Super-hydrophobic fluorescent anti-icing coating as well as preparation method and application thereof

Abstract

The invention discloses a super-hydrophobic fluorescent anti-icing coating as well as a preparation method and application thereof. The coating comprises a primer layer and a finish paint layer, the primer layer is used for being attached to the surface of a base material and providing an adhesive force basis for the finish paint layer; the finish paint layer comprises hydrophobic resin, fluorescent functionalized super-hydrophobic powder, a solvent, an auxiliary agent, a flatting agent and an ultraviolet stabilizer; the fluorescent functionalized super-hydrophobic powder comprises super-hydrophobic micro-nano powder and a fluorescent component adsorbed or bonded on the surface of the super-hydrophobic micro-nano powder. The anti-icing coating disclosed by the invention has excellent super-hydrophobicity and low ice adhesion strength, can effectively delay icing and is easy to deice. A fluorescence indication function is innovatively introduced, rapid and visual in-situ monitoring of the anti-icing function state of the coating is achieved through the corresponding relation between the fluorescence intensity and the micro-nano structure integrity, the engineering pain point that failure of an existing coating is difficult to judge is solved, and the operation and maintenance efficiency and accuracy are remarkably improved.

Description

Technical Field

[0001] This invention belongs to the field of coatings, specifically relating to a superhydrophobic fluorescent anti-icing coating, its preparation method, and its application. Background Technology

[0002] Icing is one of the major threats to power grids, wind power, and other energy infrastructure in cold and humid environments. In power grid systems, icing on transmission lines, insulators, and towers can trigger a series of cascading failures, including mechanical overload, conductor galloping, and insulator flashover short circuits, severely jeopardizing the safe and stable operation of the grid. Similarly, in the wind power sector, icing on turbine blades leads to deteriorated aerodynamic performance, a sharp drop in power generation efficiency, increased turbine vibration, and even shutdown, hindering the effective utilization of wind energy resources. Currently, the main technical means to address icing are divided into active de-icing and passive anti-icing. Active de-icing technologies, such as current-based de-icing based on the Joule heating effect, are highly effective, but suffer from significant equipment investment, high energy consumption, and potential damage to line lifespan. Mechanical de-icing methods, on the other hand, are inefficient and are merely "post-hoc" remedial measures, unable to prevent damage to equipment caused in the early stages of icing formation. In contrast, passive protection technologies, represented by anti-icing coatings, achieve delayed icing and reduced ice adhesion strength from the source by constructing functional coatings on the equipment surface. They have significant advantages such as low energy consumption, wide applicability, and no need to interrupt operation, and are currently a research hotspot.

[0003] However, existing passive anti-icing coatings, especially superhydrophobic coatings based on micro-nano rough structures, still face severe challenges in practical engineering applications. Their technical bottlenecks mainly lie in: Insufficient functional durability: The core of superhydrophobicity lies in its fragile micro-nano secondary structure. Under harsh outdoor conditions such as long-term rain erosion, wind and sand abrasion, ultraviolet aging and freeze-thaw cycles, this structure is easily damaged, causing the coating to quickly lose its superhydrophobicity and low ice adhesion properties, and the anti-icing life is far lower than the equipment maintenance cycle. Lack of condition monitoring methods: The degradation of coating performance is a gradual and invisible process. Maintenance personnel cannot visually and quickly determine on-site whether the coating is still in effective condition. Often, coating failure is only realized after icing has already occurred, at which point remedial action is too late. This leads to significant delays in maintenance work, and traditional methods of periodic inspections and laboratory testing are costly and inefficient. Limited Functionality: Most existing coatings only provide basic anti-icing functionality and lack the ability to sense and provide feedback on their own health status. This fails to meet the development needs of smart grids and intelligent operation and maintenance for real-time perception of equipment status and predictive maintenance.

[0004] Therefore, developing a new type of intelligent coating that not only has long-term anti-icing capabilities but also enables in-situ visualization and monitoring of its own status is of great engineering value and practical significance for breaking through the application bottleneck of current passive anti-icing technology and improving the intelligent operation and maintenance level and safety and reliability of energy infrastructure. Summary of the Invention

[0005] Objectives of the Invention: The first objective of this invention is to provide a fluorescent indicator-type anti-icing coating with superhydrophobic anti-icing function and whose functional status can be visualized and monitored in situ, so as to solve the engineering problem that the failure status of existing anti-icing coatings cannot be intuitively judged; the second objective of this invention is to provide a preparation method for the coating, which is simple in process, easy to scale up production, and can ensure the stable combination of fluorescent components and superhydrophobic structure; the third objective of this invention is to provide the application of the coating in coating status monitoring.

