Anti-icing coatings, functional layers and multifunctional coatings, preparation methods and applications

Abstract

This invention discloses a multifunctional coating, its preparation method, and its application, belonging to the technical field of bridge protection materials. This invention utilizes a micro-nano composite structure of MOF and molybdenum disulfide grown in a graded manner on the surface of a thin sheet material, synergistically with fluorosilicone resin to prepare an anti-icing coating. The anti-icing coating prepared using this method exhibits excellent anti-icing performance, achieving ultra-low ice adhesion. Furthermore, molybdenum disulfide has high photothermal conversion efficiency; in cloudy conditions, it converts ultraviolet light into heat energy, increasing the surface temperature and significantly delaying the icing initiation time. This invention also provides a multifunctional coating that achieves integrated fireproofing and ice-repelling through a gradient structure design of "aerogel felt - sealing layer - anti-icing layer," exhibiting high durability in extreme environments and a long service life, providing long-term protection. Specifically, the aerogel felt can insulate against flames up to 1100℃, and the anti-icing functional layer maintains low ice adhesion strength, simultaneously achieving efficient ice repellency and active fireproofing and heat insulation.

Description

Technical Field

[0001] This invention belongs to the technical field of bridge protection materials, and relates to a multifunctional coating with fireproof, heat-insulating, and anti-icing properties, its preparation method, and its application in the protection of bridge cables and tie rods. Specifically, it relates to anti-icing coatings, functional layers and multifunctional coatings, preparation methods, and applications. Background Technology

[0002] The information disclosed in this background section is intended only to enhance understanding of the overall background of the invention and is not necessarily to be construed as an admission or in any way implying that such information constitutes prior art known to those skilled in the art.

[0003] In bridge engineering, cables and tie rods, as core load-bearing structures, are directly related to the overall safety of the bridge. In recent years, two major problems have become increasingly prominent:

[0004] Firstly, there is an urgent need to prevent icing: In cold and humid environments (such as the Erqi Yangtze River Bridge), the cable surface is prone to icing, which leads to a surge in structural load and falling icicles threaten the safety of traffic under the bridge.

[0005] Secondly, the fire prevention challenges are escalating: with the popularization of electric vehicles, the risk of bridge fires is increasing (such as electric vehicle spontaneous combustion accidents). Traditional silicone anti-icing coatings cannot withstand high temperatures, while intumescent fire-retardant coatings lack active anti-icing capabilities.

[0006] Existing material systems have significant limitations: single-function coatings (such as pure fireproof layers or anti-icing coatings) cannot simultaneously address both fire and ice hazards, and layering them can easily lead to poor interfacial compatibility and insufficient durability. Therefore, there is an urgent need to develop a material system that integrates structure and function, simultaneously achieving efficient ice-repellent and active fireproofing and heat insulation while ensuring the long-term service life of the coating. Summary of the Invention

[0007] To address the shortcomings of existing technologies, the present invention aims to provide a multifunctional coating, its preparation method, and its application. The multifunctional coating provided by the present invention has fireproof, heat-insulating, and anti-icing properties, and can simultaneously meet the fireproof and anti-icing requirements of bridge cables and tie rods.

[0008] To achieve the above objectives, the technical solution of the present invention is as follows:

[0009] In a first aspect, the present invention provides an anti-icing coating comprising a fluorosilicone resin and a special pigment, wherein the special pigment comprises a flake material, a MOF grown on the flake material, and molybdenum disulfide nanosheets grown on the surface of the MOF.

[0010] In some embodiments of the present invention, the mass ratio of the fluorosilicone resin to the special pigment is (6.5-7.5):(2.5-3.5), preferably 7:3.

[0011] In some embodiments of the present invention, the sheet material is basalt flakes or glass flakes.

[0012] In some embodiments of the present invention, the MOF is MOF-5 or ZIF-8.

[0013] In some embodiments of the present invention, the fluorine content of the fluorosilicone resin is 20%-26%.

[0014] In a second aspect, the present invention provides an anti-icing coating, wherein the above-mentioned anti-icing coating is applied to a substrate and cured to obtain the coating.

[0015] In some embodiments of the present invention, the curing temperature is room temperature or 50-80°C.

[0016] A third aspect of the present invention provides an anti-icing functional layer, which is obtained by coating the above-mentioned anti-icing coating onto a sealing cloth and curing it.

[0017] In some embodiments of the present invention, the curing temperature is room temperature or 50-80°C.

[0018] In some embodiments of the present invention, the anti-icing coating is applied to the sealing cloth with a thickness of 80-120 μm.

[0019] A fourth aspect of the present invention provides a multifunctional coating comprising a fireproof and heat-insulating layer, a sealing and adhesive layer laminated on the fireproof and heat-insulating layer, and the aforementioned anti-icing functional layer laminated on the sealing and adhesive layer.

[0020] The fireproof and heat-insulating layer includes fiber composite aerogel felt;

[0021] The sealing and bonding layer comprises an inorganic fiber mesh and a silicone rubber sealant coated on the surface of the inorganic fiber mesh.

[0022] In some embodiments of the present invention, the thickness of the fireproof and heat-insulating layer is 3-8 mm, the thickness of the sealing and adhesive layer is 1.2-3 mm, and the thickness of the anti-icing functional layer is 0.5-1.5 mm.

[0023] In some embodiments of the present invention, the fibers in the fiber composite aerogel felt include any one of inorganic fibers and carbonized organic fibers, and the aerogel includes any one of silica aerogel, alumina aerogel and titanium dioxide aerogel.

[0024] In some embodiments of the present invention, the fiber composite aerogel felt is selected from any one or more of inorganic fiber aerogel felt and carbonized organic fiber composite aerogel felt.

[0025] In some embodiments of the present invention, the inorganic fiber includes any one or more of glass fiber, basalt fiber and aluminosilicate fiber.

[0026] In some embodiments of the present invention, the organic fiber includes any one of natural fibers and synthetic fibers; more preferably, the natural fiber includes any one or more of cotton fibers and linen fibers, and the synthetic fiber includes any one or more of polyester fibers, polyamide fibers, polyacrylonitrile fibers and phenolic fibers.

[0027] In some embodiments of the present invention, the inorganic fiber mesh fabric has a mesh spacing of (1.5-4 mm) × (1.5-4 mm) and a thickness of 0.1-0.2 mm.

[0028] In some embodiments of the present invention, the inorganic fiber mesh fabric includes any one or more of basalt fiber mesh fabric, glass fiber mesh fabric, and aluminosilicate fiber mesh fabric.

[0029] In some embodiments of the present invention, the components of the silicone rubber sealant, by mass parts, include 100 parts silicone rubber, 5-8 parts nano-sized montmorillonite, 8-12 parts fumed silica, 15-20 parts precipitated silica, and 10-15 parts nano-sized calcium carbonate.

[0030] A fifth aspect of the present invention provides a method for preparing the above-mentioned multifunctional coating, comprising:

[0031] Fiber composite aerogel felt is wrapped around the surface of the substrate to form a fireproof and heat-insulating layer;

[0032] Inorganic fiber mesh is wrapped around the surface of the fiber composite aerogel felt, and then silicone rubber sealant is coated on the surface of the inorganic fiber mesh to form a sealing and bonding layer.

[0033] An anti-icing functional layer is wrapped around the surface of the sealing and adhesive layer to obtain a multifunctional coating.

[0034] In some embodiments of the present invention, the substrate includes any one or more of bridge cables, bridge hangers, and bridge tie rods.

[0035] In some embodiments of the present invention, after the silicone rubber sealant is applied, the anti-icing functional layer is wrapped within 40 minutes.

[0036] A sixth aspect of the present invention provides the application of the above-described anti-icing coating, or the above-described anti-icing layer, or the above-described anti-icing functional layer, or the above-described multifunctional coating in bridge protection.

[0037] The beneficial effects of this invention are as follows:

[0038] This invention utilizes a micro / nano composite structure of MOF and molybdenum disulfide grown in stages on the surface of a thin sheet material, combined with fluorosilicone resin, to prepare an anti-icing coating, further resulting in an anti-icing coating with excellent anti-icing effect. Testing showed a static contact angle of 155-160° and an ice adhesion strength of 2-6 kPa (ASTM D7336). The ice layer can spontaneously detach under its own weight, achieving ultra-low ice adhesion. Furthermore, molybdenum disulfide has high photothermal conversion efficiency; in cloudy conditions, it converts ultraviolet light into heat energy to increase the surface temperature, significantly delaying the icing initiation time. The anti-icing coating provided by this invention can serve a long-term service life.

[0039] This invention also provides a multifunctional coating that achieves integrated fireproofing and de-icing through a gradient structure design of "aerogel felt - sealing layer - anti-icing layer," exhibiting high durability in extreme environments and a long service life, providing long-lasting protection. Specifically, the aerogel felt can insulate against flames at 1100℃, while the anti-icing functional layer maintains low ice adhesion strength, simultaneously achieving efficient de-icing and active fireproofing and heat insulation. Attached Figure Description

[0040] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an improper limitation of the invention.

[0041] Figure 1 The images show SEM images of the MOF-5 modified basalt flake composite material (A) and the special pigment (B) obtained in Example 1 of this invention.

[0042] Figure 2 These are SEM images of the ZIF-8 modified basalt flake composite material (A) and the special pigment (B) obtained in Example 3 of this invention. Detailed Implementation

[0043] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims.

[0044] The sources of all raw materials used in this invention are not particularly limited; they can be purchased commercially or prepared using conventional methods well-known to those skilled in the art. The purity of all raw materials used in this invention is not particularly limited; however, analytical grade or conventional purity used in anti-icing coatings and multifunctional coatings is preferred. The designations and abbreviations of all raw materials used in this invention are conventional designations and abbreviations in the art, and each designation and abbreviation is clearly defined within its relevant application. Those skilled in the art can obtain these materials from commercial sources or prepare them using conventional methods based on the designation, abbreviation, and corresponding application.

[0045] Given the poor anti-icing effect of existing anti-icing coatings and the lack of multifunctional coatings that combine efficient fire resistance and heat insulation with excellent anti-icing performance, this invention proposes a multifunctional coating, its preparation method, and its application. The multifunctional coating provided by this invention has fire resistance, heat insulation, and anti-icing properties, and can simultaneously meet the fire resistance and anti-icing requirements of bridge cables and tie rods.

[0046] This invention provides an anti-icing coating composed of fluorosilicone resin and special pigments, wherein the special pigments include flake materials, MOFs grown on the flake materials, and molybdenum disulfide nanosheets grown on the surface of the MOFs.

[0047] This invention involves growing MOF (Metal-Oxide-Foil) material uniformly on the surface of a thin sheet, forming a nanoscale porous structure. Subsequently, molybdenum disulfide nanomaterials are grown on the MOF material surface. These nanomaterials adhere to the MOF material surface in a nanosheet layered structure. When mixed with fluorosilicone resin, a unique super-slippery surface is formed, further improving the anti-icing performance.

