performance of the coating.

In the micro-scale, the materials for the modification are mainly nano-scale fillers, such as nano-silica (SiO₂) and graphene-based nano-scale fillers. This review discusses the impact of modification materials in different scales on the performance of inorganic silicate coatings and elucidates their modification mechanisms. This review addresses the existing shortcomings of modification materials in various scales in current research and outlines the future development trends. Nano-SiO₂ enhances the bonding strength and anti-corrosion performance of inorganic silicate coatings via participating in the construction of the silicate network, thereby increasing the internal connectivity of the coating. Meanwhile, nano graphene-based fillers can improve the weather resistance and anti-corrosion performance of the inorganic silicate coatings due to their exceptional chemical stability, conductivity, and barrier properties.

Summary and Prospects

In the macro-scale modification, constructing an environmentally friendly coating system to reduce the use of organic solvents is a future development direction. However, inorganic modifiers have some limitations in enhancing the coating performance. The use of organic modifiers can lead to the emission of volatile organic compounds (VOCs), which negatively impacts the environment. It is thus important for the dual goals of optimizing coating performance and environmental protection to develop eco-friendly inorganic silicate coatings that balance the use of inorganic and organic modifiers. The performance of the prepared inorganic silicate anti-corrosion coatings is relatively singular. A future research can explore multifunctional composite anti-corrosion coatings that can be used under various environmental conditions, such as super-hydrophobicity, self-cleaning, self-healing, oxidation resistance, and wear resistance. In the micro-scale, the modification of inorganic silicate coatings with nanoparticles may reduce economic viability due to the high cost of nano-materials. A future research should focus on the development of more cost-effective methods for synthesizing nanoparticles, such as microwave-assisted synthesis, solvothermal methods, and sol-gel techniques. In addition, introducing specific functional groups on the surface of nanoparticles or combining them with other materials to impart the coatings with multifunctional properties like self-healing, super-hydrophobicity, antibacterial activity, and flame retardancy can be an important development direction. In the molecular/atomic scale, studies on the modification of inorganic silicate coatings primarily focus on experimental approaches, failing to delve into the molecular or atomic mechanisms. This results in an incomplete understanding of the coatings performance. A future research should focus on molecular design and optimization, as well as molecular dynamics simulations, to clarify the modification mechanisms for inorganic silicate coatings.

Key words

anti-corrosion coatings / silicate coatings / coating modification / multi-scale

引用本文

李伟华, 李舒婷, 付波, 王晓军, 赵利, 郑海兵. 硅酸盐防腐涂层多尺度改性研究进展. 硅酸盐学报, 2025 , 53 (4) : 1018 -1030 . DOI: 10.14062/j.issn.0454-5648.20240656

Weihua LI, Shuting LI, Bo FU, Xiaojun WANG, Li ZHAO, Haibing ZHENG. Research Progress on Multi-Scale Modification of Silicate Anti-Corrosion Coatings[J]. Journal of the Chinese Ceramic Society, 2025 , 53 (4) : 1018 -1030 . DOI: 10.14062/j.issn.0454-5648.20240656

基金

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国家自然科学基金(52271355; 52308247)
河南省自然科学基金(242300421187)
河南省科技研发计划联合基金(225200810081)

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2025年第53卷第4期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240656

接收时间：2024-10-22
首发时间：2026-10-22
出版时间：2025-04-20

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出版历史

收稿日期：2024-10-22
修回日期：2024-11-11

基金

国家自然科学基金(52271355; 52308247)

河南省自然科学基金(242300421187)

河南省科技研发计划联合基金(225200810081)

作者信息

^1．华北水利水电大学土木与交通学院，郑州 450045

^2．河南省科学院化学研究所，郑州 450046

^3．河南省科学院，郑州 450046

^4．山东龙泉管业股份有限公司，山东淄博 255200

通讯作者:

郑海兵（1988—），男，博士，副研究员。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240656

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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