A method for preparing a high-durability, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics.

Abstract

This invention relates to a method for preparing a high-durability transparent cooling self-cleaning coating for the protection of stone cultural relics, comprising the following steps: (1) dispersing silica nanoparticles, titanium dioxide nanoparticles and zinc oxide nanoparticles in a mixed solution and ultrasonicating to obtain a mixed dispersion; (2) dispersing silica nanoparticles in the mixed solution and ultrasonicating to obtain a dispersion containing only silica nanoparticles; (3) adding silane coupling agent and hydrochloric acid to the mixed dispersion and silica dispersion respectively to obtain solution A and solution B; (4) adding water-diluted aqueous emulsion to solution B to obtain an adhesive layer solution for spraying; (5) ultrasonicating the adhesive layer solution and spraying it onto the sample, allowing it to cure naturally; (6) ultrasonicating solution A and continuing to spray it onto the sample; (7) drying the sprayed sample at room temperature to obtain a transparent superhydrophobic coating; the coating has high light transmittance and excellent hydrophobicity, oleophobicity and self-cleaning properties.

Description

Technical Field

[0001] This invention relates to the field of materials technology, specifically to a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics. Background Technology

[0002] Cultural relics are invaluable legacies created by humankind in its long and rich history; protecting them is preserving the history of civilization. Some stone artifacts are exposed to the outdoors, and due to long-term erosion from various forms of water and the continuous accumulation of pollutants and microorganisms on their surfaces, their appearance undergoes significant changes. Therefore, timely preventative protection of these artifacts is crucial.

[0003] Superhydrophobic materials repel water and most liquids. Like a lotus leaf, water droplets form spherical shapes upon contact with the surface and easily roll off. Such surfaces typically have a contact angle greater than 150° and a sliding angle less than 10°, preventing water droplets from spreading out. This is due to the surface's rough microstructure and low surface energy, with numerous tiny protrusions that reduce the actual contact area between the water droplet and the material. Furthermore, the surface's chemical composition is often inherently hydrophobic, further enhancing the liquid repellency. The rough structure of superhydrophobic materials also increases the scattering of incident light, significantly reducing the light transmittance of the coating surface.

[0004] Some outdoor stone artifacts are exposed to strong light and high temperature environments all year round, which may cause changes in appearance such as cracks and discoloration on the surface. Therefore, it is crucial to develop a superhydrophobic coating with high transparency. Summary of the Invention

[0005] To address the aforementioned problems, the present invention aims to provide a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics. This self-cleaning coating can provide preventative protection for cultural relics without altering their original appearance, and it exhibits sufficient resistance to mechanical damage and chemical attack. It can effectively prevent damage to cultural relics under high temperature and strong light, and it has strong cleaning performance for dust, dirt, and other pollutants on the surface of cultural relics.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics includes the following steps:

[0008] (1) Weigh silica nanoparticles, titanium dioxide nanoparticles and zinc oxide nanoparticles with a mass ratio of 1:(0.5-1.5):(1-2) and disperse them in a mixed solution of anhydrous ethanol and isopropanol with a volume ratio of 1:(1-1.5). After sonication for 15 min, a mixed dispersion with a concentration of 1-10 mg / mL is obtained.

[0009] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL anhydrous ethanol and 10mL isopropanol. After sonication for 10-15min, a silica dispersion is obtained.

[0010] (3) Slowly add silane coupling agent and hydrochloric acid to the above mixed dispersion and silica dispersion respectively, and then add 5% ammonia solution dropwise to each for activation and modification. After magnetic stirring, composite sol solution A and single silica sol solution B are obtained respectively.

[0011] (4) Add water-diluted aqueous emulsion to single silica sol solution B. The mass of aqueous emulsion is 3-4 times the mass of single silica sol solution B. Stir for 0.5-1h and then sonicate for 0.5-1h to obtain an adhesive layer solution for spraying.

[0012] (5) After ultrasonic treatment, the obtained adhesive layer solution is sprayed onto the sample in 20-80 layers and allowed to cure naturally at room temperature for 0.5-1.5 hours;

[0013] (6) After sonicating the above-obtained composite sol solution A for 15 minutes, continue to spray 200 layers onto the sample. During spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray onto the sample.

[0014] (7) The sprayed sample is dried at room temperature for 1-3 days to obtain a transparent superhydrophobic coating.

[0015] Preferably, the silica nanoparticles have a particle size of 10-40 nm, the titanium dioxide nanoparticles have a particle size of 5-10 nm, and the zinc oxide nanoparticles have a particle size of 20-40 nm.

