Sub-black high-stability hydrophobic anti-icing / deicing composite coating and controllable construction method thereof

Abstract

The invention discloses a sub-black high-stability hydrophobic anti-icing / deicing composite coating and a controllable construction method thereof.The construction method comprises the steps that 0.8-1.2 g of a silane coupling agent and 10 ml of absolute ethyl alcohol are weighed and mixed, and a mixed solution is obtained; weighing 0.08-0.12 g of hydrophilic silicon dioxide nanoparticles, adding the hydrophilic silicon dioxide nanoparticles into the mixed solution, and carrying out ultrasonic treatment until the hydrophilic silicon dioxide nanoparticles are uniformly dispersed to obtain silicon dioxide dispersion liquid; weighing 0.8 to 0.15 g of epoxy resin, 0.8 to 0.15 g of a curing agent and 0.01 to 0.03 g of polydimethylsiloxane, and adding the epoxy resin, the curing agent and the polydimethylsiloxane into 10ml of ethyl acetate, so as to obtain an epoxy solution; the preparation method comprises the following steps: mixing 10.8-11.2 mL of a silicon dioxide dispersion liquid and 11.5-12.8 mL of an epoxy solution, adding 0.07-0.13 g of a carbon nanotube, fully stirring, and spraying on a sample; the sprayed sample is cured for 2-2.5 h in a drying oven at the temperature of 120-150 DEG C, and a sub-black hydrophobic coating is obtained; the prepared composite coating has excellent hydrophobicity, chemical stability, mechanical stability and photo-thermal performance, and preventive protection for effectively avoiding formation of an ice layer is realized on the premise that the original appearance of infrastructures is not changed in a low-temperature and high-humidity environment.

Description

Technical Field

[0001] This invention belongs to the field of functional materials technology, and relates to a hydrophobic anti-icing / de-icing composite coating, specifically a semi-black, highly stable hydrophobic anti-icing / de-icing composite coating and its controllable construction method. Background Technology

[0002] Icing is a common phenomenon in nature and various engineering applications, causing numerous inconveniences to daily life and posing a serious threat to the safe and stable operation of critical infrastructure such as transportation and power systems. Currently used de-icing methods mainly include heat treatment, chemical de-icing agents, and mechanical removal. Although these methods can remove ice to some extent, they generally suffer from problems such as low efficiency, high energy consumption, high cost, and potential environmental burden.

[0003] Inspired by the lotus effect, superhydrophobic surfaces, through the synergistic effect of micro / nanoscale structures and low surface energy, prevent water droplets from spreading into a continuous liquid film in low-temperature environments. Instead, water droplets rapidly detach from the surface in an approximately spherical shape, thus weakening the interfacial conditions required for ice nucleation and delaying icing. However, under even lower temperatures or long-term service conditions, once ice forms, superhydrophobic surfaces struggle to actively remove it. The ice may also become embedded in the micro / nanostructure, creating "mechanical locking," which in turn disrupts the surface's structural stability and renders it incapable of effective de-icing. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a sub-black, highly stable hydrophobic anti-icing / de-icing composite coating and its controllable construction method. This composite coating possesses excellent hydrophobicity, chemical stability, mechanical stability, and photothermal properties, achieving effective preventative protection against ice formation in low-temperature and high-humidity environments without altering the original appearance of the infrastructure.

[0005] To achieve the above objectives, the present invention employs the following technical solution: A semi-black, highly stable hydrophobic anti-icing / de-icing composite coating and its controllable construction method include the following steps: Step 1: Weigh 0.8~1.2g of silane coupling agent and mix with 10ml of anhydrous ethanol to obtain a mixed solution; Step 2: Weigh 0.08~0.12g of hydrophilic silica nanoparticles and add them to the mixed solution. Sonicate until the particles are evenly dispersed to obtain a silica dispersion. Step 3: Weigh 0.8~0.15g of epoxy resin, 0.8~0.15g of curing agent and 0.01~0.03g of polydimethylsiloxane and add them to 10ml of ethyl acetate to obtain an epoxy solution; Step 4: Mix 10.8-11.2 mL of silica dispersion and 11.5-12.8 mL of epoxy solution, add 0.07-0.13 g of carbon nanotubes, stir thoroughly, and then spray onto the sample. Step 5: After spraying, the sample is cured in an oven at 120~150℃ for 2~2.5h to obtain a matte black hydrophobic coating.