[0006] Technical Solution: The superhydrophobic fluorescent anti-icing coating of this invention comprises a primer layer and a topcoat layer. The primer layer adheres to the surface of the substrate and provides a foundation for the adhesion of the topcoat layer. The topcoat layer comprises the following components by mass fraction: hydrophobic resin, fluorescent functionalized superhydrophobic powder, solvent, additives, leveling agent, and UV stabilizer. The fluorescent functionalized superhydrophobic powder comprises superhydrophobic micro / nano powder and fluorescent components adsorbed or bonded to the surface of the superhydrophobic micro / nano powder. The fluorescence intensity of the topcoat layer corresponds to the integrity of the micro / nano rough structure. By monitoring changes in the fluorescence signal, the attenuation state of the coating's superhydrophobicity and anti-icing ability can be indirectly indicated.

[0007] Preferably, the topcoat layer comprises the following components by mass fraction: 30-50 parts hydrophobic resin, 10-25 parts fluorescent functionalized superhydrophobic powder, 30-50 parts solvent, 1-3 parts additives, 0.5-2 parts leveling agent, and 1-4 parts UV stabilizer.

[0008] Preferably, the fluorescent component is modified with a silane coupling agent and then adsorbed or bonded to the superhydrophobic micro / nano powder.

[0009] Preferably, the superhydrophobic micro / nano powder includes one or more of nano-silica, calcium carbonate, and titanium dioxide.

[0010] More preferably, the superhydrophobic micro / nano powder is nano-silica or nano-titanium dioxide with a particle size of 10-100 nm.

[0011] More preferably, the silane coupling agent is a fluorosilane or a long-chain alkylsilane, which is also used to hydrophobically modify the superhydrophobic micro / nano powder.

[0012] More preferably, the silane coupling agent is at least one of heptadecafluorodecyltrimethoxysilane, methyltrimethoxysilane, or n-octyltriethoxysilane.

[0013] Preferably, the fluorescent component includes one or more of rare earth complexes and organic fluorescent dyes; preferably, the fluorescent component is a substance that emits visible light when excited by ultraviolet light.

[0014] Preferably, the fluorescent component is at least one of rare earth europium complex, zinc sulfide-based quantum dots, or rhodamine B-type organic dyes.

[0015] More preferably, the molar ratio of the fluorescent component to the silane coupling agent is 1:1 to 1:3.

[0016] More preferably, the hydrophobic resin is at least one of fluorocarbon resin, fluorosilicone resin, and hyperbranched fluorinated polyester.

[0017] More preferably, the solvent is at least one of ethanol, butyl acetate, and xylene.

[0018] More preferably, the additive is at least one of BYK-066N defoamer and BYK-163 dispersant.

[0019] More preferably, the leveling agent is BYK-333; the UV stabilizer is UV-327 or UV-770. Preferably, the primer layer is at least one of epoxy resin, polyurethane, fluorosilicone, fluorocarbon, or organosilicon resin primers, and its surface is roughened to enhance the mechanical interlocking effect with the topcoat layer.

[0020] The preparation method of the superhydrophobic fluorescent anti-icing coating of the present invention includes dissolving the fluorescent component in a solvent, adding a silane coupling agent to carry out a modification reaction to obtain a fluorescent modified liquid; adding superhydrophobic micro-nano powder to the fluorescent modified liquid, stirring, adsorbing, filtering, and drying to obtain fluorescent functionalized superhydrophobic powder; dispersing the fluorescent functionalized superhydrophobic powder in a solvent, adding additives, leveling agents, and UV stabilizers, stirring and dispersing thoroughly to obtain a topcoat; first coating a primer on the treated substrate surface, and after the primer has cured, coating a topcoat, and after curing, forming a superhydrophobic fluorescent anti-icing coating.

[0021] A further preferred embodiment of the preparation method of the superhydrophobic fluorescent anti-icing coating of the present invention includes the preparation of the topcoat and double-layer application, the specific steps of which are as follows: (1) Preparation of fluorescent functionalized superhydrophobic powder: The fluorescent component is dissolved in anhydrous ethanol, a silane coupling agent is added, and the mixture is refluxed at 60-70℃ for 2-4 hours to obtain a fluorescent modified solution; the hydrophilic nanoparticles are added to the fluorescent modified solution and stirred at 50-60℃ for 2-3 hours for adsorption, followed by filtration, washing and drying to obtain the fluorescent functionalized superhydrophobic powder; (2) Preparation of topcoat: The fluorescent functionalized superhydrophobic powder obtained in step (1) is mixed with solvent and ultrasonically pre-dispersed; then additives, leveling agents and UV stabilizers are added, and the mixture is dispersed for 2-4 hours by a combination of high-speed mechanical stirring and ball milling to obtain a uniform and stable topcoat; (3) Coating construction: On the cleaned substrate surface, first apply a commercial epoxy resin or polyurethane primer and cure it; after the primer is dry, apply the topcoat obtained in step (2) onto the primer by spraying or brushing, and after curing at room temperature or by heating, the superhydrophobic fluorescent anti-icing composite coating is formed.

