Super-hydrophobic anti-icing coating and preparation method and application thereof

Abstract

This invention provides a superhydrophobic anti-icing coating, its preparation method, and its application. The preparation method includes the following steps: S1. Mixing anhydrous ethanol, nanoparticles, and a modifier, stirring for 3-4 hours, and then drying to obtain hydrophobic modified nanoparticles; S2. Dissolving polyphenylene alcohol resin in an organic solvent, and after complete dissolution, adding silicone resin and hydrophobic modified nanoparticles, stirring for 2-3 hours, then adding a silicone resin curing agent, and continuing to stir for 30-60 minutes to obtain a superhydrophobic anti-icing coating; S3. Applying the superhydrophobic anti-icing coating to the surface of a substrate and curing to obtain a superhydrophobic anti-icing coating. The use of polystyrene resin and silicone resin to form a composite bonding system, combined with hydrophobic modified nanoparticles to construct a micro-nano rough structure, is beneficial for simultaneously obtaining low surface energy and stable surface morphology, enabling it to function effectively at lower temperatures, providing both hydrophobic and anti-icing effects. The synergistic effect of these three components gives the coating both excellent superhydrophobic and anti-icing properties.

Description

Technical Field

[0001] This invention relates to the field of functional coating materials technology, and more specifically, to a superhydrophobic anti-icing coating, its preparation method, and its application. Background Technology

[0002] Hydrophobic or superhydrophobic functional coatings have good application prospects in fields such as superhydrophobicity, self-cleaning, antifouling, anti-corrosion, and anti-icing due to their high water contact angle and low droplet adhesion.

[0003] Existing methods for preparing superhydrophobic anti-icing coatings typically rely on chemical etching, electrochemical deposition, electrospinning, and plasma spraying to construct surface micro-nano rough structures. However, these methods generally suffer from high equipment requirements, complex processes, high costs, and limited substrate adaptability, hindering large-area application and industrialization. Furthermore, while some hydrophobic coatings possess high static contact angles, their surface micro-nano structures lack stability and are easily damaged by mechanical friction or environmental influences, leading to a decline in superhydrophobic and anti-icing performance. Therefore, developing a superhydrophobic anti-icing coating and its preparation method that utilizes readily available raw materials, employs simple processes, is easy to apply, and is applicable to various substrates is of significant practical importance. Summary of the Invention

[0004] In view of this, the present invention aims to propose a superhydrophobic anti-icing coating, its preparation method and application, in order to solve the problems of complex process, poor stability of micro-nano structure and insufficient substrate adaptability of superhydrophobic anti-icing coating in the prior art.

[0005] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0006] A superhydrophobic anti-icing coating comprises the following raw materials in parts by weight:

[0007] 5-10 parts polystyrene resin, 30-70 parts organic solvent, 10-20 parts silicone resin, 3-10 parts hydrophobic modified nanoparticles, and 1-2 parts silicone resin curing agent.

[0008] Furthermore, the hydrophobic modified nanoparticles comprise the following raw materials in parts by weight: 60-80 parts anhydrous ethanol, 5-15 parts nanoparticles, and 5-10 parts modifier.

[0009] Furthermore, the modifier is selected from at least one of n-octyltriethoxysilane, dodecyltrimethoxysilane, trichlorooctadecylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0010] Furthermore, the nanoparticles are selected from at least one of nano-silica, nano-titanium dioxide, and nano-alumina.

[0011] Furthermore, the organic solvent is selected from at least one of ethyl acetate and butyl acetate.

[0012] This invention also proposes a method for preparing a superhydrophobic anti-icing coating. The method comprises the following steps:

[0013] S1. Mix anhydrous ethanol, nanoparticles and modifier, stir for 3-4 hours and then dry to obtain hydrophobic modified nanoparticles;

[0014] S2. Dissolve polyphenylene alcohol resin in an organic solvent. After it is completely dissolved, add silicone resin and hydrophobic modified nanoparticles. Stir for 2-3 hours, then add silicone resin curing agent and continue stirring for 30-60 minutes to obtain a superhydrophobic anti-icing coating.