[0048] It should be noted that this invention does not require specific loading amounts of MOF and molybdenum disulfide, nor does it require a specific mass ratio between MOF and molybdenum disulfide. After MOF material is grown on the surface of the thin sheet, a nanoscale porous structure is formed, followed by the re-growth of molybdenum disulfide nanomaterials, resulting in a unique microstructure. When a special pigment with this unique microstructure is mixed with fluorosilicone resin, a special ultra-smooth surface can be formed.

[0049] In this invention, the mass ratio of the fluorosilicone resin to the special pigment is (6.5-7.5):(2.5-3.5). This mass range is a key parameter for achieving multifunctional synergy and structural stability of the coating. Within this range, the fluorosilicone resin and the special pigment synergistically enhance the coating's superhydrophobicity, icing-repellency, flame retardancy, mechanical strength, and processability. This range ensures that the continuous phase fluorosilicone resin fully encapsulates the special pigment, forming a superhydrophobic surface, allowing the special pigment to reach the percolation threshold in the coating, achieving a surface micro / nano roughness exceeding 1.5 μm, and triggering the Cassie-Baxter icing-repellent state. Within this range, the special pigment forms a continuous thermal barrier in the coating, improving the limiting oxygen index (LOI), and the fluorosilicone resin provides sufficient matrix adhesion, preventing stress concentration cracking caused by high special pigment content. Within this range, the resin phase is ensured to fully penetrate into the interfacial spaces. Through coordination bonding between silanol groups (Si-OH) and the MOF on the flake surface (e.g., Zn-O-Si), the interfacial bonding strength is improved. Furthermore, the flake spacing is controlled to be less than the critical nucleation size of ice crystals, blocking the ice nucleus propagation path and enhancing the anti-icing effect. Within this range, the highly flexible resin matrix can absorb the thermal deformation difference between the flakes and the resin, preventing cracking caused by thermal cycling. This range gives the coating moderate shear thinning properties, ensuring no sagging during vertical cable spraying and avoiding extrusion difficulties caused by high flake content. The fluorosilicone resin provides sufficient active silane groups (Si-OR) to complete hydrolysis and condensation under ambient humidity, shortening the curing time. The amount of special pigments does not affect the crosslinking network of the fluorosilicone resin, avoiding incomplete curing caused by high filler content.

[0050] If the fluorosilicone resin content is too low, the special pigments will accumulate and form pores, leading to the problem of de-icing agents penetrating and corroding the substrate. Furthermore, the coating will lose its flexibility and easily peel off under wind vibration when used for cable protection. If the fluorosilicone resin content is too high, the special pigments will be excessively embedded, resulting in a surface roughness of <1.0 μm and failure to resist de-icing.

[0051] In this invention, the mass ratio of the fluorosilicone resin to the special pigment is 7:3. At this mass ratio, the resulting anti-icing coating exhibits optimal performance.

[0052] In this invention, the sheet material is basalt flakes or glass flakes.

[0053] Both basalt flakes and glass flakes are plate-like structures, possessing excellent mechanical properties and corrosion resistance, providing rigid support for MOFs. MOF crystals construct nanoscale protrusions on the surface of the thin-film material, superimposing with the micron-scale flake structure of the thin-film material to form a hydrophobic and ice-repellent surface. Furthermore, the organic ligands in MOFs reduce surface energy, inhibiting ice nucleation. Layered molybdenum disulfide not only reduces ice adhesion and promotes ice shedding, but also absorbs solar radiation and converts it into heat energy, actively raising the temperature to prevent icing.

[0054] Special pigments are mixed with fluorosilicone resin to form an anti-icing coating. The fluorosilicone resin encapsulates the special pigments to form a continuous film layer, which enhances hydrophobicity and interfacial bonding, thereby improving the anti-icing effect.

[0055] In this invention, the thickness of the sheet material is 2.5-3.5 μm, and the size is 25 μm-3 mm.

[0056] In this invention, the MOFs are mainly isoreticular metal-organic frameworks (IRMOFs) and zeolitic imidazolate frameworks (ZIFs). MOF-5 has the advantages of macroporous anti-icing effect and ultraviolet photothermal conversion. Specifically, its internal ultra-large pore size (≈1.29nm) forms nanoscale cavitation, locking in an air layer to greatly reduce ice adhesion, and absorbs ultraviolet light through charge transfer from ligands to metal, increasing the local temperature and overcoming icing on cloudy days. ZIF-8 has the advantages of molecular sieve-like hydrophobicity and chemical flame retardant enhancement. Specifically, its small pore size (3.4Å) selectively repels water molecules (kinetic diameter ≈2.8Å) while allowing nitrogen gas (3.6Å) to enter, forming an air cushion barrier with a contact angle as high as 150°. After pyrolysis, a ZnO ceramic layer (>400℃) is generated, which can synergistically enhance the flame retardant effect with components such as basalt flakes, glass flakes, and SiO2. Therefore, MOF-5 or ZIF-8 are preferred.

[0057] Other MOFs are not suitable, such as the MIL series (MIL-101), which requires a strong acid environment for synthesis and will damage the basalt flake structure; the UiO series (UiO-66), which requires a synthesis temperature >120℃ and is prone to thermal stress cracking of the flakes; and HKUST-1, which is prone to collapse when exposed to water.

[0058] In this invention, the fluorine content of the fluorosilicone resin is 20%-26%, specifically 20%, 21%, 22%, 23%, 24%, 25%, 26%, etc.

[0059] The term "fluorine content" refers to the percentage of the mass of fluorine (F) in a fluorosilicone resin relative to the total mass of the resin's solid components.

[0060] This invention limits the fluorine content of the fluorosilicone resin. Within this range, the fluorosilicone resin and special pigments synergistically enhance each other. A fluorine content of 20-26% allows the surface energy of the fluorosilicone resin to form a gradient transition with the hydrophobic MOF layer, eliminating the interfacial energy barrier, ensuring uniform dispersion of nanomaterials, and achieving wettability matching. Furthermore, an appropriate amount of siloxane bonds in the fluorosilicone resin bond with the hydroxyl groups of basalt flakes / glass flakes and MOF, improving adhesion, preventing nanolayer peeling, and strengthening the anchoring effect. If the fluorine content in the fluorosilicone resin is too low (below 20%), the fluorocarbon chains are oriented on the resin surface, forming a low-density perfluorinated end-group shielding layer, causing a sharp drop in surface energy and exceeding the superhydrophobic threshold at the contact angle, affecting anti-icing performance. If the fluorine content in the fluorosilicone resin is too high (above 26%), although the excessive fluorine content can further reduce ice adhesion strength, the synthesis of high-fluorine-content fluorosilicone resin is difficult, costs surge, and elongation at break decreases, leading to embrittlement.

[0061] In this invention, the fluorosilicone rubber is a methyl fluorosilicone resin with a fluorine content of 25%, which has extremely low surface energy (≤18 mN / m) and can effectively reduce the adhesion of ice.

[0062] The present invention also provides a method for preparing the above-mentioned anti-icing coating, comprising the following steps:

[0063] MOF materials are grown on the surface of thin-film materials using a hydrothermal synthesis method, so that the MOF materials uniformly cover the surface of the thin-film materials and form a nanoscale porous structure. After the reaction, the materials are centrifuged, washed, and dried. Molybdenum disulfide nanomaterials are grown on the surface of the MOF materials using chemical vapor deposition. The molybdenum disulfide nanomaterials are attached to the surface of the MOF materials in a nanosheet layer structure to obtain a special pigment. The special pigment is mixed with fluorosilicone resin in a certain proportion to obtain an anti-icing coating.

[0064] In this invention, special pigments and fluorosilicone resins are mixed in a certain proportion and then mixed evenly in a high-speed disperser at a dispersion speed of 1500 r / min for 60 minutes.

[0065] In this invention, when the MOF is ZIF-8, the hydrothermal synthesis method includes:

[0066] The flake material was repeatedly washed with deionized water to remove surface impurities and dust. The washed flakes were then vacuum dried at 80℃ for 12 h for later use. Zinc nitrate hexahydrate (Zn(NO3)2·6H2O, purity ≥99%) was weighed and dissolved in deionized water to prepare a 0.1 mol / L solution A. 2-Methylimidazole (C4H6N2, purity ≥99%) was weighed and dissolved in deionized water to prepare a 0.4 mol / L solution B. Under stirring, solution B was added dropwise to solution A at a rate of 1-2 drops / second. After the addition was complete, stirring was continued for 30 min to ensure homogeneous mixing, resulting in a white, turbid mixed solution. The pretreated flake material was added to the above mixed solution, ensuring the flakes were completely submerged. The mixed solution was then transferred to a reaction vessel and the reaction vessel was sealed. The reaction vessel was placed in an oven and heated to 120°C at a rate of 5°C / min, and held at this temperature for 12 h. After the reaction, the reaction vessel was allowed to cool naturally to room temperature. The product was then transferred to centrifuge tubes and centrifuged at 8000 r / min for 10 min to collect the precipitate. The precipitate was washed 3-4 times alternately with deionized water and anhydrous ethanol to remove unreacted substances and impurities from the surface. The washed precipitate was then placed in a vacuum drying oven and dried at 60°C for 6 h to obtain the ZIF-8 modified sheet material composite.

[0067] The ZIF-8-modified sheet composite material prepared by the above method exhibits a complete and uniformly distributed ZIF-8 structure on its surface. Furthermore, controlling the hydrothermal reaction time allows for the control of the ZIF-8 loading on the sheet material.

[0068] In this invention, when the MOF is MOF-5, the hydrothermal synthesis method includes:

[0069] The thin film material was ultrasonically cleaned three times with deionized water for 10 minutes each time to remove surface impurities. The cleaned thin film material was then placed in a vacuum and dried at 60°C for 6 hours for later use. 0.595 g of zinc nitrate (Zn(NO3)2·6H2O, purity ≥99%, 2 mmol, metal source, used as the metal center source for MOF-5) was weighed and added to 20 mL of N,N-dimethylformamide (DMF, analytical grade, solvent, used to dissolve the reactants). The mixture was magnetically stirred until completely dissolved to obtain solution A. 0.166 g of terephthalic acid (H2BDC, purity ≥98%, 1 mmol, organic ligand, used as the bridging ligand for MOF-5) was weighed and added to 20 mL of DMF. The mixture was magnetically stirred until dissolved to obtain solution B. Under stirring conditions, solution B was slowly poured into solution A, and stirring was continued for 15 minutes. Then, 0.5 mL of triethylamine (analytical grade, auxiliary reagent, used to adjust the pH of the reaction system) was added dropwise, and the mixture was stirred until homogeneous to obtain a mixed reaction solution. The pretreated sheet material was added to the above-mentioned mixed reaction solution, ensuring complete immersion. The mixture was transferred to a polytetrafluoroethylene-lined reactor, sealed, and placed in an oven. The temperature was increased to 120°C at a rate of 5°C / min and maintained at this temperature for 24 hours. After the reaction, the mixture was allowed to cool naturally to room temperature, and the reactor was removed. The reaction solution was transferred to centrifuge tubes and centrifuged at 8000 r / min for 10 minutes to collect the precipitate. The precipitate was washed three times with DMF and then twice with anhydrous ethanol to remove unreacted ligands and solvents. The washed product was placed in a vacuum drying oven and dried at 80°C for 12 hours to obtain the MOF-5 modified sheet material composite material.