[0022] The application of the superhydrophobic fluorescent anti-icing coating described in this invention in coating condition monitoring.

[0023] Preferably, the application method includes: recording the initial fluorescence signal intensity or image as a reference before the coating is put into use or when it is in good condition; during use, periodically or irregularly exciting the coating surface with ultraviolet light and detecting its fluorescence signal; comparing the detected fluorescence signal with the reference; when the fluorescence signal is significantly weakened or quenched, it is determined that the micro-nano structure of the topcoat layer has been damaged, and the superhydrophobic and anti-icing functions have deteriorated or failed, requiring maintenance or recoating.

[0024] The term "significant" refers to brightness changes that can be clearly distinguished by the naked eye or simple equipment.

[0025] More preferably, the fluorescence signal is detected by using a portable ultraviolet flashlight in conjunction with visual observation or by using a camera equipped with a specific filter.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: 1. Real-time visual monitoring of anti-icing status was achieved: By specifically bonding fluorescent components to superhydrophobic nanostructures, a direct correlation between the integrity of the micro / nano structure and the fluorescence intensity was established. When the coating fails due to wear, the fluorescence is simultaneously quenched. Engineers can use simple tools such as UV flashlights for quick and intuitive in-situ diagnosis, realizing a leap from "regular maintenance" to "on-demand maintenance," greatly improving the efficiency and accuracy of operation and maintenance. 2. Excellent anti-icing performance and long-term durability: Based on an optimized micro-nano composite structure and low surface energy resin, the coating has an initial water contact angle greater than 150° and a roll-off angle less than 5°. Meanwhile, the introduction of UV stabilizers and a robust chemical bonding method ensures the coating's long-term service capability in harsh outdoor environments. 3. The preparation process is simple and easy to promote: The present invention adopts the route of first functionalizing powder and then formulating coating. The process is stable, has good reproducibility, is suitable for large-scale production, and has significant economic and engineering application value. Attached Figure Description

[0027] Figure 1 This is a process flow diagram for preparing the superhydrophobic fluorescent anti-icing coating of the present invention. Detailed Implementation

[0028] The present invention will be further described in detail below with reference to specific embodiments. The present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0030] The technical solution of the present invention will be further described below with reference to the accompanying drawings, embodiments, and comparative examples.

[0031] Examples 1-3 and Comparative Example 1 The superhydrophobic fluorescent anti-icing coatings of Examples 1-3 and Comparative Example 1 consist of a primer and a topcoat.

[0032] The primer comprises the following components by weight: 50-70 parts epoxy resin E-44, 10-15 parts polyamide curing agent 650, 15-25 parts xylene diluent, and 1-3 parts silane coupling agent KH-560.

[0033] The topcoat comprises the following components by weight: 30-50 parts hydrophobic resin, 10-25 parts fluorescent functionalized superhydrophobic powder, 30-50 parts solvent, 1-3 parts additives; 0.5-2 parts leveling agent, and 1-4 parts UV stabilizer.

[0034] The fluorescent functionalized superhydrophobic powder is composed of hydrophilic nano-silica (particle size 20±5nm) and rare earth europium complexes bonded to its surface by heptadecafluorodecyltrimethoxysilane.

[0035] All reagents used were commercially available. The specific compositions of the primer and topcoat in Examples 1-3 and Comparative Example 1 are shown in Tables 1 and 2, respectively. Example 1 primarily used the lower limit or near the lower limit of the formulation ratio, Example 2 used the intermediate value ratio, and Example 3 used the upper limit or near the upper limit of the formulation ratio, to verify the feasibility of different formulations within the scope of the claims.

[0036] All reagents used were commercially available. The specific compositions of the primer and topcoat in Examples 1-3 and Comparative Example 1 are shown in Tables 1 and 2, respectively.

[0037] Table 1. Composition of primers in Examples 1-3 and Comparative Example 1

[0038] Table 2. Topcoat composition of Examples 1-3 and Comparative Example 1

[0039] Preparation methods of Examples 1-3: Preparation of the primer: According to the formula shown in Table 1, mix epoxy resin E-44 with xylene, stir until dissolved, add silane coupling agent KH-560, and continue stirring for 10 minutes. Before use, add polyamide curing agent 650, stir until dissolved, and let stand for 10 minutes to defoam.

[0040] Preparation of fluorescent functionalized superhydrophobic powder: 1 part by mass of rare earth europium complex was dissolved in 50 parts by mass of anhydrous ethanol, and 2 parts by mass of heptadecafluorodecyltrimethoxysilane were added. The mixture was refluxed at 65°C for 3 hours to obtain a fluorescent modified solution. 20 parts by mass of hydrophilic nano-silica were added to the fluorescent modified solution, and the mixture was stirred and adsorbed at 55°C for 2.5 hours. The mixture was then filtered, washed with ethanol, and vacuum dried at 80°C for 6 hours to obtain a red fluorescent functionalized powder.