[0015] S3. Apply the superhydrophobic anti-icing coating to the substrate surface and cure it to obtain a superhydrophobic anti-icing coating.

[0016] Furthermore, in step S1, the drying temperature is 40~80℃. Even further, in step S1, the drying temperature is 40℃, 50℃, 60℃, 70℃, or 80℃.

[0017] Furthermore, in step S3, the superhydrophobic anti-icing coating is applied to the substrate surface by spraying, brushing, or spin coating.

[0018] Furthermore, in step S3, the substrate is a steel plate, stainless steel mesh, wood, glass, or fabric.

[0019] This invention also proposes the application of the above-mentioned superhydrophobic anti-icing coating in superhydrophobic antifouling, self-cleaning surfaces, and low-temperature environment protection.

[0020] Compared with existing technologies, the superhydrophobic anti-icing coating, its preparation method, and its application described in this invention have the following advantages:

[0021] (1) A composite bonding system is constructed using polystyrene resin and silicone resin, and a micro-nano rough structure is constructed by combining hydrophobic modified nanoparticles. This is beneficial for obtaining both low surface energy and stable surface morphology, and can also function at low temperatures, providing hydrophobic and anti-icing effects. The synergy of the three components gives the coating both excellent superhydrophobic and anti-icing properties.

[0022] (2) The preparation process of this invention is simple, requires little equipment, and is suitable for spraying, brushing or spin coating. Moreover, the raw materials are readily available and can be applied to various substrates such as steel plates, stainless steel mesh, wood, glass, and fabrics, and have good prospects for promotion and application. Attached Figure Description

[0023] 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 undue limitation of the invention. In the drawings:

[0024] Figure 1 The surface microstructure of Embodiment 1 of the present invention;

[0025] Figure 2 The static contact angle test results of the superhydrophobic anti-icing coating obtained in Example 1 of this invention;

[0026] Figure 3 The results of the freezing experiment of Example 1 of the present invention at -15℃ are shown.

[0027] Figure 4 The infrared spectral test results are from Example 1 of this invention;

[0028] Figure 5 The static contact angle test results of the superhydrophobic anti-icing coating obtained in Example 2 of this invention;

[0029] Figure 6 a represents the detachment distance of the superhydrophobic anti-icing coating obtained in Example 1 of this invention. Figure 6 b represents the detachment distance of the superhydrophobic anti-icing coating obtained in Example 3 of this invention;

[0030] Figure 7 The results of the icing test of the superhydrophobic anti-icing coating obtained in Example 4 of the present invention at -15℃ are shown.

[0031] Figure 8 a1 is a 3D outline diagram of the coating in Example 1. Figure 8 b1 is a 3D outline diagram of the coating in Example 5;

[0032] Figure 9 a represents the contact angle of the coating in Example 6. Figure 9 b is the roll-off angle of the coating in Example 6;

[0033] Figure 10 To assess the antifouling properties of immersing the empty glass plate and the coated glass plate from Example 7 in wastewater;

[0034] Figure 11 This is a icing experiment of Comparative Example 1 at -15℃. Detailed Implementation

[0035] The present invention will be further described below with reference to specific embodiments. First, it should be noted that the data in the following experimental examples were obtained by the inventors through numerous experiments. Due to space limitations, only a portion of these data is shown in the specification, and those skilled in the art can understand and implement the present invention based on this data. These embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the contents of this invention, those skilled in the art can make various modifications or alterations to the invention, and these modifications or alterations also fall within the scope of protection of this application.

[0036] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other.

[0037] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0038] The present invention discloses a superhydrophobic anti-icing coating comprising the following raw materials in parts by weight: 5-10 parts polystyrene resin, 30-70 parts organic solvent, 10-20 parts silicone resin, 3-10 parts hydrophobic modified nanoparticles, and 1-2 parts silicone resin curing agent, wherein the hydrophobic modified nanoparticles comprise the following raw materials in parts by weight: 60-80 parts anhydrous ethanol, 5-15 parts nanoparticles, and 5-10 parts modifier.