[0070] The MOF-5-modified sheet composite material prepared by the above method exhibits a complete and uniformly distributed MOF-5 structure on its surface. Furthermore, controlling the hydrothermal reaction time allows for the control of the MOF-5 loading on the sheet material.

[0071] In this invention, the chemical vapor deposition method includes:

[0072] (1) Preparation before reaction:

[0073] Thin sheets of ZIF-8 or MOF-5 are ultrasonically cleaned with anhydrous ethanol for 15-20 min to remove any impurities and organic matter on the surface. They are then rinsed with deionized water and dried in a vacuum drying oven at 60℃ for 2-3 h. A quartz tube is installed in a tube furnace, and the gas pipeline and mass flow controller are connected. The airtightness of the entire apparatus is checked. This can be achieved by introducing nitrogen gas at a certain pressure into the apparatus and observing the pressure change. If the pressure does not decrease significantly within 10-15 min, the airtightness is good. Appropriate amounts of molybdenum trioxide powder (purity ≥99.99%, used as a raw material to provide molybdenum atoms) and sulfur powder (purity ≥99.99%, used to provide sulfur atoms for the formation of molybdenum disulfide) are accurately weighed using an electronic balance. The mass of the molybdenum trioxide powder is 0.05-0.1 g, and the mass of the sulfur powder is 0.2-0.3 g. The molybdenum trioxide powder is evenly spread in one ceramic boat, and the sulfur powder is placed in another ceramic boat. After cleaning and drying, carefully place the thin sheet material with ZIF-8 or MOF-5 in a ceramic boat near the molybdenum trioxide powder using tweezers, ensuring that the composite material is at a suitable distance (3-5 cm) from the molybdenum trioxide powder.

[0074] (2) Vapor phase chemical deposition process:

[0075] Nitrogen gas (≥99.999% purity, used as a protective gas to purge the reaction chamber before and after the reaction to prevent interference from impurity gases) is introduced into the reaction apparatus at a flow rate of 200-300 sccm for 15-20 min to remove air from the apparatus and prevent impurities such as oxygen from affecting the reaction. The nitrogen gas is then switched off and replaced with argon gas (≥99.999% purity, used to carry the gaseous reactants and maintain an inert environment for the reaction system) at a flow rate of 100-150 sccm. The temperature of the tube furnace is increased to 800-900℃ at a heating rate of 5-10℃ / min. Once the set temperature is reached, it is maintained at this temperature for 30-60 min. During the heating process, molybdenum trioxide powder gradually sublimates into a gaseous state. As the argon gas flows, it encounters the sublimated sulfur vapor at high temperature, undergoing a chemical reaction on the surface of the ZIF-8 or MOF-5 coated material to generate molybdenum disulfide, which is then deposited on its surface. After the reaction is complete, stop heating, but continue to purge with argon gas, allowing the tube furnace to cool naturally to room temperature. The cooling time should be 2-3 hours to avoid stress or defects within the material caused by rapid cooling. Once the temperature has dropped to room temperature, carefully remove the ceramic boat with tweezers to obtain the special pigment.

[0076]

[0077] Understandably, controlling the reaction time can control the loading of molybdenum disulfide on MOF-loaded sheet materials.

[0078] The present invention also provides an anti-icing coating, which is obtained by applying the above-mentioned anti-icing coating onto a substrate and then curing it.

[0079] In this invention, the curing temperature is room temperature or 50-80℃.

[0080] It is understood that the substrate may be a metallic substrate or a non-metallic substrate.

[0081] In this invention, the anti-icing coating is applied to the substrate with a thickness of 70-120 μm, specifically 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, etc. It is understood that a thickness of 70-120 μm is a core parameter for achieving synergistic optimization of anti-icing and fire resistance. When the thickness is less than 70 μm, the MOF micro / nano structure is embedded in resin, resulting in anti-icing failure; when the thickness is greater than 120 μm, internal stress increases dramatically, leading to freeze-thaw cycle cracking. 100 μm is the optimal point, allowing the micro / nano roughness to trigger super-icing, while simultaneously matching the flame-retardant felt to form a complete heat-insulating carbon layer with high adhesion.

[0082] The present invention also provides an anti-icing functional layer, which is obtained by coating the above-mentioned anti-icing coating onto a sealing cloth and then curing it.

[0083] In some embodiments of the present invention, the curing temperature is room temperature or 50-80°C.

[0084] In some embodiments of the present invention, the thickness of the anti-icing coating applied to the sealing cloth is 70-120 μm, specifically 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, etc. It is understood that a thickness of 70-120 μm is a core parameter for achieving synergistic optimization of anti-icing and fire resistance. When the thickness is less than 70 μm, the MOF micro / nano structure is embedded in resin, resulting in anti-icing failure; when the thickness is greater than 120 μm, internal stress increases dramatically, leading to cracking during freeze-thaw cycles. 100 μm is the optimal point, allowing the micro / nano roughness to trigger super-icing, while simultaneously matching the flame-retardant felt to form a complete heat-insulating carbon layer with high adhesion.

[0085] In this invention, the sealing cloth is a conventional commercially available product in the field of anti-icing coatings, which can be obtained by purchase or by preparation. To improve the overall performance of the coating, an inorganic fiber sealing cloth with flame-retardant and smoke-suppressing properties and the ability to prevent blackening after combustion is preferred as the substrate.

[0086] Specifically, the sealing cloth can be an inorganic fiber calendered adhesive sealing cloth composed of inorganic fiber cloth and silicone.

[0087] In this invention, the preparation process of the inorganic fiber calendered adhesive sealing cloth is as follows:

[0088] (1) Preparation process of calendered adhesive with 120℃ curing system

[0089] A. Formula composition (parts by weight)

[0090] Base compound: 100 parts (using methyl vinyl silicone rubber raw material, vinyl content 0.1%-0.3%, to ensure good processing performance and crosslinking efficiency); Reinforcing filler: 30-50 parts (fumed silica, specific surface area 200-300 m² / g). 2 / g, to improve mechanical properties); Structure control agent: 2-5 parts (hexamethyldisilazane, to prevent silica agglomeration and improve the flowability of the adhesive); Crosslinking agent: 1.5-3 parts (benzoyl peroxide, which can effectively decompose at 120℃ to generate free radicals to initiate crosslinking); Co-crosslinking agent: 0.5-1 parts (trimethylene isocyanurate, to improve crosslinking density and heat resistance); Water resistant agent: 0.5-2 parts heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane or per (tetrafluorooctyl)triethoxysilane; Weather resistant agent: 0.05-1 parts (nano silica, added to fluorosilicone anti-icing coating to improve the strength and weather resistance of the coating, and also to enhance the hydrophobicity of the coating and improve the anti-icing performance; or, UV-absorbing fluorosilicated hydroxyl acrylic resin: such as HLT-UV20 weather-resistant UV-absorbing resin, which can actively intercept 300-400 nm ultraviolet rays, delay coating aging, and improve weather resistance).

[0091] B. Preparation process

[0092] Add the raw methyl vinyl silicone rubber to an open mixing mill or internal mixer and plasticize at 50-60℃ for 3-5 minutes to soften the compound. Gradually add fumed silica and mix for 5-8 minutes until evenly dispersed. Then add hexamethyldisilazane and continue mixing for 3-5 minutes to eliminate the structuring effect of the silica. At this point, the compound should be uniform and fine. Add the weather-resistant additives and water-resistant agents in sequence and mix for 2-3 minutes to ensure even dispersion of the additives. Lower the temperature of the mixing mill to below 40℃, add benzoyl peroxide and triallyl isocyanurate, and mix for 2-4 minutes to prevent premature decomposition of the crosslinking agent. After mixing, sheet the compound for later use. Place the mixed compound in a vacuum degassing machine and degas at a vacuum of 0.08-0.1 MPa for 10-15 minutes to remove air bubbles generated during mixing and ensure the purity of the compound.

[0093] (2) Composite process of inorganic fiber cloth and calendered adhesive

[0094] A. Raw material preparation

[0095] Inorganic fiber dense fabric: Twill or straight weave is used to ensure a dense fabric surface without obvious damage. The width is adjusted according to subsequent processing equipment. The density of the inorganic fiber dense fabric is as follows: glass fiber dense fabric weighs 0.15-0.3 kg per square meter, basalt fiber dense fabric weighs 0.2-0.5 kg per square meter, and aluminosilicate fiber dense fabric weighs 0.08-0.3 kg per square meter.

[0096] 120℃ curing system calendering adhesive: The 120℃ curing system calendering adhesive obtained in step (1) needs to be tested in advance for parameters such as its fluidity and curing time to ensure that it meets the coating requirements.

[0097] B. Preparation process

[0098] Basalt fiber dense fabric is placed in a cleaning device and cleaned with deionized water to remove dust, oil, and other impurities from its surface. After cleaning, it is dried in an oven at 60-80℃ for later use. The cleaned and dried basalt fiber dense fabric is then placed on the unwinding device of a coating equipment, and the fabric tension is adjusted for smooth operation. A 120℃ curing system calendering adhesive is evenly coated onto the fiber fabric surface using coating rollers. The gap between the coating rollers is adjusted according to the target thickness (0.5-1.5 mm) to control the coating amount. The coated fiber fabric enters a calendering device, where it is calendered by upper and lower calendering rollers to further adjust the thickness, ensuring a tight bond between the 120℃ curing system calendering adhesive and the basalt fiber dense fabric, while eliminating any potential air bubbles. During calendering, the calendering temperature is controlled at 40-60℃, and the calendering speed is set according to production efficiency and silicone properties, generally 5-10 meters per minute. The calendered composite material is then sent to a curing oven, with the oven temperature set to 120℃ and the curing time set to 15-30 minutes to allow the silicone to fully cure. After curing, the composite material is removed from the oven and allowed to cool naturally to room temperature. The cooled composite material is then trimmed to remove irregular edges and cut to the specified dimensions as needed. The finished product undergoes quality testing, including checks on thickness, weather resistance, and water permeability. Qualified products are then stored in the warehouse.

[0099] The inorganic fiber calendered adhesive sealing cloth prepared by the above method has excellent flame retardant and smoke suppression properties.

[0100] The present invention also provides a multifunctional coating comprising a fireproof and heat-insulating layer, a sealing and adhesive layer laminated on the fireproof and heat-insulating layer, and the aforementioned anti-icing functional layer laminated on the sealing and adhesive layer;

[0101] The fireproof and heat-insulating layer includes fiber composite aerogel felt;

[0102] The sealing and bonding layer comprises an inorganic fiber mesh and a silicone rubber sealant coated on the surface of the inorganic fiber mesh.

[0103] This invention provides a multifunctional coating that combines fireproofing, heat insulation, and anti-icing properties. Aerogel felt serves as the fireproof base layer, constructing a strong heat insulation barrier on the fire-prone surface. A silicone rubber adhesive layer coated with a mesh fabric forms an elastic stress buffer, relieving deformation stress while providing waterproofing. The anti-icing functional layer maintains its icing-repellent properties in extreme environments. This three-layer structure is not simply stacked but achieves overall durability through a functional gradient design. This invention achieves a triple breakthrough through a gradient structure of "fireproof and heat-insulating layer - sealing and adhesive layer - anti-icing layer":

[0104] Functional integration: Aerogel felt serves as a fireproof base layer to insulate against high temperatures of 1100℃, while the surface anti-icing layer actively de-ices, simultaneously mitigating the dual hazards of ice and fire in bridge cables.