[0016] Preferably, the silane coupling agent in step (3) is diethoxydimethylsilane, and its mass is 3-4 times the total mass of the nanoparticles in the solution to be added, while the mass of hydrochloric acid is 0.5-1 times the mass of the nanoparticles in the solution to be added, and the volume of ammonia added is 0.5%-1% of the total volume of the solution to be added.

[0017] Preferably, the stirring conditions in step (3) are 25-30°C at room temperature and the stirring duration is 24-48h.

[0018] Preferably, the aqueous emulsion in step (4) is a styrene-acrylic emulsion.

[0019] Preferably, the ultrasound time in step (5) is 10-30 min.

[0020] Preferably, in step (6), the spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sample is 15-20 cm.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] This application uses a diluted aqueous emulsion mixed with modified silica to form a hydrophobic adhesive substrate, followed by a transparent protective coating formed by mixing various nanoparticles. The styrene-acrylic emulsion exhibits excellent hydrophobicity and durability, curing at room temperature to a transparent state with high light transmittance, requiring no heat or UV curing. Silica's surface is rich in hydroxyl groups, exhibiting strong hydrophilicity. The hydrolysis of the silane coupling agent diethoxydimethylsilane reduces the hydroxyl groups on the silica surface, enhancing its hydrophobicity. This coating possesses excellent hydrophobicity, oleophobicity, and self-cleaning properties; it also exhibits excellent chemical and mechanical stability, provides some heat insulation and cooling effects, and repels most liquids found in daily life. The materials used are environmentally friendly and non-toxic, ensuring long-term stable application in various indoor and outdoor cultural relics. Attached Figure Description

[0023] Figure 1 The image shows the water droplet contact angle test results of the high-durability transparent cooling self-cleaning coating prepared in Example 1;

[0024] Figure 2 A comparison of UV transmittance of high-durability transparent cooling self-cleaning coatings with different numbers of layers is shown in the figure. The inset in the figure is a photograph taken on a sandstone block with different numbers of coatings.

[0025] Figure 3 AFM image of the high-durability transparent cooling self-cleaning coating prepared in Example 1;

[0026] Figure 4 SEM image of the high-durability transparent cooling self-cleaning coating prepared in Example 1;

[0027] Figure 5 A schematic diagram illustrating the self-cleaning performance of the high-durability transparent cooling self-cleaning coating prepared in Example 1;

[0028] Figure 6 The graph shows the changes in the water droplet contact angle and sliding angle of the high-durability transparent cooling self-cleaning coating prepared in Example 1 after a tape bonding cycle test.

[0029] Figure 7 The graph shows the changes in contact angle and sliding angle of water droplets with different pH values ​​on the surface of the high-durability transparent cooling self-cleaning coating prepared in Example 1.

[0030] Figure 8 The images show the infrared thermometry results after spraying different numbers of layers onto sandstone blocks in Example 4, with (a) to (d) representing 0 layers, 200 layers, 300 layers, and 400 layers, respectively. Detailed Implementation

[0031] The present invention will be further described below with reference to specific embodiments.

[0032] Example 1

[0033] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0034] (1) Weigh 2g of silica nanoparticles, 2g of titanium dioxide nanoparticles and 3g of zinc oxide nanoparticles and disperse them in a mixed solution of 20mL of anhydrous ethanol and 20mL of isopropanol. After sonication for 15min, a mixed dispersion with a concentration of 1-10mg / mL is obtained.

[0035] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 15min, a dispersion containing only silica nanoparticles is obtained.

[0036] (3) Slowly add 24g of diethoxydimethylsilane and 4g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.5mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After magnetic stirring at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0037] (4) Add 4g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 0.5h to obtain an adhesive layer solution for spraying.

[0038] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 40 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0039] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray 200 layers on the sandstone block. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone block. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone block is 15-20 cm.

[0040] (7) The sprayed sandstone block was dried at room temperature for 24 hours to obtain a transparent superhydrophobic coating.

[0041] The contact angle of the prepared coating was tested, and the test results are attached. Figure 1 As shown, it exhibits a contact angle of over 150°. And as attached... Figure 2 As shown, attached Figure 2 To compare the light transmittance after spraying different numbers of layers, it is easy to see that the light transmittance of sandstone blocks with different numbers of layers is slightly lower than that of unsprayed sandstone blocks, but all remain above 70%; while through the attachment Figure 3and attached Figure 4 Observation of the sandstone surface structure indicates that the nanoparticles are uniformly distributed on the coating surface, forming a sufficiently rough structure; as shown in the attached image. Figure 5 This is a schematic diagram illustrating the self-cleaning performance of a transparent superhydrophobic coating prepared on sandstone. Comparing the surface of the sandstone before and after cleaning demonstrates the coating's excellent self-cleaning properties; water droplets rolling off the coating easily carry away contaminants. (Attached) Figure 6 For the tape adhesion test, the tape was repeatedly applied to and then torn off the coating surface. After 30 cycles, the coating still had a water droplet contact angle of more than 150°. Figure 7 The graph shows the changes in the contact angle of droplets with different pH values ​​on the coating surface, demonstrating the excellent chemical stability of the coating.