[0041] Preparation of topcoat: According to the formula shown in Table 2, the powder obtained in step 2 (comparative example 1 used ordinary hydrophobic powder) was mixed with butyl acetate and ultrasonically dispersed for 30 minutes. Then, methyl silicone resin and other additives were added, and the mixture was dispersed by a combination of high-speed mechanical stirring (1200 rpm, 1 hour) and ball milling (4 hours) to obtain a uniform and stable topcoat.

[0042] Coating application: On a cleaned aluminum substrate, spray or brush the primer prepared in this embodiment, controlling the dry film thickness to 60±5μm, and cure at room temperature for 24 hours. Subsequently, spray the topcoat prepared in this embodiment on the cured primer, controlling the wet film thickness to approximately 30μm, and cure for 2 hours to form a complete composite coating.

[0043] The preparation method of Comparative Example 1 is the same as that of Examples 1-3, but ordinary hydrophobic powder is used in the topcoat instead of fluorescent functionalized superhydrophobic powder.

[0044] Performance testing experiment The composite coatings prepared in Examples 1-3 and Comparative Example 1 were subjected to performance tests, and the results are shown in Table 3: Table 3 Performance test results of composite coating

[0045] The technical features of the above embodiments can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as the combination of these technical features does not contradict each other, it should be considered within the scope of this specification. The above embodiments only illustrate several implementation methods of the present invention, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the present invention. It should be noted that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this patent should be determined by the appended claims.

Claims

1. A superhydrophobic fluorescent anti-icing coating, characterized in that, It includes a primer layer and a topcoat layer; the primer layer is used to adhere to the surface of the substrate and provide a basis for the adhesion of the topcoat layer; the topcoat layer includes a hydrophobic resin, a fluorescent functionalized superhydrophobic powder, a solvent, an additive, a leveling agent, and a UV stabilizer; the fluorescent functionalized superhydrophobic powder includes superhydrophobic micro-nano powder and fluorescent components adsorbed or bonded to the surface of the superhydrophobic micro-nano powder.

2. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The topcoat layer comprises the following components by mass fraction: 30-50 parts hydrophobic resin, 10-25 parts fluorescent functionalized superhydrophobic powder, 30-50 parts solvent, 1-3 parts additives, 0.5-2 parts leveling agent, and 1-4 parts UV stabilizer.

3. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The fluorescent component is modified with a silane coupling agent and then adsorbed or bonded to superhydrophobic micro / nano powder.

4. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The superhydrophobic micro / nano powder includes one or more of nano-silica, calcium carbonate, and titanium dioxide.

5. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The fluorescent component includes one or more of rare earth complexes and organic fluorescent dyes.

6. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The fluorescent component is at least one of rare earth europium complex, zinc sulfide-based quantum dots, or rhodamine B-type organic dyes.

7. The superhydrophobic fluorescent anti-icing coating according to claim 1, characterized in that, The primer layer is at least one of epoxy resin, polyurethane, fluorosilicone, fluorocarbon, or organosilicon resin primers.

8. A method for preparing the superhydrophobic fluorescent anti-icing coating according to any one of claims 1-7, characterized in that, The process includes dissolving the fluorescent component in a solvent, adding a silane coupling agent to carry out a modification reaction, and obtaining a fluorescent modified liquid; adding superhydrophobic micro / nano powder to the fluorescent modified liquid, stirring, adsorbing, filtering, and drying to obtain fluorescent functionalized superhydrophobic powder; dispersing the fluorescent functionalized superhydrophobic powder in a solvent, adding additives, leveling agents, and UV stabilizers, and stirring and dispersing thoroughly to obtain a topcoat; first coating a primer on the treated substrate surface, and after the primer has cured, coating a topcoat, which, after curing, forms a superhydrophobic fluorescent anti-icing coating.

9. The application of a superhydrophobic fluorescent anti-icing coating according to any one of claims 1-7 or a superhydrophobic fluorescent anti-icing coating prepared by the preparation method according to claim 8 in coating condition monitoring.

10. The application according to claim 9, characterized in that, The application method includes: recording the initial fluorescence signal intensity or image as a reference before the coating is put into use or when it is in good condition; during use, periodically or irregularly exciting the coating surface with ultraviolet light and detecting its fluorescence signal; comparing the detected fluorescence signal with the reference; when the fluorescence signal is significantly weakened or quenched, it is determined that the micro-nano structure of the topcoat layer has been damaged, and the superhydrophobic and anti-icing functions have deteriorated or failed, requiring maintenance or recoating.

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