[0105] Structural reliability: Silicone rubber sealant permeates the inorganic fiber mesh to form a flexible adhesive layer, absorbing the difference in interlayer thermal deformation and ensuring no interface peeling under cycling conditions of -30℃ to 78℃;

[0106] Long-lasting protection: The gradient structure blocks the penetration of de-icing agents, and the adhesion retention rate is high after 50 freeze-thaw cycles, resulting in a long service life.

[0107] In this invention, the thickness of the fireproof and heat-insulating layer is 3-8 mm, the thickness of the sealing and adhesive layer is 1.2-3 mm, and the thickness of the anti-icing functional layer is 0.5-1.5 mm.

[0108] In some embodiments of the present invention, the fibers in the fiber composite aerogel felt include inorganic fibers and carbonized organic fibers, and the aerogel includes, but is not limited to, any one of silica aerogel, alumina aerogel and titanium dioxide aerogel.

[0109] In some embodiments of the present invention, the fiber composite aerogel felt is selected from any one or more of inorganic fiber aerogel felt and carbonized organic fiber composite aerogel felt.

[0110] Fiber-reinforced aerogel felt has an extremely low thermal conductivity (0.018-0.023 W / (m•K)), effectively blocking heat transfer, and its thickness is 3-8 mm. The inorganic fibers and carbonized organic fibers possess high-temperature resistance, allowing for long-term stable use at temperatures of 1100℃-1200℃. This insulation layer can be directly wrapped around the surface of bridge cables (after anti-corrosion treatment) or bridge suspension rods or tie rods formed by cables wrapped in high-molecular-weight polyethylene pipes, achieving fireproofing and thermal insulation.

[0111] In this invention, the inorganic fibers include, but are not limited to, any one or more of glass fibers, basalt fibers, and aluminosilicate fibers.

[0112] In this invention, the organic fiber includes any one of natural fibers and synthetic fibers; more preferably, the natural fiber includes, but is not limited to, any one or more of cotton fiber and linen fiber, and the synthetic fiber includes, but is not limited to, any one or more of polyester fiber (polyester), polyamide fiber (nylon), polyacrylonitrile fiber and phenolic fiber.

[0113] In this invention, the inorganic fiber composite aerogel felt can be a commercially available product or can be prepared in-house. To improve the overall performance of the multifunctional coating, an inorganic fiber composite aerogel felt with flame-retardant and smoke-suppressing properties, and the ability to prevent blackening after combustion, is preferred.

[0114] The inorganic fiber composite aerogel felt can be prepared by the following method:

[0115] (1) Substrate selection

[0116] Inorganic fiber felt types: glass fiber, basalt fiber, or aluminosilicate fiber. Continuous fiber diameter 5-8 μm, fiber length 30-50 mm; density: 80-120 kg / m³ 3 Thickness 3-5 mm, porosity 85%-90%, hot-pressed and shaped, with a smooth surface and no slag.

[0117] (2) Preparation of hydrolysate (choose one of the three)

[0118] Tetraethyl orthosilicate hydrolysate: Tetraethyl orthosilicate: ethanol: deionized water: hydrochloric acid (0.1 mol / L) = 1:3:1.5:0.05 by volume, and stirred in a constant temperature water bath at 30℃ for 60 min to form a transparent sol (pH=3-4, viscosity 5-8 mPa·s).

[0119] Aluminum isopropoxide hydrolysate: Aluminum isopropoxide is dissolved in isopropanol (mass ratio 1:5), deionized water (molar ratio of aluminum ions to water molecules 1:5) and nitric acid (0.01 mol / L, adjust pH=4) are added, and the mixture is refluxed and stirred at 50℃ for 90 min to obtain a semi-transparent sol (viscosity 10-15 mPa·s).

[0120] Hydrolysate of titanate coupling agent: Tetrabutyl titanate and anhydrous ethanol are mixed at a mass ratio of 1:4, deionized water (molar ratio of titanium ions to water molecules of 1:4) and glacial acetic acid are added dropwise (to adjust pH=3.5), and the mixture is stirred at 25℃ for 45 min to form a pale yellow transparent sol (viscosity 6-9 mPa·s).

[0121] (3) Spraying, impregnation and supercritical drying

[0122] Inorganic fiber mats were fixed on a vacuum adsorption stage (adsorption pressure 0.03 MPa). Hydrolysate was uniformly sprayed onto the mat using an air spray gun (nozzle diameter 0.8 mm, working pressure 0.3 MPa), with a spray volume of 120%-150% of the inorganic fiber mat's mass (ensuring thorough wetting of the fiber surface and pores). After spraying, the mats were allowed to stand for 30 minutes to allow the sol to spread evenly on the fiber surface and begin to gel. The gelled inorganic fiber mats were then placed in an autoclave, using supercritical CO2 as the medium, and maintained at 40℃ and 8 MPa for 2 hours to allow for complete solvent replacement. The temperature was then raised to 60℃, and the pressure was slowly released (depressurization rate 0.5 MPa / h) until atmospheric pressure was reached, yielding inorganic fiber aerogel mats with an aerogel loading of 15%-20% and an overall bulk density increasing to 100-150 kg / m³. 3 .

[0123] In this invention, the carbonized organic fiber composite aerogel felt can be a commercially available product or can be prepared in-house. To improve the overall performance of the multifunctional coating, a carbonized organic fiber composite aerogel felt with flame-retardant and smoke-suppressing properties is preferred.

[0124] The carbonized organic fiber composite aerogel felt can be prepared using the following method:

[0125] (1) Substrate selection

[0126] Organic fiber felt types: Polyester fiber (polyester), polyamide fiber (nylon), polyacrylonitrile (PAN) fiber felt, or phenolic fiber felt; fiber diameter 8-12 μm, length 20-40 mm. Density: 50-80 kg / m³ 3 The thickness is 4-6 mm, the porosity is 90%-95%, and it is pre-oxidized (PAN fiber felt needs to be pre-oxidized in air at 200℃ for 30 min) to remove surface impurities.

[0127] (2) Preparation of hydrolysate, spraying and impregnation, supercritical drying and carbonization treatment

[0128] The hydrolysate formulation and preparation method are the same as those for inorganic fiber composite aerogel felt (choose one of tetraethyl orthosilicate / aluminum isopropoxide / titanium ester coupling agent hydrolysate). The spraying amount is 100%-130% of the organic fiber felt mass. After spraying, it is allowed to stand for 25 minutes to ensure that the sol penetrates to the fiber interlacing points. The process of inorganic fiber composite aerogel felt is as follows: supercritical CO2 medium, displacement at 40℃ and 8 MPa for 2 h, and slow depressurization to atmospheric pressure at 60℃ to obtain organic fiber-sol composite felt (aerogel loading of 12%-18%, bulk density increased to 70-100 kg / m³). 3The organic fiber-sol composite felt was placed in a tubular carbonization furnace, and nitrogen (99.99% purity) was introduced as a protective atmosphere at a flow rate of 500 mL / min. Carbonization was carried out by heating: room temperature → 200℃ (heating rate 5℃ / min, holding for 30 min to remove residual solvent) → 600℃ (heating rate 2℃ / min, holding for 1 h, initial carbonization of organic fibers) → 1000℃ (heating rate 1℃ / min, holding for 2 h, completion of carbonization). After natural cooling to room temperature, carbonized organic fiber composite aerogel felt was obtained, with a carbon residue rate of 35%-45% and a density of 80-120 kg / m³. 3 A carbon layer with a thickness of 5-10 nm is uniformly coated on the fiber surface.

[0129] In this invention, the inorganic fiber mesh fabric has a mesh spacing of (1.5-4 mm) × (1.5-4 mm) and a thickness of 0.1-0.2 mm.

[0130] In this invention, the inorganic fiber mesh fabric includes, but is not limited to, any one or more of basalt fiber mesh fabric, glass fiber mesh fabric, and aluminosilicate fiber mesh fabric. The basalt fiber mesh fabric has a high temperature resistance of ≥600℃, the glass fiber mesh fabric has a high temperature resistance of ≥450℃, and the aluminosilicate fiber mesh fabric has a high temperature resistance of ≥1000℃. The mesh spacing is (1.5-4 mm) × (1.5-4 mm), and the thickness is 0.1-0.2 mm, which can enhance the tensile and tear resistance of the sealing adhesive layer.

[0131] In this invention, the silicone rubber sealant can be a commonly used silicone rubber sealant in the sealing field, or it can be prepared in-house. To improve the overall performance of the multifunctional coating, a silicone rubber sealant with flame-retardant and smoke-suppressing properties, and the ability to prevent carbonization and blackening after combustion, is preferred.

[0132] The silicone rubber sealant may be composed of silicone rubber, nano-sized montmorillonite (modified with long-chain silanes), fumed silica, precipitated silica, and nano-calcium carbonate. Specifically, by mass parts, the silicone rubber sealant comprises: 100 parts silicone rubber, 5-8 parts nano-sized montmorillonite (modified with long-chain silanes), 8-12 parts fumed silica, 15-20 parts precipitated silica, and 10-15 parts nano-calcium carbonate.

[0133] The long-chain silane modification includes the following steps:

[0134] Prepare a 5%-10% (w / w) suspension of montmorillonite by adding deionized water. After stirring and dispersing for 30 minutes, adjust the pH to 4-5 with dilute phosphoric acid (an acidic environment is conducive to silane hydrolysis). Continue stirring for 10 minutes and set aside. Weigh out 5%-15% of long-chain silanes (e.g., octadecyltriethoxysilane, octyltriethoxysilane, etc.) by weight of montmorillonite. Add an appropriate amount of anhydrous ethanol (long-chain silane to ethanol volume ratio 1:3-5), stir evenly, and then add a small amount of deionized water (long-chain silane to water molar ratio 1:3-4). Stir at 40-50℃. Hydrolyze the solution for 30-60 minutes until it becomes transparent or slightly turbid (generating silanol groups). Slowly add the hydrolyzed silane solution dropwise to the pretreated montmorillonite suspension, controlling the temperature at 60-80℃ and stirring for 2-4 hours to allow the silanol groups to condense with the hydroxyl groups on the surface of montmorillonite. After the reaction is complete, allow the mixture to stand and separate into layers. Discard the supernatant and wash the precipitate 3-4 times with anhydrous ethanol (to remove unreacted silane). Then dry the precipitate in a vacuum drying oven at 80-100℃ for 6-12 hours, grind and sieve to obtain long-chain silane-modified nano-sized montmorillonite.

[0135] The silicone rubber is methyl vinyl silicone rubber with a vinyl content of 0.15%-0.3% and an oxygen index ≥30%, exhibiting excellent flame retardancy and elasticity. The nano-sized montmorillonite is modified with long-chain silanes, with a sheet thickness of 1-5 nm and an aspect ratio >200, significantly improving the mechanical properties and flame retardant effect of the silicone rubber. The fumed silica has a specific surface area of ​​200-300 m². 2 / g, with a native particle size of 7-15 nm. The average particle size of the nano-calcium carbonate is 50-80 nm, and the activation degree is >95%. The composite of silicone rubber, nano-sized montmorillonite (modified with long-chain silanes), fumed silica, precipitated silica, and nano-calcium carbonate greatly improves the mechanical properties, flame retardant properties, and sealing properties of silicone rubber.