[0006] The present invention also has the following technical features: Preferably, the silane coupling agent comprises any one of γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

[0007] Preferably, the hydrophilic silica nanoparticles have a particle size of 10~40nm.

[0008] Preferably, the ultrasound in step two involves simultaneously ultrasonicating and stirring for 25-30 minutes.

[0009] Preferably, the curing agent includes any one of PA650, T-31, or D-400.

[0010] Preferably, the thorough stirring in step four is carried out at 25~30℃ for 12~24 hours.

[0011] Preferably, in step four, the spraying pressure of the spray gun is 0.2 MPa, the distance between the spray gun and the sample is 15-20 cm, and the moving speed of the spray gun is 2-4 cm / s.

[0012] This invention also protects a matte black, highly stable hydrophobic anti-icing / de-icing composite coating constructed using the method described above.

[0013] Compared with the prior art, the present invention has the following technical effects: This invention first prepares a substrate material with both hydrophobicity and adhesion by combining an epoxy network with modified silica; then, it further combines carbon nanotubes to form a composite coating with photothermal anti-icing and de-icing functions. The epoxy resin possesses excellent mechanical properties, high bonding strength, and chemical corrosion resistance, and is easily combined with various functional fillers. The silica surface is rich in hydroxyl groups, exhibiting strong hydrophilicity. After hydrolysis modification with a silane coupling agent, the number of hydroxyl groups on its surface decreases, significantly improving hydrophobicity. This composite coating possesses excellent hydrophobicity, chemical stability, mechanical stability, photothermal performance, and anti-icing and de-icing properties. Furthermore, the raw materials used are environmentally friendly and non-toxic, enabling long-term stable and widespread application in various indoor and outdoor infrastructures. Attached Figure Description

[0014] Figure 1 The image shows the water droplet contact angle test results of the hydrophobic anti-icing coating prepared in Example 1; Figure 2 SEM image of the hydrophobic anti-icing coating prepared in Example 1; Figure 3 The images show the photothermal effects of the hydrophobic anti-icing coatings prepared in Examples 1 to 4. Figure 4 Photographs of the surface icing conditions of the hydrophobic anti-icing coatings prepared in Examples 1 to 4 at different times under a temperature of -10℃; Figure 5 Photographs of the surface ice melting of the hydrophobic anti-icing coatings prepared in Examples 1 to 4 at different times under single-fold sunlight irradiation and an ambient temperature of -15°C. Figure 6 The graph shows the changes in the water droplet contact angle and sliding angle of the hydrophobic anti-icing coating prepared in Example 1 after a tape bonding cycle test.

[0015] Figure 7 The graph shows the changes in the water droplet contact angle and sliding angle of the hydrophobic anti-icing coating prepared in Example 1 after a friction cycle test. Detailed Implementation

[0016] The following detailed explanation of the specific content of the present invention is provided in conjunction with embodiments. These descriptions are intended to explain the present invention and not to limit it.

[0017] In the following examples, the particle size of hydrophilic silica nanoparticles is 10~40nm; the outer diameter of carbon nanotubes is 8-15nm and the length is ≤20μm; and the degree of polymerization of polydimethylsiloxane is >200.

[0018] Example 1 This embodiment provides a controllable construction method for a matte black, highly stable hydrophobic anti-icing / de-icing composite coating, comprising the following steps: Step 1: Weigh 1g of γ-aminopropyltriethoxysilane and 10ml of anhydrous ethanol, mix them, and stir on a magnetic stirrer for 30 minutes to form a transparent mixed solution. Step 2: Weigh 0.1g of hydrophilic silica nanoparticles and add them to the mixed solution. Stir while sonicating for 30min, then continue magnetic stirring for 1h to form a uniform silica dispersion. Step 3: Weigh 0.15g of AG-80 epoxy resin, 0.15g of PA650 curing agent and 0.02g of monoglycidyl ether-terminated polydimethylsiloxane and add them to 10ml of ethyl acetate. Place the mixture on a magnetic stirrer and stir thoroughly to obtain a pale yellow epoxy solution. Step 4: Mix 10.8 mL of silica dispersion and 11.5 mL of epoxy solution, and add 0.07 g of carbon nanotubes; stir the solution continuously at 25 °C for 12 h, and then spray it onto a tinplate sheet. When spraying, use a spray gun with a moving speed of 2 cm / s to continuously and evenly spray onto the tinplate sheet. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the tinplate sheet is 15 cm. Step 5: After spraying, place the sample in an oven at 120°C for 2 hours to cure. After cooling, a matte black hydrophobic coating is obtained.