[0039] The modifier is selected from at least one of n-octyltriethoxysilane, dodecyltrimethoxysilane, trichlorooctadecylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0040] The nanoparticles are selected from at least one of nano-silica, nano-titanium dioxide, and nano-alumina.

[0041] The organic solvent is selected from at least one of ethyl acetate and butyl acetate.

[0042] The method for preparing the superhydrophobic anti-icing coating of the present invention includes the following steps:

[0043] S1. Mix anhydrous ethanol, nanoparticles and modifier, stir for 3-4 hours and then dry to obtain hydrophobic modified nanoparticles;

[0044] S2. Dissolve polyphenylene alcohol resin in an organic solvent. After it is completely dissolved, add silicone resin and hydrophobic modified nanoparticles. Stir for 2-3 hours, then add silicone resin curing agent and continue stirring for 30-60 minutes to obtain a superhydrophobic anti-icing coating.

[0045] S3. Apply the superhydrophobic anti-icing coating to the substrate surface and cure it to obtain a superhydrophobic anti-icing coating.

[0046] Specifically, in step S1, the drying temperature is 40~80℃.

[0047] In step S3, the superhydrophobic anti-icing coating is applied to the substrate surface by spraying, brushing, or spin coating.

[0048] In step S3, the curing method is room temperature curing or heat curing. The room temperature curing time is 4~24h, and the heat curing temperature is 50~110℃, with a heat curing time of 1~4h.

[0049] In step S3, the substrate is a steel plate, stainless steel mesh, wood, or fabric.

[0050] The superhydrophobic anti-icing coating of the present invention can be used for superhydrophobic antifouling, self-cleaning surfaces, and low-temperature environment protection.

[0051] This invention employs a composite bonding system of polystyrene resin and silicone resin, combined with hydrophobically modified nanoparticles to construct a micro / nano rough structure. This approach facilitates both low surface energy and stable surface morphology, allowing the coating to function effectively at lower temperatures, providing both hydrophobic and anti-icing properties. Specifically, polyphenylene ethanol resin facilitates the formation of a continuous coating and provides support for the rough structure. Silicone resin offers flexibility and weather resistance, preventing cracking during coating use, while also providing low surface energy and intrinsic hydrophobicity. The hydrophobically modified nanoparticles construct the micro / nano rough structure, which, supported by the polystyrene resin, is more stable and less prone to damage, reducing the contact area between water droplets and the substrate surface, resulting in an extremely high water contact angle and extremely low adhesion. The synergistic effect of these three components gives the coating both excellent superhydrophobic and anti-icing properties.

[0052] The preparation process of this invention is simple, requires minimal equipment, and is suitable for spraying, brushing, or spin coating. Furthermore, the raw materials are readily available, and the invention works on various substrates such as steel plates, stainless steel mesh, wood, glass, and fabrics, demonstrating promising prospects for widespread application.

[0053] Example 1

[0054] Weigh 5g of nano-silica, 75mL of anhydrous ethanol and 3mL of n-octyltriethoxysilane, stir for 4h to form a suspension, and then dry at 60℃ to obtain hydrophobically modified nanoparticles.

[0055] 6g of polyphenylethanol resin was dissolved in 45mL of butyl acetate and stirred until completely dissolved. Then, 12g of hydroxydimethylsiloxane and 6g of the hydrophobic modified nanoparticles prepared above were added and stirred for 2 hours. Then, 1.2g of methacryloyloxypropylmethyldiethoxysilane was added and stirred for 30 minutes to obtain a superhydrophobic anti-icing coating.

[0056] The obtained superhydrophobic anti-icing coating was sprayed onto the surface of a steel plate and cured at room temperature for 6 hours to obtain a superhydrophobic anti-icing coating.

[0057] Example 2

[0058] The formulation and preparation method of Example 2 are basically the same as those of Example 1. The only difference is that the modifier used in Example 2 is 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

[0059] Example 3

[0060] The formulation and preparation method of Example 3 and Example 1 are basically the same, the only difference being that the nanoparticles used in Example 2 are nano-alumina.