[0136] The silicone rubber sealant further includes a crosslinking agent and a catalyst. The crosslinking agent includes, but is not limited to, methyltriacetoxysilane, and is added at 1%-3% of the total mass of the silicone rubber sealant. The catalyst includes, but is not limited to, dibutyltin dilaurate, and is added at 0.05%-0.1% of the total mass of the silicone rubber sealant, and is diluted to a 5% concentration with anhydrous ethanol beforehand.

[0137] In this invention, the preparation method of the silicone rubber sealant includes the following steps:

[0138] Add 100 parts of methyl vinyl silicone rubber (vinyl content 0.15%-0.3%) to a planetary mixer, set the temperature to 60-70℃ (to avoid high temperature affecting the activity of subsequent curing agents), and the speed to 50-60 r / min, and stir for 10-15 min until the rubber is in the form of a fluid paste (without obvious particles).

[0139] The nanofiller was dispersed in stages (humidity controlled <40% to avoid premature curing: maintain humidity <40% to avoid premature curing, keep the temperature at 60℃, and the rotation speed at 60 r / min). 5-8 parts of long-chain silane-modified nano-sized montmorillonite were slowly added while stirring (addition time controlled within 10 min). After addition, stirring continued for 30 min. The shear force of the planetary stirrer caused the montmorillonite layers to peel off (laser particle size analyzer detection, agglomerate particle size ≤3 μm). The temperature was lowered to 50℃, and the rotation speed was adjusted to 80 r / min. 8-12 parts of fumed silica were added first (vacuum was applied while adding, vacuum degree -0.08 MPa, to reduce air bubbles), and stirring for 25 min. Then, 15-20 parts of precipitated silica were added, and stirring continued for 20 min. The difference in particle size between the two types of silica was used to construct a gradient filling structure, improving the thixotropic properties of the system (static viscosity ≥100000 mPa·s, viscosity after shearing reduced to 50000-60000 mPa·s). Maintain a temperature of 50°C and a rotation speed of 60 r / min, add 10-15 parts of nano-calcium carbonate (activation degree > 95%), stir for 15 min to ensure that the calcium carbonate is uniformly filled into the rubber network and reduce the internal stress of the system.

[0140] Introducing the curing system (key control: moisture isolation): Cool to 30-35℃, reduce the rotation speed to 30 r / min, add the crosslinking agent (methyltriacetoxysilane, accounting for 1%-3% of the total mass) and the catalyst (dibutyltin dilaurate, accounting for 0.05%-0.1% of the total mass, diluted with anhydrous ethanol to a concentration of 5% beforehand), and stir for 15 min until completely dispersed (maintain a vacuum of -0.09 MPa throughout the process to remove air bubbles).

[0141] Vacuum sealing: Before breaking the vacuum, check the humidity of the system (≤0.1%, tested with a moisture meter). After confirming that there are no air bubbles, transfer the adhesive into a sealed aluminum tube or plastic tube (the inner wall is treated with silane to prevent sticking) under nitrogen protection. Seal quickly (avoid contact with moisture in the air). Store at room temperature (25℃) away from light. Shelf life is 6 months.

[0142] Room temperature curing characteristics: During construction, the silicone rubber sealant is extruded and, upon contact with moisture in the air (humidity 50%-70%), cures at room temperature through a hydrolytic condensation reaction with a crosslinking agent: Surface drying time: 45-12 min (25℃, 50%RH); Complete curing time: 7 days (25℃, 50%RH); Shore A hardness after curing: 35-45; Elongation at break: >450%; It possesses excellent room temperature sealing properties and weather resistance.

[0143] In this invention, the sealing and bonding layer is applied by directly wrapping an inorganic fiber mesh fabric around a fiber composite aerogel felt, followed by applying silicone rubber sealant to the surface of the inorganic fiber mesh fabric, thus achieving a composite of the silicone rubber sealant and the inorganic fiber mesh fabric. The total thickness of this sealing and bonding layer is controlled at 2-3 mm, and it is evenly distributed over the fireproof and heat-insulating layer.

[0144] Specifically, an inorganic fiber mesh (weighing 110-150 g per square meter) is applied as a single layer to the surface of the fireproof and heat-insulating layer, and then bound with inorganic fibers. Silicone rubber sealant is then applied to the inorganic fiber mesh, and the overall thickness after curing is controlled to be 1.2-2.5 mm, ensuring it is uniform and flat, thus obtaining a sealing and bonding layer.

[0145] The present invention also provides a method for preparing the above-mentioned multifunctional coating, comprising:

[0146] Fiber composite aerogel felt is wrapped around the surface of the substrate to form a fireproof and heat-insulating layer;

[0147] Inorganic fiber mesh is wrapped around the surface of the fiber composite aerogel felt, and then silicone rubber sealant is coated on the surface of the inorganic fiber mesh to form a sealing and bonding layer.

[0148] An anti-icing functional layer is wrapped around the surface of the sealing and adhesive layer to obtain a multifunctional coating.

[0149] In this invention, the aforementioned anti-icing coating is applied to a sealing cloth, and after curing, an anti-icing functional layer is obtained. The sealing cloth is an inorganic fiber calendered adhesive sealing cloth, with one side being calendered adhesive and the other side being a dense inorganic fiber cloth. During the preparation of the multifunctional coating, the anti-icing coating is uniformly sprayed onto the surface of the inorganic fiber calendered adhesive sealing cloth using a spray gun. The coating is sprayed onto the dense inorganic fiber cloth side, with the spray thickness controlled at 70-120 μm. The calendered adhesive side is in contact with the sealing adhesive layer. Curing is performed at room temperature or at a high temperature (50-80℃) to obtain the multifunctional coating.

[0150] In this invention, during the preparation of the multifunctional coating, the anti-icing functional layer is wrapped around the surface of the sealing adhesive layer within one hour after the sealant bonding layer is applied. Preferably, the anti-icing functional layer is wrapped within 40 minutes after the silicone rubber sealant is applied.

[0151] In this invention, the substrate includes, but is not limited to, any one or more of bridge cables, bridge hangers, and bridge tie rods.

[0152] The present invention also provides an application of the above-mentioned anti-icing coating, or the above-mentioned anti-icing layer, or the above-mentioned anti-icing functional layer, or the above-mentioned multifunctional coating in bridge protection.

[0153] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be described in detail below with reference to specific embodiments.

[0154] Example 1

[0155] An anti-icing coating, prepared by the following method:

[0156] MOF-5 material was grown on the surface of basalt flakes via hydrothermal synthesis. After the reaction, the material was centrifuged, washed, and dried. Then, molybdenum disulfide nanomaterials were grown on the MOF-5 material surface using chemical vapor deposition to obtain a special pigment. A methyl fluorosilicone resin with a fluorine content of 25% was mixed with the special pigment at a mass ratio of 3:7 in a high-speed disperser at a dispersion speed of 1500 r / min for 60 minutes to obtain an anti-icing coating.

[0157] The hydrothermal synthesis method includes:

[0158] Basalt flakes (3 μm thick, 25 μm-3 mm in size) were ultrasonically cleaned three times with deionized water for 10 minutes each time to remove surface impurities. The cleaned basalt flakes were then vacuum dried at 60°C for 6 hours for later use.

[0159] Weigh 0.595 g of zinc nitrate (2 mmol), add 20 mL of DMF, and stir magnetically until completely dissolved to obtain solution A. Weigh 0.166 g of terephthalic acid (1 mmol), add 20 mL of DMF, and stir magnetically until dissolved to obtain solution B. Under stirring conditions, slowly pour solution B into solution A, continue stirring for 15 minutes, then add 0.5 mL of triethylamine (analytical grade), and stir until homogeneous to obtain a mixed reaction solution.

[0160] Pretreated basalt flakes were added to the above-mentioned mixed reaction solution, ensuring complete immersion of the basalt flakes. The mixture was transferred to a polytetrafluoroethylene-lined reactor, sealed, and placed in an oven. The temperature was increased to 120°C at a rate of 5°C / min and maintained at this temperature for 24 hours. After the reaction, the mixture was allowed to cool naturally to room temperature, and the reactor was removed. The reaction solution was transferred to centrifuge tubes and centrifuged at 8000 r / min for 10 minutes to collect the precipitate. The precipitate was washed three times with DMF and then twice with anhydrous ethanol to remove unreacted ligands and solvents. The washed product was placed in a vacuum drying oven and dried at 80°C for 12 hours to obtain the MOF-5 modified basalt flake composite material.

[0161] The chemical vapor deposition method includes:

[0162] The MOF-5 modified basalt flake composite material was ultrasonically cleaned with anhydrous ethanol for 15-20 min, then rinsed with deionized water, and dried in a vacuum drying oven at 60℃ for 2-3 h.

[0163] Install the quartz tube in the tube furnace, connect the gas pipeline and mass flow controller, and check the airtightness of the entire device. This can be done by filling the device with nitrogen at a certain pressure and observing the pressure change. If the pressure does not drop significantly within 10-15 minutes, it indicates good airtightness.

[0164] Accurately weigh 0.075 g of molybdenum trioxide powder (purity ≥99.99%) and 0.25 g of sulfur powder (purity ≥99.99%) using an electronic balance. Spread the molybdenum trioxide powder evenly in one ceramic boat and place the sulfur powder in another. Carefully place the cleaned and dried MOF-5-modified basalt flakes into the ceramic boat closest to the molybdenum trioxide powder using tweezers, ensuring a suitable distance (4 cm) between the composite material and the molybdenum trioxide powder.

[0165] Nitrogen gas (purity ≥99.999%) was introduced into the reaction apparatus at a flow rate of 250 sccm for 20 min. The nitrogen gas was then turned off, and argon gas (purity ≥99.999%) was introduced at a flow rate of 125 sccm. The tube furnace temperature was increased to 900℃ at a rate of 7.5℃ / min. Once the set temperature was reached, it was maintained at this temperature for 60 min. After the reaction was complete, heating was stopped, but argon gas was continuously introduced, allowing the tube furnace to cool naturally to room temperature. After the temperature dropped to room temperature, the ceramic boat was carefully removed with tweezers to obtain the special pigment.

[0166] Example 2

[0167] An anti-icing coating differs from Example 1 in that basalt flakes are replaced with glass flakes, while the remaining steps are completely identical to those in Example 1.

[0168] Example 3

[0169] An anti-icing coating differs from Example 1 in that ZIF-8 material is grown on the surface of basalt flakes using a hydrothermal synthesis method, while the remaining steps are completely consistent with those of Example 1.

[0170] The hydrothermal synthesis method includes:

[0171] Basalt flakes were repeatedly washed with deionized water, and then vacuum dried at 80°C for 12 hours for later use.