[0019] Example 2 This embodiment provides a controllable construction method for a matte black, highly stable hydrophobic anti-icing / de-icing composite coating, comprising the following steps: Step 1: Weigh 1g of γ-glycidyl oxypropyltrimethoxysilane and 10ml of anhydrous ethanol, mix them, and stir on a magnetic stirrer for 30 minutes to form a transparent mixed solution. Step 2: Weigh 0.12g of hydrophilic silica nanoparticles and add them to the mixed solution. Stir with sonication for 28min and then continue to stir magnetically for 1h to form a uniform silica dispersion. Step 3: Weigh 0.1g of E-44 epoxy resin, 0.1g of T-31 curing agent and 0.03g of hydroxyl-terminated polydimethylsiloxane, add them to 10mL of ethyl acetate, and mix thoroughly under magnetic stirring to obtain an epoxy coating solution. Step 4: Mix 11.2 mL of silica dispersion and 12.8 mL of epoxy solution, and add 0.09 g of carbon nanotubes; stir the solution continuously at 30 °C for 24 h, and then spray it onto a tinplate sheet. When spraying, use a spray gun with a moving speed of 4 cm / s to continuously and evenly spray onto the tinplate sheet. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the tinplate sheet is 18 cm. Step 5: After spraying, place the sample in an oven and cure at 130°C for 2.2 hours. After cooling, a transparent hydrophobic coating is obtained.

[0020] The prepared transparent hydrophobic coating has a water contact angle of 110° and can be heated up to 51°C under sunlight.

[0021] Example 3 This embodiment provides a controllable construction method for a matte black, highly stable hydrophobic anti-icing / de-icing composite coating, comprising the following steps: Step 1: Weigh 0.8g of γ-methacryloxypropyltrimethoxysilane and 10ml of anhydrous ethanol and mix them. Stir under magnetic stirring for 30min to form a transparent mixed solution. Step 2: Weigh 0.1g of hydrophilic silica nanoparticles and add them to the mixed solution. Stir with sonication for 25min and then continue to stir magnetically for 1h to form a uniform silica dispersion. Step 3: Weigh 0.12g of E-51 epoxy resin, 0.12g of D-400 polyetheramine curing agent and 0.01g of methyl-terminated polydimethylsiloxane, add them to 10mL of ethyl acetate, and mix thoroughly under magnetic stirring to obtain an epoxy coating solution. Step 4: Mix 11 mL of silica dispersion and 12 mL of epoxy solution, and add 0.10 g of carbon nanotubes. Stir continuously to obtain a uniform composite coating solution. Stir continuously at 28°C for 14 hours, and then spray it onto a tinplate sheet. When spraying, use a spray gun with a moving speed of 4 cm / s to continuously and evenly spray onto the tinplate sheet. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the tinplate sheet is 15 cm. Step 5: After spraying, place the sample in an oven at 150°C for 2 hours to cure. After cooling, a matte black hydrophobic coating is obtained.

[0022] The prepared black hydrophobic coating has a water contact angle of 114° and can be heated to a maximum temperature of 62°C under sunlight.

[0023] Example 4 This embodiment provides a controllable construction method for a matte black, highly stable hydrophobic anti-icing / de-icing composite coating, comprising the following steps: Step 1: Weigh 1.2g of γ-glycidoxypropyltrimethoxysilane and add it to 20mL of anhydrous ethanol. Stir for 30min under magnetic stirring to form a transparent mixed solution. Step 2: Weigh 0.08g of hydrophilic silica nanoparticles and add them to the mixed solution. Stir while sonicating for 30min, then continue to stir magnetically for 1h to form a uniform silica dispersion. Step 3: Weigh 0.8g of E-44 epoxy resin, 0.8g of T-31 curing agent and 0.02g of hydroxyl-terminated polydimethylsiloxane and add them to 10ml of ethyl acetate. Place the solution on a magnetic stirrer and stir thoroughly to obtain an epoxy coating solution. Step 4: Mix 11.2 mL of silica dispersion and 12.8 mL of epoxy solution, and add 0.13 g of carbon nanotubes. Stir continuously to obtain a uniform composite coating solution. Stir the solution continuously at 30°C for 12 hours, and then spray it onto a tinplate sheet. When spraying, use a spray gun with a moving speed of 3 cm / s to continuously and evenly spray the solution onto the tinplate sheet. The spraying pressure of the spray gun is 0.2 MPa, and the distance between the spray gun and the tinplate sheet is 20 cm. Step 5: After spraying, place the sample in an oven and cure at 120°C for 2.5 hours. After cooling, a matte black hydrophobic coating is obtained.