[0042] Example 2

[0043] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0044] (1) Weigh 1g of silica nanoparticles, 1g of titanium dioxide nanoparticles and 1.5g of zinc oxide nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 10min, a mixed dispersion is obtained.

[0045] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 10min, a dispersion containing only silica nanoparticles is obtained.

[0046] (3) Slowly add 12g of diethoxydimethylsilane and 2g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.2mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After stirring magnetically at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0047] (4) Add 6g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 1h to obtain an adhesive layer solution for spraying.

[0048] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 30 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0049] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray 150 layers on the sandstone block. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone block. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone block is 15-20 cm.

[0050] (7) The sandstone block after spraying was dried at room temperature for 48 hours to obtain a transparent superhydrophobic coating.

[0051] The prepared coating has a water contact angle of 158° and a transmittance of up to 78% in the visible light range.

[0052] Example 3

[0053] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0054] (1) Weigh 0.6g of silica nanoparticles, 0.6g of titanium dioxide nanoparticles and 0.9g of zinc oxide nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 15min, a mixed dispersion is obtained.

[0055] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 15min, a dispersion containing only silica nanoparticles is obtained.

[0056] (3) Slowly add 7g of diethoxydimethylsilane and 1g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.2mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After magnetic stirring at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0057] (4) Add 6g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 0.5h to obtain an adhesive layer solution for spraying.

[0058] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 60 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0059] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray 200 layers on the sandstone block. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone block. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone block is 15-20 cm.

[0060] (7) The sprayed sandstone block was dried at room temperature for 24 hours to obtain a transparent superhydrophobic coating.

[0061] The prepared transparent superhydrophobic coating has a water contact angle of 160° and a transmittance of up to 75% in the visible light range.

[0062] Example 4

[0063] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0064] (1) Weigh 2g of silica nanoparticles, 1g of titanium dioxide nanoparticles and 2g of zinc oxide nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 15mL of isopropanol. After sonication for 10min, a mixed dispersion is obtained.

[0065] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL anhydrous ethanol and 15mL isopropanol. After sonication for 10min, a dispersion containing only silica nanoparticles is obtained.

[0066] (3) Slowly add 17g of diethoxydimethylsilane and 3g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.3mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After stirring magnetically at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0067] (4) Add 4g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 0.5h to obtain an adhesive layer solution for spraying.

[0068] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 60 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0069] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray 200 layers on the sandstone block. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone block. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone block is 15-20 cm.

[0070] (7) The sprayed sandstone block was dried at room temperature for 24 hours to obtain a transparent superhydrophobic coating.

[0071] The prepared transparent superhydrophobic coating has a water contact angle of 156° and a maximum transmittance of 71% in the visible light range.

[0072] Example 5

[0073] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0074] (1) Weigh 1g of silica nanoparticles, 1.5g of titanium dioxide nanoparticles and 2g of zinc oxide nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 15mL of isopropanol. After sonication for 10min, a mixed dispersion is obtained.

[0075] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL anhydrous ethanol and 15mL isopropanol. After sonication for 10min, a dispersion containing only silica nanoparticles is obtained.

[0076] (3) Slowly add 15g of diethoxydimethylsilane and 3g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.3mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After stirring magnetically at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0077] (4) Add 4g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 0.5h to obtain an adhesive layer solution for spraying.

[0078] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 80 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0079] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray 200 layers on the sandstone block. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone block. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone block is 15-20 cm.

[0080] (7) The sprayed sandstone block was dried at room temperature for 24 hours to obtain a transparent superhydrophobic coating.

[0081] The prepared transparent superhydrophobic coating has a water contact angle of 157° and a maximum transmittance of 72% in the visible light range.

[0082] Example 6

[0083] This embodiment provides a method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, including the following steps:

[0084] (1) Weigh 2g of silica nanoparticles, 2g of titanium dioxide nanoparticles and 3g of zinc oxide nanoparticles and disperse them in a mixed solution of 20mL of anhydrous ethanol and 20mL of isopropanol. After sonication for 15min, a mixed dispersion with a concentration of 1-10mg / mL is obtained.

[0085] (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL of anhydrous ethanol and 10mL of isopropanol. After sonication for 15min, a dispersion containing only silica nanoparticles is obtained.

[0086] (3) Slowly add 24g of diethoxydimethylsilane and 4g of hydrochloric acid to the mixed dispersion, and slowly add 3.5g of diethoxydimethylsilane and 0.6g of hydrochloric acid to the silica dispersion. Then add 0.5mL and 0.1mL of 5% ammonia solution respectively for activation and modification. After magnetic stirring at room temperature for 24h, composite sol solution A and single silica sol solution B are obtained respectively.