[0172] Weigh zinc nitrate hexahydrate (purity ≥99%) and dissolve it in deionized water to prepare a solution A with a concentration of 0.1 mol / L. Weigh 2-methylimidazole (purity ≥99%) and dissolve it in deionized water to prepare a solution B with a concentration of 0.4 mol / L. Under stirring, add solution B dropwise to solution A at a rate of 1-2 drops / second. After the addition is complete, continue stirring for 30 minutes to ensure the solutions are thoroughly mixed, resulting in a white, turbid mixed solution.

[0173] Pretreated basalt flakes were added to the above mixed solution, ensuring the flakes were completely submerged. The mixed solution was then transferred to a reaction vessel and sealed. The reaction vessel was placed in an oven and heated to 120°C at a rate of 5°C / min, and held at this temperature for 12 h. After the reaction, the reaction vessel was allowed to cool naturally to room temperature. The product from the reaction vessel was then transferred to centrifuge tubes and centrifuged at 8000 r / min for 10 min, and the precipitate was collected. The precipitate was washed 3-4 times alternately with deionized water and anhydrous ethanol to remove unreacted substances and impurities from the surface. The washed precipitate was placed in a vacuum drying oven and dried at 60°C for 6 h to obtain the ZIF-8 modified basalt flake composite material.

[0174] Example 4

[0175] An anti-icing coating differs from Example 3 in that basalt flakes are replaced with glass flakes, while the remaining steps are completely identical to those in Example 3.

[0176] Comparative Example 1

[0177] An anti-icing coating differs from Example 1 in that: MOF-5 material is grown on the surface of basalt flakes via hydrothermal synthesis. After the reaction, the material is centrifuged, washed, and dried to obtain pigment. Methyl fluorosilicone resin with a fluorine content of 25% is mixed with the pigment at a mass ratio of 3:7 in a high-speed disperser at a dispersion speed of 1500 r / min for 60 minutes to obtain the anti-icing coating. The remaining steps are completely consistent with those of Example 1.

[0178] Comparative Example 2

[0179] An anti-icing coating differs from Example 1 in that: molybdenum disulfide nanomaterials are grown on the surface of basalt flakes using chemical vapor deposition to obtain pigments. Methyl fluorosilicone resin with a fluorine content of 25% is mixed with the pigments at a mass ratio of 3:7 in a high-speed disperser at a dispersion speed of 1500 r / min for 60 minutes to obtain the anti-icing coating. The remaining steps are completely consistent with those of Example 1.

[0180] Comparative Example 3

[0181] An anti-icing coating differs from Example 1 in that methyl fluorosilicone resin with a fluorine content of 25% is mixed with special pigments at a mass ratio of 2:8 in a high-speed disperser, while the remaining steps are completely consistent with those of Example 1.

[0182] Comparative Example 4

[0183] An anti-icing coating differs from Example 1 in that methyl fluorosilicone resin with a fluorine content of 25% is mixed with special pigments in a high-speed disperser at a mass ratio of 4:6, while the remaining steps are completely consistent with those of Example 1.

[0184] Performance verification:

[0185] The anti-icing coatings obtained in Examples 1-4 and Comparative Examples 1-4 were applied to one side of the inorganic fiber dense fabric of the inorganic fiber calendered sealant cloth, with a coating thickness of 100 μm, and cured at room temperature to obtain an anti-icing functional layer.

[0186] (1) The surface structure was observed using a scanning electron microscope and its hydrophobic angle was detected.

[0187] Figure 1 Figure A in the middle is a SEM image of the MOF-5 modified basalt flake composite material obtained in Example 1 of this invention. Figure 1 Figure B shows a SEM image of the special pigment obtained in Example 1 of this invention. Figure 2 Figure A in the middle is a SEM image of the ZIF-8 modified basalt flake composite material obtained in Example 3 of the present invention. Figure 2 Figure B shows a SEM image of the special pigment obtained in Example 3 of this invention.

[0188] Depend on Figure 1 and Figure 2 It can be seen that the ZIF-8 or MOF-5 structures grown on the basalt flakes are complete and uniformly distributed; molybdenum disulfide nanosheets are grown in situ on the surface of the MOF material, and the molybdenum disulfide nanosheets have a flower-like structure.

[0189] (2) Hydrophobicity

[0190] The surface hydrophobicity of coatings prepared using the anti-icing coatings of Examples 1-4 and Comparative Examples 1-4 was tested using an OCA50 contact angle meter. 5 μL of water was dropped onto the sample surface, and the water contact angle and sliding angle were measured. The results are shown in Table 1.

[0191] Table 1. Contact angle and sliding angle of the embodiments and comparative examples

[0192]

[0193] As shown in Table 1, the coatings prepared using the anti-icing coatings of Examples 1-4 have a water contact angle of 155-160° and a roll-off angle of 3-5°, indicating they are superhydrophobic coatings. The water contact angle of this coating far exceeds 150°, indicating that water droplets are almost perfectly spherical on the surface, making them extremely difficult to spread and wet. Furthermore, the extremely low roll-off angle means that water droplets cannot remain stably on the surface; even slight disturbances or tilting will cause them to roll off. The difficulty in water droplet adhesion reduces the likelihood of icing.

[0194] The anti-icing coatings prepared using Comparative Examples 1-4 exhibit water contact angles of 100-105° and sliding angles of 89-91°. They are hydrophobic, causing water droplets on the coating to form spherical shapes and making it difficult to wet the surface. However, the sliding angle is extremely high; the surface almost needs to be vertical for the water droplets to slide off. The coating has a strong adhesion to the water droplets, making it difficult for them to roll off and significantly increasing the likelihood of icing. This may be due to a micron-level rough structure, but lack of sufficient nanoscale structure, or an uneven chemical composition, causing the water droplets to be firmly "pinned" into the rough surface structure, requiring a large tilt angle to escape.

[0195] (3) De-icing test

[0196] Photothermal passive de-icing test: Under conditions of -15℃, the freezing process of water droplets on the coating surface of the sample prepared in Example 1 was recorded under infrared irradiation, that is, the process of water droplets changing from transparent to opaque.

[0197] Photothermal active de-icing test: Conversely, under conditions of -15°C, the melting process of ice droplets on the coating surface prepared by the sample of Example 1 was recorded, that is, the process of ice droplets changing from opaque to transparent water droplets.

[0198] Table 2 Results of photothermal passive de-icing and photothermal active de-icing tests

[0199]

[0200] Table 2 shows that the coating prepared using the anti-icing coating of Example 1 has good anti-icing performance and can actively and passively de-ic under infrared irradiation. The coatings prepared using the anti-icing coatings of Comparative Examples 1-4 have poor anti-icing performance. In the photothermal active de-icing test, the ice sliding time is ≥10 min, which is more than 30 times that of the examples; in the photothermal passive de-icing test, the icing time is 27-38 s, only 13.5-19% of that of the examples. This is consistent with the hydrophobicity test results.

[0201] The anti-icing coatings used in the following examples (Examples 5-14) differ from the anti-icing coating in Example 1 in that the mass ratio of MOF to molybdenum disulfide is different. By adjusting the time of the hydrothermal reaction and the chemical vapor deposition reaction, anti-icing coatings with different mass ratios of MOF to molybdenum disulfide are obtained.

[0202] Example 5

[0203] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0204] The fireproof and heat-insulating layer is a 3 mm thick basalt silica aerogel felt with a thermal conductivity of ≤0.028 W / (m·K).

[0205] Sealing and bonding layer: basalt mesh (110 g per square meter) + basalt fiber binding + single-component room temperature curing silicone rubber (surface drying time 25 min, thickness after curing 2 mm).

[0206] Anti-icing functional layer: Anti-icing coating (MOF-5 loaded on basalt flakes in a mass ratio of 1:1 to molybdenum disulfide) is sprayed onto basalt straight-weave fabric (0.3 kg per square meter) after silicone calendering treatment, with a coating thickness of 80 μm and cured at 80℃ for 30 min.

[0207] The method for preparing the multifunctional layer is as follows:

[0208] (1) Fireproof and heat-insulating layer

[0209] Inorganic fiber mats were fixed on a vacuum adsorption stage (adsorption pressure 0.03 MPa), and tetraethyl orthosilicate hydrolysate was uniformly sprayed onto the fiber surface using an air spray gun (nozzle diameter 0.8 mm, working pressure 0.3 MPa), with a spraying amount of 120% of the inorganic fiber mat's mass. After spraying, the mats were allowed to stand for 30 min to allow the sol to spread evenly on the fiber surface and begin to gel. The gelled inorganic fiber mats were then subjected to supercritical drying to obtain 3 mm basalt silica aerogel mats.

[0210] Basalt silica aerogel felt is directly wrapped around the surface of bridge cables (which have undergone anti-corrosion treatment) and bridge hangers or tie rods formed by cables wrapped with high molecular weight polyethylene pipes.

[0211] (2) Sealing adhesive layer

[0212] Basalt fiber is used to bind basalt mesh cloth to basalt silica aerogel felt, and then single-component room-temperature curing silicone rubber is applied on top to obtain a sealing and bonding layer.

[0213] The preparation method of the single-component room-temperature curing silicone rubber is as follows:

[0214] Add 100 parts of methyl vinyl silicone rubber (vinyl content 0.15%-0.3%) to a planetary mixer, set the temperature to 65℃, the speed to 55 r / min, and mix for 12 min until the rubber is in the form of a fluid slurry (without obvious particles).

[0215] Control humidity <40%, maintain temperature 60℃, rotation speed 60 r / min, slowly add 6.5 parts of long-chain silane modified nano-sized montmorillonite while stirring (addition time controlled within 10 min), continue stirring for 30 min after addition, and use the shear force of planetary stirring to peel off the montmorillonite sheets (laser particle size analyzer detection, agglomerate particle size ≤3 μm).

[0216] Cool to 50℃, adjust the speed to 80 r / min, add 10 parts of fumed silica (while adding, evacuate to -0.08 MPa to reduce bubbles), and stir for 25 min; then add 17.5 parts of precipitated silica and continue stirring for 20 min. Utilize the difference in particle size between the two types of silica to construct a gradient-filled structure, thereby improving the thixotropic properties of the system (static viscosity ≥100000 mPa·s, viscosity after shearing decreases to 50000-60000 mPa·s).

[0217] Maintain a temperature of 50°C and a rotation speed of 60 r / min. Add 12.5 parts of nano-calcium carbonate (activation degree > 95%) and stir for 15 min to ensure that the calcium carbonate is uniformly filled into the rubber network and reduce the internal stress of the system.

[0218] Cool to 30-35℃, reduce the rotation speed to 30 r / min, add crosslinking agent (methyltriacetoxysilane, 2% of total mass) and catalyst (dibutyltin dilaurate, 0.075% of total mass, diluted to 5% concentration with anhydrous ethanol beforehand), stir for 15 min until completely dispersed (maintain vacuum of -0.09 MPa throughout the process to remove bubbles).

[0219] Before breaking the vacuum, check the system humidity (≤0.1%). After confirming that there are no air bubbles, transfer the adhesive into a sealed aluminum tube under nitrogen protection, seal it quickly, and store it at room temperature (25℃) away from light.