[0024] The prepared black hydrophobic coating has a water contact angle of 133° and can be heated up to 67°C under sunlight.

[0025] 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 133°. And through the attached... Figure 2 Observation of the coating surface structure shows that the nanoparticles are uniformly distributed on the coating surface, forming a sufficiently rough structure; as shown in the attached figure. Figure 3 This image shows the photothermal effect of a matte black hydrophobic anti-icing coating prepared on a tinplate sheet. Under sunlight, the surface temperature of the coating rises from room temperature to 70°C. (Attached image) Figure 4 The hydrophobic, anti-icing coating exhibits a freezing time of up to 1500 seconds at -10℃. Figure 5 The hydrophobic anti-icing coating melts surface ice droplets within 150 seconds under single-level sunlight exposure and an ambient temperature of -15℃; (Attached) Figure 6 For the adhesion test of the hydrophobic anti-icing coating tape prepared in Example 1, the tape was repeatedly applied to and removed from the coating surface. After 300 cycles, the coating still had a water droplet contact angle higher than 130° and a water sliding angle lower than 10°. Figure 7 For the friction test of the hydrophobic anti-icing coating prepared in Example 1, sandpaper was continuously rubbed on the coating surface. After 300 rubs, the coating still had a water droplet contact angle of more than 130° and a water sliding angle of less than 10°.

[0026] 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 sub-black, high-stability, hydrophobic de / anti-icing composite coating and its controllable construction method, characterized in that, The method comprises the following steps: Step one, mixing 0.8-1.2 g of silane coupling agent and 10 ml of anhydrous ethanol to obtain a mixed solution; Step two, adding 0.08-0.12 g of hydrophilic silica nanoparticles into the mixed solution and ultrasonicating until the silica nanoparticles are uniformly dispersed to obtain a silica dispersion solution; Step three, adding 0.8-0.15 g of epoxy resin, 0.8-0.15 g of curing agent and 0.01-0.03 g of polydimethylsiloxane into 10 ml of ethyl acetate to obtain an epoxy solution; Step four, mixing 10.8-11.2 mL of the silica dispersion solution and 11.5-12.8 mL of the epoxy solution, and adding 0.07-0.13 g of carbon nanotubes, and then fully stirring to obtain a hydrophobic coating solution; Step five, spraying the hydrophobic coating solution on a sample, and then curing the sample in an oven at 120-150 ℃ for 2-2.5 h to obtain a dark brown hydrophobic coating.

2. The sub-black, high-stability, hydrophobic de / anti-icing composite coating and its controllable construction method according to claim 1, characterized in that, The silane coupling agent comprises any one of γ-aminopropyl triethoxysilane, γ-glycidyl ether propyl trimethoxysilane and γ-methacryloyl propyl trimethoxysilane.

3. The sub-stable black hydrophobic anti-ice / anti-icing composite coating and its controllable construction method according to claim 1, characterized in that, The hydrophilic silica nanoparticles have a particle size of 10-40 nm.

4. The sub-black, high-stability, hydrophobic de / anti-icing composite coating and its controllable construction method according to claim 1, characterized in that, The ultrasonicating in step two is performed for 25-30 min with stirring.

5. The sub-stable black hydrophobic anti-ice / de-ice composite coating and its controllable construction method according to claim 1, characterized in that, The curing agent comprises any one of PA650, T-31 or D-400.

6. The sub-stable black hydrophobic anti-ice / de-ice composite coating and its controllable construction method according to claim 1, characterized in that, The fully stirring in step four is performed for 12-24 h at 25-30 ℃.

7. The sub-stable black hydrophobic anti-ice / anti-ice composite coating and its controllable construction method according to claim 1, characterized in that, The spraying pressure of the spray gun during the spraying in step four is 0.2 MPa, the distance between the spray gun and the sample is 15-20 cm, and the moving speed of the spray gun is 2-4 cm / s.

8. A dark brown high-stability hydrophobic anti- / de-icing composite coating constructed by the method according to any one of claims 1-7.

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