[0061] Example 4

[0062] The formulation and preparation method of Example 4 are basically the same as those of Example 1, the only difference being that the amount of polystyrene resin used is 7.5g and the amount of silicone resin used is 15g.

[0063] Example 5

[0064] The formulation and preparation method of Example 5 are basically the same as those of Example 1. The only difference is that the amount of hydrophobic modified nanoparticles used in step S2 is 7.5g.

[0065] Example 6

[0066] The formulation and preparation method of Example 6 and Example 5 are basically the same, the only difference being that the substrate in step S3 is made of 2000 mesh 304 stainless steel mesh.

[0067] Example 7

[0068] The formulation and preparation method of Example 7 and Example 5 are basically the same, the only difference being that the substrate in step S3 is a glass plate.

[0069] Comparative Example 1

[0070] The formulation and preparation method of Comparative Example 1 and Example 1 are basically the same, the only difference being that the polystyrene resin used in Comparative Example 1 is 15g.

[0071] The superhydrophobic anti-icing coatings obtained in Examples 1-7 of this invention were characterized, and their surface micromorphologies were identical. Due to space limitations, this invention only uses examples from... Figure 1 The surface microstructure of Example 1 is shown as an example. The hydrophobic anti-icing coating of Example 1 has a rough structure, which is beneficial to improving the superhydrophobic performance.

[0072] The static contact angle test results of the superhydrophobic anti-icing coating obtained in Example 1 are as follows: Figure 2As shown, the static contact angle can reach 162°, proving that it has superhydrophobic properties. The adhesion between water droplets and the substrate is greatly reduced, and superhydrophobicity is also the physical basis for achieving anti-icing function.

[0073] The freezing experiment results of Example 1 at -15℃ are as follows: Figure 3 As shown, the infrared spectroscopy test results are as follows: Figure 4 As shown. From Figure 3 It can be seen that, at a low temperature of -15℃, Example 1 exhibits good delayed freezing performance, with water droplets taking 1095s to completely freeze. From Figure 4 It can be seen that 3025cm -1 absorption peak at 2924 cm⁻¹ -1 The absorption peak at 1629 cm⁻¹ represents the stretching vibrations of CH and methylene groups on the benzene ring. -1 absorption peak at 1493 cm⁻¹ -1 absorption peak at 1452 cm⁻¹ -1 The absorption peak at 1095 cm⁻¹ represents the stretching vibration of the benzene ring skeleton, indicating that polystyrene was introduced in Example 1. -1 The absorption peak at 1260 cm⁻¹ represents the asymmetric stretching vibration of the Si-O-Si bond. -1 The absorption peak at 1095 cm⁻¹ represents the symmetrical deformation vibration of Si-CH₃, indicating that an organosilicon resin was introduced in Example 1. -1 absorption peak at 465 cm⁻¹ -1 The absorption peak at the point represents the Si-O-Si antisymmetric stretching and bending vibrations of the nano-SiO2 particles themselves, indicating that Example 1 successfully introduced nanoparticles into the coating.

[0074] like Figure 5 The static contact angle test results of the superhydrophobic anti-icing coating obtained in Example 2 are shown, with a static contact angle of 148.98°.

[0075] The desorption distances of the superhydrophobic anti-icing coatings obtained in Examples 1 and 3 are respectively as follows: Figure 6 As shown in 6a and 6b, the distance between the syringe and the coated substrate first decreases and then increases. The decreasing distance ensures that the water droplet from the syringe makes complete contact with the coating. The increasing distance primarily observes whether the water droplet detaches from the coating. Detachment indicates that the adhesion between the water droplet and the syringe is greater than the adhesion between the water droplet and the coating. The smaller the distance between the coating and the syringe during detachment, the weaker the adhesion between the coating and the water droplet. The detachment distance in Example 1 was 4.1 mm, and in Example 3 it was 3.5 mm. A smaller detachment distance indicates weaker adhesion between the water droplet and the coating, making it easier for the water droplet to roll off and delaying freezing.

[0076] like Figure 7The results of the icing test of the superhydrophobic anti-icing coating obtained in Example 4 at -15°C are shown. Example 4 exhibits good delayed icing performance, with water droplets taking 855 seconds to completely freeze.