[0220] (3) Anti-icing functional layer

[0221] The anti-icing coating was sprayed onto a 0.8 mm thick basalt straight-weave fabric (weighing 0.3 kg per square meter) that had been calendered with silicone. The coating was applied to the basalt straight-weave fabric side, with a thickness of 80 μm, and cured at 80°C for 30 minutes. The silicone calendered side was then bonded to the sealing adhesive layer, and the bonding of the anti-icing functional layer was completed within 25 minutes (no more than 30 minutes after the silicone rubber application was finished). During bonding, the functional fabric was gently pressed to ensure close contact with the not-fully-cured silicone rubber, with no air bubbles at the edges.

[0222] Example 6

[0223] A multifunctional coating comprises, from the inside out, a fire-resistant and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer. The difference from Example 5 is that the fire-resistant and heat-insulating layer is a 6 mm thick basalt alumina aerogel felt (high temperature resistance ≥800℃, density 220 kg / m³). 3 The sealing and bonding layer consists of basalt mesh (110 g / m²) + basalt fiber binding + single-component room-temperature cured silicone rubber (surface drying time 35 min, cured thickness 2 mm). The anti-icing functional layer consists of an anti-icing coating (MOF-5 loaded on basalt flakes at a mass ratio of 1:1.2 to molybdenum disulfide) sprayed onto a 0.8 mm thick glass fiber twill fabric (0.32 kg / m²) treated with silicone calendering, with a spray thickness of 80 μm, cured at 80°C for 30 min. After the silicone rubber is applied, the cured anti-icing functional fabric is adhered to the surface of the sealing layer within 35 min. Utilizing the tackiness of the silicone rubber before it is fully surface-dried, interlayer air is removed by roller pressing to ensure a firm bond. The remaining steps are completely consistent with those in Example 5.

[0224] Example 7

[0225] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0226] The difference from Example 5 is as follows: the fireproof and heat-insulating layer is a 10 mm thick basalt titanium dioxide aerogel felt (thermal conductivity ≤0.030 W / (m·K); the sealing and bonding layer is basalt mesh cloth (weight 110 g per square meter) + basalt fiber binding + single-component room temperature cured silicone rubber (surface drying time 28 min, cured thickness 2 mm); the anti-icing functional layer is an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 1:0.8) sprayed onto a 0.8 mm thick aluminosilicate straight-weave cloth (temperature resistance ≥600℃) after silicone calendering treatment, with a spray thickness of 80 μm and a curing time of 30 min at 80℃. After the silicone rubber is applied, the pretreatment of the anti-icing functional cloth (pre-drying and cutting) is completed simultaneously, and the bonding is completed within 28 min (≤30 min). A "same-scraping and bonding" assembly line operation is adopted to reduce waiting time and ensure sufficient wetting between layers. The remaining steps are completely consistent with those of Example 5.

[0227] Example 8

[0228] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0229] The difference from Example 5 is that the fireproof and heat-insulating layer is a 5 mm thick glass fiber silica aerogel felt (density 180 kg / m³). 3The thermal conductivity is ≤0.030W / (m·K); the sealing and bonding layer consists of basalt mesh (110g per square meter) + basalt fiber binding + single-component room-temperature cured silicone rubber (surface drying time 32 min, cured thickness 2 mm); the anti-icing functional layer consists of an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a 1:1 mass ratio) sprayed onto a 0.8 mm thick glass fiber straight-weave cloth after silicone calendering, with a spray thickness of 80 μm, cured at 80℃ for 30 min. After silicone rubber application, the functional cloth is bonded within 32 min (≤35 min), using the fluidity of the silicone rubber before surface drying to fill tiny gaps in the cloth surface. The edges are sealed with silicone rubber to ensure overall sealing. The remaining steps are completely consistent with those in Example 5.

[0230] Example 9

[0231] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0232] The difference from Example 5 is that the fireproof and heat-insulating layer is an 8mm thick aluminum silicate titanium dioxide aerogel felt (high temperature resistance ≥1000℃, density 250kg / m³). 3 The sealing and bonding layer consists of basalt mesh (110 g per square meter) + basalt fiber binding + single-component room-temperature curing silicone rubber (surface drying time 38 min, cured thickness 2 mm); the anti-icing functional layer consists of an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 1:1.1) sprayed onto a 0.8 mm thick aluminum silicate twill fabric after silicone calendering treatment, with a spray thickness of 80 μm, cured at 80℃ for 30 min. After silicone rubber application, the functional fabric is adhered within 38 min (≤40 min) under strict timing, utilizing the initial tack of the silicone rubber to achieve temporary interlayer fixation. External impacts are avoided for 24 hours after adhesion to ensure complete curing and stable bonding of the silicone rubber. The remaining steps are completely consistent with those in Example 5.

[0233] Example 10

[0234] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0235] The difference from Example 5 is as follows: the fireproof and heat-insulating layer is a 4 mm thick glass fiber alumina aerogel felt (thermal conductivity ≤0.032W / (m·K), temperature resistance ≥600℃); the sealing and bonding layer is basalt mesh cloth (110 g per square meter) + basalt fiber binding + single-component room temperature cured silicone rubber (surface drying time 20 min, cured thickness 2 mm); the anti-icing functional layer is an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 2:1) sprayed onto a 0.7 mm thick basalt twill cloth (0.28 kg per square meter) after silicone calendering treatment, with a spray thickness of 70 μm, cured at 80℃ for 30 min. Timing is started immediately after the silicone rubber is applied. Because the surface drying time is only 20 min, the anti-icing functional cloth must be applied within 25 min (with a 5 min buffer). A continuous process of "applying adhesive while bonding" is adopted to reduce waiting time and ensure sufficient wetting between layers. The remaining steps are completely consistent with those in Example 5.

[0236] Example 11

[0237] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0238] The difference from Example 5 is that the fireproof and heat-insulating layer is a 7 mm thick aluminum silicate aerogel felt (density 210 kg / m³). 3 The fire resistance limit is ≥1.5 h); the sealing and bonding layer consists of basalt mesh (110 g per square meter) + basalt fiber binding + single-component room-temperature cured silicone rubber (surface drying time 35 min, cured thickness 2 mm); the anti-icing functional layer consists of anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 1:2) sprayed onto 0.9 mm thick glass fiber straight-weave cloth (weather resistance grade UVB-313 test showed no aging after 800 h) after silicone calendering treatment, with a spray thickness of 90 μm, cured at 80℃ for 30 min. After silicone rubber application, the functional cloth is bonded within 38 min using the 35 min surface drying period, utilizing the adhesiveness of the not fully cured silicone rubber to fill the texture of the cloth surface. A "same-scraping-and-bonding" assembly line operation is adopted to reduce waiting time and ensure sufficient wetting between layers. The remaining steps are completely consistent with those in Example 5.

[0239] Example 12

[0240] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0241] The difference from Example 5 is that the fireproof and heat-insulating layer is a 9 mm thick organic fiber carbonized titanium dioxide aerogel felt (density 190 kg / m³). 3The thermal conductivity is ≤0.035W / (m·K); the sealing and bonding layer consists of basalt mesh (110g per square meter) + basalt fiber binding + single-component room-temperature cured silicone rubber (surface drying time 28 min, cured thickness 2 mm); the anti-icing functional layer consists of an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 1:1.5) sprayed onto a 0.8 mm thick aluminosilicate straight-weave cloth (temperature resistance ≥800℃) after silicone calendering treatment, with a spray thickness of 90 μm, cured at 80℃ for 30 min. After the silicone rubber is applied, the functional cloth is bonded within 38 min using the 35 min surface drying period, utilizing the adhesiveness of the not fully cured silicone rubber to fill the texture of the cloth surface. After bonding, the edges are quickly blown with a hot air gun (40℃) to accelerate local initial adhesion and fixation. The remaining steps are completely consistent with those in Example 5.

[0242] Example 13

[0243] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0244] The difference from Example 5 is that the fireproof and heat-insulating layer is a 5 mm thick organic fiber carbonized titanium dioxide aerogel felt (density 170 kg / m³). 3 (Excellent weather resistance); the sealing and bonding layer consists of basalt mesh (110 g per square meter) + basalt fiber binding + single-component room-temperature cured silicone rubber (surface drying time 30 min, cured thickness 2 mm); the anti-icing functional layer consists of anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 1:0.7) sprayed onto 0.9 mm thick glass fiber twill fabric (0.32 kg per square meter) after silicone calendering treatment, with a spray thickness of 90 μm, cured at 80℃ for 30 min. After silicone rubber application, pre-cut functional fabric is used to complete the bonding within 35 min (finishing 5 min before surface drying), utilizing the slight fluidity of the adhesive layer to fill the texture of the twill fabric. The edges are sealed with silicone rubber to prevent moisture penetration later. The remaining steps are completely consistent with those in Example 5.

[0245] Example 14

[0246] A multifunctional coating comprises, from the inside out, a fireproof and heat-insulating layer, a sealing and adhesive layer, and an anti-icing functional layer.

[0247] The difference from Example 5 is as follows: the fireproof and heat-insulating layer is a 10 mm thick basalt silica-alumina composite aerogel felt (thermal conductivity ≤0.026W / (m·K), temperature resistance ≥900℃); the sealing and bonding layer is basalt mesh cloth (weight 110 g per square meter) + basalt fiber binding + single-component room temperature curing silicone rubber (surface drying time 35 min, cured thickness 2 mm); the anti-icing functional layer is an anti-icing coating (MOF-5 loaded on basalt flakes and molybdenum disulfide in a mass ratio of 3:1) sprayed onto a 0.8 mm thick aluminosilicate twill cloth (temperature resistance ≥700℃) after silicone calendering treatment, with a spray thickness of 80 μm and curing at 80℃ for 30 min. Due to the large thickness of the composite aerogel, the functional cloth needs to be bonded within 40 minutes after silicone rubber application, utilizing the extensibility of the adhesive layer before surface drying to adapt to the flatness of the substrate. After bonding, roll the adhesive layer in sections to ensure complete contact between the adhesive layer and the functional fabric, with no air bubbles remaining. The remaining steps are exactly the same as in Example 5.

[0248] Comparative Example 5

[0249] A comparative example designed based on existing bridge steel wire cable protection methods.

[0250] (1) Protective reinforcement layer: Wrap 2 layers of impregnated glass fiber tape (50 mm wide and 0.5 mm thick), using unsaturated polyester resin as impregnating adhesive, with a winding tension of 0.5 MPa, and a total thickness of about 1.2 mm after curing. Cured at room temperature for 5 days.

[0251] (2) Outer wear-resistant layer: spray polyurethane elastomer coating (Shore hardness 85A) in 2 coats, with a total dry film thickness of 200 μm. After curing, it forms a smooth surface with basic wear resistance and waterproof performance.

[0252] Comparative Example 6

[0253] A multifunctional coating differs from Example 5 in that it consists of a fire-resistant and heat-insulating layer and a sealing and adhesive layer, arranged sequentially from the inside out. The remaining steps are completely identical to those of Example 5.

[0254] Comparative Example 7

[0255] A multifunctional coating differs from Example 5 in that it consists of a fire-resistant and heat-insulating layer and an anti-icing functional layer, arranged sequentially from the inside out. The remaining steps are completely consistent with those of Example 5.