[0087] (4) Add 4g of styrene-acrylic emulsion diluted with water to a single silica sol solution B, stir for 1h and then sonicate for 0.5h to obtain an adhesive layer solution for spraying.

[0088] (5) After ultrasonicating the obtained bonding layer solution for 15 minutes, spray 40 layers onto the sandstone block and allow it to cure naturally at room temperature for 0.5 hours.

[0089] (6) After ultrasonicating the composite sol solution A for 15 minutes, continue to spray three sandstone blocks with 200, 300 and 400 layers respectively. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray on the sandstone blocks. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sandstone blocks is 15-20 cm.

[0090] (7) The sprayed sandstone block was dried at room temperature for 24 hours to obtain a transparent superhydrophobic coating.

[0091] The prepared transparent superhydrophobic coating has a water contact angle of 161° and a transmittance of up to 70% in the visible light range. Infrared thermometry was performed on high-durability transparent cooling self-cleaning coatings prepared on sandstone blocks with different coatings. The surface temperatures of the sandstone blocks with no coating, 200 layers of coating, 300 layers of coating, and 400 layers of coating were 62.4℃, 60.4℃, 59.4℃, and 57.7℃, respectively. This indicates that the coating prepared in this invention has a certain cooling effect on cultural relic protection, effectively reducing the damage caused by high temperatures and strong light to cultural relics, and facilitating more comprehensive protection of cultural relics.

[0092] The above are preferred embodiments of this application, but not all embodiments, and should not be used to limit the scope of protection of this application. Therefore, all equivalent changes made to the products, methods and principles of this application should be covered within the scope of protection of this application.

Claims

1. A method for preparing a highly durable, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics, characterized in that, Includes the following steps: (1) Weigh silica nanoparticles, titanium dioxide nanoparticles and zinc oxide nanoparticles with a mass ratio of 1:(0.5-1.5):(1-2) and disperse them in a mixed solution of anhydrous ethanol and isopropanol with a volume ratio of 1:(1-1.5). After sonication for 15 min, a mixed dispersion with a concentration of 1-10 mg / mL is obtained. (2) Weigh 1g of silica nanoparticles and disperse them in a mixed solution of 10mL anhydrous ethanol and 10mL isopropanol. After sonication for 10-15min, a silica dispersion is obtained. (3) Add silane coupling agent and hydrochloric acid slowly to the above mixed dispersion and silica dispersion respectively, and then add 5% ammonia solution dropwise to each for activation and modification. After magnetic stirring, composite sol solution A and single silica sol solution B are obtained respectively. (4) Add water-diluted aqueous emulsion to single silica sol solution B. The mass of aqueous emulsion is 3-4 times the mass of single silica sol solution B. Stir for 0.5-1h and then sonicate for 0.5-1h to obtain an adhesive layer solution for spraying. (5) After ultrasonic treatment, the obtained adhesive layer solution is sprayed onto the sample in 20-80 layers and allowed to cure naturally at room temperature for 0.5-1.5 hours; (6) After sonicating the above-obtained composite sol solution A for 15 minutes, continue to spray 200 layers onto the sample. When spraying, use a spray gun with a moving speed of 2-4 cm / s to continuously and evenly spray onto the sample. (7) The sprayed sample is dried at room temperature for 1-3 days to obtain a transparent superhydrophobic coating.

2. The method for preparing a high-durability, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, The silica nanoparticles have a particle size of 10-40 nm, the titanium dioxide nanoparticles have a particle size of 5-10 nm, and the zinc oxide nanoparticles have a particle size of 20-40 nm.

3. The method for preparing a high-durability, transparent, cooling, self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, In step (3), the silane coupling agent is diethoxydimethylsilane, and its mass is 3-4 times the total mass of the nanoparticles in the solution to be added. The mass of hydrochloric acid is 0.5-1 times the mass of the nanoparticles in the solution to be added, and the volume of ammonia added is 0.5%-1% of the total volume of the solution to be added.

4. The method for preparing a high-durability, transparent, cooling, self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, The stirring conditions in step (3) are 25-30°C at room temperature and the stirring duration is 24-48h.

5. The method for preparing a high-durability, transparent, cooling, and self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, The aqueous emulsion used in step (4) is a styrene-acrylic emulsion.

6. The method for preparing a high-durability, transparent, cooling, self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, The ultrasound time in step (5) is 10-30 min.

7. The method for preparing a high-durability, transparent, cooling, self-cleaning coating for the protection of stone cultural relics according to claim 1, characterized in that, In step (6), the spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the sample is 15-20 cm.

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