[0077] like Figure 8 (a1) and (b1) are 3D contour diagrams of the coatings in Example 1 and Example 5, respectively, which can reflect the roughness of the coating. The greater the roughness, the better the hydrophobic performance. The roughness of the coating in Example 1 is Ra=192nm, and the roughness of the coating in Example 5 is Ra=215nm.

[0078] like Figure 9 a and 9b represent the contact angle and roll-off angle of the coating in Example 6, respectively. The contact angle is 152.28° and the roll-off angle is 3°.

[0079] The empty glass plate and the coated glass plate from Example 7 were respectively immersed in sewage for 30 seconds, and their antifouling performance was as follows: Figure 10 As shown, the empty glass plate had dirt residue, while the glass plate of Example 7 remained clean, indicating that the coating of the present invention has anti-fouling properties.

[0080] Comparative Example 1 altered the ratio of polystyrene resin to silicone resin, resulting in a higher amount of polystyrene resin and a reduced anti-icing performance of the prepared coating. For example... Figure 11 The figure shows the icing experiment of Comparative Example 1 at -15℃. It was completely iced in 360s, and its anti-icing performance was not as good as that of Examples 1 to 7 of the present invention.

[0081] While the present invention has been disclosed above, it is not limited thereto. Any person skilled in the art can make various alterations and modifications without departing from the spirit and scope of the invention; therefore, the scope of protection of the present invention should be determined by the scope defined in the claims.

Claims

1. A superhydrophobic anti-icing coating, characterized in that, The ingredients include the following parts by weight: 5-10 parts polystyrene resin, 30-70 parts organic solvent, 10-20 parts silicone resin, 3-10 parts hydrophobic modified nanoparticles, and 1-2 parts silicone resin curing agent.

2. The superhydrophobic anti-icing coating according to claim 1, characterized in that, The hydrophobic modified nanoparticles comprise the following raw materials in parts by weight: 60-80 parts anhydrous ethanol, 5-15 parts nanoparticles, and 5-10 parts modifier.

3. The superhydrophobic anti-icing coating according to claim 2, characterized in that, The modifier is selected from at least one of n-octyltriethoxysilane, dodecyltrimethoxysilane, trichlorooctadecylsilane, and 1H,1H,2H,2H-perfluorodecyltriethoxysilane.

4. The superhydrophobic anti-icing coating according to claim 2, characterized in that, The nanoparticles are selected from at least one of nano-silica, nano-titanium dioxide, and nano-alumina.

5. The superhydrophobic anti-icing coating according to claim 1, characterized in that, The organic solvent is selected from at least one of ethyl acetate and butyl acetate.

6. A method for preparing a superhydrophobic anti-icing coating, characterized in that, The preparation method is used to prepare the superhydrophobic anti-icing coating according to any one of claims 1 to 5, and the preparation method includes the following steps: S1. Mix anhydrous ethanol, nanoparticles and modifier, stir for 3-4 hours and then dry to obtain hydrophobic modified nanoparticles; S2. Dissolve polyphenylene alcohol resin in an organic solvent. After it is completely dissolved, add silicone resin and hydrophobic modified nanoparticles. Stir for 2-3 hours, then add silicone resin curing agent and continue stirring for 30-60 minutes to obtain a superhydrophobic anti-icing coating. S3. Apply the superhydrophobic anti-icing coating to the substrate surface and cure it to obtain a superhydrophobic anti-icing coating.

7. The preparation method according to claim 6, characterized in that, In step S1, the drying temperature is 40~80℃.

8. The preparation method according to claim 6, characterized in that, In step S3, the superhydrophobic anti-icing coating is applied to the substrate surface by spraying, brushing, or spin coating.

9. The preparation method according to claim 6, characterized in that, In step S3, the substrate is a steel plate, stainless steel mesh, wood, glass, or fabric.

10. The application of a superhydrophobic anti-icing coating as described in any one of claims 1 to 5 in superhydrophobic antifouling, self-cleaning surface, and low-temperature environment protection.

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