[0256] The performance of the material combination systems prepared in Examples 5-14 and Comparative Examples 5-7 was tested:

[0257] 1. Fire resistance performance test: The test was conducted according to GB / T 9978.1-2008 "Fire resistance test method for building components - Part 1: General requirements". The sample was placed in a high-temperature furnace at 1100℃ for 1 hour, and the temperature change of the internal cable or tie rod surface was detected. The results are shown in Table 3.

[0258] Table 3 Surface Temperature Statistics of Internal Cables and Tie Rods

[0259]

[0260] As shown in Table 3, in Examples 5-14, the surface temperature of the internal cables and tie rods did not exceed 300°C (285-300°C) within 60 minutes. This indicates that the multifunctional coating prepared in Examples 5-14 of the present invention can provide excellent and stable fireproof and heat insulation performance, and can provide an extremely effective thermal barrier for the internal cables and tie rods, maintaining the temperature of the cables and tie rods at a level far below their critical strength loss temperature (the strength of steel usually drops sharply above 500°C).

[0261] The complete three-layer structure forms a highly efficient and synergistic system. The sealing and bonding layer ensures a firm and seamless bond between the fireproof and heat-insulating layer and the substrate, isolating it from direct impact from oxygen and flames. The fireproof and heat-insulating layer plays a crucial role at high temperatures, effectively blocking heat transfer to the substrate. The anti-icing layer, as the outermost layer, did not demonstrate its function in fire resistance testing, but its presence does not affect the performance of the inner layers.

[0262] The temperatures in Comparative Examples 5 and 7 reached as high as 998℃ / 1001℃ and 908℃ / 912℃, respectively. This indicates that the applied fireproof and heat insulation protection was completely ineffective; at these temperatures, the steel strength was almost completely lost, and the structure would fail instantly.

[0263] A comparison of the data from Comparative Example 7 and Examples 5-14 shows that without a sealing adhesive layer, the fireproof and heat-insulating system completely collapses. Possible reasons: the anti-icing layer cannot replace the function of the sealing adhesive layer; flames and high-temperature gases directly impact the substrate surface through the gaps, causing the coating to lose its protective effect.

[0264] The temperature of Comparative Example 6 was comparable to that of the Example Group (298℃ / 299℃). A comparison of the data from Comparative Examples 6, 7, and the Example Group shows that the absence of the anti-icing layer had almost no impact on the fire resistance of the system. The combination of the sealing adhesive layer and the fire-resistant insulation layer is crucial for fire resistance.

[0265] 2. Anti-icing performance test: Under simulated cold environment (temperature -15℃, relative humidity 85%), 5 μL of liquid was dropped onto the low-temperature surface, and the icing situation and coating surface condition were observed. The specific results are shown in Table 4.

[0266] Table 4. Anti-icing performance test results

[0267]

[0268] As shown in Table 4, the freezing time of the first ice crystal on the sample surface in Examples 5-14 was 130-200 s, much longer than that in the comparative examples. This indicates that the "anti-icing functional layer" significantly delayed the formation and growth of ice crystals, providing valuable de-icing response time. The freezing time in the comparative examples was extremely short, only between 10-12 s. This is orders of magnitude different from the examples, indicating poor anti-icing performance, with the surface freezing instantly.

[0269] The surface condition reveals that all examples maintained a "frost-free state" and "isolated solid ice particles." This not only signifies slow icing but also that the icing on the surface consists of isolated small ice particles, rather than a continuous layer of ice. These isolated ice particles have weak adhesion and are more easily blown away by wind or removed by slight vibration, achieving a true anti-icing / ice-suppressing effect, rather than merely delaying icing. The comparative examples, on the other hand, all formed a "frost-covered state." The surface was covered by a continuous, uniform layer of ice or frost, which would severely impact the substrate's functionality.

[0270] Furthermore, the excellent anti-icing performance of the embodiments (including the anti-icing layer) is directly attributed to the outermost "anti-icing functional layer." This layer has superhydrophobic and low surface energy properties, making it difficult for water droplets to wet and spread, thus greatly delaying the formation of ice nuclei and promoting the existence of ice as isolated particles with weak adhesion. The anti-icing performance of Comparative Example 6 is as poor as that of Comparative Examples 5 and 7. This proves that the inner fireproof insulation layer and sealing adhesive layer themselves do not have anti-icing function; the anti-icing function is entirely provided by the outermost dedicated anti-icing functional layer. The anti-icing performance of Comparative Example 7 also fails. This again confirms the previous conclusion regarding fire resistance testing: without the sealing adhesive layer, the entire coating system may not be able to adhere firmly to the substrate. In the anti-icing test, the anti-icing functional layer broke or peeled off prematurely due to poor adhesion, exposing the inner, non-anti-icing fireproof insulation layer, which then quickly iced. This, in turn, also illustrates the fundamental role of the sealing adhesive layer in ensuring the normal functioning of the outer layer.

[0271] 3. Fire resistance and firmness of the sealing adhesive layer: The oxygen index of the sealing adhesive layer in Examples 5-14 was tested, and after 50 cycles of temperature cycling from -30℃ (12 h) to 80℃ (12 h), cracking and peeling were observed.

[0272] Table 5. Results of Oxygen Index and Firmness Tests

[0273]

[0274] As shown in Table 5, the sealing adhesive layer used in Examples 5-14 is not only a highly flame-retardant material (Oxygen Index ≥ 32%), but it also does not become fuel even when exposed to flames; instead, it effectively blocks the flames. Comparative Example 5 has an OI of only 18%, classifying it as a flammable material. Comparative Examples 6 and 7 have an OI < 27%, classifying them as combustible materials. This means that the sealing adhesive layer in the comparative examples may ignite and burn itself in a fire, failing to protect the internal fireproof layer and instead exacerbating the fire, accelerating the destruction of the entire system.

[0275] As shown in Table 5, after 50 temperature cycles from -30℃ (12 h) to 80℃ (12 h), the example group showed no cracking or peeling, and its flame retardant and adhesive properties remained stable. This indicates that the sealing and adhesive layer of the examples has extremely strong adhesion, excellent flexibility, and anti-aging ability; it can withstand the stress generated by extreme temperature changes and remains tightly and completely bonded to the anti-icing functional layer and the fireproof and heat-insulating layer, forming an airtight protective shell. The comparative example group cracked and peeled after cycling, indicating that the sealing and adhesive layer of the comparative example group could not withstand environmental stress and failed. Once cracked and peeled, the fireproof function was lost, and the anti-icing function was also lost.

[0276] As demonstrated by the above embodiments and performance tests, the material combination system and its preparation process for fireproof and heat-insulating protection of bridge cables and tie rods with anti-icing properties of the present invention successfully combines high-efficiency fireproof and heat-insulating properties with excellent anti-icing performance, providing a reliable solution for the safety protection of bridge cables and tie rods, and has broad application prospects.

[0277] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. An anti-icing coating material, characterized by, The fluorosilicone resin and the special pigment are composed of flake material, MOF grown on the flake material, and molybdenum disulfide nanosheet grown on the surface of the MOF; The mass ratio of the fluorosilicone resin and the special pigment is (6.5-7.5):(2.5-3.5); The flake material is basalt flake or glass flake; The MOF is MOF-5 or ZIF-8; The fluorosilicone resin has a fluorine content of 20%-26%; The flake material has a thickness of 2.5-3.5 μm and a size of 25 μm-3 mm; The preparation method of the anti-icing coating comprises the following steps: The MOF material is grown on the surface of the flake material by a hydrothermal synthesis method, so that the MOF material uniformly covers the surface of the flake material and forms a nanoscale pore structure; after the reaction is completed, centrifugal separation, washing, and drying treatment are performed; the molybdenum disulfide nanomaterial is grown on the surface of the MOF material by a chemical vapor deposition method, the molybdenum disulfide nanomaterial is attached to the surface of the MOF material in a nanosheet layered structure, and the special pigment is obtained; the special pigment and the fluorosilicone resin are mixed in a certain proportion to obtain the anti-icing coating.

2. An anti-icing coating characterized in that, The anti-icing coating of claim 1 is coated on a substrate and cured to obtain the anti-icing coating.

3. An anti-icing functional layer characterized by, The anti-icing coating of claim 1 is coated on a sealing cloth and cured to obtain the anti-icing coating. The anti-icing coating has a thickness of 80-120 μm when coated on the sealing cloth.

4. A multifunctional coating characterized by, The anti-icing functional layer of claim 3 is compounded on the sealing and bonding layer which is compounded on the fireproof and heat-insulating layer; The fireproof and heat-insulating layer comprises a fiber composite aerogel felt; The sealing and bonding layer comprises an inorganic fiber mesh cloth and a silicone rubber sealant coated on the surface of the inorganic fiber mesh cloth; The thickness of the fireproof and heat-insulating layer is 3-8 mm, the thickness of the sealing and bonding layer is 1.2-3 mm, and the thickness of the anti-icing functional layer is 0.5-1.5 mm.

5. The multifunctional coating of claim 4, wherein, The fibers in the fiber composite aerogel felt include any one of inorganic fibers and carbonized organic fibers, and the aerogel includes any one of silica aerogel, alumina aerogel, and titanium oxide aerogel; The fiber composite aerogel felt is selected from any one or more of inorganic fiber aerogel felt and carbonized organic fiber composite aerogel felt; The inorganic fibers include any one or more of glass fibers, basalt fibers, and aluminum silicate fibers; The organic fibers include any one of natural fibers and synthetic fibers; the natural fibers include any one or more of cotton fibers and hemp fibers, and the synthetic fibers include any one or more of polyester fibers, polyamide fibers, polyacrylonitrile fibers, and phenolic fibers.

6. The multifunctional coating of claim 4, wherein, The mesh spacing of the inorganic fiber mesh cloth is (1.5-4 mm)×(1.5-4 mm), and the thickness is 0.1-0.2 mm; The inorganic fiber mesh cloth includes any one or more of basalt fiber mesh cloth, glass fiber mesh cloth, and aluminum silicate fiber mesh cloth; The components of the silicone rubber sealant include 100 parts of silicone rubber, 5-8 parts of nano montmorillonite, 8-12 parts of fumed silica, 15-20 parts of precipitated silica, and 10-15 parts of nano calcium carbonate.

7. A method of producing a multifunctional coating according to any one of claims 4 to 6, characterized in that, It comprises: The fiber composite aerogel felt is wrapped on the surface of the substrate to form a fireproof and heat-insulating layer; The inorganic fiber mesh cloth is wrapped on the surface of the fiber composite aerogel felt, and then the silicone rubber sealant is coated on the surface of the inorganic fiber mesh cloth to form a sealing and bonding layer; The anti-icing functional layer is wrapped on the surface of the sealing and bonding layer to obtain a multifunctional coating.

8. The production method according to claim 7, wherein The substrate includes any one or more of a bridge cable, a bridge suspender, and a bridge tension rod; After the coating of the silicone rubber sealant is completed, the wrapping of the anti-icing functional layer is completed within 40 min.

9. Application of the anti-icing coating of claim 1, or the anti-icing coating layer of claim 2, or the anti-icing functional layer of claim 3, or the multifunctional coating of any one of claims 4-6 in bridge protection.

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